Condensed heterocylic compounds and herbicides containing them as active ingredients

TECHNICAL FIELD

[0001] The present invention relates to condensed heterocyclic compounds and their use.

DISCLOSURE OF INVENTION

[0002] The present inventors have extensively studied to find compounds having excellent herbicidal activity. As a result, they have found that the condensed heterocyclic compounds of general formula I as depicted below have excellent herbicidal activity, thereby completing the present invention.

[0003] The present invention provides condensed heterocyclic compounds of general formula I:

[0004] (hereinafter referred to as the present compounds)

[0005] wherein T is carbon or nitrogen; when T is carbon, then the bond between T and A is a double bond, the bond between A and Y is a single bond, and Y is oxygen, sulfur, or N—R142; or when T is nitrogen, then the bond between T and A is a single bond, the bond between A and Y is a double bond, and Y is nitrogen or C—R152;

[0006] wherein R142 is hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, cyano, —COR143, —N(R145)R146, or —N═C(R147)R148; R152 is hydrogen, halogen, C1-C3 alkyl, nitro, amino, cyano, or —COR153;

[0007] wherein R143 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxyl, C1-C5 alkoxy, or —N(R156)N157; R145 and R146 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, formyl, (C1-C5 alkyl)carbonyl, (C1-C5 haloalkyl)carbonyl, or (C1-C5 alkoxy)carbonyl; R147 and R148 are independently hydrogen or C1-C5 alkyl; R15 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxyl, C1-C5 alkoxy, or —N(R154)R155;

[0008] wherein R156 and R157 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, formyl, (C1-C5 alkyl)carbonyl, (C1-C5 haloalkyl)carbonyl, or (C1-C5 alkoxy)carbonyl; R154 and R155 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, (C1-C5 alkoxy)carbonyl, formyl, (C1-C5 alkyl)carbonyl, or (C1-C5 haloalkyl)carbonyl;

[0009] A is nitrogen or C—R141 wherein R141 is hydrogen, halogen, or C1-C3, alkyl;

[0010] R1 is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxymethyl, nitro, or cyano;

[0011] R2 is hydrogen, halogen, C1-C11 alkyl, C1-C11 haloalkyl, hydroxymethyl, nitro, cyano, —N(R9)R10, —OR11, —SR12, —SO2R13, —COX, —COOR14, —CON—(R15)R16, —COR17, —C(R26)═NOR19, —C(R27)═C(R21)R22, or —CH(R23)—CH(R24)R25;

[0012] R3 is hydrogen, halogen, C1-C11 alkyl, C1-C11 haloalkyl, hydroxymethyl, nitro, cyano, —N(R59)R60, —OR61, —SR62, —SO2R63, —COX, —COOR64, —CO—N(R65)R66, —COR67, —C(R76)═NOR69, —C(R77)═C(R71)R72, or —CH(R73)—CH(R74)R75;

[0013] R4 is hydrogen, halogen, C1-C3 alkyl, C1-C3 haloalkyl, hydroxymethyl, nitro, or cyano;

[0014] wherein X is chlorine or bromine;

[0015] R9 and R59 are independently hydrogen, C1-C5 alkyl, (C1-C5 alkyl)-carbonyl, or (C1-C5 alkoxy)carbonyl;

[0016] R10, R11, and R12 are independently hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C3-C10 alkenyl, C3-C10 haloalkenyl, C3-C10 alkynyl, C3-C10 haloalkynyl, cyano C1-C6 alkyl, (C1-C5 alkyl)carbonyl, (C1-C5 haloalkyl)carbonyl, (C3-C10 cycloalkyl)carbonyl, (C1-C5 alkyl)carbonyl C1-C5 alkyl, (C1-C5 haloalkyl)carbonyl C1-C5 alkyl, hydroxy C1-C5 alkyl, C1-C5 alkoxy C1-C5 alkyl, C1-C5 alkylthio C1-C5 alkyl, (C1-C5 alkoxy)carbonyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl, —C(R43)(R44)—C(═O)ON(R45)R46, —C(R47)(R48)—CON(R49)R50, —CH2—C(R56)═N—OR55, —CHMe—C(R56)═NOR57, (C3-C10 alkenoxy)carbonyl C1-C5 alkyl, (C3-C10 alkynoxy)carbonyl C1-C5 alkyl, phenoxycarbonyl, benzyloxycarbonyl, carboxy (C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 alkoxy)carbonyl (C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10 alkenoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10alkynoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, carboxy(C1-C5 alkyl)carbonyl, (C1-C10 alkoxy)carbonyl(C1-C5 alkyl)carbonyl, (C1-C10 haloalkoxy)carbonyl(C1-C5 alkyl)carbonyl, C1-C5 alkylsulfonyl, C1-C5 haloalkylsulfonyl, —SO2N—(R51)R52, —CON(R53)R54, optionally substituted benzyl, or optionally substituted phenyl;

[0017] R60, R61, and R62 are independently hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 halocycloalkyl, C3-C10cycloalkyl C1-C3 alkyl, C3-C10 alkenyl, C1-C10 haloalkenyl, C3-C10 alkynyl, C3-C10 haloalkynyl, cyano C1-C6 alkyl, (C1-C5 alkyl)carbonyl, (C1-C5 haloalkyl)carbonyl, (C3-C10 cycloalkyl)carbonyl, (C1-C5 alkyl)carbonyl C1-C5 alkyl, (C1-C5 haloalkyl)carbonyl C1-C5 alkyl, hydroxy C1-C5 alkyl, C1-C5 alkoxy C1-C5 alkyl, C1-C5 alkylthio C1-C5 alkyl, (C1-C5 alkoxy)carbonyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl, —C(R163)(R164)—C(═O)ON(R165)R166, —C(R167)R168)—CON(R169)R170, —CH2—C—(═NOR175)R176, —CHMe—C(═NOR177)R178, (C3-C10 alkenoxy)carbonyl C1-C5 alkyl, (C3-C10 alkynoxy)carbonyl C1-C5 alkyl, phenoxycarbonyl, benzyloxycarbonyl, carboxy(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 alkoxy)carbonyl (C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl (C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10 alkenoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, (C3-C10 alkynoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl, carboxy(C1-C5 alkyl)carbonyl, (C1-C10alkoxy)carbonyl(C1-C5 alkyl)carbonyl, (C1-C1-0haloalkoxy)carbonyl(C1-C5 alkyl)carbonyl, C1-C5 alkylsulfonyl, C1-C5 haloalkylsulfonyl, —SO2N(R171)R172, —CON(R173)R174, optionally substituted benzyl, or optionally substituted phenyl;

[0018] wherein R43, R44, R163, and R164 are independently hydrogen, halogen, C1-C5 alkyl, or C1-C5 haloalkyl;

[0019] R45, R46, R165, and R166 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R45 and R46 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring, or R165 and R166 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring;

[0020] R47, R48, R167, and R168 are independently hydrogen, halogen, C1-C5 alkyl, or C1-C5 haloalkyl;

[0021] R49, R50, R169, and R170 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R49 and R50 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring, or R169 and R170 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0022] R51, R52, R171, and R172 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C0-C6 alkynyl; or R51 and R52 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring, or R171 and R172 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0023] R53, R54, R173, and R174 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R1 and R54 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring, or R173 and R174 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0024] R56, R57, R175, and R177 are independently hydrogen or C1-C3 alkyl;

[0025] R56, R58, R176, and R178 are independently hydrogen, C1-C5 alkyl (C1-C5 alkoxy)carbonyl, (C1-C5 haloalkoxy)carbonyl, (C3-C5 cycloalkoxy)carbonyl, (C3-C5 alkenoxy)carbonyl, or (C3-C5 alkynoxy)carbonyl;

[0026] R13 is hydroxy, chlorine, C1-C10 alkyl, C1-C10 haloalkyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10halocycloalkoxy)carbonyl C1-C5 alkyl, —N(R79)R80, or —OR81;

[0027] R63 hydroxy, chlorine, C1-C10alkyl, C1-C10 haloalkyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl, —N(R179)R180, or —OR181;

[0028] wherein R79 and R179 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl; R80 and R180 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R79 and R80 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- or 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring; or R179 and R180 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- or 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring; and R81 and R181 are independently C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl;

[0029] R14 is hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 halocycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C3-C10 alkenyl, C3-C10haloalkenyl, C1-C10 alkynyl, C3-C10 haloalkynyl, carboxy C0-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 alkenoxy)carbonyl C1-C5 alkyl, (C3-C10 alkynoxy)carbonyl C1-C5 alkyl, —N(R82)R83, optionally substituted benzyl, or optionally substituted phenyl;

[0030] R64 is hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10cycloalkyl, C3-C10halocycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C3-C10 alkenyl, C3-C10 haloalkenyl, C3-C10 alkynyl, C3-C10 haloalkynyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10halocycloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 alkenoxy)carbonyl C1-C5 alkyl, (C3-C10alkynoxy)carbonyl C1-C5 alkyl, —N(R182)R183, optionally substituted benzyl, or optionally substituted phenyl;

[0031] wherein R82 and R182 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl; R83 and R183 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R82 and R83 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring; or R182 and R183 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0032] R15 and R65 are independently hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C1-C10cycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C1-C10 alkenyl, C3-C10alkynyl, cyano C1-C6 alkyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, optionally substituted benzyl, or optionally substituted phenyl; R16 and R66 are independently hydrogen, C1-C10 alkyl, or C1-C10 haloalkyl; or R15 and R16 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring; or R65 and R66 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0033] R17, R26, R27, R67, R76, and R77 are independently hydrogen, cyano, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10cycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, (C1-C6 alkoxy)carbonyl, or (C1-C6 alkoxy)carbonylmethyl;

[0034] R19 and R69 are independently hydrogen, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C3-C10 halocycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C3-C10 alkenyl, C3-C10 haloalkenyl, C3-C10 alkynyl, C3-C10 haloalkynyl, cyano C1-C6 alkyl, carboxy C1-C5 alkyl, (C1-C10alkoxy)carbonyl C1-C5 alkyl, (C1-C10haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl;

[0035] R21 and R71 are independently hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl;

[0036] R22 and R25 are independently carboxy, (C1-C10 alkoxy)carbonyl, (C1-C10 haloalkoxy)carbonyl, (C3-C10 cycloalkoxy)carbonyl, (C1-C10 halocycloalkoxy)carbonyl, carboxy(C1-C5 alkoxy)carbonyl, (C1-C10 alkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C1-C10 haloalkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10 cycloalkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10 alkenoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10 alkynoxy)carbonyl (C1-C5 alkoxy)carbonyl, —CON(R84)R85, or —C(═O)ON(R86)R87;

[0037] R72 and R75 are independently carboxy, (C1-C10 alkoxy)carbonyl, (C1-C10haloalkoxy)carbonyl, (C3-C10 cycloalkoxy)carbonyl, (C3-C10halocycloalkoxy)carbonyl, carboxy(C1-C5 alkoxy)carbonyl, (C1-C10 alkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C1-C10 haloalkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10cycloalkoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10alkenoxy)carbonyl (C1-C5 alkoxy)carbonyl, (C3-C10 alkynoxy)carbonyl (C1-C5 alkoxy)carbonyl, —CON(R184)R185, or —C(═O)ON(R186)R187;

[0038] wherein R84 and R184 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C5 alkenyl, C3-C6 alkynyl, carboxy C1-C5 alkyl, (C1-C10alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl; R85 and R185 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R84 and R85 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring; or R184 and R185 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring containing zero to one oxygen atom or NH group in the ring;

[0039] R86 and R186 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C3-C8 Cycloalkyl, C3-C6 alkenyl, C3-C6 alkynyl, carboxy C1-C5 alkyl, (C1-C10 alkoxy)carbonyl C1-C5 alkyl, (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl, (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl, or (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl; R87 and R187 are independently hydrogen, C1-C5 alkyl, C1-C5 haloalkyl, C1-C8 cycloalkyl, C3-C6 alkenyl, or C3-C6 alkynyl; or R86 and R87 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring; or R186 and R187 may be combined at their ends to form, together with the adjacent nitrogen atom, a 3- to 7-membered saturated ring;

[0040] R23, R , R73, and R74 are independently hydrogen, halogen, C1-C3 alkyl, or C1-C3 haloalkyl; and

[0041] Q is any one group of Q1 to Q23 of the general formula:

[0042] wherein:

[0043] in Q1, E1 and E2 are independently C1-C6 alkyl optionally substituted with halogen, or C3-C6 cycloalkyl optionally substituted with halogen; or E1 and E2 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring (which unsaturated ring includes no aromatic rings), and the ring may optionally be substituted with methyl or halogen;

[0044] in Q2, E3 and E4 are independently C1-C6 alkyl optionally substituted with halogen, or C3-C6 cycloalkyl optionally substituted with halogen; or E3 and E4 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen; D1 and D2 are independently oxygen or sulfur; and Z1 is nitrogen or CH;

[0045] in Q3, E5 is hydrogen or C1-C6 alkyl optionally substituted with halogen; and D3 is oxygen or sulfur;

[0046] in Q4, E6 and E7 are independently hydrogen, C1-C6 alkyl optionally substituted with halogen, or C3-C6 cycloalkyl optionally substituted with halogen; or E6 and E7 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen;

[0047] in Q5, E8 and E9 are independently hydrogen, C1-C6 alkyl optionally substituted with halogen, or C3-C6 cycloalkyl optionally substituted with halogen; or E8 and E9 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen;

[0048] in Q6, E10 is hydrogen, C1-C6 alkyl optionally substituted with halogen, or C1-C3 alkoxy optionally substituted with halogen; E11 is hydrogen or C1-C6 alkyl optionally substituted with halogen; or E10 and E11 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring (which unsaturated ring includes no aromatic rings), and the ring may optionally be substituted with methyl or halogen; and E44 is halogen or C1-C3 alkyl;

[0049] in Q7, E12 is C1-C6 alkyl optionally substituted with halogen; and D4 is oxygen or sulfur;

[0050] in Q8, E13 is C1-C6 alkyl optionally substituted with halogen; and E14 is hydrogen or halogen;

[0051] in Q9, E15 is hydrogen or C1-C6 alkyl; E16 is C1-C6 alkyl optionally substituted with halogen; or E15 and E16 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring (which unsaturated ring includes no aromatic rings), and the ring may optionally be substituted with methyl or halogen;

[0052] in Q10, E17, E18, and E19 are independently hydrogen or C1-C6 alkyl; and D5 is oxygen or sulfur;

[0053] in Q11, E20 and E21 are independently hydrogen or C1-C6 alkyl; and D6 is oxygen or sulfur;

[0054] in Q12, E22 and E23 are independently hydrogen or C1-C6 alkyl;

[0055] in Q13, E24 is hydrogen or C1-C3 alkyl;

[0056] in Q14, E25 is hydrogen, C1-C3 alkyl, or halogen; E26 is C1-C3 alkyl optionally substituted with halogen; E27 is hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, or optionally substituted benzyl; and D7 is oxygen or sulfur;

[0057] in Q15, E28 is C1-C3 alkyl optionally substituted with halogen; E29 is hydrogen, amino, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, or optionally substituted benzyl; and D8 is oxygen or sulfur;

[0058] in Q16, E30 is C1-C3 alkyl optionally substituted with halogen, E31 is hydrogen or C1-C3 alkyl optionally substituted with halogen; or E30 and E31 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring (which unsaturated ring includes no aromatic rings), and the ring may optionally be substituted with methyl or halogen; and E42 is hydrogen or C1-C3 alkyl optionally substituted with halogen;

[0059] in Q17, E32 is C1-C3 alkyl optionally substituted with halogen; E33 is hydrogen, halogen, amino, C1-C3 alkyl optionally substituted with halogen, C1-C3 alkoxy optionally substituted with halogen, or C1-C3 alkylthio optionally substituted with halogen; and E43 is hydrogen or C1-C3 alkyl optionally substituted with halogen;

[0060] in Q18, E34 is C1-C3 alkyl optionally substituted with halogen;

[0061] in Q19, D9 is oxygen or sulfur; and V1 is —CH2—, —CH2—CH2—, or —CH2—CH2—CH2—;

[0062] in Q20, E35 is C1-C3 alkyl optionally substituted with halogen; Z2 is nitrogen or CH; and V2 is —CH2—CH2—, —CH═CH—, —N═CH—, —CH═N—, or —N═N—;

[0063] in Q21, E36 and E37 are independently C1-C6 alkyl; or E36 and E37 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen; D10 and D11 are independently oxygen or sulfur; and Z3 is nitrogen or CH;

[0064] in Q22, E38 is hydrogen or C1-C6 alkyl; E39 is C1-C3 alkyl optionally substituted with halogen; or E38 and E39 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen; and D12 is oxygen or sulfur; and

[0065] in Q23, E40 is hydrogen or C1-C6 alkyl; E41 is C1-C3 alkyl, or C3-C6 cycloalkyl; or E40 and E41 may be combined at their ends to form, together with the atoms attached thereto, a 4- to 7-membered saturated or unsaturated ring containing zero to two O, S, SO, SO2, or NH groups in the ring, and the ring may optionally be substituted with methyl or halogen; and D13 is oxygen or sulfur.

[0066] The present invention further provides herbicides containing them as active ingredients, and condensed heterocyclic compounds of general formula II:

[0067] wherein A1 is C—R31 and Y11 is oxygen, sulfur, or N—R32; wherein R31 is nitro, amino, cyano, carboxyl, or (C1-C3 alkoxy)carbonyl, and R32 is hydrogen, C1-C5 alkyl, C3-C8 alkenyl, or C3-C6 alkynyl; and Q, R1, R2, R3, and R4 are as defined above, which heterocyclic compounds are useful as intermediates for the production of the present compounds.

MODE FOR CARRYING OUT THE INVENTION

[0068] For the groups represented by R142, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0069] For the groups represented by R143, C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl; C1-C3 haloalkyl may include trifluoromethyl and difluoromethyl; and C1-C5 alkoxy may include methoxy, ethoxy, propoxy, and isopropoxy.

[0070] For the groups represented by R145 or R146, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; (C1-C5 alkyl)carbonyl may include acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl; (C1-C5 haloalkyl)carbonyl may include trifluoroacetyl, difluoroacetyl, chlorodifluoroacetyl, and dichloroacetyl; and (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, and isopropoxycarbonyl.

[0071] For the groups represented by R147 or R148, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl.

[0072] For the elements or groups represented by R152, halogen may include fluorine, chlorine, bromine, and iodine; and C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl.

[0073] For the groups represented by R153, C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl; C1-C3 haloalkyl may include trifluoromethyl and difluoromethyl; and C1-C5 alkoxy may include methoxy, ethoxy, propoxy, and isopropoxy.

[0074] For the groups represented by R156 or R157, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; (C1-C5 alkyl)carbonyl may include acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl; (C1-C5 haloalkyl)carbonyl may include trifluoroacetyl, difluoroacetyl, chlorodifluoroacetyl, and dichloroacetyl; and (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, and isopropoxycarbonyl.

[0075] For the groups represented by R154 or R155, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; (C1-C5 alkyl)carbonyl may include acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl; (C1-C5 haloalkyl)carbonyl may include trifluoroacetyl, difluoroacetyl, chlorodifluoroacetyl, and dichloroacetyl; and (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, and isopropoxycarbonyl.

[0076] For the groups or elements represented by R141, C1-C3 alkyl may include methyl, ethyl, and isopropyl; and halogen may include fluorine, chlorine, bromine, and iodine.

[0077] For groups represented by R31, (C1-C3 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and isopropoxycarbonyl.

[0078] For the groups represented by R32, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0079] For the elements or groups-represented by R1, halogen may include fluorine, chlorine, bromine, and iodine; C1-C3 alkyl may include methyl and ethyl; and C1-C3 haloalkyl may include trifluoromethyl and difluoromethyl.

[0080] For the elements or groups represented by R2 or R3, halogen may include fluorine, chlorine, bromine, and iodine; C1-C11 alkyl may include methyl, ethyl, and isopropyl; and C1-C11 haloalkyl may include trichloromethyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, pentafluoroethyl, and 1,1-difluoroethyl.

[0081] For the elements or groups represented by R4, halogen may include fluorine, chlorine, bromine, and iodine; C1-C3 alkyl may include methyl and ethyl; and C1-C3 haloalkyl may include trifluoromethyl and difluoromethyl.

[0082] For the groups represented by R9 or R59, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl (wherein “t” means “tertiary”; this also holds below), and isoamyl; (C1-C5 alkyl)carbonyl may include acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl; and (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and t-butoxycarbonyl.

[0083] For the groups represented by R10, R11, R12, R60, R61, or R62, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; C1-C10 haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl; C3-C10cycloalkyl may include cyclopentyl and cyclohexyl; C3-C10halocycloalkyl may include 4,4,-difluorocyclopentyl and 3-chlorocyclohexyl; C3-C10cycloalkyl C1-C3 alkyl may include cyclopropylmethyl, cyclopentylmethyl, and cyclohexylmethyl; C3-C10 alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C10 haloalkenyl may include 2-chloro-2-propenyl and 3,3-dichloro-2-propenyl; C1-C10 alkynyl may include propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, and 1,1-dimethyl-2-propynyl; C3-C10 haloalkynyl may include 3-iodo-2-propynyl and 3-bromo-2-propynyl; cyano C1-C6 alkyl may include cyanomethyl and cyanoethyl; (C1-C5 alkyl)carbonyl may include acetyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, and butylcarbonyl; (C1-C5 haloalkyl)carbonyl may include trifluoroacetyl, difluoroacetyl, chlorodifluoroacetyl, and dichloroacetyl; (C3-C10cycloalkyl)carbonyl may include cyclopropylcarbonyl and cyclopentylcarbonyl; (C1-C5 alkyl)carbonyl C1-C5 alkyl may include 2-oxopropyl, 3-methyl-2-oxobutyl, and 3-oxopentyl; (C1-C5 haloalkyl)carbonyl C1-C5 alkyl may include 3,3,3-trifluoro-2-oxopropyl; hydroxy C1-C5 alkyl may include 2-hydroxyethyl and 4-hydroxybutyl; C1-C5 alkoxy C1-C5 alkyl may include methoxymethyl, 1-methoxyethyl, and ethoxymethyl; C1-C5 alkylthio C1-C5 alkyl may include methylthiomethyl and methylthioethyl; (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and t-butoxycarbonyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl; (C3-C10alkenoxy)carbonyl C1-C5 alkyl may include allyoxycarbonylmethyl, 1-methyl-2-propenyloxycarbonylmethyl, 1-allyloxycarbonylethyl, and 1-(1-methyl-2-propenyloxy)carbonylethyl; (C1-C10 alkynoxy)carbonyl C1-C5 alkyl may include propargyloxycarbonylmethyl, 1-methyl-2-propynyloxycarbonylmethyl, 1-propargyloxycarbonylethyl, 1-(1-methyl-2-propynyloxy)carbonylethyl; carboxy(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include carboxymethoxycarbonylmethyl, 1-carboxyethoxycarbonylmethyl, 1-carboxy-1-methylethoxycarbonylmethyl, 1-(carboxymethoxycarbonyl)ethyl, 1-(1-carboxyethoxycarbonyl)ethyl, and 1-(1-carboxy-1-methylethoxycarbonyl)ethyl; (C1-C10alkoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethoxycarbonylmethyl, 1-methoxycarbonylethoxycarbonylmethyl, 1-methoxycarbonyl-1-methylethoxycarbonylmethyl, 1-(methoxycarbonylmethoxycarbonyl)ethyl, 1-(1-meth oxycarbonylethoxycarbonyl)ethyl, 1-(1-methoxycarbonyl-1-methylethoxycarbonyl)ethyl, ethoxycarbonylmethoxycarbonylmethyl, 1-ethoxycarbonylethoxycarbonylmethyl, 1-ethoxycarbonyl-1-methylethoxycarbonylmethyl, 1-(ethoxycarbonylmethoxycarbonyl)ethyl, 1-(1-ethoxycarbonylethoxycarbonyl)ethyl, 1-(1-ethoxycarbonyl-1-methylethoxycarbonyl)ethyl, isopropoxycarbonylmethoxycarbonylmethyl, 1-isopropoxycarbonylethoxycarbonylmethyl, 1-isopropoxycarbonyl-1-methylethoxycarbonylmethyl, 1-(isopropoxycarbonylmethoxycarbonyl)ethyl, 1-(1-isopropoxycarbonylethoxycarbonyl)ethyl, and 1-(1-isopropoxycarbonyl-1-methylethoxycarbonyl)ethyl; (C1-C10 haloalkoxy)carbonyl-(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethoxycarbonylmethyl, 1-(2-chloroethoxycarbonyl)ethoxycarbonylmethyl, 1-(2-chloroethoxycarbonyl)-1-methylethoxycarbonylmethyl, 1-(2-chloroethoxycarbonylmethoxycarbonyl)ethyl, 1-{1-(2-chloroethoxycarbonyl)ethoxycarbonyl}ethyl, and 1-{1-(2-chloroethoxycarbonyl)-1-methylethoxycarbonyl}ethyl; (C3-C10 cycloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethoxycarbonylmethyl, 1-cyclopentyloxycarbonylethoxycarbonylmethyl, 1-cyclopentyloxycarbonyl-1-methylethoxycarbonylmethyl, 1-(cyclopentyloxycarbonylmethoxycarbonyl)ethyl, 1-(1-cyclopentyloxycarbonylethoxycarbonyl)ethyl, 1-(1-cyclopentyloxycarbonyl-1-methylethoxycarbonyl)ethyl, cyclohexyloxycarbonylmethoxycarbonylmethyl, 1-cyclohexyloxycarbonylethoxycarbonylmethyl, 1-cyclohexyloxycarbonyl-1-methylethoxycarbonylmethyl, 1-(cyclohexyloxycarbonylmethoxycarbonyl)ethyl, 1-(1-cyclohexyloxycarbonylethoxycarbonyl)ethyl, and 1-(1-cyclohexyloxycarbonyl-1-methylethoxycarbonyl)ethyl; (C3-C10 alkenoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include allyloxycarbonylmethoxycarbonylmethyl, 1-allyloxycarbonylethoxycarbonylmethyl, 1-allyloxycarbonyl-1-methylethoxycarbonylmethyl, 1-(allyloxycarbonylmethoxycarbonyl)ethyl, 1-(1-allyloxycarbonylethoxycarbonyl)ethyl, and 1-(1-allyloxycarbonyl-1-methylethoxycarbonyl)ethyl; (C3-C10 alkynoxy)carbonyl(C1-C5 alkoxy)carbonyl C1-C5 alkyl may include propargyloxycarbonylmethoxycarbonylmethyl, 1-propargyloxycarbonylethoxycarbonylmethyl, 1-propargyloxycarbonyl-1-methylethoxycarbonylmethyl, 1-(propargyloxycarbonylmethoxycarbonyl)ethyl, 1-(1-propargyloxycarbonylethoxycarbonyl) ethyl, and 1-(1-propargyloxycarbonyl-1-methylethoxycarbonyl)ethyl; carboxy(C1-C5 alkyl)carbonyl may include carboxymethylcarbonyl, carboxyethylcarbonyl, 1-carboxy-1-methylethylcarbonyl, 2-carboxyethylcarbonyl, 3-carboxypropylcarbonyl, and 3-carboxy-1-methylpropylcarbonyl; (C1-C10 alkoxy)carbonyl(C1-C5 alkyl)carbonyl may include methoxycarbonylmethylcarbonyl, 1-methoxycarbonylethylcarbonyl, 1-methoxycarbonyl-1-methylethylcarbonyl, 2-methoxycarbonylethylcarbonyl, 3-methoxycarbonylpropylcarbonyl, 3-methoxycarbonyl-1-methylpropylcarbonyl, ethoxycarbonylmethylcarbonyl, 1-ethoxycarbonylethylcarbonyl, 1-ethoxycarbonyl-1-methylethylcarbonyl, 2-ethoxycarbonylethylcarbonyl, 3-ethoxycarbonylpropylcarbonyl, and 3-ethoxycarbonyl-1-methylpropylcarbonyl; (C1-C10haloalkoxy)carbonyl(C1-C5 alkyl)carbonyl may include 2-chloroethoxycarbonylmethylcarbonyl, 2,2,2-trifluoroethoxycarbonylmethylcarbonyl, 3-bromopropoxycarbonylmethylcarbonyl, 1-(2-chloroethoxy)carbonylethylcarbonyl, and 1-(2,2,2-trifluoroethoxy)carbonylethylcarbonyl; C1-C5 alkylsulfonyl may include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and butylsulfonyl; C1-C5 haloalkylsulfonyl may include chloromethylsulfonyl, and trifluoromethylsulfonyl; optionally substituted benzyl may include benzyl; and optionally substituted phenyl may include phenyl.

[0084] For the groups represented by R13 or R63, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, and isoamyl; C1-C10 haloalkyl may include trifluoromethyl; carboxy C1-C5 alkyl may include carboxymethyl, carboxyethyl, 1-carboxyethyl, and 2-carboxypropyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C110 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclo hexyloxycarbonylmethyl.

[0085] For the groups represented by R14 or R64, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; C1-C10haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl; C3-C10cycloalkyl may include cyclopentyl and cyclohexyl; C3-C10 halocycloalkyl may include 4,4,-difluorocyclopentyl and 3-chlorocyclohexyl; C3-C10cycloalkyl C1-C3 alkyl may include cyclopropylmethyl, cyclopentylmethyl, and cyclohexylmethyl; C3-C10alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C10 haloalkenyl may include 2-chloro-2-propenyl, and 3,3-dichloro-2-propenyl; C3-C10 alkynyl may include propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, and 1,1-dimethyl-2-propynyl; C3-C10 haloalkynyl may include 3-iodo-2-propynyl, and 3-bromo-2-propynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, and 1-carboxy-1-methylethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-methoxycarbonyl-1-methylethyl, 1-ethoxycarbonyl-1-methylethyl, 1-propoxycarbonyl-1-methylethyl, 1-isopropoxycarbonyl-1-methylethyl, 1-butoxycarbonyl-1-methylethyl, 1-isobutoxycarbonyl-1-methylethyl, 1-t-butoxycarbonyl-1-methylethyl, 1-amyloxycarbonyl-1-methylethyl, 1-isoamyloxycarbonyl-1-methylethyl, and 1-t-butoxycarbonyl-1-methylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, 1-(2,2,2-trifluoroethoxy)carbonylethyl, 1-(2-chloroethoxy)carbonyl-1-methylethyl, and 1-(2,2,2-trifluoroethoxy)carbonyl-1-methylethyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, 1-cyclohexyloxycarbonylethyl, 1-cyclopentyloxycarbonyl-1-methylethyl, and 1-cyclohexyloxycarbonyl-1-methylethyl; (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl, and 1-(4-fluorocyclohexyloxycarbonyl)-1-methylethyl; (C3-C10 alkenoxy)carbonyl C1-C5 alkyl may include allyloxycarbonylmethyl, 1-methyl-2-propenyloxycarbonylmethyl, 1-allyloxycarbonylethyl, 1-(1-methyl-2-propenyloxy)carbonylethyl, 1-allyloxycarbonyl-1-methylethyl, and 1-(1-methyl-2-propenyloxy)carbonyl-1-methylethyl; (C1-C10 alkynoxy)carbonyl C1-C5 alkyl may include propargyloxycarbonylmethyl, 1-methyl-2-propynyloxycarbonylmethyl, 1-propargyloxycarbonylethyl, 1-(1-methyl-2-propynyloxy)carbonylethyl, 1-propargyloxycarbonyl-1-methylethyl, and 1-(1-methyl-2-propynyloxy)carbonyl-1-methylethyl; optionally substituted benzyl may include benzyl; and optionally substituted phenyl may include phenyl.

[0086] For the groups represented by R15 or R65, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; C1-C10 haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl; C3-C10cycloalkyl may include cyclopentyl, and cyclohexyl; C3-C10cycloalkyl C1-C3 alkyl may include cyclopropylmethyl, cyclopentylmethyl, and cyclohexylmethyl; C3-C10 alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C10 alkynyl may include propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, and 1,1-dimethyl-2-propynyl; cyano C1-C6 alkyl may include cyanomethyl, and cyanoethyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; optionally substituted benzyl may include benzyl; and optionally substituted phenyl may include phenyl.

[0087] For the groups represented by R16 or R16, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; and C1-C10 haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl.

[0088] The 3- to 7-membered saturated ring, which is formed by combining R15 and R16 or R65 and R66 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0089] For the groups represented by R17, R26, R27, R67, R76, or R77, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; C1-C10 haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl; C3-C10cycloalkyl may include cyclopentyl, and cyclohexyl; C3-C10cycloalkyl C1-C3 alkyl may include cyclopropylmethyl, cyclopentylmethyl, and cyclohexylmethyl; (C1-C6 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, and isopropoxycarbonyl; and (C1-C6 alkoxy)carbonylmethyl may include methoxy carbonylmethyl, ethoxycarbonylmethyl, and isopropoxycarbonylmethyl.

[0090] For the groups represented by R19 or R69, C1-C10 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, t-butyl, isoamyl, pentyl, hexyl, heptyl, and octyl; C1-C10haloalkyl may include 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 3-chlorobutyl, 3-bromobutyl, difluoromethyl, and 2,2,2-trifluoroethyl; C3-C10cycloalkyl may include cyclopentyl and cyclohexyl; C3-C10 halocycloalkyl may include 4,4,-difluorocyclopentyl and 3-chlorocyclohexyl; C3-C1 cycloalkyl C1-C3 alkyl may include cyclopropylmethyl, cyclopentylmethyl, and cyclohexylmethyl; C3-C10alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C10 haloalkenyl may include 2-chloro-2-propenyl, and 3,3-dichloro-2-propenyl; C3-CC1, alkynyl may include propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, and 1,1-dimethyl-2-propynyl; C3-C10 haloalkynyl may include 3-iodo-2-propynyl, and 3-bromo-2-propynyl; cyano C1-C6 alkyl may include cyanomethyl and cyanoethyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1- ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2, 2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0091] For the elements or groups represented by R21 or R71, halogen may include fluorine, chlorine, bromine, and iodine; C1-C3 alkyl may include methyl and ethyl; and C1-C3 haloalkyl may include trifluoromethyl.

[0092] For the groups represented by R22, R25, R72, or R75, (C1-C10 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, amyloxycarbonyl, and isoamyloxycarbonyl; (C1-C10 haloalkoxy)carbonyl may include 2-chloroethoxycarbonyl, 2-fluoroethoxycarbonyl,-3-bromopropoxycarbonyl, 3-chlorobutoxycarbonyl, and 5,5-dichloroamyloxycarbonyl; (C3-C10cycloalkoxy)carbonyl may include cyclopentyloxycarbonyl and cyclohexylcarbonyl; (C3-C10halocycloalkoxy)carbonyl may include 4,4-difluorocyclohexyloxycarbonyl; carboxy(C1-C5 alkoxy)carbonyl may include carboxymethoxycarbonyl, 1-carboxyethoxycarbonyl, and 1-carboxy-1-methylethoxycarbonyl; (C1-C10alkoxy)carbonyl(C1-C5 alkoxy)carbonyl may include methoxycarbonylmethoxycarbonyl, 1-methoxycarbonylethoxycarbonyl, 1-methoxycarbonyl-1-methylethoxycarbonyl, ethoxycarbonylmethoxycarbonyl, 1-ethoxycarbonylethoxycarbonyl, 1-ethoxycarbonyl-1-methylethoxycarbonyl, isopropoxycarbonylmethoxycarbonyl, 1-isopropoxycarbonylethoxycarbonyl, and 1-isopropoxycarbonyl-1-methylethoxycarbonyl; (C1-C10 haloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl may include 2-chloroethoxycarbonylmethoxycarbonyl, 1-(2-chloroethoxycarbonyl)ethoxycarbonyl, and 1-(2-chloroethoxycarbonyl)-1-methylethoxycarbonyl; (C3- C10 cycloalkoxy)carbonyl(C1-C5 alkoxy)carbonyl may include cyclopentyloxycarbonylmethoxycarbonyl, 1-cyclopentyloxycarbonylethoxycarbonyl, 1-cyclopentyloxycarbonyl-1-methylethoxycarbonyl, cyclohexyloxycarbonylmethoxycarbonyl, 1-cyclohexyloxycarbonylethoxycarbonyl, and 1-cyclohexyloxycarbonyl-1-methylethoxycarbonyl; (C3-C10 alkenoxy)carbonyl(C1-C5 alkoxy)carbonyl may include allyloxycarbonylmethoxycarbonyl, 1-allyloxycarbonylethoxycarbonyl, and 1-allyloxycarbonyl-1-methylethoxycarbonyl; and (C3-C10 alkynoxy)carbonyl(C1-C5 alkoxy)carbonyl may include propargyloxycarbonylmethoxycarbonyl, 1-propargyloxycarbonylethoxycarbonyl, and 1-propargyloxycarbonyl-1-methylethoxy carbonyl.

[0093] For the elements or groups represented by R23, R24, R73, or R74, halogen may include fluorine, chlorine, bromine, and iodine; C1-C3 alkyl may include methyl, and ethyl; and C1-C3 haloalkyl may include trifluoromethyl.

[0094] For the elements or groups represented by R43, R44, R13, or R164, halogen may include fluorine, chlorine, bromine, and iodine; C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; and C1-C5 haloalkyl may include trifluoromethyl.

[0095] For the groups represented by R45, R46, R165, or R166, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0096] The 3- to 7-membered saturated ring, which is formed by combining R45 and R46 or R165 and R166 at their ends, together with the adjacent nitrogen atom, may include aziridine ring, azetidine ring, pyrrolidine ring, and piperidine ring.

[0097] For the elements and groups represented by R47, R48, R167, or R168, halogen may include fluorine, chlorine, bromine, and iodine; C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; and C1-C5 haloalkyl may include trifluoromethyl.

[0098] For the groups represented by R49, R50, R169, or R170, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl, and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0099] The 3- to 7-membered ring, which is formed by combining R49 and R50 or R169 and R170 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0100] For the groups represented by R51, R52, R171, or R172, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0101] The 3- to 7-membered ring, which is formed by combining R51 and R52 or R171 and R172 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0102] For the groups represented by R53, R54, R1, or R174, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0103] The 3- to 7-membered ring, which is formed by combining R53 and R54 or R173 and R174 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0104] For the groups represented by R55, R57, R75, or R177, C1-C3 alkyl may include methyl, ethyl, and propyl.

[0105] For the groups represented by R55, R57, R175, or R177, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; (C1-C5 alkoxy)carbonyl may include methoxycarbonyl, ethoxycarbonyl, and propyloxycarbonyl; (C1-C5 haloalkoxy)carbonyl may include trifluoromethoxycarbonyl and 2,2,2-trifluoroethoxycarbonyl; (C3-C5 cycloalkoxy)carbonyl may include cyclopropyloxycarbonyl; (C3-C5 alkenoxy)carbonyl may include allyloxycarbonyl; and (C3-C5 alkynoxy)carbonyl may include propargyloxy carbonyl.

[0106] For the groups represented by R79 or R179, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2 ,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; C1-C6 alkynyl may include propargyl and 1-methylpropynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C1-C10 halocycloalkoxy) carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0107] For the groups represented by R80 or R180, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methyl propenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0108] The 3- to 7-membered ring, which is formed by combining R79 and R80 or R179 and R180 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0109] For the groups represented by R81 or R181, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; C3-C6 alkynyl may include propargyl and 1-methylpropynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0110] For the groups represented by R82 or R182, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; C3-C6 alkynyl may include propargyl and 1-methylpropynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamylpxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10halocydoalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0111] For the groups represented by R83 or R183, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C1-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C1-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0112] The 3- to 7-membered ring, which is formed by combining R82 and R83 or R182 and R183 at their ends, together with the adjacent nitrogen, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0113] For the groups represented by R84 or R184, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; C3-C6 alkynyl may include propargyl and 1-methylpropynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10 cycloalkoxy)carbonyl C1-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0114] For the groups represented by R85 or R185, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0115] The 3- to 7-membered ring, which is formed by combining R84 and R85 or R84 and R185 at their ends, together with the adjacent nitrogen atom, and which contains zero to one oxygen atom or NH group in the ring, may include aziridine ring, azetidine ring, pyrrolidine ring, piperidine ring, morpholine ring, and piperazine ring.

[0116] For the groups represented by R16 or R186, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; C3-C6 alkynyl may include propargyl and 1-methylpropynyl; carboxy C1-C5 alkyl may include carboxymethyl, 1-carboxyethyl, and 2-carboxyethyl; (C1-C10 alkoxy)carbonyl C1-C5 alkyl may include methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl, isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-ethoxycarbonylethyl, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1-butoxycarbonylethyl, 1-isobutoxycarbonylethyl, 1-t-butoxycarbonylethyl, 1-amyloxycarbonylethyl, 1-isoamyloxycarbonylethyl, and 1-t-butoxycarbonylethyl; (C1-C10 haloalkoxy)carbonyl C1-C5 alkyl may include 2-chloroethoxycarbonylmethyl, 2,2,2-trifluoroethoxycarbonylmethyl, 3-bromopropoxycarbonylmethyl, 1-(2-chloroethoxy)carbonylethyl, and 1-(2,2,2-trifluoroethoxy)carbonylethyl; (C3-C10 cycloalkoxy)carbonyl C3-C5 alkyl may include cyclopentyloxycarbonylmethyl, cyclohexyloxycarbonylmethyl, 1-cyclopentyloxycarbonylethyl, and 1-cyclohexyloxycarbonylethyl; and (C3-C10 halocycloalkoxy)carbonyl C1-C5 alkyl may include 4-fluorocyclohexyloxycarbonylmethyl.

[0117] For the groups represented by R87 or R187, C1-C5 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl; C1-C5 haloalkyl may include 2-chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, and 3-bromopropyl; C3-C8 cycloalkyl may include cyclopentyl, cyclohexyl, and cycloheptyl; C3-C6 alkenyl may include allyl and 1-methylpropenyl; and C3-C6 alkynyl may include propargyl and 1-methylpropynyl.

[0118] The 3- to 7-membered ring, which is formed by combining R86 and R87 or R186 and R187 at their ends, together with the adjacent nitrogen atom, may include aziridine ring, azetidine ring, pyrrolidine ring, and piperidine ring.

[0119] For the groups represented by E1 or E2, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, and chlorodifluoromethyl; and C1-C6 cycloalkyl optionally substituted with halogen may include cyclopropyl, cyclobutyl, and cyclopentyl.

[0120] The 4- to 7-membered unsaturated ring, which is formed by combining E1 and E2 at their ends and which contains, together with the atoms attached thereto on Q1, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E1 and E2.

[0121] For the groups represented by E3 or E4, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and 3-fluoropropyl; and C3-C6 cycloalkyl optionally substituted with halogen may include cyclopropyl, cyclobutyl, and cyclopentyl.

[0122] The 4- or 7-membered saturated or unsaturated ring, which is formed by combining E3 and E4 at their ends and which contains, together with the atoms attached thereto on Q2, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E3 and E4.

[0123] For the groups represented by E5, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 3-fluoropropyl, and 4-fluorobutyl.

[0124] For the groups or elements represented by E6 or E7, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and 3-fluoropropyl; and C3-C6 cycloalkyl optionally substituted with halogen may include cyclopropyl, cyclobutyl, and cyclopentyl.

[0125] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E6 and E7 at their ends and which contains, together with the atoms attached thereto on Q4, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E6 and E7.

[0126] For the groups represented by E8 or E9, C1-C8 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and 3-fluoropropyl; and C3-C6 cycloalkyl optionally substituted with halogen may include cyclopropyl, cyclobutyl, and cyclopentyl.

[0127] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E8 and E9 at their ends and which contains, together with the atoms attached thereto on Q5, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E8 and E9.

[0128] For the groups represented by E10, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and 3-fluoropropyl; and C1-C3 alkoxy optionally substituted with halogen may include methoxy, ethoxy, propoxy, isopropoxy, trifluoromethoxy, and difluoromethoxy.

[0129] For the groups represented by E11, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, pentafluoroethyl, and 3-fluoropropyl.

[0130] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E10 and E11 at their ends and which contains, together with the atoms attached thereto on Q6, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E10 and E11.

[0131] For the elements or groups represented by E44, halogen may include fluorine, chlorine, bromine, or iodine; and C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl.

[0132] For the groups represented by E12, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0133] For the groups represented by E13, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0134] For the elements represented by E14, halogen may include chlorine, bromine, and iodine.

[0135] For the groups represented by E15, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and amyl.

[0136] For the groups represented by E16, C1-C6 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0137] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E15 and E16 at their ends and which contains, together with the atoms attached thereto on Q9, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include those in which tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E15 and E6.

[0138] For the groups represented by E17, E18, or E19, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl.

[0139] For the groups represented by E20 or E21, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl.

[0140] For the groups represented by E22 or E23, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and amyl.

[0141] For the groups represented by E24, C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl.

[0142] For the groups or elements represented by E25, C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl; and halogen may include fluorine, chlorine, bromine, and iodine.

[0143] For the groups represented by E26, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chloro difluoromethyl, and pentafluoroethyl.

[0144] For the groups represented by E27, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, isoamyl, pentyl, and hexyl; C3-C6 alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C6 alkynyl may include propargyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, and 1,1-dimethyl-2-propynyl; and optionally substituted benzyl may include benzyl.

[0145] For the groups represented by E28, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0146] For the groups represented by E29, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, isoamyl, pentyl, and hexyl; C3-C6 alkenyl may include allyl, 1-methyl-2-propenyl, 3-butenyl, 2-butenyl, 3-methyl-2-butenyl, and 2-methyl-3-butenyl; C3-C6 alkynyl may include propargyl, 1-methyl-3-propynyl, 2-butynyl, 3-butynl, and 1,1-dimethyl-2-propynyl; and optionally substituted benzyl may include benzyl.

[0147] For the groups represented by E30 or E31, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0148] The 4- to 7-membered unsaturated ring, which is formed by combining E30 and E31 at their ends and which contains zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include the cases where tetramethylene or trimethylene is formed by E30 and E31.

[0149] For the groups represented by E42, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0150] For the groups represented by E32, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0151] For the elements or groups represented by E33, halogen may include chlorine, bromine, and iodine; C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl and pentafluoroethyl; C1-C3 alkoxy optionally substituted with halogen may include methoxy and ethoxy; and C1-C3 alkylthio optionally substituted with halogen may include methylthio and ethylthio.

[0152] For the groups represented by E43, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoro ethyl.

[0153] For the groups represented by E34, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0154] For the groups represented by E35, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0155] For the groups represented by E36 or E37, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, isoamyl, pentyl, and hexyl.

[0156] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E36 and E37 at their ends and which contains, together with the atoms attached thereto on Q21, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include the cases where tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E36 and E37.

[0157] For the groups represented by E38, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, isoamyl, pentyl, and hexyl.

[0158] For the groups represented by E39, C1-C3 alkyl optionally substituted with halogen may include methyl, ethyl, propyl, isopropyl, trifluoromethyl, difluoromethyl, chlorodifluoromethyl, and pentafluoroethyl.

[0159] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E38 and E39 at their ends and which contains, together with the atoms attached thereto on Q22, zero to two O, S, SO, SO2 or NH groups (which ring may optionally be substituted with methyl or halogen), may include the cases where tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E38 and E39.

[0160] For the groups represented by E40, C1-C6 alkyl may include methyl, ethyl, propyl, isopropyl, isobutyl, butyl, isoamyl, pentyl, and hexyl.

[0161] For the groups represented by E41, C1-C3 alkyl may include methyl, ethyl, propyl, and isopropyl; and C3-C6 cycloalkyl may include cyclopropyl, cyclopentyl, and cyclohexyl.

[0162] The 4- to 7-membered saturated or unsaturated ring, which is formed by combining E40 and E41 at their ends and which contains, together with the atoms attached thereto on Q23 (which ring may optionally be substituted with methyl or halogen), may include the cases where tetramethylene, trimethylene, or 2,2-dimethyltrimethylene is formed by E40 and E41.

[0163] For the present compounds, there may exist geometrical isomers based on the presence of a double bond, or optical isomers and diastereomers based on the presence of at least one asymmetric carbon atom, and all of these isomers and their mixtures are also included within the scope of the present invention.

[0164] The preferred substituents from the viewpoint of herbicidal activity may include CH, CCH3, CCl, CBr and N, more preferably CH and N, for A, and Q1, Q2, Q4, Q6, Q14, Q16, Q18, Q19 and Q20 for Q.

[0165] When Q is Q1, compounds in which E1 and E2 are combined at their ends to form, together with the atoms attached thereto, a 5- to 7-membered unsaturated ring are preferred, and in particular, compounds in which the unsaturated ring is a 6-membered ring are more preferred.

[0166] When Q is Q2, compounds in which E3 and E4 are combined at their ends to form, together with the atoms attached thereto, a 5- to 7-membered saturated or unsaturated ring are preferred, and in particular, compounds in which the saturated or unsaturated ring is a 6-membered ring and D1 and D2 are oxygen are more preferred.

[0167] When Q is Q4, compounds in which E6 is C1-C6 alkyl optionally substituted with halogen and E7 is C1-C6 alkyl optionally substituted with halogen are preferred, and in particular, compounds in which E6 is methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl) or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1,1-difluoroethyl) and E7 is methyl or ethyl are more preferred. In addition, compounds in which E6 and E7 are combined at their ends to form, together with the atoms attached thereto, a 5- or 7-membered saturated or unsaturated ring are preferred, and in particular, compounds in which the saturated or unsaturated ring is a 6-membered ring are more preferred.

[0168] When Q is Q6, compounds in which E10 is C1-C6 alkyl optionally substituted with halogen, E11 is C1-C6 alkyl optionally substituted with halogen, and E44 is chlorine or bromine are preferred, and in particular, compounds in which E10 is methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl) or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1,1-difluoroethyl) and E11 is methyl or ethyl are more preferred. In addition, compounds in which E10 and E11 are combined at their ends to form, together with the atoms attached thereto, a 5- to 7-membered saturated or unsaturated ring are preferred, and in particular, compounds in which the saturated or unsaturated ring is a 6-membered ring are more preferred.

[0169] When Q is Q14, compounds in which D7 is oxygen, E25 is hydrogen, E26 is C1-C, alkyl optionally with halogen, and E27 is C1-C3 alkyl are preferred, and in particular, compounds in which E26 is methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl) or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1, 1-difLuoroethyl) and E27 is methyl or ethyl are more preferred.

[0170] When Q is Q16, compounds in which E30 is C1-C3 alkyl optionally substituted with halogen, E31 is hydrogen or C1-C3 alkyl, and E42 is hydrogen or C1-C3 alkyl are preferred, and in particular, compounds in which E30 is methyl, methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl), or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1,1-difluoroethyl), E31 is hydrogen or methyl, and E42 is hydrogen or methyl are more preferred. In addition, compounds in which E30 and E31 are combined at their ends to form, together with the atoms attached thereto, a 5- or 7-membered saturated or unsaturated ring are preferred, and in particular, compounds in which the saturated or unsaturated ring is a 5- or 6-membered ring are more preferred.

[0171] When Q is Q18, compounds in which E34 is C1-C3 alkyl optionally substituted with halogen are preferred, and in particular, compounds in which E34 is methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl) or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1,1-difluoroethyl) are more preferred.

[0172] When Q is Q19, compounds in which V1 is —CH2— or —CH2—CH2— are preferred.

[0173] When Q is Q20, compounds in which E35 is C1-C3 alkyl optionally substituted with halogen, Z2 is nitrogen, and V2 is —CH2—CH2— or —CH═CH— are preferred, and in particular, compounds in which E11 is methyl substituted with fluorine (e.g., trifluoromethyl, chlorodifluoromethyl, difluoromethyl) or ethyl substituted with fluorine (e.g., pentafluoroethyl, 1,1-difluoroethyl) are more preferred.

[0174] Specific examples of the preferred compounds are recited below:

[0175] Methyl 3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0176] Ethyl 3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydro pyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0177] Isopropyl 3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetra hydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0178] Methyl 3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydro pyrimidin-1-yl]-6-nitrobenzo[b]furan-5-carboxylate;

[0179] Ethyl 3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydro pyrimidin-1-yl]-6-nitrobenzo[b]furan-5-carboxylate;

[0180] Methyl 6-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0181] Ethyl 6-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0182] Methyl 7-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0183] Ethyl 7-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-carboxylate;

[0184] 3-(5-Methoxybenzo[b]furan-3-yl)-1-methyl-6-(trifluoromethyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0185] 3-(5-Methoxy-6-nitrobenzo[b]furan-3-yl)-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0186] 3-(6-Chloro-5-methoxyb enzo[b]furan-3-yl)-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0187] 3-(7-Chloro-5-methoxybenzo[b]furan-3-yl)-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0188] 3-[5-(Allyloxy)benzo[b]furan-3-yl]-1-methyl-6-(trifluoromethyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0189] 3-[5-(Allyloxy)-6-nitrobenzo[b]furan-3-yl]-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0190] 3-[5-(Allyloxy)-6-chlorobenzo[b]furan-3-yl]-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0191] 3-[5-(Allyloxy)-7-chlorobenzo[b]furan-3-yl]-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0192] 1-Methyl-3-[5-(prop-2-ynyloxy)benzo[b]furan-3-yl]-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0193] 1-Methyl-3-[6-nitro-5-(prop-2-ynyloxy)b enzo[b]furan-3-yl]-6-(tri fluoromethyl)-1,2,3 ,4-tetrahydropyrimidine-2,4-dione;

[0194] 3-[6-Chloro-5-(prop-2-ynyloxy)benzo[b]furan-3-yl]-1-methyl-6-(tri fluoromethyl)-1,2,3,4-tetrahydiopyrimidine-2,4-dione;

[0195] 3-[7-Chloro-5-(prop-2-ynyloxy)benzo[b]furan-3-yl]-1-methyl-6-(tri fluoromethyl)-1,2,3 ,4-tetrahydropyrimidine-2,4-dione;

[0196] Ethyl 2-({3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetra hydropyr imidin-1-yl]benzo[b]furan-5-yl}oxy)propanoate;

[0197] Ethyl 2-({6-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-yl}oxy)propanoate;

[0198] Ethyl 2-({7-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-yl}oxy)propanoate;

[0199] 1-Methyl-3-[5-(methylthio)benzo[b]furan-3-yl]-6-(trifluoromethyl) -1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0200] 1-Methyl-3-[5-(methylthio)-6-nitrobenzo[b]furan-3-yl]-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0201] 3-[6-Chloro-5-(methylthio)benzo[b]furan-3-yl]-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0202] 3-[7-Chloro-5-(methylthio)benzo[b]furan-3-yl]-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0203] Ethyl 2-({3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetra hydropyrimidin-1-yl]-6-nitrobenzo[b]furan-5-yl}thio)propanoate;

[0204] Ethyl 2-({6-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-yl}thio)propanoate;

[0205] Ethyl 2-({7-chloro-3-[3-methyl-2,6-dioxo-4-(trifluoromethyl)-1,2,3,6-tetrahydropyrimidin-1-yl]benzo[b]furan-5-yl}thio)propanoate;

[0206] 3-(5,7-Dichlorobenzo[b]furan-3-yl)-1-methyl-6-(trifluoromethyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione;

[0207] 3-(5-Bromo-7-chlorobenzo[b]furan-3-yl)-1-methyl-6-(trifluoromethyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione; and

[0208] 3-(7-Chloro-5-methylbenzo[b]furan-3-yl)-1-methyl-6-(trifluoro methyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione.

[0209] The present compounds can be produced, for example, by Producing Processes 1 to 27 as described below.

[0210] Producing Process 1

[0211] In the process, compound a-1 of the general formula:

[0212] wherein T, A, Y, R1, R2, R3, and R4 are as defined above, is reacted with acid anhydride a-5 of the general formula:

[0213] wherein E1 and E2 are as defined above.

[0214] The reaction is carried out without solvent or in a solvent. The reaction temperature is usually in the range of 50° C. to 200° C. The reaction time is usually in the range of 1 to 100 hours. The amounts of reagents to be used in the reaction are 1 mole of acid anhydride a-5 relative to 1 mole of compound a-1, which is the stoichiometric ratio but can be freely changed depending upon the reaction conditions.

[0215] The solvent which can be used may include aliphatic hydrocarbons such as hexane, heptane, octane, and ligroin; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and methyl t-butyl ether; nitro compounds such as nitromethane and nitrobenzene; organic acids such as acetic acid and propionic acid; acid amides such as N,N-dimethylformamide; sulfur compounds such as dimethyl-sulfoxide and sulforane; and mixtures thereof. In addition, acids such as p-toluenesulfonic acid can also be used as a reaction catalyst.

[0216] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography. (see JP-A55-139359.)

[0217] Producing Process 2

[0218] This is the producing process according to the following scheme:

[0219] wherein R1, R2, R3, R4, D1, D2, E3, E4, T, A, and Y are as defined above, R200 is C1-C5 alkyl (e.g., methyl, ethyl) or hydrogen.

[0220] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 61-27985, or for example, by the following processes.

[0221] 1) Process of Producing Compound a-2 from Compound a-1

[0222] Compound a-2 can be produced by converting compound a-1 into an isocyanate or isothiocyanate derivative in a solvent or without solvent.

[0223] Agent for conversion into isocyanate or isothiocyanate derivatives: phosgene, trichloromethyl chloroformate, oxalyl chloride, thiophosgene, etc.

[0224] Amount of agent for conversion into isocyanate or isothiocyanate derivatives: 1 equivalent to an excess amount relative to 1 mole of compound a-1

[0225] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; etc.

[0226] Reaction temperature: room temperature to the reflux temperature of the agent for conversion into isocyanate or isothiocyanate derivatives Reaction time: a moment to 48 hours

[0227] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected -by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0228] 2) Process of Producing Compound a-3 from Compound a-2

[0229] Compound a-3 can be produced by reacting compound a-2 with compound a-6 of the general formula:

[0230] wherein D1, E3, E4, and R200 are as defined above, in a solvent in the presence of a base.

[0231] Amount of compound a-6: 1 to 5 moles relative to 1 mole of compound a-2

[0232] Kind of base: inorganic bases such as sodium hydride and potassium carbonate; organic bases such as triethylamine; metal alcoholates such as sodium methylate; etc.

[0233] Amount of base: 0.1 to 10 moles relative to 1 mole of compound a-2

[0234] Solvents: ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as ethanol; and mixtures thereof; etc.

[0235] Reaction temperature: −15° C. to the reflux temperature of the solvent

[0236] Reaction time: a moment to 96 hours

[0237] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0238] Compound a-4 may be directly obtained depending upon the reaction conditions of this process.

[0239] 3) Process of Producing Compound a-4 from Compound a-3

[0240] Compound a-4 can be produced by reacting compound a-3 in a solvent in the presence of a base.

[0241] Kind of base: inorganic bases such as sodium hydride; metal alcoholates such as sodium methylate; etc.

[0242] Amount of base: 1 to 5 moles relative to 1 mole of compound a-3

[0243] Solvent: ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as methanol and ethanol; and mixtures thereof, etc.

[0244] Reaction temperature: −10° C. to the reflux temperature of the solvent Reaction time: a moment to 96 hours

[0245] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0246] Producing Process 3

[0247] This is the producing process according to the following scheme:

[0248] wherein R1, R2, R3, R4, R200, D1, D2, E3, E4, T, A, and Y are as defined above.

[0249] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 61-27985, or for example, by the following processes.

[0250] 1) Process of Producing Compound b-3 from Compound a-2 Compound b-3 can be Produced by Reacting Compound a-2 With Compound b-5 of the General Formula:

[0251] wherein D1, E3, E4, and R200 are as defined above, in a solvent in the presence of a base.

[0252] Amount of compound b-5: 1 to 5 moles relative to 1 mole of compound a-2

[0253] Kind of base: inorganic bases such as sodium hydride and potassium carbonate; organic bases such as triethylamine; metal alcoholates such as sodium methylate; etc.

[0254] Amount of base: 0.1 to 10 moles relative to 1 mole of compound a-2 Solvent: ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as ethanol; and mixtures thereof; etc.

[0255] Reaction temperature: −15° C. to the reflux temperature of the solvent

[0256] Reaction time: a moment to 96 hours

[0257] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0258] Compound b-4 may be directly obtained depending upon the reaction conditions of this process.

[0259] 2) Process of Producing Compound b-4 from Compound b-3 Compound b-4 can be Produced by Reacting Compound b-3 in a Solvent in the Presence of a base.

[0260] Kind of base: inorganic bases such as sodium hydride; metal alcoholates such as sodium methylate; etc.

[0261] Amount of base: 1 to 5 moles relative to 1 mole of compound b-3

[0262] Solvent: ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as methanol and ethanol; and mixtures thereof; etc.

[0263] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0264] Reaction time: a moment to 96 hours

[0265] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0266] Producing Process 4

[0267] This is the producing process according to the following scheme:

[0268] wherein R1, R2, R3, R4, D3, E5, T, A, and Y are as defined above.

[0269] The reactions in the respective steps can be carried out, for example, according to the processes as described in WO87/03873, or for example, by the following processes.

[0270] 1) Process of Producing Compound c-1 from Compound a-1

[0271] Compound c-1 can be produced from compound a-1 according to the process as described above in Producing Process 2, Step 1).

[0272] 2) Process of Producing Compound c-2 from Compound c-1

[0273] Compound c-2 can be produced by reacting compound c-1 and trimethylsilyl azide in a solvent or without solvent

[0274] Amount of trimethylsilyl azide: 1 to 3 moles relative to 1 mole of compound c-1

[0275] Solvent: benzene, toluene, chlorobenzene, etc.

[0276] Reaction temperature: room temperature to the reflux temperature

[0277] Reaction time: a moment to 48 hours

[0278] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0279] 3) Process of Producing Compound c-3 from Compound c-2

[0280] Compound c-3 can be produced by reacting compound c-2 and compound c-4 of the general formula:

M1-E5 c-4

[0281] wherein E5 is as defined above and M1 is chlorine, bromine, iodine, or methanesulfonyloxy, in a solvent in the presence of a base.

[0282] Amount of compound c-4: 1 to 3 moles relative to 1 mole of compound c-2

[0283] Kind of base: sodium hydride, potassium carbonate, etc.

[0284] Amount of base: 1 to 10 moles relative to 1 mole of compound c-2

[0285] Solvent: N,N-dimethylformamide, tetrahydrofuran, etc.

[0286] Reaction temperature: room temperature to 150° C.

[0287] Reaction time: a moment to 48 hours

[0288] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0289] Producing Process 5

[0290] This is the producing process according to the following scheme:

[0291] wherein R201 is methoxy, ethoxy or dimethylamino; and R1, R2, R3, R4, E6, E7, T, A, and Y are as defined above.

[0292] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 60-149571, or for example, by the following processes.

[0293] 1) Process of Producing Compound d-1 from Compound a-1

[0294] Compound d-1 can be produced by converting compound a-1 into a diazonium salt with sodium nitrite in the presence of an acid and then reacting the diazonium salt with a reducing agent such as tin (II) chloride. (see Organic Synthesis Collective Volume 1, p. 442.)

[0295] (Diazonium Salt Formation)

[0296] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound a-1

[0297] Kind of acid: hydrochloric acid etc.

[0298] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound a-1

[0299] Solvent: water, ethanol, hydrochloric acid, etc.

[0300] Reaction temperature: −15° C. to room temperature

[0301] Reaction time: a moment to 24 hours

[0302] (Reduction Reaction)

[0303] Kind of reducing agent: tin (II) chloride etc.

[0304] Amount of reducing agent: 3 to 10 moles relative to 1 mole of compound a-1

[0305] Solvent: hydrochloric acid etc.

[0306] Reaction temperature: −15° C. to room temperature

[0307] Reaction time: a moment to 48 hours

[0308] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0309] 2) Process of Producing Compound d-3 from Compound d-1

[0310] Compound d-3 can be produced by reacting compound d-1 and compound d-5 of the general formula:

[0311] wherein E7 and R201 are as defined above and R202 is methyl or ethyl, in a solvent, if necessary, in the presence of a base, to give intermediate d-2 and then reacting the intermediate d-2 in the presence of a base.

[0312] Intermediate d-2 may be isolated.

[0313] (Reaction of Compound d-1 into Compound d-2)

[0314] Amount of compound d-5: 1 to 3 moles relative to 1 mole of compound d-1.

[0315] Kind of base: organic bases such as triethylamine and pyridine; metal alcoholates such as sodium methylate and sodium ethylate; inorganic bases such as sodium hydroxide and potassium carbonate; etc.

[0316] Solvent: aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as ethanol and isopropanol; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran and 1,4-dioxane; etc.

[0317] Reaction temperature: 0° C. to the reflux temperature of the solvent

[0318] Reaction time: a moment to 48 hours

[0319] (Reaction of Compound d-2 into Compound d-3)

[0320] Kind of base: organic bases such as triethylamine and pyridine; metal alcoholates such as sodium methylate and sodium ethylate; inorganic bases such as sodium hydroxide and potassium carbonate; etc.

[0321] Amount of base: 0.1 to 10 moles relative to 1 mole of compound a-1

[0322] Solvent: aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated aromatic hydrocarbons such as chlorobenzene; alcohols such as ethanol and isopropanol; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran and 1,4-dioxane; etc.

[0323] Reaction temperature: 0° C. to the reflux temperature of the solvent Reaction time: a moment to 48 hours After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0324] 3) Process of Producing Compound d-4 from Compound d-3

[0325] Compound d-4 can be produced by reacting compound d-3 with compound d-6 of the general formula:

M1-E6 d-6

[0326] wherein E6 and M1 are as defined above, in a solvent in the presence of a base.

[0327] Amount of compound d-6: 1 to 3 moles relative to 1 mole of compound d-3

[0328] Kind of base: sodium hydride, potassium carbonate, etc.

[0329] Amount of base: 1 to 10 moles relative to 1 mole of compound d-3

[0330] Solvent: N,N-dimethylformamide, tetrahydrofuran, etc.

[0331] Reaction temperature: 0° C. to the reflux temperature of the solvent

[0332] Reaction time: a moment to 48 hours

[0333] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0334] Compound d-3 can also be produced according to the following scheme. (see JP-A 7-503253.)

[0335] wherein R1, R2, R3, R4, E7, T, A, and Y are as defined above.

[0336] 1) Process of Producing Compound e-1 from Compound d-1

[0337] Compound e-1 can be produced by reacting compound d-1 with compound e-3 of the general formula:

[0338] wherein E7 is as defined above, in a solvent.

[0339] Amount of compound e-3: 1 to 10 moles relative to 1 mole of compound d-1

[0340] Solvent: water; alcohols such as ethanol and t-butanol; and mixtures thereof; etc.

[0341] Reaction temperature: −15° C. to 70° C.

[0342] Reaction time: a moment to 24 hours

[0343] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0344] Compound e-1 can also be used as such for the reaction in the next step without isolation.

[0345] 2) Process of Producing Compound e-2 from Compound e-1

[0346] Compound e-2 can be produced by reacting compound e-1 with an alkali metal cyanate, in a solvent, if necessary, in the presence of an acid.

[0347] Kind of alkali metal cyanate: NaOCN, KOCN, etc.

[0348] Amount of alkali metal cyanate: 1 to 3 moles relative to 1 mole of compound e-1

[0349] Kind of acid: organic acids such as acetic acid

[0350] Amount of acid: 0.01 to 1 mole relative to 1 mole of compound e-1

[0351] Solvent: water; alcohols such as ethanol and t-butanol; and mixtures thereof; etc.

[0352] Reaction temperature: −15° C. to 80° C.

[0353] Reaction time: a moment to 48 hours

[0354] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0355] Compound e-2 can also be used as such in the next step without isolation.

[0356] 3) Process of Producing Compound d-3 from Compound e-2

[0357] Compound d-3 can be produced by oxidizing compound e-2 with an oxidizing agent such as halogen, hypohalous acid, or hypohalite in a solvent.

[0358] Kind of oxidizing agent: chlorine, hypochlorous acid, sodium hypochlorite, etc.

[0359] Amount of oxidizing agent: 1 to 3 moles relative to 1 mole of compound e-2

[0360] Solvent: water; alcohols such as ethanol and t-butanol; and mixtures thereof; etc.

[0361] Reaction temperature: −15° C. to 60° C.

[0362] Reaction time: a moment to 48 hours

[0363] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0364] Producing Process 6

[0365] This is the producing process according to the following scheme:

[0366] wherein R1, R2 R3, R4, E10, E11, T, A, and Y are as defined above; E144 is halogen; and R203 is methyl or ethyl.

[0367] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 60-233061, or for example, by the following processes.

[0368] 1) Process of Producing Compound f-2 from Compound d-1

[0369] Compound f-2 can be produced by reacting compound d-1 with compound f-4 of the general formula:

[0370] wherein E10, E11, and R203 are as defined above, in a solvent, if necessary, in the presence of an acid.

[0371] Amount of compound f-4: 1 to 10 moles relative to 1 mole of compound d-1

[0372] Solvent: water; alcohols such as ethanol, isopropanol and butanol; aromatic hydrocarbons such as benzene and toluene; organic acids such as acetic acid and propionic acid; and mixtures thereof; etc.

[0373] Kind of acid: p-toluenesulfonic acid, hydrochloric acid, acetic acid, etc.

[0374] Amount of acid: 0.0001 mole to an excess amount relative to 1 mole of compound d-1

[0375] Reaction temperature: room temperature to the reflux temperature of the solvent

[0376] Reaction time: a moment to 96 hours

[0377] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0378] 2) Process of Producing Compound f-3 from Compound f-2

[0379] Compound f-3 can be produced by reacting compound f-2 with a halogenating agent in a solvent or without solvent under normal pressure or increased pressure.

[0380] Kind of halogenating agent: phosphorous oxychloride, phosphorous pentachloride, oxalyl chloride, phosgene, trichloromethyl chloroformate, etc.

[0381] Amount of halogenating agent: 1 mole to an excess amount relative to 1 mole of compound f-2

[0382] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; etc.

[0383] Reaction temperature: 50° C. to 250° C.

[0384] Reaction time: a moment to 96 hours

[0385] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0386] The compounds wherein E10 is CF2H can also be produced according to the following scheme:

[0387] wherein R1, R2, R3, R4, E11, E144, T, A, and Y are as defined above.

[0388] 1) Process of Producing Compound g-2 from Compound g-1

[0389] Compound g-2 can be produced by reacting compound g-1 with a Vilsmeier reagent (prepared from dimethylformamide and a halide such as phosphorous oxychloride, phosphorous pentachloride, oxalyl chloride, phosgene or trichloromethyl chloroformate; see Jikken Kagaku Koza, 4th Edition, 21, p. 110) in a solvent or without solvent.

[0390] Amount of Vilsmeier reagent: 1 to 20 moles relative to 1 mole of compound g-1

[0391] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0392] Reaction temperature: −10° C. to 150° C.

[0393] Reaction time: a moment to 96 hours

[0394] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0395] 2) Process of Producing Compound g-3 from Compound g-2

[0396] Compound g-3 can be produced by reacting compound g-2 with a fluorinating agent in a solvent.

[0397] Kind of fluorinating agent: dimethylaminosulfur trifluoride etc.

[0398] Amount of fluorinating agent: 1 to 10 moles relative to 1 mole of compound g-2

[0399] Solvent: halogenated aromatic hydrocarbons such as chlorobenzene; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0400] Reaction temperature: −10° C. to room temperature

[0401] Reaction time: a moment to 96 hours

[0402] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and diied; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0403] Producing Process 7

[0404] This is the producing process according to the following scheme:

[0405] wherein R1, R2, R3, R4, E12, D4, T, A, and Y are as defined above.

[0406] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 60-109578, or for example, by the following processes.

[0407] 1) Process of Producing Compound h-1 from Compound d-1

[0408] Compound h-1 can be produced by reacting compound d-1 with an acylating agent selected from compound h-3 of the general formula:

[0409] wherein E1 2 is as defined above and R204 is hydrogen, methyl, or ethyl, compound h-4 of the general formula:

[0410] wherein E12 is as defined above, and compound h-5 of the general formula:

[0411] wherein E12 is as defined above, in a solvent or without solvent.

[0412] Amount of acylating agent: 1 to 5 moles relative to 1 mole of compound d-1

[0413] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0414] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0415] Reaction time: a moment to 96 hours

[0416] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0417] 2) Process of Producing Compound h-2 from Compound h-1

[0418] Compound h-2 can be produced by reacting compound h-1 with compound h-6 of the general formula:

[0419] wherein D4 is as defined above, in a solvent in the presence of a base.

[0420] Amount of compound h-6: 1 to 5 moles of compound h-1

[0421] Kind of base: organic bases such as triethylamine and pyridine; inorganic bases such as potassium carbonate; etc.

[0422] Amount of base: 1 to 5 moles relative to 1 mole of compound h-1

[0423] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0424] Reaction temperature: −10° C. to room temperature

[0425] Reaction time: a moment to 96 hours

[0426] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0427] Producing Process 8

[0428] This is the producing process according to the following scheme:

[0429] wherein R1, R2, R3, R4, E13, T, A, and Y are as defined above; E114 is halogen; and R205 is methyl or ethyl.

[0430] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 6-145011, or for example, by the following processes.

[0431] 1) Process of Producing Compound i-1 from Compound a-1

[0432] Compound i-1 can be produced by reacting compound a-1 with a chloroformate i-5 of the general formula:

ClCOOR205 i-5

[0433] wherein R205 is as defined above, in a solvent in the presence of a base.

[0434] Amount of chloroformate i-5: 1 to 10 moles relative to 1 mole of compound a-1

[0435] Kind of base: N,N-dimethylaniline, N,N-diethylaniine, etc.

[0436] Amount of base: 1 to 10 moles relative to 1 mole of compound a-1

[0437] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0438] Reaction temperature: room temperature to the reflux temperature of the solvent

[0439] Reaction time: a moment to 96 hours

[0440] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0441] 2) Process of Producing Compound i-2 from Compound i-1

[0442] Compound i-2 can be produced by reacting compound i-1 with compound i-6 of the general formula:

[0443] wherein E13 is as defined above and M6 is chlorine or bromine, in a solvent in the presence of lithium bis(trimethylsilyl)amide.

[0444] Amount of compound i-6: 1 to 10 moles relative to 1 mole of compound i-1

[0445] Amount of lithium bis(tlimethylsilyl)amide: 1 to 10 moles relative to 1 mole of compound i-1

[0446] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0447] Reaction temperature: room temperature to the reflux temperature of the solvent

[0448] Reaction time: a moment to 96 hours

[0449] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0450] 3) Process of Producing Compound i-3 from Compound i-2

[0451] Compound i-3 can be produced by reacting compound i-2 with a halogenating agent in a solvent.

[0452] Kind of halogenating agent: chlorine, bromine, etc.

[0453] Amount of halogenating agent: 1 mole to large excess relative to 1 mole of compound i-2

[0454] Solvent: halogenated aromatic hydrocarbons such as chlorobenzene; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0455] Reaction temperature: 10° C. to the reflux temperature of the solvent

[0456] Reaction time: a moment to 96 hours

[0457] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0458] 4) Process of Producing Compound i-4 from Compound i-3

[0459] Compound i-4 can be produced by reacting compound i-3 with a base in a solvent.

[0460] Kind of base: organic bases such as triethylamine and 1,8-diaza-bicylo[5.4.0]undec-7-ene; etc.

[0461] Amount of base: 1 mole to large excess relative to 1 mole of compound i-3

[0462] Solvent: dimethylsulfoxide etc.

[0463] Reaction temperature: 10° C. to the reflux temperature of the solvent

[0464] Reaction time: a moment to 96 hours

[0465] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0466] Producing Process 9

[0467] This is the producing process according to the following scheme:

[0468] wherein R1, R2, R3, R4, E15, E16, T, A, and Y are as defined above.

[0469] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 60-104073, or for example, by the following processes.

[0470] 1) Process of Producing Compound j-1 from Compound d-1

[0471] Compound j-1 can be produced by reacting compound d-1 with compound j-3 of the general formula:

[0472] wherein E15 and E16 are as defined above, in a solvent, if necessary, in the presence of an acid.

[0473] Amount of compound j-3: 1 to 5 moles relative to 1 mole of compound d-1

[0474] Solvent: toluene, ethanol, acetic acid, tetrahydrofuran, etc.

[0475] Acid: p-toluenesulfonic acid etc.

[0476] Reaction temperature: −10° C. to 100° C.

[0477] Reaction time: a moment to 48 hours

[0478] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried, or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0479] 2) Process of Producing Compound j-2 from Compound j-1

[0480] Compound j-2 can be produced by reacting compound j-1 with an oxidizing agent in a solvent in the presence of a pyridine.

[0481] Amount of pyridine: 1 to 2 moles relative to 1 mole of compound j-1

[0482] Kind of oxidizing agent: copper (II) sulfate etc.

[0483] Amount of oxidizing agent: 1 to 5 moles relative to 1 mole of compound j-1

[0484] Solvent: toluene, ethanol, acetic acid, tetrahydrofuran, etc.

[0485] Reaction temperature: −10° C. to 100° C.

[0486] Reaction time: a moment to 48 hours

[0487] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0488] Producing Process 10

[0489] This is the producing process according to the following scheme:

[0490] wherein R1, R2, R3, R4, E7, E18, E19, D5, T, A, and Y are as defined above and R206 is methyl or ethyl.

[0491] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 63-183567, or for example, by the following processes.

[0492] 1) Process of Producing Compound k-1 from Compound a-1

[0493] Compound k-1 can be produced from compound a-1 according to the process as described above in Producing Process 2, Step 1).

[0494] 2) Process of Producing Compound k-2 from Compound k-1

[0495] Compound k-2 can be produced by reacting compound k-1 with compound k-5 of the general formula:

[0496] wherein E18, E19, and R206 are as defined above, in a solvent in the presence of a base.

[0497] Amount of compound k-5: 1 to 2 moles relative to 1 mole of compound k-1

[0498] Kind of base: triethylamine, potassium carbonate, sodium hydride, sodium methylate, etc.

[0499] Amount of base: 1 to 5 moles relative to 1 mole of compound k-1 Solvent: toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, etc.

[0500] Reaction temperature: −10° C. to 100° C. Reaction time: a moment to 48 hours

[0501] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0502] Compound k-3 may be obtained directly depending upon the reaction conditions of this process.

[0503] 3) Process of Producing Compound k-3 from Compound k-2

[0504] Compound k-3 can be produced by reacting compound k-2 in a solvent in the presence of a base.

[0505] Kind of base: potassium carbonate, sodium hydride, sodium methylate, etc.

[0506] Amount of base: 1 to 5 moles relative to 1 mole of compound k-2

[0507] Solvent: toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, etc.

[0508] Reaction temperature: −10° C. to 100° C.

[0509] Reaction time: a moment to 48 hours

[0510] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0511] 4) Process of Producing Compound k-4 from Compound k-3

[0512] Compound k-4 can be produced by reacting compound k-3 with compound k-6 of the general formula:

M7-E17 k-6

[0513] wherein E17 is as defined above and M7 is iodine, bromine, or chlorine, in a solvent in the presence of a base.

[0514] Amount of compound k-6: 1 to 2 moles relative to 1 mole of compound k-3

[0515] Kind of base: triethylamine, potassium carbonate, sodium hydride, sodium methylate, etc.

[0516] Amount of base: 1 to 5 moles relative to 1 mole of compound k-3

[0517] Solvent: toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, etc.

[0518] Reaction temperature: −10° C. to 100° C. Reaction time: a moment to 48 hours

[0519] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0520] Producing Process 11

[0521] This is the producing process according to the following scheme:

[0522] wherein R1, R2, R3, R4, E20, E21, D6, T, A, and Y are as defined above and R207 is methyl or ethyl.

[0523] The reactions in the respective steps can be carried out, for example, according to the processes as described in WO87/62357, or for example, by the following processes.

[0524] 1) Process of Producing Compound 1-1 from Compound a-1

[0525] Compound 1-1 can be produced from compound a-1 according to the process as described above in Producing Process 2, Step 1).

[0526] 2) Process of Producing Compound 1-2 from Compound 1-1

[0527] Compound 1-2 can be produced by reacting compound 1-1 with compound 1-4 of the general formula:

[0528] wherein E20, E21, and R207 are as defined above, in a solvent in the presence of a base.

[0529] Amount of compound 1-4: 1 to 2 moles relative to 1 mole of compound 1-1

[0530] Kind of base: triethylamine, potassium carbonate, sodium hydride, sodium methylate, etc.

[0531] Amount of base: 1 to 5 moles relative to 1 mole of compound 1-1

[0532] Solvent: toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, etc.

[0533] Reaction temperature: −10° C. to 100° C.

[0534] Reaction time: a moment to 48 hours

[0535] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0536] Compound 1-3 may be obtained directly depending upon the reaction conditions of this process.

[0537] 3) Process of Producing Compound 1-3 from Compound 1-2

[0538] Compound 1-3 can be produced by reacting compound 1-2 in a solvent in the presence of a base.

[0539] Kind of base: potassium carbonate, sodium hydride, sodium methylate, etc.

[0540] Amount of base: 1 to 5 moles relative to 1 mole of compound 1-2

[0541] Solvent: toluene, ethanol, tetrahydrofuran, N,N-dimethylformamide, etc.

[0542] Reaction temperature: −10° C. to 100° C.

[0543] Reaction time: a moment to 48 hours

[0544] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0545] Producing Process 12

[0546] This is the producing process according to the following scheme:

[0547] wherein R1, R2, R3, R4, E22, E23, T, A, and Y are as defined above.

[0548] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 61-103801, or for example, by the following processes.

[0549] 1) Process of Producing Compound m-1 from Compound a-1

[0550] Compound m-1 can be produced by reacting compound a-1 with acid anhydride m-2 of the general formula:

[0551] wherein E22 and E23 are as defined above, usually without solvent, or in a solvent, if necessary, in the presence of an acid.

[0552] The reaction temperature is usually in the range of 50° C. to 200° C.

[0553] The reaction time is usually in the range of 1 to 100 hours. The amounts of agents to be used in the reaction are 1 mole of acid anhydride m-2 relative to 1 mole of compound a-1, which is the stoichiometric ratio but can be freely changed depending upon the reaction conditions.

[0554] The solvent which can be used may include aliphatic hydrocarbons such as hexane, heptane, octane, and ligroin; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and mesitylene; halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and methyl t-butyl ether; nitro compounds such as nitromethane and nitrobenzene; organic acids such as acetic acid and propionic acid; acid amides such as N,N-dimethylformamide; sulfur compounds such as dimethylsulfoxide and sulforane; and mixtures thereof. As the acid, p-toluenesulfonic acid can be used.

[0555] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example,- the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0556] Producing Process 13

[0557] This is the producing process according to the following scheme:

[0558] wherein R1, R2, R3, R4, E24 T, A, and Y are as defined above.

[0559] The reactions in the respective steps can be carried out, for example, according to the processes as described in WO86/00072, or for example, by the following processes.

[0560] 1) Process of Producing Compound n-1 from Compound a-1

[0561] Compound n-1 can be produced by converting compound a-1 into a diazonium salt with sodium nitrite in a solvent in the presence of an acid and then reacting the diazonium salt with compound n-5 of the formula:

[0562] in a solvent in the presence of a base.

[0563] (Diazonium Salt Formation)

[0564] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound a-1

[0565] Kind of acid: hydrochloric acid etc.

[0566] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound a-1

[0567] Solvent: water, ethanol, hydrochloric acid, etc.

[0568] Reaction temperature: −15° C. to room temperature

[0569] Reaction time: a moment to 24 hours

[0570] (Reaction with Compound n-5)

[0571] Amount of compound n-5: 1 to 5 moles relative to 1 mole of compound a-1

[0572] Kind of base: sodium acetate etc.

[0573] Amount of base: 0.8 to 3 moles relative to 1 mole of acid used in the forgoing step

[0574] Solvent: ethanol, water, etc.

[0575] Reaction temperature: 0° C. to 60° C.

[0576] Reaction time: a moment to 48 hours

[0577] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0578] 2) Process of Producing Compound n-2 from Compound n-1

[0579] Compound n-2 can be produced by reacting compound n-1 in a solvent in the presence of a base.

[0580] Kind of base: sodium hydroxide, potassium hydroxide, etc.

[0581] Amount of base: 1 to 10 moles relative to 1 mole of compound n-1

[0582] Solvent: ethanol, N,N-dimethylformamide, water, and mixtures thereof; etc.

[0583] Reaction temperature: 0° C. to 110° C.

[0584] Reaction time: a moment to 48 hours

[0585] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0586] 3) Process of Producing Compound n-3 from Compound n-2

[0587] Compound n-3 can be Produced by reacting compound n-2 in a solvent in the presence of thioacetic acid.

[0588] Amount of thioacetic acid: 0.1 to 10 moles relative to 1 mole of compound n-2

[0589] Solvent: xylene etc.

[0590] Reaction temperature: reflux temperature

[0591] Reaction time: a moment to 72 hours

[0592] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0593] 4) Process of Producing Compound n-4 from Compound n-3

[0594] Compound n-4 can be produced by reacting compound n-3 with compound n-6 of the general formula:

M8-E24 n-6

[0595] wherein E24 is as defined above and M8 is iodine, bromine, or chlorine, in a solvent in the presence of a base.

[0596] Amount of compound n-6: 1 to 10 moles relative to 1 mole of compound n-3

[0597] Kind of base: potassium carbonate, sodium hydride, etc.

[0598] Amount of base: 1 to 10 moles relative to 1 mole of compound n-3

[0599] Solvent: acetone, tetrahydrofuran, N,N-dimethylformamide, etc.

[0600] Reaction temperature: 0° C. to 100° C.

[0601] Reaction time: a moment to 72 hours

[0602] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0603] Producing Process 14

[0604] This is the producing process according to the following scheme:

[0605] wherein R1, R2, R3, R4 E25, E26, E27, T, A, and Y are as defined above, and R208 and R209 are independently C1-C5 alkyl (e.g., methyl, ethyl, propyl).

[0606] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 5-4959 and JP-A 63-41466, or for example, by the following processes.

[0607] 1) Process of Producing Compound o-1 from Compound a-1

[0608] Compound o-1 can be produced from compound a-1 and chloroformate o-4 of the general formula:

ClCOOR208 o-4

[0609] wherein R208 is as defined above, according to the process as described above in Producing Process 8, Step 1).

[0610] 2) Process of Producing Compound o-11 from Compound o-1

[0611] Compound o-11 can be produced by reacting compound o-1 with compound o-5 of the general formula:

[0612] wherein E25, E26, and R209 are as defined above, in a solvent in the presence of a base.

[0613] Amount of compound o-5: 0.9 to 10 moles relative to 1 mole of compound o-1

[0614] Kind of base: inorganic bases such as sodium hydride; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0615] Amount of base: 0.1 to 10 moles relative to 1 mole of compound o-1

[0616] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; and mixtures thereof; etc.

[0617] Reaction temperature: room temperature to the reflux temperature of the solvent

[0618] Reaction time: a moment to 120 hours

[0619] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0620] Compound o-11 can also be used as such for the reaction in the next step without isolation.

[0621] 3) Process of Producing Compound o-2 from Compound o-11

[0622] Compound o-2 can be produced by reacting compound o-11 in a solvent in the presence of a base.

[0623] Kind of base: inorganic bases such as sodium hydride and potassium carbonate; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0624] Amount of base: 0.1 to 10 moles relative to 1 mole of compound o-11

[0625] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; sulfur compound such as dimethylsulfoxide; and mixtures thereof

[0626] Reaction temperature: room temperature to the reflux temperature of the solvent

[0627] Reaction time: a moment to 120 hours

[0628] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0629] Compound o-2 can also be used as such for the reaction in the next step without isolation.

[0630] 4) Process of Producing Compound o-3 from Compound o-2

[0631] Compound o-3 can be produced by reacting compound o-2 with compound o-6 of the general formula:

M9E27 o-6

[0632] wherein E27 is as defined above and M9 is iodine, bromine, chlorine, methanesulfonyloxy, or 2,4-dinitrophenoxy, in a solvent in the presence of a base.

[0633] Amount of compound o-6: 0.9 to 10 moles relative to 1 mole of compound o-2

[0634] Kind of base: inorganic bases such as sodium hydride, potassium carbonate, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0635] Amount of base: 0.1 to 10 moles relative to 1 mole of compound o-2

[0636] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0637] Reaction temperature: 0° C. to the reflux temperature of the solvent

[0638] Reaction time: a moment to 120 hours

[0639] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0640] Producing Process 15

[0641] This is the producing process according to the following scheme:

[0642] wherein R1, R2, R3, R4, D7, E25, E26, E27, T, A, andY are as defined above.

[0643] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 63-41466, or for example, by the following processes.

[0644] 1) Process of Producing Compound p-1 from Compound a-1

[0645] Compound p-1 can be produced from compound a-1 according to the process as described above in Producing Process 2, Step 1).

[0646] 2) Process of Producing Compound p-2 from Compound p-1 Compound p-2 can be produced by reacting compound p-1 with compound p-7 of the general formula:

[0647] wherein E25, E26, and R209 are as defined above, in a solvent in the presence of a base.

[0648] Amount of compound p-7: 0.9 to 10 moles relative to 1 mole of compound p-1

[0649] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0650] Amount of base: 0.1 to 10 moles relative to 1 mole of compound p-1

[0651] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; and mixtures thereof; etc.

[0652] Reaction temperature: −40° C. to the reflux temperature of the solvent

[0653] Reaction time: a moment to 72 hours

[0654] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0655] Compound p-2 can also be used as such for the reaction in the next step without isolation.

[0656] 3) Process of Producing Compound p-3 from Compound p-2

[0657] Compound p-3 can be produced by reacting compound p-2 with compound o-6 of the general formula:

M9-E27 o-6

[0658] wherein E27 and M9 are as defined above, in a solvent in the presence of a base.

[0659] Amount of compound o-6: 0.9 to 10 moles relative to 1 mole of compound p-2

[0660] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0661] Amount of base: 0.1 to 10 moles relative to 1 mole of compound p-2

[0662] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0663] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0664] Reaction time: a moment to 72 hours

[0665] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0666] Producing Process 16

[0667] This is the producing process according to the following scheme:

[0668] wherein R1, R2, R3, R4, D7, E25 E26, E27, T A, and Y as defined above.

[0669] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 63-41466, or for example, by the following processes.

[0670] 1) Process of Producing Compound p-4 from Compound p-1

[0671] Compound p-4 can be produced by reacting compound p-1 with ammonia in a solvent.

[0672] Amount of ammonia: 1 mole to large excess relative to 1 mole of compound p-1

[0673] Solvent: water, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, etc.

[0674] Reaction temperature: −20° C. to 100° C.

[0675] Reaction time: a moment to 24 hours

[0676] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0677] 2) Process of Producing Compound p-2 from Compound p-4

[0678] Compound p-2 can be produced by reacting compound p-4 with compound p-9 of the general formula:

[0679] wherein E25, E26, and R209 are as defined above and R210 is methyl, in a solvent in the presence of a base.

[0680] Amount of compound p-9: 0.9 to 10 moles relative to 1 mole of compound p-4

[0681] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0682] Amount of base: 0.1 to 10 moles relative to 1 mole of compound p-4

[0683] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0684] Reaction temperature: room temperature to the reflux temperature of the solvent

[0685] Reaction time: a moment to 120 hours

[0686] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0687] Compound p-2 can also be used as such for the reaction in the next step without isolation.

[0688] 3) Process of Producing Compound p-3 from Compound p-2

[0689] Compound p-3 can be produced by reacting compound p-2 with compound o-6 of the general formula:

M9-E27 o-6

[0690] wherein E27 and M9 are as defined above, in a solvent in the presence of a base.

[0691] Amount of compound o-6: 0.9 to 10 moles relative to 1 mole of compound p-2

[0692] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0693] Amount of base: 0.1 to 10 moles relative to 1 mole of compound p-2

[0694] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0695] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0696] Reaction time: a moment to 72 hours

[0697] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0698] Producing Process 17

[0699] This is the producing process according to the following scheme:

[0700] wherein R1, R2, R3, R4, D7, E2, E29, A, T, and Y are as defined above.

[0701] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 6-92943, or for example, by the following processes.

[0702] 1) Process of Producing Compound p-6 from Compound p-5

[0703] Compound p-6 can be produced by reducing compound p-5 in a solvent.

[0704] Kind of reducing agent: NaBH4 etc.

[0705] Amount of reducing agent: 1 to 10 moles relative to 1 mole of compound p-5

[0706] Solvent: water, methanol, ethanol, acetic acid, etc.

[0707] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0708] Reaction time: a moment to 48 hours

[0709] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound The compound can be purified by a technique such as recrystallization or column chromatography.

[0710] Producing Process 18

[0711] This is the producing process according to the following scheme:

[0712] wherein R1, R2, R3, R4, E30, E31, E42, T, A, andY are as defined above, and R211 is hydrogen, methyl, or ethyl.

[0713] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 9-323977 and WO98/17632, or for example, by the following processes.

[0714] 1) Process of Producing Compound w-1 from Compound a-1

[0715] Compound w-1 can be produced from compound a-1 according to the process as described above in Producing Process 5, Step 1).

[0716] 2) Process of Producing Compound w-2 from Compound w-1

[0717] Compound w-2 can be produced by reacting compound w-8 of the general formula:

[0718] wherein E30 and E42 are as defined above and M10 is iodine, bromine, or chlorine, with water in the presence of a base to form compound w-9 of the general formula:

[0719] wherein E30 and E42 are as defined above (reaction 1), and then reacting the carbonyl derivative with compound w-1 (reaction 2).

[0720] (Reaction 1)

[0721] Reaction 1 is usually carried out in a solvent. The reaction temperature is usually in the range of 20° C. to 100° C. The reaction time is usually in the range of a moment to 72 hours. The amounts of agents to be used in the reaction are 2 moles of each of the water and base relative to 1 mole compound w-8, which is ideal but can be freely changed depending upon the reaction conditions.

[0722] As the base to be used, both organic bases and inorganic bases can be used, examples of which are sodium acetate and potassium acetate.

[0723] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; nitro compounds such as nitromethane and nitrobenzene; nitrites such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof.

[0724] (Reaction 2)

[0725] Reaction 2 is usually carried out in a solvent. The reaction temperature is usually in the range of-20° C. to 200° C. The reaction time is usually in the range of a moment to 72 hours. The amounts of agents to be used in the reaction are 1 mole of compound w-1 relative to 1 mole of compound w-8, which is ideal but can be freely changed depending upon the reaction conditions Depending upon the conditions, salts of compound w-1, such as hydrochloride salt and sulfate salt, can also be used.

[0726] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; nitro compounds such as nitromethane and nitrobenzene; nitrites such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof.

[0727] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0728] 3) Process of Producing Compound w-3 from Compound w-2 (Route 1)

[0729] Compound w-3 can be produced by reacting compound w-2 with phosphorane compound w-10 of the general formula:

[0730] wherein E31 is as defined above; R213 is methyl or ethyl; and Ar is optionally substituted phenyl (e.g., phenyl), in a solvent.

[0731] This reaction is usually carried out in a solvent. The reaction temperature is usually in the range of −20° C. to 150° C., preferably 0° C. to 100° C. The reaction time is usually in the range of a moment to 72 hours. The amounts of agents to be used in the reaction are 1 mole of compound w-10 relative to 1 mole of compound w-2, which is ideal but can be freely changed depending upon the reaction conditions.

[0732] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof.

[0733] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0734] 4) Process of Producing Compound w-4 from Compound w-2 (Route 2)

[0735] Compound w-4 can be produced by reacting compound w-2 with compound w-11 of the general formula:

[0736] wherein E31 and R211 are as defined above, in the presence of a base.

[0737] This reaction is usually carried out in a solvent. The reaction temperature is usually in the range of 20° C. to 200° C., preferably 40° C. to 150° C. The reaction time is usually in the range of a moment to 72 hours. The amounts of agents to be used in the reaction are usually 1 to 10 moles of compound w-11, preferably 1 to 2 moles of compound w-11, which is ideal, relative to 1 mole of compound w-2. The amount of base is usually 1 mole to large excess, preferably 1 to 10 moles, relative to 1 mole of compound w-11

[0738] The base which can be used may include organic bases such as triethylamine and tributylamine.

[0739] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; nitro compounds such as nitromethane and nitrobenzene; nitrites such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof.

[0740] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0741] 5) Process of Producing Compound w-3 from Compound w-4

[0742] Compound w-3 can be produced by reacting compound w-4, if necessary, in the presence of a base or acid, or in an acid-base mixed system.

[0743] This reaction is usually carried out in a solvent. The reaction temperature is usually in the range of 20° C. to 200° C., preferably 40° C. to 150° C. The reaction time is usually in the range of a moment to 96 hours.

[0744] The kind of base used, if necessary, may include organic bases such as pyridine; and metal alcoholates such as sodium methylate. The amount of base is usually 1 mole to large excess, preferably 1 to 10 moles, which is ideal, relative to 1 mole of compound w-4.

[0745] The kind of acid used, if necessary, may include organic acids such as acetic acid and benzoic acid; and p-toluenesulfonic acid. The amount of acid is usually 1 mole to large excess, preferably 1 to 10 moles, which is ideal, relative to 1 mole of compound w-4.

[0746] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; esters such as ethyl acetate and butyl acetate; nitro compounds such as nitromethane and nitrobenzene; nitrites such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; and mixtures thereof.

[0747] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0748] Compound w-7 (i.e., compound w-2 wherein E42 is H) can also be produced according to the following scheme:

[0749] wherein R1, R2, R3, R4, E30, T, A, and Y are as defined above, and R214 is methyl or ethyl.

[0750] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 9-323977, or for example, by the following processes.

[0751] 6) Process of Producing Compound w-5 from Compound a-1 (see Tetrahedron, vol. 35, p. 2013 (1979))

[0752] Compound w-5 can be produced by converting compound a-1 into a diazonium salt with sodium nitrite in a solvent in the presence of an acid, and then reacting the diazonium salt with compound w-12 of the general formula:

[0753] wherein E30 and R214 are as defined above, in a solvent in the presence of a base.

[0754] (Diazonium Salt Formation)

[0755] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound a-1

[0756] Kind of acid: hydrochloric acid etc.

[0757] Amount of acid: 1 to 100 moles relative to 1 mole of compound a-1

[0758] Solvent: water, ethanol, hydrochloric acid, etc.

[0759] Reaction temperature: −15° C. to room temperature

[0760] Reaction time: a moment to 24 hours

[0761] (Reaction with Compound w-12)

[0762] Amount of compound w-12: 1 to 5 moles relative to 1 mole of compound a-1

[0763] Kind of base: sodium acetate etc.

[0764] Amount of base: 0.8 to 3 moles relative to 1 mole of acid used in the forgoing step

[0765] Solvent: ethanol, water, etc.

[0766] Reaction temperature: 0° C. to 60° C.

[0767] Reaction time: a moment to 48 hours

[0768] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0769] 6) Process of Producing Compound w-6 from Compound w-5

[0770] Compound w-6 can be produced by reacting compound w-5 in a solvent in the presence of a base.

[0771] The reaction temperature is usually in the range of 0° C. to 150° C. The reaction time is usually in the range of a moment to 72 hours. The amounts of agents to be used in the reaction are 1 mole of base relative to 1 mole of compound w-5, which is ideal but can be freely changed, if necessary. The base may include inorganic bases such as sodium hydroxide, lithium hydroxide, lithium hydroxide monohydrate, barium hydroxide, and potassium hydroxide.

[0772] The solvent which, can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; nitriles such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof.

[0773] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0774] 7) Process of Producing Compound w-7 from Compound w-6

[0775] Compound w-7 can be produced by heating compound w-6 in a solvent.

[0776] The reaction temperature is usually in the range of 50° C. to 200° C. The reaction time is usually in the range of a moment to 72 hours.

[0777] The solvent which can be used may include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; nitriles such as acetonitrile; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol and isopropanol; nitrogen-containing aromatic compounds such as pyridine and picoline; sulfur compounds such as dimethylsulfoxide; tertiary amines such as N,N-dimethylaniline; water; and mixtures thereof.

[0778] In this reaction, metals such as copper powder may be used as a catalyst, if necessary.

[0779] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0780] Producing Process 19

[0781] This is the producing process according to the following scheme:

[0782] wherein R1, R2, R3, R4, E32, E33, E43, T, A, and Y are as described above.

[0783] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 6-25186, or for example, by the following processes.

[0784] 1) Process of Producing Compound r-1 from Compound a-1

[0785] Compound r-1 can be produced by converting compound a-1 into an isothiocyanate derivative in a solvent or without solvent.

[0786] Agent for conversion into isothiocyanate derivatives: thiophosgene etc.

[0787] Amount of agent for conversion into isothiocyanate derivatives: 1 equivalent to an excess amount relative to 1 mole of compound a-1

[0788] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; etc.

[0789] Reaction temperature: room temperature to the reflux temperature of the solvent

[0790] Reaction time: a moment to 96 hours

[0791] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0792] 2) Process of Producing Compound r-2 from Compound r-1

[0793] Compound r-2 can be produced by reacting compound r-1 with compound r-6 of the general formula:

[0794] wherein E32 and E43 are as defined above and R215 is methyl, ethyl, or propyl in a solvent in the presence of a base.

[0795] Amount of compound r-6: 0.9 to 10 moles relative to 1 mole of compound r-1

[0796] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0797] Amount of base: 0.1 to 10 moles relative to 1 mole of compound r-1

[0798] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; etc.

[0799] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0800] Reaction time: a moment to 72 hours

[0801] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0802] 3) Process of Producing Compound r-3 from Compound r-2

[0803] Compound r-3 can be produced by reacting compound r-2 with Raney nickel in a solvent in the presence of a base.

[0804] Amount of Raney nickel: 1 to 20 moles relative to 1 mole of compound r-2

[0805] Kind of base: nitrogen-containing compounds such as pyridine; organic bases such as triethylamine; ammonia; etc.

[0806] Amount of base: 0.1 to 20 moles relative to compound r-2

[0807] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; alcohols such as methanol and ethanol; water; and mixtures thereof; etc.

[0808] Reaction temperature: −10° C. to the reflux temperature of the solvent Reaction time: a moment to 72 hours After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography. 4) Process of Producing Compound r-4 from Compound r-3

[0809] Compound r-4 can be produced by reacting compound r-3 in a solvent in the presence of a base.

[0810] Kind of base: metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0811] Amount of base: 1 to 20 moles relative to compound r-3 Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; alcohols such as methanol and ethanol; water; and mixtures thereof; etc.

[0812] Reaction temperature: 20° C. to the reflux temperature of the solvent

[0813] Reaction time: a moment to 96 hours

[0814] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0815] 5) Process of Producing Compound r-5 from Compound r-4

[0816] Compound r-5 can be produced by reacting compound r-4 with an acylating agent selected from compound r-7 of the general formula:

[0817] wherein E33 is as defined above, or compound r-8 of the general formula:

[0818] wherein E33 is as defined above, in a solvent.

[0819] Amount of acylating agent: 1 to 5 moles relative to 1 mole of compound r-4

[0820] Solvent: organic acids such as acetic acid and propionic acid; etc.

[0821] Reaction temperature: the reflux temperature of the solvent

[0822] Reaction time: a moment to 96 hours

[0823] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0824] Producing Process 20

[0825] This is the producing process according to the following scheme:

[0826] wherein R1, R2, R3, R4, E34, T, A, and Y are as defined above.

[0827] The reaction can be carried out, for example, according to the process as described in JP-A 4-356463, or for example, by the following process.

[0828] 1) Process of Producing Compound s-1 from Compound a-1

[0829] Compound s-1 can be produced by reacting compound a-1 with acid anhydride s-2 of the general formula:

[0830] wherein E34 is as defined above, in a solvent, if necessary, in the presence of an acid.

[0831] Amount of acid anhydride s-2: 1 to 5 moles relative to 1 mole of compound a-1

[0832] Solvent: organic acids such as acetic acid and propionic acid; aromatic hydrocarbons such as benzene and toluene; etc.

[0833] Kind of acid: p-toluenesulfonic acid etc.

[0834] Reaction temperature: room temperature to the reflux temperature of the solvent

[0835] Reaction time: a moment to 96 hours

[0836] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0837] Producing Process 21

[0838] This is the producing process according to the following scheme:

[0839] wherein R1, R2, R3, R4, D9, V1, T, A, and Y are as defined above.

[0840] The reactions in the respective steps can be carried out, for example, according to the processes as described in JP-A 5-25173, or for example, by the following processes.

[0841] 1) Process of Producing Compound t-1 from Compound a-1

[0842] Compound t-1 can be produced from compound a-1 according to the process as described above in Producing Process 2, Step 1).

[0843] 2) Process of Producing Compound t-2 from Compound t-1

[0844] Compound t-2 can be produced by reacting compound t-1 with compound t-3 of the general formula:

[0845] wherein V1 is as defined above, in a solvent in the presence of a base.

[0846] Amount of compound t-3: 0.9 to 10 moles relative to 1 mole of compound t-1

[0847] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0848] Amount of base: 0.1 to 10 moles relative to 1 mole of compound t-1

[0849] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; and mixtures thereof; etc.

[0850] Reaction temperature: −40° C. to the reflux temperature of the solvent

[0851] Reaction time: a moment to 72 hours

[0852] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0853] Producing Process 22

[0854] This is the producing process according to the following schemes:

[0855] wherein R1, R2, R3, R4, E35, A, T, and Y are as defined above.

[0856] The reactions in the respective steps can be carried out, for example, according to the processes as described in WO98/14452, or for example, by the following processes.

[0857] 1) Process of Producing Compound u-1 from Compound a-1

[0858] Compound u-1 can be produced from compound a-1 according to the process as described above in Producing Process 19, Step 1).

[0859] 2) Process of Producing Compound u-2 from Compound u-1

[0860] Compound u-2 can be produced by reacting compound u-1 with compound u-12 of the general formula:

[0861] wherein E35 and R215 are as defined above, in a solvent in the presence of a base.

[0862] Amount of compound u-12: 0.9 to 10 moles relative to 1 mole of compound u-1

[0863] Kind of base: inorganic bases such as sodium hydride, potassium hydroxide, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[0864] Amount of base: 0.1 to 10 moles relative to 1 mole of compound u-1

[0865] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N,N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; and mixtures thereof; etc.

[0866] Reaction temperature: −10° C. to the reflux temperature of the solvent

[0867] Reaction time: a moment to 72 hours

[0868] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0869] 3) Process of Producing Compound u-3 from Compound u-2

[0870] Compound u-3 can be produced by reacting compound u-2 with a methylating agent such as methyl iodide or dimethyl sulfate in a solvent in the presence of a base.

[0871] Kind of base: organic bases such as triethylamine; nitrogen-containing compounds such as pyridine; inorganic bases such as sodium hydride, potassium carbonate, and potassium hydroxide; etc.

[0872] Amount of base: 1 to 20 moles relative to 1 mole of compound u-2

[0873] Amount of methylating agent: 1 to 20 moles relative to 1 mole of compound u-2

[0874] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran; amides such as N,N-dimethylformamide; water; and mixtures thereof; etc.

[0875] Reaction temperature: −10° C. to room temperature

[0876] Reaction time: a moment to 96 hours

[0877] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0878] 4) Process of Producing Compound u-4 from Compound u-3

[0879] Compound u-4 can be produced by reacting compound u-3 with an oxidizing agent in a solvent.

[0880] Kind of oxidizing agent: m-chloroperbenzoic acid, aqueous hydrogen peroxide, etc.

[0881] Amount of oxidizing agent: 2 to 20 moles relative to 1 mole of compound u-3

[0882] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated aliphatic hydrocarbons such as chloroform; water; and mixtures thereof; etc.

[0883] Reaction temperature: −20° C. to room temperature

[0884] Reaction time: a moment to 96 hours

[0885] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0886] 5) Process of Producing Compound u-5 from Compound u-4

[0887] Compound u-5 can be produced by reacting compound u-4 with ammonia in a solvent.

[0888] Amount of ammonia: 1 mole to large excess relative to 1 mole of compound u-4

[0889] Solvent: t-butanol, isopropanol, etc.

[0890] Reaction temperature: −20° C. to 40° C.

[0891] Reaction time: a moment to 10 hours

[0892] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0893] 6) Process of Producing Compound u-6 from Compound u-4

[0894] Compound u-6 can be produced by reacting compound u-4 with an azidizing agent such as sodium azide or trimethylsilyl azide in a solvent such as methanol, ethanol, and water.

[0895] Amount of azidizing agent: 1 equivalent to an excess amount relative to 1 mole of compound u-4

[0896] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0897] 7) Process of Producing Compound u-7 from Compound u-5

[0898] Compound u-7 can be produced by reacting compound u-5 with a haloacetaldehyde such as chloroacetaldehyde (40% aqueous solution) in a solvent.

[0899] The amount of haloacetaldehyde is 1 equivalent to an excess amount relative to 1 mole of compound u-5: The solvent may include ethers such as 1,4-dioxane and tetrahydrofuran; water; and mixtures thereof; etc. The reaction temperature is in the range of 40° C. to the reflux temperature of the solvent. The reaction time is in the range of a moment to 20 hours.

[0900] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0901] 8) Process of Producing Compound u-8 from Compound u-4

[0902] Compound u-8 can be produced by reacting compound u-4 with hydrazine (hydrate) in a solvent or without solvent.

[0903] Amount of hydrazine: 1 mole to a large excess amount relative to 1 mole of compound u-4

[0904] Solvent: t-butanol, isopropanol, etc.

[0905] Reaction temperature: −20° C. to 40° C.

[0906] Reaction time: a moment to 10 hours

[0907] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0908] 9) Process of Producing Compound u-9 from Compound u-4

[0909] Compound u-9 can be produced by reacting compound u-4 with 2-ethanolamine in a solvent or without solvent.

[0910] Amount of 2-ethanolamine: 1 mole to a large excess amount relative to 1 mole of compound u-4

[0911] Solvent: t-butanol, isopropanol, etc.

[0912] Reaction temperature: −20° C. to 40° C.

[0913] Reaction time: a moment to 10 hours

[0914] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0915] 10) Process of Producing Compound u-10 from Compound u-8

[0916] Compound u-10 can be produced by reacting compound u-8 with formic acid in a solvent or without solvent, if necessary, in the presence of another acid.

[0917] Kind of acid: p-toluenesulfonic acid, hydrochloric acid, etc.

[0918] Amount of acid: 0.001 mole to a large excess amount relative to 1 mole of compound u-8

[0919] Amount of formic acid: 1 mole to a large excess amount to 1 mole of compound u-8

[0920] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N-N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; alcohols such as methanol and ethanol; water; and mixtures thereof; etc.

[0921] Reaction temperature: 40° C. to the reflux temperature of the solvent

[0922] Reaction time: a moment to 10 hours

[0923] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0924] 11) Process of Producing Compound u-11 from Compound u-9

[0925] Compound u-11 can be produced by reacting compound u-9 in a solvent or without solvent in the presence of an acid.

[0926] Kind of acid: p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, polyphosphoric acid, etc.

[0927] Amount of acid: 0.001 mole to a large excess amount relative to 1 mole of compound u-9

[0928] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; amides such as N-N-dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; alcohols such as methanol and ethanol; water; and mixtures thereof; etc.

[0929] Reaction temperature: 40° C. to the reflux temperature of the solvent

[0930] Reaction time: a moment to 48 hours

[0931] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystaliization or column chromatography.

[0932] Producing Process 23

[0933] This is the producing process according to the following scheme:

[0934] wherein R1, R2, R3, R4, R215, E32, E33, E43, T, A, and Y are as defined above; and R216 is C1-C5 alkoxy (e.g., methoxy, ethoxy) or NR217(R218) (e.g., dimethylamino, diethylamino) wherein R217 and R218 are independently C1-C5 alkyl.

[0935] The reactions in the respective steps can be carried out, for example, according to the processes as described in Bull. Soc. Chim. Fr. (134, pp. 47-57, 1997), or for example, by the following processes.

[0936] 1) Process of Producing Compound r-9 from Compound r-6

[0937] Compound r-9 can be produced by reacting compound r-6 with compound r-10 of the general formula:

[0938] wherein E33 and R216 are as defined above; R219 and R220 are independently C1-C5 alkyl (e.g., methyl, ethyl), in a solvent, if necessary, in the presence of an acid.

[0939] Amount of compound r-10: 1 mole to an excess amount relative to 1 mole of compound r-6

[0940] Kind of acid: organic acids such as acetic acid and p-toluenesulfonic acid

[0941] Amount of acid: a catalytic amount to large excess relative to 1 mole of compound r-6

[0942] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof, etc.

[0943] Reaction temperature: 10° C. to the reflux temperature of the solvent

[0944] Reaction time: a moment to 96 hours

[0945] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0946] 2) Process of Producing Compound r-5 from Compound r-9

[0947] Compound r-5 can be produced by reacting compound r-9 with compound a-1 in a solvent, if necessary, in the presence of an acid.

[0948] Amount of compound a-1: 0.9 to 1.1 moles relative to 1 mole of compound r-9

[0949] Kind of acid: organic acids such as acetic acid and p-toluenesulfonic acid

[0950] Amount of acid: a catalytic amount to large excess relative to 1 mole of compound r-9

[0951] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[0952] Reaction temperature: 10° C. to the reflux temperature of the solvent

[0953] Reaction time: a moment to 96 hours

[0954] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0955] Depending upon the kinds of R1, R2, R3, R4, Y, T and A, the formation of Q may be followed by the introduction or formation of R1, R2, R3, R4, Y, T, and A. In these producing processes, protective groups may be used, if necessary, for the protection of functional groups from the reactions. (see “Protective Groups in Organic Synthesis” written by T. W. Greene.) The following are examples of these producing processes.

[0956] Producing Process 24

[0957] This is the producing process according to the following scheme:

[0958] wherein R1, R2, R3, R4, Y11, and Q are as defined above; R221 is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, aminocarbonyl, or nitrile; and M23 is fluorine, chlorine, or bromine. The reactions in the respective steps can be carried out, for example, by the following processes.

[0959] 1) Process of Producing Compound z-2 from Compound z-1

[0960] Compound z-2 can be produced by reacting with compound z-1 in a solvent in the presence of a base or acid, and, if necessary, in the presence of a phase transfer catalyst.

[0961] Kind of base: inorganic bases such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; etc.

[0962] Amount of base: 0.9 to 10 moles relative to 1 mole of compound z-1

[0963] Kind of acid: hydrochloric acid, sulfuric acid, etc.

[0964] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound z-1

[0965] Kind of phase transfer catalyst: tetrabutylammonium bromide etc.

[0966] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[0967] Reaction temperature: 10° C. to the reflux temperature of the solvent

[0968] Reaction time: a moment to 96 hours

[0969] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0970] 2) Process of Producing Compound z-3 from Compound z-2

[0971] Compound z-3 can be produced by heating compound z-2 in a solvent, if necessary, in the presence of an acid or base.

[0972] Kind of base: nitrogen-containing compounds such as quinoline and pyridine; amides such as N,N-dimethylformamide; sulfur compounds such as sulforane; aromatic hydrocarbons such as xylene and mesitylene; and mixtures thereof; etc.

[0973] Amount of base: 0.9 mole to an excess amount relative to 1 mole of compound z-2

[0974] Kind of acid: hydrochloric acid, sulfuric acid, etc.

[0975] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound z-2

[0976] Kind of phase transfer catalyst: tetrabutylammonium bromide etc.

[0977] Solvent: amides such as N,N-dimethylformamide; sulfur compounds such as sulforane; aromatic hydrocarbons such as xylene and mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; and mixtures thereof; etc.

[0978] Reaction temperature: 50° C. to the reflux temperature of the solvent

[0979] Reaction time: a moment to 96 hours

[0980] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0981] In this process, metal catalysts such as copper may be used in their catalytic amounts.

[0982] 3) Process of Producing Compound z-24 from Compound z-23

[0983] Compound z-24 can be produced by reducing compound z-23 with iron powder in a solvent.

[0984] Amount of iron powder: 2 to 10 moles relative to 1 mole of compound z-23

[0985] Solvent: acetic acid, water, and mixtures thereof, etc.

[0986] Reaction temperature: 15° C. to 110° C.

[0987] Reaction time: a moment to 100 hours

[0988] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[0989] 4) Process of Producing Compound z-25 from Compound z-24

[0990] Compound z-25 can be produced by converting compound z-24 into a diazonium salt with sodium nitrite in the presence of an acid and then reacting the diazonium salt with copper halide such as copper (I) chloride or copper (I) bromide.

[0991] (Diazonium Salt Formation)

[0992] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound z-24

[0993] Kind of acid: sulfuric acid, hydrochloric acid, etc.

[0994] Amount of acid: 1 mole to 100 moles relative to 1 mole of compound z-24

[0995] Solvent: water, ethanol, hydrochloric acid, etc.

[0996] Reaction temperature: −15° C. to room temperature

[0997] Reaction time: a moment to 24 hours

[0998] (Reaction with Copper Halide)

[0999] Kind of copper halide: copper (I) chloride, copper (I) bromide, etc.

[1000] Amount of copper halide: 1 to 10 moles relative to 1 mole of compound z-24

[1001] Solvent: hydrochloric acid, hydrobromic acid, etc.

[1002] Reaction temperature: −10° C. to 80° C.

[1003] Reaction time: a moment to 48 hours

[1004] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1005] 5) Process of Producing Compound z-3 from Compound z-24 Compound z-3 can be produced by converting compound z-24 into a diazonium salt with sodium nitrite in the presence of an acid and then reacting the diazonium salt in a solvent.

[1006] (Diazonium Salt Formation)

[1007] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound z-24

[1008] Kind of acid: sulfuric acid, hydrochloric acid, etc.

[1009] Amount of acid: 1 mole to 100 moles relative to 1 mole of compound z-24

[1010] Solvent: water, ethanol, hydrochloric acid, etc.

[1011] Reaction temperature: −15° C. to room temperature

[1012] Reaction time: a moment to 24 hours

[1013] (Thermal Decomposition)

[1014] Solvent: sulfuric acid, water, etc.

[1015] Reaction temperature: room temperature to 200° C.

[1016] Reaction time: a moment to 48 hours

[1017] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1018] Producing Process 25

[1019] This is the producing process according to the following scheme:

[1020] wherein R1, R3, R4, R11, Q, T, A, and Y are as defined above.

[1021] The reactions in the respective steps can be carried out, for example, by the following processes.

[1022] 1) Process of Producing Compound z-5 from Compound z-4

[1023] Compound z-5 can be produced by demethylating compound z-4 in a solvent in the presence of an acid or trimethylsilane iodide.

[1024] Kind of acid: inorganic acids such as hydrochloric acid and sulfuric acid; Lewis acids such as boron tribromide and aluminum chloride; etc.

[1025] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound z-4

[1026] Amount of trimethylsilane iodide: 1 mole to an excess amount relative to 1 mole of compound z-4

[1027] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1028] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1029] Reaction time: a moment to 168 hours

[1030] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1031] 2) Process of Producing Compound z-6 from Compound z-5

[1032] Compound z-6 can be produced by reacting compound z-5 with compound z-18 of the general formula:

M9-R11 z-18

[1033] wherein M9 and R11 are as defined above, in a solvent in the presence of a base.

[1034] Amount of compound z-18: 1 to 2 moles relative to 1 mole of compound z-5

[1035] Kind of base: potassium carbonate, sodium hydride, etc.

[1036] Amount of base: 1 to 5 moles relative to 1 mole of compound z-5

[1037] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1038] Reaction temperature: −10° C. to 100° C.

[1039] Reaction time: a moment to 48 hours

[1040] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1041] Producing Process 26

[1042] This is the producing process according to the following scheme:

[1043] wherein R1, R4, Q, T, A, and Y are as defined above, R222 is —OR11 or —SR12 wherein R11 and R12 are as defined above; and R223 is —OR224 or —SR225 wherein R224 and R225 are the same or different and independently hydrogen, C1-C10 alkyl, C3-C10 cycloalkyl, C3-C10 cycloalkyl C1-C3 alkyl, C1-C10 alkenyl, C3-C10 alkynyl, C1-C5 alkoxy C1-C5 alkyl, C1-C5 alkylthio C1-C5 alkyl, or optionally substituted phenyl.

[1044] The reactions in the respective steps can be carried out, for example, by the following processes.

[1045] 1) Process of Producing Compound z-8 from Compound z-7

[1046] Compound z-8 can be produced by reacting compound z-19 of the general formula:

H-R222 z-19

[1047] wherein R222 is as defined above, in a solvent in the presence of a base.

[1048] Amount of compound z-19: 1 to 5 moles relative to 1 mole of compound z-7

[1049] Kind of base: organic bases such as triethylamine, inorganic bases such as potassium carbonate and sodium hydride; alkoxides such as sodium methoxide and sodium thiomethoxide; etc.

[1050] Amount of base: 1 to 5 moles relative to 1 mole of compound z-7

[1051] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1052] Reaction temperature: −10° C. to the reflux temperature of the solvent

[1053] Reaction time: a moment to 72 hours

[1054] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1055] Compound z-8 wherein R222 is —OR224 or —SR225; and R224 and R225 are as defined above (hereinafter referred to as compound z-8′) can be used to produce compound z-9 or compound z-10 as shown in the following processes.

[1056] 2) Process of Producing Compound z-9 from Compound z-8′

[1057] Compound z-9 can be produced by reducing compound z-8′ with iron powder in a solvent.

[1058] Amount of iron powder: 2 to 10 moles relative to 1 mole of compound z-8′

[1059] Solvent: acetic acid, water, and mixtures thereof; etc.

[1060] Reaction temperature: 15° C. to 110° C.

[1061] Reaction time: a moment to 100 hours

[1062] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1063] 3) Process of Producing Compound z-10 from Compound z-9

[1064] Compound z-10 can be produced by converting compound z-9 into a diazonium salt with sodium nitrite in the presence of an acid and then reacting the diazonium salt with a chloride such as copper (I) chloride.

[1065] (Diazonium Salt Formation)

[1066] Amount of sodium nitrite: 1 to 2 moles relative to 1 mole of compound z-9

[1067] Kind of acid: hydrochloric acid, etc.

[1068] Amount of acid: 1 mole to 100 moles relative to 1 mole of compound z-9

[1069] Solvent: water, ethanol, hydrochloric acid, etc.

[1070] Reaction temperature: −15° C. to room temperature

[1071] Reaction time: a moment to 24 hours

[1072] (Reaction with Chloride)

[1073] Kind of chloride: copper (I) chloride etc.

[1074] Amount of chloride: 1 to 10 moles relative to 1 mole of compound z-9

[1075] Solvent: hydrochloric acid etc.

[1076] Reaction temperature: −10° C. to 80° C.

[1077] Reaction time: a moment to 48 hours

[1078] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1079] Producing Process 27

[1080] This is the producing process according to the following process:

[1081] wherein R1, R3, R4, R14, R17, R19, Q, T, A, and Y are as defined above.

[1082] The reactions in the respective steps can be carried out, for example, by the following processes.

[1083] 1) Process of Producing Compound z-12 from Compound z-11

[1084] Compound z-12 can be produced by reacting compound z-11 with copper (I) cyanide in a solvent.

[1085] Amount of copper (1) cyanide: 1 to 4 moles relative to 1 mole of compound z-11

[1086] Kind of solvent: amides such as N,N-dimethylformamide and N-methylpyrrolidone; sulfur compound such as dimethylsulfoxide; etc.

[1087] Reaction temperature: 40° C. to the reflux temperature of the solvent

[1088] Reaction time: a moment to 120 hours

[1089] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1090] 2) Process of Producing Compound z-13 from Compound z-12

[1091] Compound z-13 can be produced by reacting compound z-12 with water in the presence of an acid.

[1092] Amount of water: 1 mole to an excess amount relative to 1 mole of compound z-12

[1093] Kind of acid: hydrochloric acid, sulfuric acid, etc.

[1094] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound z-12

[1095] Reaction temperature: 10° C. to 50° C.

[1096] Reaction time: a moment to 24 hours

[1097] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1098] 3) Process of Producing Compound z-14 from Compound z-13

[1099] Compound z-14 can be produced by reacting compound z-13 with water in the presence of an acid or base.

[1100] Amount of water: 1 equivalent to an excess amount relative to 1 mole of compound z-13

[1101] Kind of acid: hydrochloric acid, sulfuric acid, etc.

[1102] Amount of acid: 1 equivalent to an excess amount relative to 1 mole of compound z-13

[1103] Kind of base: sodium hydroxide, potassium hydroxide, etc.

[1104] Amount of base: 1 to 3 equivalents relative to 1 mole of compound z-13

[1105] Reaction temperature: room-temperature to 150° C.

[1106] Reaction time: a moment to 120 hours

[1107] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1108] 4) Process of Producing Compound z-17 from Compound z-14

[1109] Compound z-17 can be produced by reacting compound z-14 with thionyl chloride to form an acid chloride compound (reaction 1) and then reacting the acid chloride compound with compound z-20 of the general formula:

HO—R14 z-20

[1110] wherein R14 is as defined above, in a solvent in the presence of a base (reaction 2).

[1111] (Reaction 1)

[1112] Amount of thionyl chloride: 1 mole to an excess amount relative to compound z-14

[1113] Reaction temperature: 40° C. to the reflux temperature of thionyl chloride

[1114] Reaction time: a moment to 10 hours

[1115] After completion of the reaction, the reaction mixture was concentrated and used as the starting material for reaction 2.

[1116] (Reaction 2)

[1117] Amount of compound z-20: 1 mole to an excess amount relative to 1 mole of compound z-14

[1118] Kind of base: pyridine, triethylamine, potassium carbonate, etc.

[1119] Amount of base: 1 to 5 moles relative to 1 mole of compound z-14

[1120] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1121] Reaction temperature: −10° C. to the reflux temperature of the solvent

[1122] Reaction time: a moment to 120 hours

[1123] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1124] 5) Process of Producing Compound z-17 from Compound z-13

[1125] Compound z-17 can be produced by reacting compound z-13 with compound z-20 of the general formula:

HO—R14z-20

[1126] wherein R14 is as defined above, in a solvent in the presence of a boron trihalide compound.

[1127] Amount of compound z-20: 1 mole to an excess amount relative to 1 mole of compound z-13

[1128] Kind of boron trihalide compound: boron trifluoride, boron trichloride, boron tribromide, etc.

[1129] Amount of boron trihalide compound: 1 mole to an excess amount relative to 1 mole of compound z-13

[1130] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof, etc.

[1131] Reaction temperature: 50° C. to the reflux temperature of the solvent

[1132] Reaction time: a moment to 120 hours

[1133] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1134] 6) Process of Producing Compound z-15 from Compound z-12

[1135] Compound z-15 can be produced by reacting compound z-12 with compound z-21 of the general formula:

M11-Mg—R17 z-21

[1136] wherein R17 is as defined above and M11 is chlorine or bromine, in a solvent.

[1137] Amount of compound z-21: 1 to 1.3 moles relative to 1 mole of compound z-12

[1138] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; halogenated hydrocarbons such as chloroform; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1139] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1140] Reaction time: a moment to 48 hours

[1141] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1142] 7) Process of Producing Compound z-16 from Compound z-15

[1143] Compound z-16 can be produced by reacting compound z-15 with compound z-22 of the general formula:

R19ONH2 z-22

[1144] wherein R19 is as defined above, in a solvent, if necessary, in the presence of a base.

[1145] Amount of compound z-22: 1 to 3 moles relative to 1 mole of compound z-15

[1146] Kind of base: triethylamine, pyridine, potassium carbonate, etc.

[1147] Amount of base: 1 to 5 moles relative to 1 mole of compound z-15

[1148] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1149] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1150] Reaction time: a moment to 120 hours

[1151] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1152] In addition to the above processes, the present compounds can also be produced by making reference to, for example, JP-A 5-213970, EP 683160-A1, and JP-A 61-161288.

[1153] The processes of producing some of the starting materials used in the production of the present compounds are explained below.

[1154] Reference Producing Process 1

[1155] This is the producing process according to the following scheme:

[1156] wherein R1, R2, R3, R4, and Y11 are as defined above; and R250 is carboxy, methoxycarbonyl, ethoxycarbonyl, aminocarbonyl, or nitrile.

[1157] The reactions in the respective steps can be carried out, for example, according to the processes as described in Indian Journal of Chemistry (vol. 20B, pp. 391-393, 1981), Indian Journal of Chemistry (vol. 14B, pp. 6886-6891, 1981), Organic Syntheses (vol. 33, p. 43, 1953), or for example, by the following processes.

[1158] 1) Process of Producing Compound v-2 from Compound v-1

[1159] Compound v-2 can be produced by reacting compound v-1 with compound v-19 of the general formula:

[1160] wherein R250 is as defined above and M20 is chlorine, bromine, or iodine, in a solvent in the presence of a base.

[1161] Kind of base: inorganic bases such as potassium carbonate, sodium hydride, and sodium hydroxide; organic bases such as triethylamine; nitrogen-containing compounds such as pyridine; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[1162] Amount of base: 1 to 5 moles relative to 1 mole of compound v-1 Amount of compound v-19: 0.9 to 3 moles relative to 1 mole of compound v-1

[1163] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ketones such as acetone; ethers such as tetrahydrofuran; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1164] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1165] Reaction time: a moment to 48 hours

[1166] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1167] 2) Process of Producing Compound v-3 from Compound v-2

[1168] Compound v-3 can be produced by reacting compound v-2 in a solvent in the presence of a base.

[1169] Kind of base: inorganic bases such as potassium carbonate, sodium hydride, and sodium hydroxide; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[1170] Amount of base: 1 to 10 moles relative to 1 mole of compound v-2

[1171] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1172] Reaction temperature: 10° C. to the reflux temperature of the solvent

[1173] Reaction time: a moment to 96 hours

[1174] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1175] 3) Process of Producing Compound v-4 from Compound v-3

[1176] Compound v-4 can be produced by reacting compound v-3 in a solvent in the presence of a base or acid and, if necessary, in the presence of a phase transfer catalyst.

[1177] Kind of base: inorganic bases such as sodium hydroxide and potassium hydroxide; etc.

[1178] Amount of base: 0.9 to 10 moles relative to 1 mole of compound v-3

[1179] Kind of acid: hydrochloric acid, sulfuric acid, etc.

[1180] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound v-3

[1181] Kind of phase transfer catalyst: tetrabutylammonium bromide etc.

[1182] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; water; and mixtures thereof; etc.

[1183] Reaction temperature: 10° C. to the reflux temperature of the solvent

[1184] Reaction time: a moment to 96 hours

[1185] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1186] 4) Process of Producing Compound v-5 from Compound v-4

[1187] Compound v-5 can be produced by heating compound v-4 in a solvent, if necessary, in the presence of a base or acid.

[1188] Kind of base: nitrogen-containing compounds such as quinoline and pyridine; amides such as N,N-dimethylformamide; sulfur compounds such as sulforane; aromatic hydrocarbons such as xylene and mesitylene; and mixtures thereof; etc.

[1189] Amount of base: 0.9 mole to an excess amount relative to 1 mole of compound v-4 Kind of acid: hydrochloric acid, sulfuric acid, etc.

[1190] Amount of acid: 1 mole to an excess amount relative to 1 mole of compound v-4

[1191] Solvent: amides such as N,N-dimethylformamide; sulfur compounds such as sulforane; aromatic hydrocarbons such as xylene and mesitylene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran and 1,4-dioxane; and mixtures thereof; etc.

[1192] Reaction temperature: 50° C. to the reflux temperature of the solvent

[1193] Reaction time: a moment to 96 hours

[1194] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1195] In this process, metal catalysts such as copper may be used.

[1196] Compound v-1 as the starting material in this producing process can also be produced from the corresponding benzaldehyde derivative by making reference to, for example, Shin Jikken Kagaku Koza (published by Maruzen Kabushiki Kaisha) vol. 14, pp. 1466-1470. The benzaldehyde derivative to be used as the starting material at that time can also be produced by making reference to, for example, EP 0312338-A1, Synthetic Communication, 24(12), pp. 1757-1760 (1994), and J. Chem. Soc. Perkin I, pp. 318-321 (1978).

[1197] Compound v-2 as the intermediate can also be produced according to the following scheme 1 or 2.

[1198] wherein R1, R2, R3, R4, R250, and Y11 are as defined above; and M21 is fluorine, chlorine, or bromine.

[1199] 5) Process of Producing Compound v-2 from Compound v-6

[1200] Compound v-2 can be produced by reacting compound v-6 with compound v-17 of the formula:

[1201] wherein Y11 and R250 are as defined above, in a solvent in the presence of a base.

[1202] Kind of base: inorganic bases such as potassium carbonate, sodium hydride, sodium hydroxide, and potassium fluoride; organic bases such as triethylamine; nitrogen-containing compounds such as pyridine; etc.

[1203] Amount of base: 1 to 10 moles relative to 1 mole of compound v-6

[1204] Amount of compound v-17: 0.9 to 10 moles relative to 1 mole of compound v-6

[1205] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ketones such as acetone; ethers such as tetrahydrofuran and 1,4-dioxane; amides such as N,N-dimethylformamide; and mixtures thereof; etc.

[1206] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1207] Reaction time: a moment to 72 hours

[1208] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1209] wherein R1, R2, R3, R4, R250, and Y11 are as defined above.

[1210] 1) Process of Producing Compound v-2 from Compound v-16

[1211] Compound v-2 can be produced by reacting compound v-16 with copper (I) cyanide in a solvent.

[1212] Amount of copper (I) cyanide: 1 to 4 moles relative to 1 mole of compound v-16

[1213] Kind of solvent: amides such as N,N-dimethylformamide and N-methylpyrrolidone; sulfur compound such as dimethylsulfoxide; etc.

[1214] Reaction temperature: 40° C. to the reflux temperature of the solvent

[1215] Reaction time: a moment to 120 hours

[1216] After completion of the reaction, ammonia water is added, if necessary, to the reaction mixture, which is then extracted with an organic solvent, and the organic layer is dried and concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1217] Reference Producing Process 2

[1218] This is the producing process according to the following scheme:

[1219] wherein R1, R2, R3, and R4 are is defined above; and M22 is fluorine or chlorine.

[1220] The reactions in the respective steps can be carried out, for example, according to the processes as described in Tetrahedron Letters (vol. 37, No. 17, pp. 2885-2886, 1996), or for example, by the following processes.

[1221] 1) Process of Producing Compound v-8 from Compound v-7

[1222] Compound v-8 can be produced by reacting compound v-7 with acetohydroxamic acid in a solvent in the presence of a base.

[1223] Amount of hydroxamic acid: 1 to 3 moles relative to 1 mole of compound v-7

[1224] Kind of base: potassium t-butoxide, sodium hydride, etc.

[1225] Amount of base: 1 to 3 moles relative to 1 mole of compound v-7

[1226] Solvent: N,N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, etc.

[1227] Reaction temperature: room temperature to 100° C.

[1228] Reaction time a moment to 100 hours

[1229] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1230] Reference Producing Process 3

[1231] This is the producing process according to the following scheme:

[1232] wherein R1, R2, R3, and R4 are as defined above; Y1 is oxygen, sulfur, or N—R142; and R142 is as defined above.

[1233] The reactions in the respective steps can be carried out, for example, by the following processes.

[1234] 1) Process of Producing Compound v-10 from Compound v-9

[1235] Compound v-10 can be produced by reacting compound v-9 with a nitrating agent in a solvent or without solvent.

[1236] Kind of nitrating agent: nitric acid etc.

[1237] Amount of nitrating agent: 1 to 15 moles relative to 1 mole of compound v-9

[1238] Solvent: acetic anhydride etc.

[1239] Reaction temperature: −10° C. to 50° C.

[1240] Reaction time: a moment to 100 hours

[1241] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1242] 2) Process of producing compound v-11 from compound v-10

[1243] Compound v-11 can be produced by reducing compound v-10 with iron powder in a solvent.

[1244] Amount of iron powder: 1 to 10 moles relative to 1 mole of compound v-10

[1245] Solvent: acetic acid, water, and mixtures thereof, etc.

[1246] Reaction temperature: 15° C. to 110° C.

[1247] Reaction time: a moment to 100 hours

[1248] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1249] Reference Producing Process 4

[1250] This is the producing process according to the following scheme:

[1251] wherein R226 is C1-C10 alkyl and M12 is fluorine or chlorine.

[1252] The reactions in the respective steps can be carried out, for example, according to the processes as described in Khim. Geterotsikl. Soedin (1990, Issue 5, pp. 597-600), Khim. Geterotsikl. Soedin (1989, Issue 5, pp. 704), or for example, by the following processes.

[1253] 1) Process of Producing Compound v-13 from Compound v-12

[1254] Compound v-13 can be produced by reacting compound v-12 with nitroenamine compound v-18 of the formula:

[1255] in a solvent and, if necessary, in the presence of an acid.

[1256] Amount of compound v-18: 1 to 3.0 moles relative to 1 mole of compound v-12

[1257] Kind of acid: acetic acid, p-toluenesulfonic acid, sulfuric acid, etc.

[1258] Amount of acid: a catalytic amount to a large excess amount relative to 1 mole of compound v-12

[1259] Solvent: aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran; organic acids such as acetic acid and propionic acid; amides such as N,N-dimethylformamide; and mixtures thereof; etc.

[1260] Reaction temperature: −10° C. to the reflux temperature of the solvent

[1261] Reaction time: a moment to 100 hours

[1262] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1263] 2) Process of Producing Compound v-14 from Compound v-13

[1264] Compound v-14 can be produced by reacting compound v-13 with an alkylcarbonylating agent in a solvent and, if necessary, in the presence of an acid and a base.

[1265] Kind of alkylcarbonylating agent: acetic anhydride, acetyl chloride, etc.

[1266] Amount of alkylcarbonylating agent: 1 to 2.0 moles relative to 1 mole of compound v-13

[1267] Kind of acid: acetic acid, p-toluenesulfonic acid, sulfuric acid, etc.

[1268] Amount of acid: a catalytic amount to a large excess amount relative to 1 mole of compound v-13

[1269] Kind of base: sodium hydroxide, potassium carbonate, triethylamine, etc.

[1270] Amount of base: a catalytic amount to a large excess amount relative to 1 mole of compound v-13

[1271] Solvent: aromatic hydrocarbons such as toluene and xylene; ethers such as tetrahydrofuran; organic acids such as acetic acid and propionic acid; inorganic acids such as sulfuric acid; amides such as N,N-dimethylformamide; and mixtures thereof; etc.

[1272] Reaction temperature: −10° C. to the reflux temperature of the solvent

[1273] Reaction time: a moment to 100 hours

[1274] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound- can be purified by a technique such as recrystallization or column chromatography.

[1275] 3) Process of Producing Compound v-15 from Compound v-14

[1276] Compound v-15 can be produced by reducing compound v-14 with iron powder in a solvent.

[1277] Amount of iron powder: 1 to 10 moles relative to 1 mole of compound v-14

[1278] Solvent: acetic acid, water, and mixtures thereof, etc.

[1279] Reaction temperature: 15° C. to 110° C.

[1280] Reaction time: a moment to 100 hours

[1281] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1282] Reference Producing Process 5

[1283] This is the producing process according to the following scheme:

[1284] wherein R1, R2, R3, R4, and A are as defined above; Y2 is nitrogen or C—R152; and R152 is as defined above.

[1285] The reaction can be carried out, for example, according to the processes as described in Synthesis (Issue 1, pp. 1-17, 1977), J. Med. Chem. (Vol. 39, pp. 570-581, 1996), or for example, by the following process.

[1286] 1) Process of Producing Compound x-3 from Compound x-5

[1287] Compound x-3 can be produced by reacting compound x-5 with an aminating agent in a solvent in the presence of a base.

[1288] Kind of base: inorganic bases such as potassium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide; etc.

[1289] Amount of base: 1 to 20 moles relative to 1 mole to compound x-75

[1290] Kind of aminating agent: hydroxylamine=O-sulfonic acid, chloramine, O-(2,4-dinitrophenyl)hydroxylamine, etc.

[1291] Amount of aminating agent: 0.9 to 5 moles relative to 1 mole of compound x-5

[1292] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ethers such as tetrahydrofuran; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; and mixtures thereof; etc.

[1293] Reaction temperature: −10° C. to the reflux temperature of the solvent

[1294] Reaction time: a moment to 48 hours

[1295] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1296] Compound x-5 used as the intermediate in the above reaction can be produced, for example, according to the processes as described in JP-A 7-508259, JP-A 7-508500, WO93/18008, and WO94/25446.

[1297] Reference Producing Process 6

[1298] This is the producing process according to the following scheme:

[1299] wherein R1, R2, R3, R4, and Y11 are as defined above.

[1300] The reaction can be carried out, for example, according to the process as described in Chem. Pharm. Bull 32(11), pp. 4260-4270 (1984), or for example, by the following scheme:

[1301] 1) Process of Producing Compound v-20 from Compound v-1

[1302] Compound v-20 can be produced by reacting compound v-1 with bromonitromethane in a solvent in the presence of a base.

[1303] Kind of base: inorganic bases such as potassium carbonate, sodium hydride, and sodium hydroxide; organic bases such as triethylamine; nitrogen-containing compounds such as pyridine; metal alcoholates such as sodium methylate and sodium ethylate; etc.

[1304] Amount of base: 1 to 5 moles relative to 1 mole of compound v-1

[1305] Amount of bromonitromethane: 0.9 to 3 moles realtive to 1 mole of compound v-1

[1306] Solvent: aromatic hydrocarbons such as benzene and toluene; halogenated aromatic hydrocarbons such as chlorobenzene; ketones such as acetone; ethers such as tetrahydrofuran; amides such as N,N-dimethylformamide; alcohols such as methanol, ethanol, and isopropanol; and mixtures thereof; etc.

[1307] Reaction temperature: 0° C. to the reflux temperature of the solvent

[1308] Reaction time: a moment to 48 hours

[1309] After completion of the reaction, the reaction mixture is subjected to post-treatments, for example, the reaction mixture is poured into water, and the deposited crystals are collected by filtration and dried; or the reaction mixture is extracted with an organic solvent, and the organic layer was dried and concentrated; or the reaction mixture is concentrated, thereby obtaining the desired compound. The compound can be purified by a technique such as recrystallization or column chromatography.

[1310] Reference Producing Process 7

[1311] This is the producing process according to the following scheme:

[1312] wherein R1, R2, R3, R4, R221, Y11, and Q are as defined above.

[1313] The reactions in the respective steps can be carried out according to the processes as described in Producing Processes 1 to 23.

[1314] The benzonitrile derivatives used in Reference Producing Processes 1 and 2 can be produced from the corresponding benzaldehyde derivatives or benzamide derivatives. (see Shin Jikken Kagaku Koza, edited by Nihon Kagaku Kai, Maruzen Kabushiki Kaisha, 14, pp. 1466-1474.)

[1315] Examples of the present compounds which can be prepared according to the above producing process are illustrated below; however, the present invention is not limited to these examples.

[1316] In the examples, Me indicates methyl; Et, ethyl; Pr, propyl; Bu, butyl; Pen, pentyl; Hex, hexyl; Hep, heptyl; Oct, octyl; i-, iso-; s-, sec-; c-, cyclo-; and groups not particularly indicated are in normal form.

[1317] Compounds of the general formulas:

[1318] wherein

[1319] A's are selected from nitrogen or CH;

[1320] Y1's are selected from oxygen or sulfur;

[1321] Y2's are selected from nitrogen or CH;

[1322] R2's are selected from hydrogen, fluorine, chlorine, bromine, iodine, CH2OH, CHO, COOH, CONH2, COC1, SO2Cl, COCH3, SH, OH, NH2, NO2, CN, CH3, CH2Br, CHB2, CBr3, CH2F, CHF2, CF3, O—Me, O-Et, O—Pr, O-i-Pr, O-Bu, O-i-Bu, O-s-Bu, O-Pen, O-c-Pen, O-Hex, O-c-Hex, O-Hep, O-Oct, OCH2CH2F, OCH2CH2Cl, OCH2CH2Br, OCH2CF3, OCH2OCH3, OCH2CH2OCH3, OCH2—CH2OCH2CH3, OCH2SCH3, OCH2CH2SCH3, OCH2CH2SCH2CH3, OCH2—CH═CH2, OCH(CH3)CH═CH2, OC(CH3)2CH═CH2, OCH2C(Cl)=CH2, OCH(CH3)C(Cl)=CH2, OCH2C(CH3)═CH2, OCH2C≡CH, OCH(CH3)C≡CH, OC(CH3)2C≡CH, OCH2-c-Pr, OCH2-c-Pen, OCH2-c-Hex, OCH2CN, OCH(CH3)CN, OCOMe, OCOEt, OCOPr, OCO-i-Pr, OCOCF3, OCOCF2H, OCH2COOH, OCH2COOMe, OCH2COOEt, OCH2COOPr, OCH2COO-i-Pr, OCH2COOBu, OCH2COO-s-Bu, OCH2COOPen, OCH2COOHex, OCH2—COOHep, OCH2COO-c-Pen, OCH2COO-c-Hex, OCH2COOCH2CH═CH2, OCH2COOCH2C≡CH, OCH2COOPh, OCH2COOCH2Ph, OCH2C(═NOMe)—COOMe, OCH2C(═NOMe)COOEt, OCH2C(═NOMe)COOPr, OCH2COOCH2—COOH, OCH2COOCH2COOMe, OCH2COOCH2COOEt, OCH2COOCH2—COOPr, OCH2COOCH2COO-i-Pr, OCH2COOCH2COOBu, OCH2COOCH2—COO-c-Pen, OCH2COOCH2COO-c-Hex, OCH2COOCH2COOCH2CH═CH2, OCH2COOCH2COOCH2C≡CH, OCH2COOCH(CH3)COOH, OCH2COO—CH(CH3)COOMe, OCH2COOCH(CH3)COOEt, OCH2COOCH(CH3)COOPr, OCH2COOCH(CH3)COO-i-Pr, OCH2COOCH(CH3)COOBu, OCH2COO—CH(CH3)COO-c-Pen, OCH2COOCH(CH3)COO-c-Hex, OCH2COOCH(CH3)—COOCH2CH═CH2, OCH2COOCH(CH3)COOCH2C≡CH, OCH2COOC(CH3)2—COOH, OCH2COOC(CH3)2COOMe, OCH2COOC(CH3)2COOEt, OCH2COO—C(CH3)2COOPr, OCH2COOC(CH3)2COO-i-Pr, OCH2COOC(CH3)2COOBu, OCH2COOC(CH3)2COO-c-Pen, OCH2COOC(CH3)2COO-c-Hex, OCH2COO—C(CH3)2COOCH2CH═CH2, OCH2COOC(CH3)2COOCH2C≡CH, OCH(CH3)—COOH, OCH(CH3)COOMe, OCH(CH3)COOEt, OCH(CH3)COOPr, OCH(CH3)COO-i-Pr, OCH(CH3)COOBu, OCH(CH3)COO-s-Bu, OCH(CH3)—COOPen, OCH(CH3)COOHex, OCH(CH3)COOHep, OCH(CH3)COO-c-Pen, OCH(CH3)COO-c-Hex, OCH(CH3)COOCH2CH═CH2, OCH(CH3)COOCH2 C≡CH, OCH(CH3)COOPh, OCH(CH3)COOCl2Ph, OCH(CH3)C(═NOMe)—COOMe, OCH(CH3)C(═NOMe)COOEt, OCH(CH3)C(═NOMe)COOPr, OCH(CH3)COOCH2COOH, OCH(CH3)COOCH2COOMe, OCH(CH3)COOCH2—COOEt, OCH(CH3)COOCH2COOPr, OCH(CH3)COOCH2COO-i-Pr, OCH(CH3)COOCH2COOBu, OCH(CH3)COOCH2COO-c-Pen, OCH(CH3)—COOCH2COO-c-Hex, OCH(CH3)COOCH2COOCH2CH═CH2, OCH(CH3)COO—CH2COOCH2C≡CH, OCH(CH3)COOCH(CH3)COOH, OCH(CH3)COO—CH(CH3)COOMe, OCH(CH3)COOCH(CH)COOEt, OCH(CH3)COOCH(CH3)—COOPr, OCH(CH3)COOCH(CH3)COO-i-Pr, OCH(CH3)COOCH(CH3)COOBu, OCH(CH3)COOCH(CH3)COO-c-Pen, OCH(CH3)COOCH(CH3)COO-c-Hex, OCH(CH3)COOCH(CH3)COOCH2CH═CH2, OCH(CH3)COOCH(CH3)COOCH2C≡CH, OCH(CH,)COOC(CH3)2COOH, OCH(CH3)COOC(CH3)2COOMe, OCH(CH3)COOC(CH3)2COOEt, OCH(CH3)COOC(CH3)2COOPr, OCH(CH3)—COOC(CH3)2COO-i-Pr, OCH(CH3)COOC(CH3)2COOBu, OCH(CH3)COO—C(CH3)2COO-c-Pen, OCH(CH3)COOC(CH3)2COO-c-Hex, OCH(CH3)COO—C(CH3)2COOCH2CH═CH2, OCH(CH3)COOC(CH3)2COOCH2C≡CH, OCH2—CON(Me)2, OCH2CON(Et)2, OCH(CH3)CON(Me)2, OCH(CH3)CON(Et)2, S—Me, S-Et, S-Pr, S-i-Pr, S-Bu, S-1-Bu, S-s-Bu, S-Pen, S-c-Pen, S-Hex, S-c-Hex, S-Hep, S-Oct, SCH2CH2F, SCH2CH2Cl, SCH2CH2Br, SCH2CF3, SCH2OCH3, SCH2CH2OCH3, SCH2CH2OCH2CH3, SCH2SCH3, SCH2CH2SCH3, SCH2CH2—SCH2CH3, SCH2CH═CH2, SCH(CH3)CH═CH2, SC(CH3)2CH═CH2, SCH2—C(Cl)═CH2, SCH(CH3)C(Cl)═CH2, SCH2C(CH3)═CH2, SCH2C≡CH, SCH(CH3)C≡CH, SC(CH3)2C≡CH, SCH2-c-Pr, SCH2-c-Pen, SCH2-c-Hex, SCH2CN, SCH(CH3)CN, SCOMe, SCOEt, SCOPr, SCO-i-Pr, SCOCF3, SCOCF2H, SCH2COOH, SCH2COOMe, SCH2COOEt, SCH2COOPr, SCH2—COO-i-Pr, SCH2COOBu, SCH2COO-s-Bu, SCH2COOPen, SCH2COOHex, SCH2COOHep, SCH2COO-c-Pen, SCH2COO-c-Hex, SCH2COOCH2CH═CH2, SCH2COOCH2C—CH, SCH2COOPh, SCH2COOCH2Ph, SCH2COOCH2COOH, SCH2COOCH2COOMe, SCH2COOCH2COOEt, SCH2COOCH2COOPr, SCH2—COOCH2COO-i-Pr, SCH2COOCH2COOBu, SCH2COOCH2COO-c-Pen, SCH2—COOCH2COO-c-Hex, SCH2COOCH2COOCH2CH═CH2, SCH2COOCH2COO—CH2C═CH, SCH2COOCH(CH3)COOH, SCH2COOCH(CH3)COOMe, SCH2—COOCH(CH3)COOEt, SCH2COOCH(CH)COOPr, SCH2COOCH(CH3) COO-i-Pr, SCH2COOCH(CH3)COOBu, SCH2COOCH(CH3)COO-c-Pen, SCH2COO—CH(CH3)COO-c-Hex, SCH2COOCH(CH3)COOCH2CH═CH2, SCH2COO—CH(CH3)COOCH2C≡CH, SCH2COOC(CH3)2COOH, SCH2COOC(CH3)2—COOMe, SCH2COOC(CH3)2COOEt, SCH2COOC(CH3)2COOPr, SCH2COO—C(CH3)2COO-i-Pr, SCH2COOC(CH3)2COOBu, SCH2COO C(CH3)2COO-c-Pen, SCH2COOC(CH3)2COO-c-Hex, SCH2COOC(CH3)2COOCH2CH═CH2, SCH2—COOC(CH3)2COOCH2C CH, SCH(CH3)COOH, SCH(CH3)COOMe, SCH(CH3)COOEt, SCH(CH3)COOPr, SCH(CH3)COO-i-Pr, SCH(CH3)COOBu, SCH(CH3)COO-s-Bu, SCH(CH3)COOPen, SCH(CH3)COOHex, SCH(CH3)—COOHep, SCH(CH3)COO-c-Pen, SCH(CH3)COO-c-Hex, SCH(CH3)COO—CH2CH═CH2, SCH(CH3)COOCH2C═CH, SCH(CH3)COOPh, SCH(CH3)—COOCH2Ph, SCH(CH3)COOCH2COOH, SCH(CH3)COOCH2COOMe, SCH(CH3)COOCH2COOEt, SCH(CH3)COOCH2COOPr, SCH(CH3)COOCH2—COO-i-Pr, SCH(CH3)COOCH2COOBu, SCH(CH3)COOCH2COO-c-Pen, SCH(CH3)COOCH2COO-c-Hex, SCH(CH3)COOCH2COOCH2CH═CH2, SCH(CH3)COOCH2COOCH2C≡CH, SCH(CH3)COOCH(CH3)COOH, SCH(CH3)COOCH(CH3)COOMe, SCH(CH3)COOCH(CH3)COOEt, SCH(CH3)COOCH(CH3)COOPr, SCH(CH3)COOCH(CH3)COO-i-Pr, SCH(CH3)COOCH(CH3)COOBu, SCH(CH3)COOCH(CH3)COO-c-Pen, SCH(CH3)COOCH(CH3)COO-c-Hex, SCH(CH3)COOCH(CH3)COOCH2—CH═CH2, SCH(CH3)COOCH(CH3)COOCH2C≡CH, SCH(CH3)COOC(CH3)2—COOH, SCH(CH3)COOC(CH3)2COOMe, SCH(CH3)COOC(CH3)2COOEt, SCH(CH3)COOC(CH3)2COOPr, SCH(CH3)COOC(CH3)2COO-i-Pr, SCH(CH3)—COOC(CH3)2COOBu, SCH(CH3)COOC(CH3)2COO-c-Pen, SCH(CH3)COO—C(CH3)2COO-c-Hex, SCH(CH3)COOC(CH3)2COOCH2CH═CH2, SCH(CH3)—COOC(CH3)2COOCH2C≡CH, SCH2CON(Me)2, SCH2CON(Et)2, SCH(CH3)—CON(Me)2, SCH(CH3)CON(Et)2, NH-Me, NH-Et, NH-Pr, NH-i-Pr, NH-Bu, NH-i-Bu, NH-s-Bu, NH-Pen, NH-c-Pen, NH-Hex, NH-c-Hex, NH-Hep, NH-Oct, NHCH2CH═CH2, NHCH(CH3)CH═CH2, NHC(CH3)2CH═CH2, NHCH2—C(Cl)═CH2, NHCH(CH3)C(Cl)═CH2, NHCH2C(CH3)═CH2, NHCH2C═CH, NHCH(CH3)C≡CH, NHC(CH3)2C≡CH, NHCH2-c-Pr, NHCH2-c-Pen, NH—CH2-c-Hex, NHCH2CN, NHCH(CH3)CN, NHCOMe, NHCOEt, NHCOPr, NHCO-i-Pr, NHCOCF3, NHCOCF2H, NHCOOMe, NHCOOEt, NHCOOPr, NHCOO-i-Pr, NHSO2Me, NHSO2Et, NHSO2Pr, NHSO2-i-Pr, NHSO2CH2Cl, NHSO2CF3, NHCH2COOH, NHCH2COOMe, NHCH2COOEt, NHCH2COOPr, NHCH2COO-i-Pr, NHCH2COOBu, NHCH2COO-s-Bu, NHCH2COOPen, NHCH2COOHex, NHCH2COOHep, NHCH2COO-c-Pen, NHCH2COO-c-Hex, NHCH2COOCH2CH═CH2, NHCH2COOCH2C═CH, NHCH2COOPh, NHCH2—COOCH2Ph, NHCH2COOCH2COOH, NHCH2COOCH2COOMe, NHCH2—COOCH2COOEt, NHCH2COOCH2COOPr, NHCH2COOCH2COO-i-Pr, NH—CH2COOCH2COOBu, NHCH2COOCH2COO-c-Pen, NHCH2COOCH2COO-c-Hex, NHCH2COOCH2COOCH2CH═CH2, NHCH2COOCH2COOCH2C≡CH, NHCH2COOCH(CH3)COOH, NHCH2COOCH(CH3)COOMe, NHCH2COO—CH(CH3)COOEt, NHCH2COOCH(CH3)COOPr, NHCH2COOCH(CH3) COO-i-Pr, NHCH2COOCH(CH3)COOBu, NHCH2COOCH(CH3)COO-c-Pen, NHCH2—COOCH(CH3)COO-c-Hex, NHCH2COOCH(CH3)COOCH2CH═CH2, NHCH2—COOCH(CH3)COOCH2C≡CH, NHCH2COOC(CH3)2COOH, NHCH2COO—C(CH3)2COOMe, NHCH2COOC(CH3)2COOEt, NHCH2COOC(CH3)2COOPr, NHCH2COOC(CH3)2COO-i-Pr, NHCH2COOC(CH3)2COOBu, NHCH2COO—C(CH3)2COO-c-Pen, NHCH2COOC(CH3)2COO-c-Hex, NHCH2COOC(CH3)2—COOCH2CH═CH2, NHCH2COOC(CH3)2COOCH2C≡CH, NHCH(CH3)COOH, NHCH(CH)COOMe, NHCH(CH3)COOEt, NHCH(CH3)COOPr, NHCH(CH3)—COO-i-Pr, NHCH(CH3)COOBu, NHCH(CH3)COO-s-Bu, NHCH(CH3)COO-Pen, NHCH(CH3)COOHex, NHCH(CH3)COOHep, NHCH(CH3)COO-c-Pen, NHCH(CH3)COO-c-Hex, NHCH(CH)COOCH2CH═CH2, NHCH(CH3)COO—CH2C≡CH, NHCH(CH3)COOPh, NHCH(CH3)COOCH2Ph, NHCH(CH3)—COOCH2COOH, NHCH(CH3)COOCH2COOMe, NHCH(CH3)COOCH2COOEt, NHCH(CH3)COOCH2COOPr, NHCH(CH3)COOCH2COO-i-Pr, NHCH(CH3)—COOCH2COOBu, NHCH(CH3)COOCH2COO-c-Pen, NHCH(CH3)COOCH2—COO-c-Hex, NHCH(CH3)COOCH2COOCH2CH═CH2, NHCH(CH3)COOCH2—COOCH2C≡CH, NHCH(CH3)COOCH(CH3)COOH, NHCH(CH3)COO—CH(CH3)COOMe, NHCH(CH3)COOCH(CH3)COOEt, NHCH(CH3)COO—CH(CH3)COOPr, NHCH(CH3)COOCH(CH3)COO-i-Pr, NHCH(CH3)COO—CH(CH3)COOBu, NHCH(CH3)COOCH(CH3)COO-c-Pen, NHCH(CH3)COO—CH(CH3)COO-c-Hex, NHCH(CH3)COOCH(CH3)COOCH2CH═CH2, NH—CH(CH3)COOCH(CH3)COOCH2C≡CH, NHCH(CH3)COOC(CH3)2COOH, NHCH(CH3)COOC(CH3)2COOMe, NHCH(CH3)COOC(CH3)2COOEt, NH—CH(CH3)COOC(CH3)2COOPr, NHCH(CH3)COOC(CH3)2COO-i-Pr, NH—CH(CH3)COOC(CH3)2COOBu, NHCH(CH3)COOC(CH3)2COO-c-Pen, NH—CH(CH3)COOC(CH3)2COO-c-Hex, NHCH(CH3)COOC(CH3)2COOCH2—CH═CH2, NHCH(CH3)COOC(CH)2COOCH2C≡CH, NHCH2CON(Me)2, NH—CH2CON(Et)2, NHCH(CH3)CON(Me)2, NHCH(CH3)CON(Et)2, COOH, COO-Me, COOEt, COOPr, COO-i-Pr, COOBu, COO-s-Bu, COOPen, COOHex, COOCH2Ph, COO-c-Pen, COO-c-Hex, COOCH2COOH, COOCH2COOMe, COOCH2COOEt, COOCH2COOPr, COOCH2COO-i-Pr, COOCH2COOBu, COOCH2COO-c-Pen, COOCH2COO-c-Hex, COOCH2COOCH2CH≡CH2, COO—CH2COOCH2C≡CH, COOCH(CH3)COOH, COOCH(CH3)COOMe, COO—CH(CH3)COOEt, COOCH(CH3)COOPr, COOCH(CH3)COO-i-Pr, COO—CH(CH3)COOBu, COOCH(CH3)COO-c-Pen, COOCH(CH3)COO-c-Hex, COO—CH(CH3)COOCH2CH═CH2, COOCH(CH3)COOCH2C≡CH, COOC(CH3)2—COOH, COOC(CH3)2COOMe, COOC(CH3)2COOEt, COOC(CH3)2COOPr, COOC(CH3)2COO-i-Pr, COOC(CH3)2COOBu, COOC(CH3)2COO-c-Pen, COO—C(CH3)2COO-c-Hex, COOC(CH3)2COOCH2CH═CH2, COOC(CH3)2COOCH2 C≡CH, CON(Me)2, CON(Et)2, CON(Me)2, CON(Et)2, CH2CH2COOH, CH2—CH2COOMe, CH2CH2COOEt, CH2CH2COOPr, CH2CH2COO-i-Pr, CH2CH2—COOBu, CH2CH(Cl)COOH, CH2CH(Cl)COOMe, CH2CH(Cl)COOEt, CH2—CH(Cl)COOPr, CH2CH(Cl)COO-i-Pr, CH2CH(Cl)COOBu, CH═CHCOOH, CH═CHCOOMe, CH═CHCOOEt, CH═CHCOOPr, CH═CHCOO-i-Pr, CH═CHCOOBu, CH═C(Cl)COOH, CH═C(Cl)COOMe, CH═C(Cl)COOEt, CH═C(Cl)COOPr, CH═C(Cl)COO-i-Pr, CH═C(Cl)COOBu, C(Me)═CHCOOH, C(Me)═CHCOOMe, C(Me)═CHCOOEt, C(Me)═CHCOOPr, C(Me)═CHCOO-i-Pr, C(Me)═CHCOOBu, CH═C(Me)COOH, CH═C(Me)COOMe, CH═C(Me)—COOEt, CH═C(Me)COOPr, CH═C(Me)COO-i-Pr, CH═C(Me)COOBu, CH═N—OH, CH═NOMe, CH═NOEt, CH═NOPr, CH═NO-i-Pr, CH═NOBu, C(Me)═N—OH, C(Me)—NOMe, C(Me)=NEt, C(Me)=NOPr, C(Me)=NO-i-Pr, C(Me)=N—OBu, CH═NOCH2COOMe, CH═NOCH2COOEt, CH═NOCH2COOPr, CH═N—OCH2COO-i-Pr, CH═NOCH2COOBu, C(Me)═NOCH2COOMe, C(Me)═NO—CH2COOEt, C(Me)=NOCH2COOPr, C(Me)=NOCH2COO-i-Pr, or (Me)═NO CH2COOBu;

[1323] R3's are selected from hydrogen, fluorine, chlorine, bromine, iodine, NO2, CN, O-Me, O-Et, O-Pr, O-i-Pr, O-Bu, O-1-Bu, O-s-Bu, O-Pen, O-c-Pen, O-Hex, O-c-Hex, O-Hep, O-Oct, OCH2COOMe, OCH2COOEt, OCH2COOPr, OCH2COO-i-Pr, OCH2COOBu, OCH2COO-s-Bu, OCH2COOPen, OCH2CO—OHex, OCH2COOHep, OCH2C(═NOMe)COOMe, OCH2C(═NOMe)COOEt, OCH2C(═NOMe)COOPr, OCH(CH3)COOMe, OCH(CH3)COOEt, OCH(CH3)—COOPr, OCH(CH3)COO-i-Pr, OCH(CH8)COOBu, OCH(CH3)COO-s-Bu, OCH(CH3)COOPen, OCH(CH3)COOHex, OCH(CH3)COOHep, OCH(CH3)—C(═NOMe)COOMe, OCH(CH3)C(═NOMe)COOEt, or OCH(CH3)C(═NOMe)—COOPr; and

[1324] R4's are selected from hydrogen, fluorine, chlorine, bromine, iodine, NO2, or CN.

EXAMPLES

[1325] The present invention will be further illustrated by the following Production Examples, Formulation Examples, and Test Examples; however, the present invention is not limited to these Examples. The numbers of the present compounds are those as shown in Tables 1 to 54.

Production Example 1

[1326]

[1327] To a suspension of 60.0 g of potassium carbonate in 300 ml of acetone was added 25 g of compound 1a and then added 35.7 g of ethyl bromoacetate, and the mixture was heated and stirred at the reflux temperature of acetone for 1 hour. The reaction mixture was then cooled to room temperature and filtered to remove insoluble matter. The filtrate was concentrated to give 45.8 g of compound 1b as a crude product

[1328] To a solution of 45.8 g of this crude product of compound 1b in 300 ml of N,N-dimethylformamide was added 30.0 g of potassium carbonate, and the mixture was heated and stirred at a temperature of 100° C. to 110° C. for 5 hours. The reaction mixture was then cooled to room temperature and poured into water, which was extracted with t-butyl methyl ether. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated to give 36.5 g of compound 1c as crystals.

[1329]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.44 (3H, t, J=7.09 Hz), 4.44 (2H, q, J=7.07 Hz), 4.65-5.38 (2H, br), 7.21-7.27 (1H, m), 7.44-7.57 (3H, m)

[1330] To a solution of 10.2 g of compound 1c in 50 ml of tetrahydrofuran was added 6.5 g of ethyl chloroformate and 7.3 g of N,N-diethylaniline, and the mixture was heated and stirred at the reflux temperature of tetrahydrofuran for 3 hours. The reaction mixture was then cooled to room temperature and poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated to give 13.05 g of compound 1d.

[1331] m.p.: 90.6° C.

[1332] To a suspension of 2.4 g of sodium hydride in 50 ml of N,N-dimethylformamide was added 11.0 g of ethyl 4,4,4-trifluoro-3-aminochrotonate below 10° C., and the mixture was stirred for 30 minutes. The reaction mixture was then warmed to room temperature, to which a solution of 13.0 g of compound 1d in 20 ml of N,N-dimethylformamide was added, and the reaction mixture was then warmed to 100° C. to 110° C., at which temperature the mixture was kept and stirred for 2.5 hours. The reaction mixture was then cooled to room temperature, to which 10.0 g of methyl iodide was added, and the mixture was stirred at room temperature overnight. The reaction mixture was then poured into water, which was extracted with t-butyl methyl ether. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=4:1) to give 4.56 g of compound 1e.

[1333] m.p.: 107.2° C.

[1334] First, 1.0 g of compound 1e was added to 5 ml of 85% sulfuric acid, and the mixture was warmed to 110° C., heated and stirred for 5 minutes. The reaction mixture was then poured into water, and the deposited crystals were collected by filtration and dried to give 0.81 g of compound 1f.

[1335]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.59-3.60 (3H, m), 6.41 (1H, s), 7.26-7.67 (4H, m)

[1336] First, 0.7 g of compound 1f and 0.05 g of copper powder were added to 3 ml of quinoline, and the mixture was warmed to 150° C., at which temperature the mixture was kept and stirred for 1 hour. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane ethyl acetate=5:1) to give 0.43 g of compound 1g (the present compound 1-1).

[1337]

1
H-NMR (250 MHz, CDCl3, TMS, 6 μm)): 3.51 (3H, m), 6.34 (1H, s), 7.21-7.54 (4H, m), 7.81 (1H, s)

Production Example 2

[1338]

[1339] To 200 ml of ethanol were added 25 g of compound 2a and 10.9 g of hydroxylamine hydrochloride, and the mixture was stirred at room temperature overnight., The reaction mixture was then poured into water, and the deposited crystals were collected by filtration and dried to give 26.06 g of compound 2b.

[1340] To a solution of 26.0 g of compound 2b in 100 ml of chloroform was added 22.4 g of 1,1′-carbonyldiimidazole under ice cooling, and the mixture was stirred at room temperature for 30 minutes, then heated and stirred at the reflux temperature of chloroform for 1 hour. The reaction mixture was then concentrated, and diluted hydrochloric acid was added to the residue, which was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated to give 15.88 g of compound 2c.

[1341]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 7.46 (1H, d, J=2.45 Hz), 7.57 (1H, d, J=2.45 Hz).

[1342] To a suspension of 16.5 g of potassium carbonate in 80 ml of acetone was added 15 g of compound 2c and then added 14.6 g of ethyl bromoacetate, and the mixture was heated and stirred at the reflux temperature of acetone for 4 hours. The reaction mixture was then cooled to room temperature and filtered to remove insoluble matter, and the filtrate was then concentrated to give compound 2d as a crude product.

[1343] To a solution of this crude product of compound 2d in 150 ml of N,N-dimethylformamide was added 50.0 g of potassium carbonate, and the mixture was heated and stirred at a temperature of 90° C. to 100° C. for 30 minutes. The reaction mixture was then cooled to room temperature and poured into water, and the deposited crystals were collected by filtration. The crystals were washed with water and dried to give 21.49 g of compound 2e.

[1344]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.44 (3H, t, J=7.07 Hz), 4.45 (2H, q, J=7.07 Hz), 4.82-5.13 (2H, br), 7.44-7.45 (2H, m)

[1345] To 60 ml of toluene were added 4.0 g of compound 2e, 2.8 g of trichloromethyl chloroformate, and 1 g of activated carbon powder), and the mixture was heated and stirred at the reflux temperature of toluene for 1 hour. The reaction mixture was then filtered, and the filtrate was concentrated to give 13.0 g of compound 2f as a crude product.

[1346] In a suspension of 0.64 g of sodium hydride in 20 ml of N,N-dimethylformamide was added 3.0 g of ethyl 4,4,4-trifluoro-3-aminichrotonate below 10° C., and the mixture was stirred for 30 minutes. To the reaction mixture was added dropwise at −30° C. a solution of 13.0 g of this crude product of compound 2f in 30 ml of tetrahydrofuran. After completion of the dropwise addition, the reaction mixture was warmed to room temperature and stirred at room temperature for 2 hours. To the reaction mixture was then added 3.0 g of methyl iodide, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, then and concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate 4:1) to give 4.51 g of compound 2g.

[1347]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.33 (3H, t, J=7.06 Hz), 3.59 (3H, m), 4.39 (2H, q, J=6.93 Hz), 6.39 (1H, s), 7.36 (1H, d, J=2.65 Hz), 7.51 (1H, d, J=2.65 Hz)

[1348] First, 4.5 g of compound 2g was added to 20 ml of 85% sulfuric acid, and the mixture was heated to 110° C., at which temperature the mixture was kept and stirred for 30 minutes. The reaction mixture was then poured into water, and the deposited crystals were collected by filtration and dried to give 3.57 g of compound 2h.

[1349]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)) 3.59-3.60 (3H, m), 6.40 (1H, s), 7.38 (1H, d, J=1.77 Hz), 7.54 (1H, d, J=1.77 Hz)

[1350] To 10 ml of quinoline were added 3.0 g of compound 2h and 0.07 g of copper powder, and the mixture was heated to 120° C. to 150° C., at which temperature the mixture was kept and stirred for 30 minutes. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 1.62 g of compound 2i (the present compound 1-2).

[1351]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.59-3.60 (3H, m), 6.40 (1H, s), 7.24 (1H, d, J=1.89), 7.37 (1H, d, J=1.89), 7.93 (1H, s)

Production Example 3

[1352]

[1353] To a solution of 9.77 g of acetohydroxamic acid in 150 ml of N,N-dimethylformamide was added 14.6 g of potassium t-butoxide at room temperature, and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture was added 10.5 g of compound 3a at room temperature, and the mixture was left undisturbed at room temperature for 3 days. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with n-hexane to give 6.95 g of compound 3b.

[1354] To 2 ml of propionic acid were added 500 mg of compound 3b and 567 mg of 3,4,5,6-tetrahydrophthalic anhydride, and the mixture was heated and stirred at the reflux temperature of propionic acid for 24 hours. The reaction mixture was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=5:1) to give 200 mg of compound 3c (the present compound 2-4).

[1355]

1
H-NMR (250 MHz, CDCl3, TMS, 6 μm)): 1.84-1.89 (4H, m), 2.48-2.52 (4H, m), 7.31-7.40 (1H, m), 7.55-7.75 (3H, m)

Production Example 4

[1356]

[1357] To a solution of 10.4 g of ethyl thioglycolate in 20 ml of N,N-dimethylformamide were added 12.4 g of potassium carbonate and 20 ml of N,N-dimethylformamide, and the mixture was warmed to 40° C. To the reaction mixture was added 10.0 g of compound 4a, and the mixture was warmed to 85° C., at which temperature the mixture was kept and stirred for 2 hours. The reaction mixture was left undisturbed at room temperature overnight. To the reaction mixture were then added 33.7 g of potassium carbonate and 30 ml of N,N-dimethylformamide, and the mixture was heated and stirred at 100° C. to 110° C. for 4 hours. The reaction solution was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=4:1) to give 14.44 g of compound 4b.

[1358]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.39 (3H, t, J=7.09 Hz), 4.36 (2H, q, J=7.11 Hz), 5.90 (2H, bs), 7.34-7.74 (4H, m)

[1359] To a solution of 4.0 g of compound 4b in 50 ml of toluene was added 3.58 g of trichloromethyl chloroformate, and the mixture was heated and stirred at the reflux temperature of toluene for 1 hour. The reaction mixture was concentrated to give compound 4c as a crude product.

[1360] To a suspension of 0.87 g of sodium hydride in 15 ml of N,N-dimethylformamide was added 4.0 g of ethyl 4,4,4-trifluoro-3-aminochrotonate below 10° C., and the mixture was stirred for 30 minutes. To the reaction was then added dropwise at −30° C. a solution of this crude product of compound 4c in the whole amount dissolved in 50 ml of tetrahydrofuran. After completion of the dropwise addition, the mixture was warmed to room temperature and left undisturbed overnight. To the reaction mixture was then added 3.85 g of methyl iodide, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=4:1) to give 2.36 g of compound 4b as crystals.

[1361] m.p.: 112.6° C.

[1362] To 15 ml of 85% sulfuric acid was added 2.3 g of compound 4d, and the mixture was warmed to 110° C., at which temperature the mixture was kept and stirred for 15 minutes. The reaction mixture was then poured into water, and the precipitated crystals were collected by filtration and dried to give 1.61 g of compound 4e.

[1363]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.58 (3H, m), 6.42 (1H, s), 7.41-7.91 (4H, m)

[1364] To 12 ml of quinoline were added 1.5 g of compound 4e and 0.06 g of copper powder, and the mixture was warmed to 120° C. to 140° C., at which temperature the mixture was kept and stirred for 30 minutes. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=4:1) to give 1.07 g of compound 4f (the present compound 1-3).

[1365] m.p.: 156.8° C.

Production Example 5

[1366]

[1367] According to the process as described above in Production Example 2, compound 5a (the present compound 1-6) was produced from 2-hydroxy-5-nitrobenzaldehyde.

[1368] m.p.: 231.9° C. (decomposition)

[1369] To a mixed solvent of 40 ml of acetic acid and 20 ml of water was added 4.5 g of iron powder, to which suspension 4.5 g of compound 5a was added, and the mixture was heated and stirred at the reflux temperature of the solvent for 20 minutes. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with saturated aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate, and then concentrated to give 2.64 g of compound 5b (the present compound 1-7).

[1370]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.25-3.82 (2H, br), 3.58 (3H, m), 6.39 (1H, s), 6.55 (1H, d, J=2.30 Hz), 6.71 (1H, dd, J=8.76 Hz, 2.30 Hz), 7.32 (1H, d, J=8.76 Hz), 7.73 (1H, s)

[1371] To a solution of 0.8 g of compound 5b dissolved in 6 ml of pyridine was added 0.3 g of methanesulfonyl chloride at room temperature, and the mixture was stirred for 2 hours. The reaction mixture was poured into water, which was extracted with ethyl acetate. The organic layer was washed with water, with aqueous hydrochloric acid solution, and then with water, dried over anhydrous magnesium sulfate, and then concentrated. The deposited crystals were washed with t-butyl methyl ether to give 0.55 g of compound 5c (the present compound 1-10).

[1372] m.p.: 105.3° C.

Production Example 6

[1373]

[1374] To 6 ml of methyl iodide was added 0.6 g of compound 5b, and the mixture was heated and stirred at the reflux temperature of methyl iodide for 4 hours. The reaction mixture was concentrated, and the residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2:1) to give 0.14 g of compound 6a (the present compound 1-8) and 0.065 g of compound 6b (the present compound 1-9).

[1375] Compound 6a

[1376]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 2.82 (3H, s), 3.57-3.58 (3H, m), 6.37-6.67 (3H, m), 7.33 (1H, d, J=8.85 Hz), 7.71 (1H, s)

[1377] Compound 6b

[1378] m.p.: 166.1C (decomposition)

Production Example 7

[1379]

100

[1380] To 10 ml of acetonitrile were added 0.53 g of copper (I) chloride and 0.57 g of isobutyl nitrite, to which 3 ml of ethyl acrylate was added under ice cooling, and the mixture was stirred for 10 minutes. A solution of 1.0 g of compound 5b dissolved in 5 ml of acetonitrile was then added to the reaction mixture under ice cooling. The mixture obtained was stirred for 2 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=3:1) to give 0.64 g of compound 7a (the present compound 1-407).

[1381]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.18 (3H, t, J=7.12 Hz), 3.18-3.48 (2H, m), 3.56-3.57 (3H, m), 4.10-4.20 (2H, m), 4.41 (1H, t, J=7.43 Hz), 6.39 (1H, s), 7.19-7.49 (3H, m), 7.82 (1H, s)

Production Example 8

[1382]

101

[1383] According to the process as described above in Production Example 2, compound 8a (the present compound 1-5) was produced from 2-hydroxy-5-methoxybenzaldehyde.

[1384] m.p.: 135.0° C.

[1385] To a solution of 0.64 g of compound 8a dissolved in 4 ml of chloroform was added 0.5 g of iodotrimethylsilane, and the mixture was kept and stirred at 40° C. to 50° C. for 10.5 hours. The mixture was then left undisturbed at room temperature for a half day, to which 0.5 g of iodotrimethylsilane was further added, and the mixture was further kept and stirred at 40° C. to 50° C. for 10.5 hours. The reaction mixture was then poured into ice water, which was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2:1) to give 0.37 g of compound 8b (the present compound 1-78).

[1386]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.58-3.59 (3H, m), 5.09 (1H, bs) 6.39 (1H, s), 6.68 (1H, d, J=2.32 Hz), 6.82 (1H, dd, J=8.83 Hz, 2.32 Hz), 7.37 (1H, d, J=8.85 Hz), 7.79 (1H, s)

[1387] To a suspension of 0.05 g of sodium hydride in 1 ml of N,N-dimethylformamide was added a solution of 0.35 g of compound 8b in 2 ml of N,N-dimethylformamide under ice cooling, and the mixture was stirred for 5 minutes. Then, 0.23 g of ethyl bromoacetate was added under ice cooling, and the mixture was stirred for 0.5 hour. The reaction mixture was poured into water, which was extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2:1) to give 0.34 g of compound 8c (the present compound 1-127).

[1388]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.21 (3H, t, J=7.06 Hz), 1.60 (3H, d, J=6.82 Hz), 3.58-3.59 (3H, m), 4.10-4.23 (2H, m), 4.73 (1H, q, J=6.82 Hz), 6.38 (1H, s), 6.74 (1H, d, J=2.52 Hz), 6.97 (1H, dd, J=9.21 Hz, 2.80 Hz), 7.43 (1H, d, J=9.29 Hz), 7.80 (1H, s)

Production Example 9

[1389]

102

[1390] In a solution of 1.0 g of compound 5b dissolved in 10 ml of acetic acid was added 0.045 g of acetic anhydride, and the mixture was stirred at room temperature for 3 hours. A mixed solution of hexane:ethyl acetate=1:1 was then added, and the deposited crystals were collected by filtration and dried to give 1.16 g of compound 9a (the present compound 1-24).

[1391]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 2.10 (3H, s), 3.59 (3H, s), 6.39 (1H, s), 7.12 (1H, dd, J=8.80 Hz, 2.10 Hz), 7.29 (1H, bs), 7.44 (1H, d, J=8.82 Hz), 7.77 (1H, d, J=1.88 Hz), 7.81 (1H, s)

[1392] In a solution of 1.0 g of compound 9a dissolved in 10 ml of dimethylformamide was added 0.11 g of sodium hydride at room temperature, and the mixture was stirred for 10 minutes. Then, 0.43 g of methyl iodide was added at room temperature, and the mixture was left undisturbed for 3 days. The reaction mixture was then poured into water, which was extracted with t-butyl methyl ether. The organic layer was washed with water and then with diluted hydrochloric acid, and dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 0.36 g of compound 9b (the present compound 1-28).

[1393] m.p.: 207.2° C.

Production Example 10

[1394]

103

[1395] According to the process as described above in Production Example 2, compound 10a (the present compound 1-75) was produced from 2-hydroxy-5-bromobenzaldehyde.

[1396] m.p.: 130.0° C.

[1397] To a solution of 1.85 g of compound 10a in 10 ml of N-methylpyrrolidone was added 0.67 g of copper (I) cyanide, and the mixture was heated and stirred at 170° C. to 180° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into water, which was extracted with t-butyl methyl ether. The organic layer was washed with cold ammonia water, with water, and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 0.85 g of compound 10b (the present compound 1-283).

[1398] m.p.: 174.3° C. (decomposition)

[1399] After 0.65 g of compound lob was dissolved in 85% sulfuric acid, the solution was kept and stirred at 50° C. to 60° C. for 0.5 hour. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 0.45 g of compound 10c (the present compound 1-293).

[1400]

1
H-NMR (300 MHz, CDCl3+DMSO, TMS, δ (ppm)) 3.60 (3H, s), 6.40 (1H, s), 7.58 (1H, d, J=8.76 Hz), 7.84-7.95 (3H, m)

[1401] First, 0.3 g of compound 10c was added to 10 ml of a solution of boron trifluoride methanol complex in methanol, and the mixture was heated and stirred at the reflux temperature for 7 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2:1) to give 0.22 g of compound lod (the present compound 1-303).

[1402]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59 (3H, m), 3.92 (3H, s), 6.40 (1H, s), 7.58 (1H, d, J=9.06 Hz), 7.89 (1H, s), 8.06-8.09 (2H, m)

Production Example 11

[1403]

104

[1404] To a solution of 10.45 g of compound 11a, which had been produced according to the process as described in the JP-A 58-79960 publication, in 30 ml of N-methylpyrrolidone was added 4.56 g of copper (1) cyanide, and the mixture was kept and stirred at 110° C. to 120° C. for 6 hours. After cooling to room temperature, the reaction mixture was poured into water, which was extracted with t-butyl methyl ether. The organic layer was washed with cold ammonia water, with water, and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 5.14 g of compound [11b].

[1405]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.32 (3H, t, J=7.17 Hz), 4.31 (2H, q, J=7.22 Hz), 4.89 (2H, s), 7.70 (1H, d, J=1.82 Hz), 7.80 (1H, d, J=8.57 Hz), 7.93-7.95 (1H, m)

[1406] To a solution of 5.1 g of compound 11b in 50 ml of N,N-dimethylformamide was added 3.3 g of potassium carbonate, and the mixture was kept and stirred at 100° C. for 30 minutes. The reaction mixture was then cooled to room temperature and poured into water. The deposited crystals were collected by filtration. The crystals were washed with water and dried to give 4.0 g of compound 11c.

[1407]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.46 (3H, t, J=7.24 Hz), 4.47 (2H, q, J=7.08 Hz), 5.30 (2H, bs), 7.69 (1H, d, J=8.67 Hz), 8.16 (1H, dd,- J=8.76 Hz, 1.77 Hz), 8.34 (1H, d, J=1.87 Hz)

[1408] To a solution of 3.8 g of compound 11c in 50 ml of toluene was added 3.3 g of trichloromethyl chloroformate, and the mixture was heated and stirred at the reflux temperature of toluene for 1 hour. The reaction mixture was then concentrated to give a crude product of isocyanate.

[1409] To a suspension of 0.67 g of sodium hydride in 5 ml of N,N-dimethylformamide was added a solution of 3.1 g of ethyl 4,4,4-trifluoro-3-aminocrotonate in 5 ml of N,N-dimethylformamide below 10° C., and the mixture was stirred for 30 minutes. To the reaction mixture was then added dropwise a solution of the crude product of isocyanate obtained from compound 11c in 100 ml of tetrahydrofuran at −30° C. After completion of the dropwise addition, the mixture was warmed to room temperature and then stirred for 1 hour. To the reaction mixture was then added 4.3 g of methyl iodide, and the mixture was left undisturbed at room temperature overnight. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate 2 : 1) to give 3.80 g of compound 11d as crystals.

[1410]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.37 (3H, t, J=7.30 Hz), 3.36 (3H, m), 4.42 (2H, q, J=6.14 Hz), 6.14 (1H, s), 7.61 (1H, d, J=8.78 Hz), 8.26 (1H, dd, J=8.67 Hz, 2.12 Hz), 8.55 (1H, d, J=1.79 Hz)

[1411] First, 3.5 g of compound 11d was added to 20 ml of 85% sulfuric acid, and the mixture was kept and stirred at a temperature of 110° C. to 120° C. for 20 minutes. The reaction mixture was then poured into water, and the deposited crystals were collected by filtration and dried. The whole amount of the crystals obtained and 0.23 g of copper powder were added to 15 ml of quinoline, and the mixture was warmed to 120° C. to 130° C., at which temperature the mixture was kept and stirred for 1 hour. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2.5:1) to give 1.05 g of compound 11e (the present compound 1-282).

[1412]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59-3.61 (3H, m), 6.42 (1H, s), 7.47 (1H, d, J=8.71 Hz), 8.11 (1H, s), 8.21 (1H, dd, J=8.79 Hz, 2.06 Hz), 8.48 (1H, d, J=1.85 Hz)

Production Example 12

[1413]

105

[1414] According to the process as described in the JP-A 58-79960 publication, 2-bromo-4-fluoro-5-nitrophenol was obtained from 4-fluorophenol and then used as the starting material to produce compound 12a (the present compound 1-431) according to the process as described above in Production Example 11.

[1415]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61-3.62 (3H, m), 6.42 (1H, s), 7.24 (1H, d, J=10.4 Hz), 8.13 (1H, s), 8.33 (1H, d, J=5.79 Hz)

[1416] To a solution of 0.6 g of compound 12a in 9 ml of N,N-dimethylformamide was added 0.12 g of sodium methylsulfide below 0° C., and the mixture was stirred for 2 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with water and then with diluted hydrochloric acid, dried over anhydrous magnesium sulfate, dried, and then concentrated. The crystals obtained were washed with t-butyl methyl ether to give 0.24 g of compound 12b (the present compound 1-201).

[1417]

1
H-NMR (300 MHz, CDCl, TMS, δ (ppm)): 2.50 (s, 3H), 3.62 (3H, m), 6.43 (1H, s), 7.19 (1H, s), 8.07 (1H, s), 8.49 (1H, d, J=5.79 Hz)

Production Example 13

[1418]

106

[1419] First, 1.0 g of compound 13a and 1.15 g of 3,4,5,6-tetrahydrophthalic anhydride were added to 15 ml of acetic acid, and the mixture was heated and stirred at the reflux temperature for 1 hour. The reaction mixture was concentrated under reduced pressure, and the residue was washed with hexane: isopropanol =1: 1 (v/v) to give 1.48 g of compound 13b (the present compound 2-2001).

[1420]

1
H-NMR (250 MHz, CDCl, TMS, δ (ppm)): 1.75-1.95 (4H, m), 2.35-2.55 (4H, m), 6.64 (1H, m), 7.01-7.15 (4H, m), 7.63 (1H, d, J=7.0 Hz)

Production Example 14

[1421]

107

[1422] First, 0.2 g of compound 13a and 0.4 g of ethyl 3-{[1-(dimethylamino)methylidene]amino}-4,4,4-trifluoro-2-butenoate were added to 5 ml of acetic acid, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen-carbonate solution and then with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography to give 0.05 g of compound 14a (the present compound 3-2001).

[1423]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 6.74 (1H, d, J=3.5 Hz), 7.00-7.06 (2H, m), 7.10 (1H, d, J=3.5 Hz), 7.21-7.32 (2H, m), 7.68 (1H, dd, J=1.8 Hz, 6.7 Hz), 8.40 (1H, s)

Production Example 15

[1424]

108

[1425] To a solution of 1.5 g of compound 15a in 15 ml of acetic acid was added 1.9 g of 3,4,5,6-tetrahydrophthalic anhydride, and the mixture was heated at reflux for 6 hours. After cooling to room temperature, the reaction mixture was poured into ice water, which was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate solution and then with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel column chromatography to give 3.0 g of compound 15b (the present compound 2-2004).

[1426] m.p.: 184.5° C.

Production Example 16

[1427]

109

[1428] First, 25 g of compound 16a was added to 40 ml of thionyl chloride, and the mixture was heated and stirred at the reflux temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, to which residue was added 100 ml of ethanol. To the reaction mixture was then added dropwise 14 ml of pyridine under ice cooling, and the mixture was stirred at room temperature for 2 days and then left undisturbed for a half day. The reaction mixture was then concentrated, to which diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen-carbonate solution and then with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated to give 27 g of compound 16b as a crude product.

[1429]

1
H-NMR (300 MHz, CDCl3, TMS, 6 μm)): 1.42 (3H, t, J=7.2 Hz), 2.66 (3H, s), 4.42 (2H, q, J=7.2 Hz), 7.43 (1H, d, J=8.0 Hz), 8.15 (1H, dd, J=1.7 Hz, 8.0 Hz), 8.60 (1H, d, J=1.7 Hz) First, 5.4 g of iron powder was added to a mixed solvent of 20 ml of acetic acid and 150 ml of water, and the mixture was heated to 70° C., to which a solution of 5.0 g of compound 16b in 20 ml of ethyl acetate was added dropwise. After completion of the dropwise addition, the mixture was left cooling to room temperature and stirred for 2 hours. Water was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate solution, dried over anhydrous magnesium sulfate, and then concentrated to give 3.8 g of compound 16c as a crude product.

[1430] m.p.: 112.6° C.

[1431] To a solution of 1.0 g of compound 16c in 50 ml of acetic acid was added dropwise a solution of 0.42 g of sodium nitrite in 5 ml of water at 10° C. After completion of the dropwise addition, the mixture was left undisturbed at room temperature for a half day. Water was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate solution and then with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography to give 0.5 g of compound 16d.

[1432]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.44 (3H, t, J=7.1 Hz), 4.44 (2H, q, J=7.1 Hz), 7.78-7.89 (2H, m), 8.16 (1H, d, J=1.1 Hz), 8.29 (1H, q, J=1.1 Hz)

[1433] To a solution of 1.0 g of compound 16d in 10 ml of N,N-dimethylformamide was added 0.2 g of sodium hydride at room temperature. After the gas evolution from the reaction mixture ceased, 1.0 g of o-(2,4-dinitrophenyl)hydroxylamine was added, and the mixture was stirred. After left undisturbed for 2 days, water was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography to give 0.36 g of compound 16e.

[1434]

1
H-NMR (300 MHz, CDCl, TMS, δ (ppm)): 1.42 (3H, t, J=7.2 Hz), 4.41 (2H, q, J=7.2 Hz), 5.45 (2H, bs), 7.61-7.78 (2H, m), 7.86 (1H, s), 8.28 (1H, d, J=0.8 Hz)

[1435] First, 0.15 g of compound 16e and 0.12 g of 3,4,5,6-tetrahydrophthalic anhydride were dissolved in 10 ml of acetic acid, and the solution was heated and stirred at the reflux temperature for 1 hour. After the reaction mixture was left cooling to room temperature, water was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogencarbonate solution and then with saturated sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=3:1) to give 0.09 g of compound 16f (the present compound 2-2011).

[1436]

1
H-NMR (300 MHz, CDCl3, TMS, 6 (ppm)) 1.42 (3H, t, J=7.2 Hz), 1.89 (4H, m), 2.50 (4H, m), 4.42 (2H, q, J=7.2 Hz), 7.79-7.84 (1H, m), 7.91-7.96 (1H, m), 8.03 (1H, m), 8.19 (1H, d, J=1.1 Hz)

Production Example 17

[1437]

110

[1438] First, 300 mg of compound 16e and 230 mg of phenyl chloroformate were dissolved in 10 ml of tetrahydrofuran, to which 120 mg of pyridine was added at room temperature. After stirring at room temperature for 1 hour, diluted hydrochloric acid was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=2:1) to give 500 mg of compound 17a.

[1439]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.45 (3H, t, J=7.1 Hz), 4.45 (2H, q, J=7.1 Hz), 7.15-7.42 (5H, m), 7.76-7.80 (1H, m), 7.89-7.94 (1H, m), 8.09 (1H, s), 8.27 (1H, s)

[1440] To a mixture of 280 mg of ethyl 4,4,4-trifluoro-3-aminochrotonate and 5 ml of N,N-dimethylformamide was added 60 mg of sodium hydride at room temperature, and the mixture was stirred for 10 minutes. To the reaction solution was added dropwise a solution of 500 mg of compound 17a in 6 ml of N,N-dimethylformamide. The mixture was stirred at 80° C. for 2 hours and then left cooling to room temperature, to which 500 mg of iodomethane was added. After stirring at room temperature for 4 hours, diluted hydrochloric acid was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and then concentrated. The residue was subjected to silica gel chromatography (eluent, hexane:ethyl acetate=5:2) to give 100 mg of compound 17b (the present compound 1-2068).

[1441]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.41 (3H, t, J=7.1 Hz), 3.59 (3H, m), 4.41 (2H, q, J=7.1 Hz), 6.44 (1H, s), 7.84 (1H, d, J=9.1 Hz), 7.93-7.97 (2H, m), 8.24 (1H, d, J=0.8 Hz)

Production Example 18

[1442]

111

[1443] To a solution of 2.0 g of compound 3b and 1.2 g of pyridine in 10 ml of tetrahydrofuran was added dropwise a solution of 1.6 g of ClCO2Et in 3 ml of tetrahydrofuran at 0° C. to 10° C. After stirring at room temperature for 1 hour, diluted hydrochloric acid was added to the reaction mixture, which was extracted with ethyl acetate. The organic layer was concentrated, and the residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=3:1) to give 2.7 g of compound 18a.

[1444]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.37 (3H, t, J=7.2 Hz), 4.33 (2H, q, J=7.2 Hz), 7.26-7.34 (2H, m), 7.48-7.58 (2H, m), 8.17 (1H, d, J=4.1 Hz)

[1445] To 15 ml of N,N-dimethylformamide was added 0.5 g of sodium hydride, to which 2.4 g of H2N(CF3)C═CHCO2Et was added dropwise under ice cooling. After stirring at room temperature for 30 minutes, a solution of compound 18a dissolved in 5 ml of N,N-dimethylformamide was added dropwise thereto. Mter heating at 100° C. for 4 hours and at 120° C. for 2 hours, the reaction mixture was cooled to room temperature. Then, 2.0 g of iodomethane was added, and the mixture was left standing overnight, to which diluted hydrochloric acid was added. The mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=3:1) to give 2.2 g of compound 18b (the present compound 1-875).

[1446] m.p.: 159.1° C.

Production Example 19

[1447]

112

[1448] First, 1.3 g of potassium tert-butoxide and 0.9 g of acetohydroxamic acid were added to 25 ml of N,N-dimethylformamide, and the mixture was stirred at room temperature for 30 minutes. A solution of 1.5 g of compound 19a dissolved in 5 ml of N,N-dimethylformamide was added dropwise thereto, and the mixture was then left standing at room temperature overnight. To the reaction mixture was added aqueous sodium chloride solution, which was extracted with ethyl acetate. The organic layer was dried with magnesium sulfate and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=2:1) to give 0.8 g of compound 19b.

[1449]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 4.38-4.64 (1H, br), 7.20-7.27 (2H, m), 7.43-7.47 (2H, m)

[1450] To 50 ml of toluene were added 2.1 g of compound 19b (produced in the same manner as described above) and 2.5 g of trichloromethyl chloroformate, and the mixture was heated at reflux for 2 hours. The reaction mixture was concentrated to give 2.5 g of compound 19c as a crude product.

[1451] To a suspension of 0.6 g of sodium hydride -in 30 ml of N,N-dimethylformamide was added 2.7 g of ethyl 4,4,4-trifluoro-3-aminochrotonate at room temperature, and the mixture was stirred for 30 minutes. To the reaction mixture was then added dropwise a solution of the whole amount of the crude product of compound 19c dissolved in 50 ml of tetrahydrofuran at 0° C. After completion of the dropwise addition, the mixture was warmed to room temperature and stirred for 3 hours, to which 2.0 g of methyl iodide was added, and the mixture was left standing overnight. The reaction mixture was then poured into diluted hydrochloric acid, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=3:1) to give 80 mg of compound 19d (the present compound 1-877).

[1452]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.57 (3H, q, J=1.2 Hz), 6.41 (1H, s), 7.36 (1H, dd, J=1.6 Hz, 8.5 Hz), 7.45 (1H, d, J=8.5 Hz), 7.71 (1H, d, J=1.6 Hz)

Production Example 20

[1453]

113

[1454] To a mixed solution of 190.0 g of compound 20a, 122.9 g of methyl chloroformate, and 150 ml of water was added dropwise aqueous sodium hydroxide solution (50 g of NaOH and 100 ml of H2O) below 10° C. After completion of the dropwise addition, the mixture was stirred for 2 hours. The crystals obtained were then collected by filtration, washed with a solution (isopropyl alcohol: water=1:1), and dried to give 160.5 g of compound 20b.

[1455] Then, 160.0 g of compound 20b was dissolved in 250 ml of concentrated sulfuric acid, to which a mixed acid (42.5 g of fuming nitric acid and 30 ml of concentrated sulfuric acid) was added dropwise below 5° C. After completion of the dropwise addition, the mixture was stirred for 2 hours. The reaction mixture was poured into ice water, and the deposited crystals were collected by filtration, washed with water, and dried to give 186.5 g of compound 20c.

[1456]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.98 (3H, s), 7.63 (1H, d, J=9.60 Hz), 8.03 (1H, d, J=6.83 Hz)

[1457] To 300 ml of water and 300 ml of ethanol was suspended 186.0 g of compound 20c, to which aqueous sodium hydroxide solution (60 g of NaOH and 120 ml of H2O) was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 1 hour and then concentrated to remove the ethanol. The residue obtained was made acidic by the addition of concentrated hydrochloric acid under ice cooling, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated to give 141.1 g of compound 20d.

[1458] According to the process as described in Production Example 2, compound 20e was produced from compound 20d.

[1459]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.32 (3H, t, J=7.11 Hz), 4.30 (2H, q, J=7.14 Hz), 4.77 (2H, s), 7.51 (1H, d, J=6.28 Hz), 7.58 (1H, d, J=9.81 Hz)

[1460] According to the process as described in Production Example 11, compound 20f was produced from compound 20e.

[1461]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.33 (3H, t, J=7.12 Hz), 4.30 (2H, q, J=7.12 Hz), 4.86 (2H, s), 7.52 (1H, d, J=5.66 Hz), 7.59 (1H, d, J=9.39 Hz)

[1462] First, 30 g of compound 20f was dissolved in 30 ml of N,N-dimethylformamide, to which 18.4 g of sodium acetate and 3 ml of water were added, and the mixture was kept and stirred at a temperature of 80° C. to 90° C. for 9 hours. After cooling to room temperature, diluted hydrochloric acid was poured into the reaction mixture, which was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and then concentrated. The residue was subjected to silica gel column chromatography (eluent, hexane:ethyl acetate=3:1) to give 13.6 g of compound 20g.

[1463]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.32 (3H, t, J=7.08 Hz), 4.29 (2H, q, J=7.08 Hz), 4.79 (2H, s), 7.48 (1H, s), 7.56 (1H, s)

[1464] First, 13 g of compound 20g was dissolved in 40 ml of N,N-dimethylformamide, to which 7.3 g of potassium carbonate was added at room temperature. Then, 6.2 g of dimethylsulfuric acid was added at 30° C. to 40° C. thereto, and the mixture was stirred for 30 minutes. The reaction mixture was then poured into water, which was extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid, dried over magnesium sulfate, and then concentrated. The crystals obtained were washed with a solution (t-butyl methyl ether: hexane=1:2) to give 10.7 g of compound 20h.

[1465]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.31 (3H, t, J=7.16 Hz), 4.00 (3H, s), 4.29 (2H, q, J=7.16 Hz), 4.78 (2H, s), 7.32 (1H, s), 7.34 (1H, s)

[1466] According to the process as described in Production Example 11, compound 20i was produced from compound 20h.

[1467] According to the process as described in Production Example 11, compound 20j (the present compound 1-86) was produced from compound 20i.

[1468]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61 (3H, m), 3.95 (3H, s), 6.42 (1H, s), 6.89 (1H, s), 8.00 (1H, s), 8.09 (1H, s)

[1469] Examples of the present compounds are shown below together with their compound numbers.

[1470] Compounds of the General Formula:

114

1TABLE 1CompoundR2R3R4AY1-1 HHHCHO1-2 ClHClCHO1-3 HHHCHS1-4 ClHHCHO1-5 OCH3HHCHO1-6 NO2HHCHO1-7 NH2HHCHO1-8 NHCH3HHCHO1-9 N(CH3)2HHCHO1-10NHSO2CH3HHCHO1-11NHCH(CH3)CO2EtHHCHO1-12NHCH(CH3)CO2EtHClCHO1-13N(CH3)CH(CH3)CO2EtHClCHO1-14N(CH3)SO2CH3HClCHO1-15NHSO2CH3HClCHO1-16NHCH(CH3)CO2EtClHCHO1-17N(CH3)CH(CH3)CO2EtClHCHO

[1471]

2

TABLE 2

Compound
R2
R3
R4
A
Y

1-18
N(CH3)SO2CH3
Cl
H
CH
O

1-19
NHSO2CH3
Cl
H
CH
O

1-20
NO2
H
Cl
CH
O

1-21
NH2
H
Cl
CH
O

1-22
NO2
Cl
H
CH
O

1-23
NH2
Cl
H
CH
O

1-24
NHCOCH3
H
H
CH
O

1-25
NHCOCF3
H
H
CH
O

1-26
NHSO2Et
H
H
CH
O

1-27
NHSO2CH2Cl
H
H
CH
O

1-28
N(CH3)COCH3
H
H
CH
O

1-29
N(CH3)COCF3
H
H
CH
O

1-30
N(CH3)SO2Et
H
H
CH
O

1-31
CO2C(CH3)2CO2Et
H
H
CH
O

1-32
N(CH3)SO2CH2Cl
H
H
CH
O

1-33
NHCOCH3
H
Cl
CH
O

1-34
NHCOCF3
H
Cl
CH
O

1-35
NHSO2Et
H
Cl
CH
O

1-36
NHSO2CH2Cl
H
Cl
CH
O

1-37
N(CH3)COCH3
Cl
H
CH
O

1-38
N(CH3)COCF3
Cl
H
CH
O

1-39
N(CH3)SO2Et
Cl
H
CH
O

1-40
N(CH3)SO2CH2Cl
Cl
H
CH
O

1-42
NHCH2CO2Me
H
H
CH
O

1-43
NHCH2CO2Et
H
H
CH
O

[1472]

3

TABLE 3

Compound
R2
R3
R4
A
Y

1-44
NHCH(CH3)COOH
H
H
CH
O

1-45
NHCH(CH3)CONH2
H
H
CH
O

1-46
NHCH(CH3)CONHCH3
H
H
CH
O

1-47
NHCH2CO2Me
H
Cl
CH
O

1-48
NHCH2CO2Et
H
Cl
CH
O

1-49
NHCH(CH3)COOH
H
Cl
CH
O

1-50
NHCH(CH3)CONH2
H
Cl
CH
O

1-51
NHCH(CH3)CONHCH3
H
Cl
CH
O

1-52
NHCH2CO2Me
Cl
H
CH
O

1-53
NHCH2CO2Et
Cl
H
CH
O

1-54
NHCH(CH3)COOH
Cl
H
CH
O

1-55
NHCH(CH3)CONH2
Cl
H
CH
O

1-56
NHCH(CH3)CONHCH3
Cl
H
CH
O

1-57
NHCH2CH2CH3
H
H
CH
O

1-58
NHCH2CH═CH2
H
H
CH
O

1-59
NHCH2C≡CH
H
H
CH
O

1-60
N(CH3)CH2CH2CH3
H
H
CH
O

1-61
N(CH3)CH2CH═CH2
H
H
CH
O

1-62
N(CH3)CH2C≡CH
H
H
CH
O

1-63
NHCH2CH2CH3
H
Cl
CH
O

1-64
NHCH2CH═CH2
H
Cl
CH
O

1-65
NHCH2C≡CH
H
Cl
CH
O

1-66
N(CH3)CH2CH2CH3
H
Cl
CH
O

1-67
N(CH3)CH2CH═CH2
H
Cl
CH
O

1-68
N(CH3)CH2C≡CH
H
Cl
CH
O

[1473]

4

TABLE 4

Compound
R2
R3
R4
A
Y

1-69
NHCH2CH2CH3
Cl
H
CH
O

1-70
NHCH2CH═CH2
Cl
H
CH
O

1-71
NHCH2C≡CH
Cl
H
CH
O

1-72
N(CH3)CH2CH2CH3
Cl
H
CH
O

1-73
N(CH3)CH2CH═CH2
Cl
H
CH
O

1-74
N(CH3)CH2C≡CH
Cl
H
CH
O

1-75
Br
H
H
CH
O

1-76
Br
H
Cl
CH
O

1-77
Br
Cl
H
CH
O

1-78
OH
H
H
CH
O

1-79
OH
H
Cl
CH
O

1-80
OH
Cl
H
CH
O

1-81
OH
H
NO2
CH
O

1-82
OH
NO2
H
CH
O

1-83
OCH3
H
Cl
CH
O

1-84
OCH3
Cl
H
CH
O

1-85
OCH3
H
NO2
CH
O

1-86
OCH3
NO2
H
CH
O

1-87
OCH(CH3)CH3
H
H
CH
O

1-88
OCH(CH3)CH3
H
Cl
CH
O

1-89
OCH(CH3)CH3
Cl
H
CH
O

1-90
OCH(CH3)CH3
H
NO2
CH
O

1-91
OCH(CH3)CH3
NO2
H
CH
O

1-92
OCH2CH═CH2
H
H
CH
O

1-93
OCH2CH═CH2
H
Cl
CH
O

[1474]

5

TABLE 5

Compound
R2
R3
R4
A
Y

1-94
OCH2CH═CH2
Cl
H
CH
O

1-95
OCH2CH═CH2
H
NO2
CH
O

1-96
OCH2CH═CH2
NO2
H
CH
O

1-97
OCH(CH3)CH═CH2
H
H
CH
O

1-98
OCH(CH3)CH═CH2
H
Cl
CH
O

1-99
OCH(CH3)CH═CH2
Cl
H
CH
O

1-100
OCH(CH3)CH═CH2
H
NO2
CH
O

1-101
OCH(CH3)CH═CH2
NO2
H
CH
O

1-102
OCH2C(Cl)═CH2
H
H
CH
O

1-103
OCH2C(Cl)═CH2
H
Cl
CH
O

1-104
OCH2C(Cl)═CH2
Cl
H
CH
O

1-105
OCH2C(Cl)═CH2
H
NO2
CH
O

1-106
OCH2C(Cl)═CH2
NO2
H
CH
O

1-107
OCH2C≡CH
H
H
CH
O

1-108
OCH2C≡CH
H
Cl
CH
O

1-109
OCH2C≡CH
Cl
H
CH
O

1-110
OCH2C≡CH
H
NO2
CH
O

1-111
OCH2C≡CH
NO2
H
CH
O

1-112
OCH(CH3)C≡CH
H
H
CH
O

1-113
OCH(CH3)C≡CH
H
Cl
CH
O

1-114
OCH(CH3)C≡CH
Cl
H
CH
O

1-115
OCH(CH3)C≡CH
H
NO2
CH
O

1-116
OCH(CH3)C≡CH
NO2
H
CH
O

1-117
OCH(CH3)COOH
H
H
CH
O

1-118
OCH(CH3)COOH
H
Cl
CH
O

[1475]

6

TABLE 6

Compound
R2
R3
R4
A
Y

1-119
OCH(CH3)COOH
Cl
H
CH
O

1-120
OCH(CH3)COOH
H
NO2
CH
O

1-121
OCH(CH3)COOH
NO2
H
CH
O

1-122
OCH(CH3)COOMe
H
H
CH
O

1-123
OCH(CH3)COOMe
H
Cl
CH
O

1-124
OCH(CH3)COOMe
Cl
H
CH
O

1-125
OCH(CH3)COOMe
H
NO2
CH
O

1-126
OCH(CH3)COOMe
NO2
H
CH
O

1-127
OCH(CH3)COOEt
H
H
CH
O

1-128
OCH(CH3)COOEt
H
Cl
CH
O

1-129
OCH(CH3)COOEt
Cl
H
CH
O

1-130
OCH(CH3)COOEt
H
NO2
CH
O

1-131
OCH(CH3)COOEt
NO2
H
CH
O

1-132
OCH(CH3)COOPr
H
H
CH
O

1-133
OCH(CH3)COOPr
H
Cl
CH
O

1-134
OCH(CH3)COOPr
Cl
H
CH
O

1-135
OCH(CH3)COOPr
H
NO2
CH
O

1-136
OCH(CH3)COOPr
NO2
H
CH
O

1-137
OCH(CH3)COO-i-Pr
H
H
CH
O

1-138
OCH(CH3)COO-i-Pr
H
Cl
CH
O

1-139
OCH(CH3)COO-i-Pr
Cl
H
CH
O

1-140
OCH(CH3)COO-i-Pr
H
NO2
CH
O

1-141
OCH(CH3)COO-i-Pr
NO2
H
CH
O

1-142
OCH(CH3)COOBu
H
H
CH
O

1-143
OCH(CH3)COOBu
H
Cl
CH
O

[1476]

7

TABLE 7

Compound
R2
R3
R4
A
Y

1-144
OCH(CH3)COOBu
Cl
H
CH
O

1-145
OCH(CH3)COOBu
H
NO2
CH
O

1-146
OCH(CH3)COOBu
NO2
H
CH
O

1-147
OCH(CH3)COOPen
H
H
CH
O

1-148
OCH(CH3)COOPen
H
Cl
CH
O

1-149
OCH(CH3)COOPen
Cl
H
CH
O

1-150
OCH(CH3)COOPen
H
NO2
CH
O

1-151
OCH(CH3)COOPen
NO2
H
CH
O

1-152
OCH(CH3)COO-c-Pen
H
H
CH
O

1-153
OCH(CH3)COO-c-Pen
H
Cl
CH
O

1-154
OCH(CH3)COO-c-Pen
Cl
H
CH
O

1-155
OCH(CH3)COO-c-Pen
H
NO2
CH
O

1-156
OCH(CH3)COO-c-Pen
NO2
H
CH
O

1-157
OCH(CH3)COOHex
H
H
CH
O

1-158
OCH(CH3)COOHex
H
Cl
CH
O

1-159
OCH(CH3)COOHex
Cl
H
CH
O

1-160
OCH(CH3)COOHex
H
NO2
CH
O

1-161
OCH(CH3)COOHex
NO2
H
CH
O

1-162
OCH(CH3)COO-c-Hex
H
H
CH
O

1-163
OCH(CH3)COO-c-Hex
H
Cl
CH
O

1-164
OCH(CH3)COO-c-Hex
Cl
H
CH
O

1-165
OCH(CH3)COO-c-Hex
H
NO2
CH
O

1-166
OCH(CH3)COO-c-Hex
NO2
H
CH
O

1-167
OCH(CH3)CO2CH2CO2H
H
H
CH
O

1-168
OCH(CH3)CO2CH2CO2H
H
Cl
CH
O

[1477]

8

TABLE 8

Compound
R2
R3
R4
A
Y

1-169
OCH(CH3)CO2CH2CO2H
Cl
H
CH
O

1-170
OCH(CH3)CO2CH2CO2H
H
NO2
CH
O

1-171
OCH(CH3)CO2CH2CO2H
NO2
H
CH
O

1-172
OCH(CH3)CO2CH2CO2Me
H
H
CH
O

1-173
OCH(CH3)CO2CH2CO2Me
H
Cl
CH
O

1-174
OCH(CH3)CO2CH2CO2Me
Cl
H
CH
O

1-175
OCH(CH3)CO2CH2CO2Me
H
NO2
CH
O

1-176
OCH(CH3)CO2CH2CO2Me
NO2
H
CH
O

1-177
OCH(CH3)CO2CH2CO2Et
H
H
CH
O

1-178
OCH(CH3)CO2CH2CO2Et
H
Cl
CH
O

1-179
OCH(CH3)CO2CH2CO2Et
Cl
H
CH
O

1-180
OCH(CH3)CO2CH2CO2Et
H
NO2
CH
O

1-181
OCH(CH3)CO2CH2CO2Et
NO2
H
CH
O

1-182
OCH(CH3)CO2CH(CH3)CO2H
H
H
CH
O

1-183
OCH(CH3)CO2CH(CH3)CO2H
H
Cl
CH
O

1-184
OCH(CH3)CO2CH(CH3)CO2H
Cl
H
CH
O

1-185
OCH(CH3)CO2CH(CH3)CO2H
H
NO2
CH
O

1-186
OCH(CH3)CO2CH(CH3)CO2H
NO2
H
CH
O

1-187
OCH(CH3)CO2CH(CH3)CO2Me
H
H
CH
O

1-188
OCH(CH3)CO2CH(CH3)CO2Me
H
Cl
CH
O

1-189
OCH(CH3)CO2CH(CH3)CO2Me
Cl
H
CH
O

1-190
OCH(CH3)CO2CH(CH3)CO2Me
H
NO2
CH
O

1-191
OCH(CH3)CO2CH(CH3)CO2Me
NO2
H
CH
O

1-192
OCH(CH3)CO2CH(CH3)CO2Et
H
H
CH
O

1-193
OCH(CH3)CO2CH(CH3)CO2Et
H
Cl
CH
O

[1478]

9

TABLE 9

Compound
R2
R3
R4
A
Y

1-194
OCH(CH3)CO2CH(CH3)CO2Et
Cl
H
CH
O

1-195
OCH(CH3)CO2CH(CH3)CO2Et
H
NO2
CH
O

1-196
OCH(CH3)CO2CH(CH3)CO2Et
NO2
H
CH
O

1-197
SCH3
H
H
CH
O

1-198
SCH3
H
Cl
CH
O

1-199
SCH3
Cl
H
CH
O

1-200
SCH3
H
NO2
CH
O

1-201
SCH3
NO2
H
CH
O

1-202
SCH(CH3)CH3
H
H
CH
O

1-203
SCH(CH3)CH3
H
Cl
CH
O

1-204
SCH(CH3)CH3
Cl
H
CH
O

1-205
SCH(CH3)CH3
H
NO2
CH
O

1-206
SCH(CH3)CH3
NO2
H
CH
O

1-207
SCHCH═CH2
H
H
CH
O

1-208
SCHCH═CH2
H
Cl
CH
O

1-209
SCHCH═CH2
Cl
H
CH
O

1-210
SCHCH═CH2
H
NO2
CH
O

1-211
SCHCH═CH2
NO2
H
CH
O

1-212
SCHC≡CH
H
H
CH
O

1-213
SCHC≡CH
H
Cl
CH
O

1-214
SCHC≡CH
Cl
H
CH
O

1-215
SCHC≡CH
H
NO2
CH
O

1-216
SCHC≡CH
NO2
H
CH
O

1-217
SCH2COOH
H
H
CH
O

1-218
SCH2COOH
H
Cl
CH
O

[1479]

10

TABLE 10

Compound
R2
R3
R4
A
Y

1-219
SCH2COOH
Cl
H
CH
O

1-220
SCH2COOH
H
NO2
CH
O

1-221
SCH2COOH
NO 2
H
CH
O

1-222
SCH2COOMe
H
H
CH
O

1-223
SCH2COOMe
H
Cl
CH
O

1-224
SCR2COOMe
Cl
H
CH
O

1-225
SCH2COOMe
H
NO2
CH
O

1-226
SCR2COOMe
NO2
H
CH
O

1-227
SCH2COOEt
H
H
CH
O

1-228
SCH2COOEt
H
Cl
CH
O

1-229
SCH2COOEt
Cl
H
CH
O

1-230
SCH2COOEt
H
NO2
CH
O

1-231
SCH2COOEt
NO2
H
CH
O

1-232
SCH(CH3)COOH
H
H
CH
O

1-233
SCH(CH3)COOH
H
Cl
CH
O

1-234
SCH(CH3)COOH
Cl
H
CH
O

1-235
SCH(CH3)COOH
H
NO2
CH
O

1-236
SCH(CH3)COOH
NO2
H
CH
O

1-237
SCH(CH3)COOMe
H
H
CH
O

1-238
SCH(CH3)COOMe
H
Cl
CH
O

1-239
SCH(CH3)COOMe
Cl
H
CH
O

1-240
SCH(CH3)COOMe
H
NO2
CH
O

1-241
SCH(CH3)COOMe
NO2
H
CH
O

1-242
SCH(CH3)COOEt
H
H
CH
O

1-243
SCH(CH3)COOEt
H
Cl
CH
O

[1480]

11

TABLE 11

Compound
R2
R3
R4
A
Y

1-244
SCH(CH3)COOEt
Cl
H
CH
O

1-245
SCH(CH3)COOEt
H
NO2
CH
O

1-246
SCH(CH3)COOEt
NO2
H
CH
O

1-247
SCH(CH3)COO-i-Pr
H
H
CH
O

1-248
SCH(CH3)COO-i-Pr
H
Cl
CH
O

1-249
SCH(CH3)COO-i-Pr
Cl
H
CH
O

1-250
SCH(CH3)COO-i-Pr
H
NO2
CH
O

1-251
SCH(CH3)COO-i-Pr
NO2
H
CH
O

1-252
SCH(CH3)CO2CH2CO2H
H
H
CH
O

1-253
SCH(CH3)CO2CH2CO2H
H
Cl
CH
O

1-254
SCH(CH3)CO2CH2CO2H
Cl
H
CH
O

1-255
SCH(CH3)CO2CH2CO2H
H
NO2
CH
O

1-256
SCH(CH3)CO2CH2CO2H
NO2
H
CH
O

1-257
SCH(CH3)CO2CH2CO2Me
H
H
CH
O

1-258
SCH(CH3)CO2CH2CO2Me
H
Cl
CH
O

1-259
SCH(CH3)CO2CH2CO2Me
Cl
H
CH
O

1-260
SCH(CH3)CO2CH2CO2Me
H
NO2
CH
O

1-261
SCH(CH3)CO2CH2CO2Me
NO2
H
CH
O

1-262
SCH(CH3)CO2CH2CO2Et
H
H
CH
O

1-263
SCH(CH3)CO2CH2CO2Et
H
Cl
CH
O

1-264
SCH(CH3)CO2CH2CO2Et
Cl
H
CH
O

1-265
SCH(CH3)CO2CH2CO2Et
H
NO2
CH
O

1-266
SCH(CH3)CO2CH2CO2Et
NO2
H
CH
O

1-267
SCH(CH3)CO2CH(CH3)CO2H
H
H
CH
O

1-268
SCH(CH3)CO2CH(CH3)CO2H
H
Cl
CH
O

[1481]

12

TABLE 12

Compound
R2
R3
R4
A
Y

1-269
SCH(CH3)CO2CH(CH3)CO2H
Cl
H
CH
O

1-270
SCH(CH3)CO2CH(CH3)CO2H
H
NO2
CH
O

1-271
SCH(CH3)CO2CH(CH3)CO2H
NO2
H
CH
O

1-272
SCH(CH3)CO2CH(CH3)CO2Me
H
H
CH
O

1-273
SCH(CH3)CO2CH(CH3)CO2Me
H
Cl
CH
O

1-274
SCH(CH3)CO2CH(CH3)CO2Me
Cl
H
CH
O

1-275
SCH(CH3)CO2CH(CH3)CO2Me
H
NO2
CH
O

1-276
SCH(CH3)CO2CH(CH3)CO2Me
NO2
H
CH
O

1-277
SCH(CH3)CO2CH(CH3)CO2Et
H
H
CH
O

1-278
SCH(CH3)CO2CH(CH)CO2Et
H
Cl
CH
O

1-279
SCH(CH3)CO2CH(CH3)CO2Et
Cl
H
CH
O

1-280
SCH(CH3)CO2CH(CH3)CO2Et
H
NO2
CH
O

1-281
SCH(CH3)CO2CH(CH3)CO2Et
NO2
H
CH
O

1-282
H
NO2
H
CH
O

1-283
C≡N
H
H
CH
O

1-284
C≡N
H
Cl
CH
O

1-285
C≡N
Cl
H
CH
O

1-286
C≡N
H
NO2
CH
O

1-287
C≡N
NO2
H
CH
O

1-288
C(═O)H
H
H
CH
O

1-289
C(═O)H
H
Cl
CH
O

1-290
C(═O)H
Cl
H
CH
O

1-291
C(═O)H
H
NO2
CH
O

1-292
C(═O)H
NO2
H
CH
O

1-293
C(═O)NH2
H
H
CH
O

[1482]

13

TABLE 13

Compound
R2
R3
R4
A
Y

1-294
C(═O)NH2
H
Cl
CH
O

1-295
C(═O)NH2
Cl
H
CH
O

1-296
C(═O)NH2
H
NO2
CH
O

1-297
C(═O)NH2
NO2
H
CH
O

1-298
CO2H
H
H
CH
O

1-299
CO2H
H
Cl
CH
O

1-300
CO2H
Cl
H
CH
O

1-301
CO2H
H
NO2
CH
O

1-302
CO2H
NO2
H
CH
O

1-303
CO2Me
H
H
CH
O

1-304
CO2Me
H
Cl
CH
O

1-305
CO2Me
Cl
H
CH
O

1-306
CO2Me
H
NO2
CH
O

1-307
CO2Me
NO2
H
CH
O

1-308
CO2Et
H
H
CH
O

1-309
CO2Et
H
Cl
CH
O

1-310
CO2Et
Cl
H
CH
O

1-311
CO2Et
H
NO2
CH
O

1-312
CO2Et
NO2
H
CH
O

1-313
CO2CH2CO2H
H
H
CH
O

1-314
CO2CH2CO2H
H
Cl
CH
O

1-315
CO2CH2CO2H
Cl
H
CH
O

1-316
CO2CH2CO2H
H
NO2
CH
O

1-317
CO2CH2CO2H
NO2
H
CH
O

1-318
CO2CH2CO2Me
H
H
CH
O

[1483]

14

TABLE 14

Compound
R2
R3
R4
A
Y

1-319
CO2CH2CO2Me
H
Cl
CH
O

1-320
CO2CH2CO2Me
Cl
H
CH
O

1-321
CO2CH2CO2Me
H
NO2
CH
O

1-322
CO2CH2CO2Me
NO2
H
CH
O

1-323
CO2CH2CO2Et
H
H
CH
O

1-324
CO2CH2CO2Et
H
Cl
CH
O

1-325
CO2CH2CO2Et
Cl
H
CH
O

1-326
CO2CH2CO2Et
H
NO2
CH
O

1-327
CO2CH2CO2Et
NO2
H
CH
O

1-328
CO2CH(CH3)CO2H
H
H
CH
O

1-329
CO2CH(CH3)CO2H
H
Cl
CH
O

1-330
CO2CH(CH3)CO2H
Cl
H
CH
O

1-331
CO2CH(CH3)CO2H
H
NO2
CH
O

1-332
CO2CH(CH3)CO2H
NO2
H
CH
O

1-333
CO2CH(CH3)CO2Me
H
H
CH
O

1-334
CO2CH(CH3)CO2Me
H
Cl
CH
O

1-335
CO2CH(CH3)CO2Me
Cl
H
CH
O

1-336
CO2CH(CH3)CO2Me
H
NO2
CH
O

1-337
CO2CH(CH3)CO2Me
NO2
H
CH
O

1-338
CO2CH(CH3)CO2Et
H
H
CH
O

1-339
CO2CH(CH3)CO2Et
H
Cl
CH
O

1-340
CO2CH(CH3)CO2Et
Cl
H
CH
O

1-341
CO2CH(CH3)CO2Et
H
NO2
CH
O

1-342
CO2CH(CH3)CO2Et
NO2
H
CH
O

1-343
CO2C(CH3)2CO2H
H
H
CH
O

[1484]

15

TABLE 15

Compound
R2
R3
R4
A
Y

1-344
CO2C(CH3)2CO2H
H
Cl
CH
O

1-345
CO2C(CH3)2CO2H
Cl
H
CH
O

1-346
CO2C(CH3)2CO2H
H
NO2
CH
O

1-347
CO2C(CH3)2CO2H
NO2
H
CH
O

1-348
CO2C(CH3)2CO2Me
H
H
CH
O

1-349
CO2C(CH3)2CO2Me
H
Cl
CH
O

1-350
CO2C(CH3)2CO2Me
Cl
H
CH
O

1-351
CO2C(CH3)2CO2Me
H
NO2
CH
O

1-352
CO2C(CH3)2CO2Me
NO2
H
CH
O

1-353
CO2C(CH3)2CO2Et
H
Cl
CH
O

1-354
CO2C(CH3)2CO2Et
Cl
H
CH
O

1-355
CO2C(CH3)2CO2Et
H
NO2
CH
O

1-356
CO2C(CH3)2CO2Et
NO2
H
CH
O

1-357
CH3
H
H
CH
O

1-358
CH3
H
Cl
CH
O

1-359
CH3
Cl
H
CH
O

1-360
CH3
H
NO2
CH
O

1-361
CH3
NO2
H
CH
O

1-362
CF3
H
H
CH
O

1-363
CF3
H
Cl
CH
O

1-364
CF3
Cl
H
CH
O

1-365
CF3
H
NO2
CH
O

1-366
CF3
NO2
H
CH
O

1-367
CH═CHCO2H
H
H
CH
O

[1485]

16

TABLE 16

Compound
R2
R3
R4
A
Y

1-368
CH═CHCO2H
H
Cl
CH
O

1-369
CH═CHCO2H
Cl
H
CH
O

1-370
CH═CHCO2H
H
NO2
CH
O

1-371
CH═CHCO2H
NO2
H
CH
O

1-372
CH═CHCO2Me
H
H
CH
O

1-373
CH═CHCO2Me
H
Cl
CH
O

1-374
CH═CHCO2Me
Cl
H
CH
O

1-375
CH═CHCO2Me
H
NO2
CH
O

1-376
CH═CHCO2Me
NO2
H
CH
O

1-377
CH═CHCO2Et
H
H
CH
O

1-378
CH═CHCO2Et
H
Cl
CH
O

1-379
CH═CHCO2Et
Cl
H
CH
O

1-380
CH═CHCO2Et
H
NO2
CH
O

1-381
CH═CHCO2Et
NO2
H
CH
O

1-382
CH2CH2CO2H
H
H
CH
O

1-383
CH2CH2CO2H
H
Cl
CH
O

1-384
CH2CH2CO2H
Cl
H
CH
O

1-385
CH2CH2CO2H
H
NO2
CH
O

1-386
CH2CH2CO2H
NO2
H
CH
O

1-387
CH2CH2CO2Me
H
H
CH
O

1-388
CH2CH2CO2Me
H
Cl
CH
O

1-389
CH2CH2CO2Me
Cl
H
CH
O

1-390
CH2CH2CO2Me
H
NO2
CH
O

1-391
CH2CH2CO2Me
NO2
H
CH
O

1-392
CH2CH2CO2Et
H
H
CH
O

[1486]

17

TABLE 17

Compound
R2
R3
R4
A
Y

1-393
CH2CH2CO2Et
H
Cl
CH
O

1-394
CH2CH2CO2Et
Cl
H
CH
O

1-395
CH2CH2CO2Et
H
NO2
CH
O

1-396
CH2CH2CO2Et
NO2
H
CH
O

1-397
CH2CH(Cl)CO2H
H
H
CH
O

1-398
CH2CH(Cl)CO2H
H
Cl
CH
O

1-399
CH2CH(Cl)CO2H
Cl
H
CH
O

1-400
CH2CH(Cl)CO2H
H
NO2
CH
O

1-401
CH2CH(Cl)CO2H
NO2
H
CH
O

1-402
CH2CH(Cl)CO2Me
H
H
CH
O

1-403
CH2CH(Cl)CO2Me
H
Cl
CH
O

1-404
CH2CH(Cl)CO2Me
Cl
H
CH
O

1-405
CH2CH(Cl)CO2Me
H
NO2
CH
O

1-406
CH2CH(Cl)CO2Me
NO2
H
CH
O

1-407
CH2CH(Cl)CO2Et
H
H
CH
O

1-408
CH2CH(Cl)CO2Et
H
Cl
CH
O

1-409
CH2CH(Cl)CO2Et
Cl
H
CH
O

1-410
CH2CH(Cl)CO2Et
H
NO2
CH
O

1-411
CH2CH(Cl)CO2Et
NO2
H
CH
O

1-412
C(═O)CH3
H
H
CH
O

1-413
C(═O)CH3
H
Cl
CH
O

1-414
C(═O)CH3
Cl
H
CH
O

1-415
C(═O)CH3
H
NO2
CH
O

1-416
C(═O)CH3
NO2
H
CH
O

1-417
C(CH3)═NOH
H
H
CH
O

[1487]

18

TABLE 18

Compound
R2
R3
R4
A
Y

1-418
C(CH3)═NOH
H
Cl
CH
O

1-419
C(CH3)═NOH
Cl
H
CH
O

1-420
C(CH3)═NOH
H
NO2
CH
O

1-421
C(CH3)═NOH
NO2
H
CH
O

1-422
C(CH3)═NOMe
H
H
CH
O

1-423
C(CH3)═NOMe
H
Cl
CH
O

1-424
C(CH3)═NOMe
Cl
H
CH
O

1-425
C(CH3)═NOMe
H
NO2
CH
O

1-426
C(CH3)═NOMe
NO2
H
CH
O

1-427
F
H
H
CH
O

1-428
F
H
Cl
CH
O

1-429
F
Cl
H
CH
O

1-430
F
H
NO2
CH
O

1-431
F
NO2
H
CH
O

1-432
Cl
H
Cl
CH
S

1-433
Cl
H
H
CH
S

1-434
OCH3
H
H
CH
S

1-435
NO2
H
H
CH
S

1-436
NH2
H
H
CH
S

1-437
NHCH3
H
H
CH
S

1-438
N(CH3)2
H
H
CH
S

1-439
NHSO2CH3
H
H
CH
S

1-440
NHCH(CH3)CO2Et
H
H
CH
S

1-441
NHCH(CH3)CO2Et
H
Cl
CH
S

1-442
N(CH3)CH(CH3)CO2Et
H
Cl
CH
S

[1488]

19

TABLE 19

Compound
R2
R3
R4
A
Y

1-443
N(CH3)SO2CH3
H
Cl
CH
S

1-444
NHSO2CH3
H
Cl
CH
S

1-445
NHCH(CH3)CO2Et
Cl
H
CH
S

1-446
N(CH3)CH(CH3)CO2Et
Cl
H
CH
S

1-447
N(CH3)SO2CH3
Cl
H
CH
S

1-448
NHSO2CH3
Cl
H
CH
S

1-449
NO2
H
Cl
CH
S

1-450
NH2
H
Cl
CH
S

1-451
NO2
Cl
H
CH
S

1-452
NH2
Cl
H
CH
S

1-453
NHCOCH3
H
H
CH
S

1-454
NHCOCF3
H
H
CH
S

1-455
NHSO2Et
H
H
CH
S

1-456
NHSO2CH2Cl
H
H
CH
S

1-457
N(CH3)COCH3
H
H
CH
S

1-458
N(CH3)COCF3
H
H
CH
S

1-459
N(CH3)SO2Et
H
H
CH
S

1-460
N(CH3)SO2CH2Cl
H
H
CH
S

1-461
NHCOCH3
H
Cl
CH
S

1-462
NHCOCF3
H
Cl
CH
S

1-463
NHSO2Et
H
Cl
CH
S

1-464
NHSO2CH2Cl
H
Cl
CH
S

1-465
N(CH3)COCH3
Cl
H
CH
S

1-466
N(CH3)COCF3
Cl
H
CH
S

1-467
N(CH3)SO2Et
Cl
H
CH
S

[1489]

20

TABLE 20

Compound
R2
R3
R4
A
Y

1-468
N(CH3)SO2CH2Cl
Cl
H
CH
S

1-469
NHCH2CO2Me
H
H
CH
S

1-470
NHCH2CO2Et
H
H
CH
S

1-471
NHCH(CH3)COOH
H
H
CH
S

1-472
NHCH(CH3)CONH2
H
H
CH
S

1-473
NHCH(CH3)CONHCH3
H
H
CH
S

1-474
NHCH2CO2Me
H
Cl
CH
S

1-475
NHCH2CO2Et
H
Cl
CH
S

1-476
NHCH(CH3)COOH
H
Cl
CH
S

1-477
NHCH(CH3)CONH2
H
Cl
CH
S

1-478
NHCH(CH3)CONHCH3
H
Cl
CH
S

1-479
NHCH2CO2Me
Cl
H
CH
S

1-480
NHCH2CO2Et
Cl
H
CH
S

1-481
NHCH(CH3)COOH
Cl
H
CH
S

1-482
NHCH(CH3)CONH2
Cl
H
CH
S

1-483
NHCH(CH3)CONHCH3
Cl
H
CH
S

1-484
NHCH2CH2CH3
H
H
CH
S

1-485
NHCH2CH═CH2
H
H
CH
S

1-486
NHCH2C≡ CH
H
H
CH
S

1-487
N(CH3)CH2CH2CH3
H
H
CH
S

1-488
N(CH3)CH2CH═CH2
H
H
CH
S

1-489
N(CH3)CH2C≡CH
H
H
CH
S

1-490
NHCH2CH2CH3
H
Cl
CH
S

1-491
NHCH2CH═CH2
H
Cl
CH
S

1-492
NHCH2C≡CH
H
Cl
CH
S

[1490]

21

TABLE 21

Compound
R2
R3
R4
A
Y

1-493
N(CH3)CH2CH2CH3
H
Cl
CH
S

1-494
N(CH3)CH2CH═CH2
H
Cl
CH
S

1-495
N(CH3)CH2C≡CH
H
Cl
CH
S

1-496
NHCH2CH2CH3
Cl
H
CH
S

1-497
NHCH2CH═CH2
Cl
H
CH
S

1-498
NHCH2C≡CH
Cl
H
CH
S

1-499
N(CH3)CH2CH2CH3
Cl
H
CH
S

1-500
N(CH3)CH2CH═CH2
Cl
H
CH
S

1-501
N(CH3)CH2C≡CH
Cl
H
CH
S

1-502
Br
H
H
CH
S

1-503
Br
H
Cl
CH
S

1-504
Br
Cl
H
CH
S

1-505
OH
H
H
CH
S

1-506
OH
H
Cl
CH
S

1-507
OH
Cl
H
CH
S

1-508
OH
H
NO2
CH
S

1-509
OH
NO2
H
CH
S

1-510
OCH3
H
Cl
CH
S

1-511
OCH3
Cl
H
CH
S

1-512
OCH3
H
NO2
CH
S

1-513
OCH3
NO2
H
CH
S

1-514
OCH(CH3)CH3
H
H
CH
S

1-515
OCH(CH3)CH3
H
Cl
CH
S

1-516
OCH(CH3)CH3
Cl
H
CH
S

1-517
OCH(CH3)CH3
H
NO2
CH
S

[1491]

22

TABLE 22

Compound
R2
R3
R4
A
Y

1-518
OCH(CH3)CH3
NO2
H
CH
S

1-519
OCH2CH═CH2
H
H
CH
S

1-520
OCH2CH═CH2
H
Cl
CH
S

1-521
OCH2CH═CH2
Cl
H
CH
S

1-522
OCH2CH═CH2
H
NO2
CH
S

1-523
OCH2CH═CH2
NO2
H
CH
S

1-524
OCH(CH3)CH═CH2
H
H
CH
S

1-525
OCH(CH3)CH═CH2
H
Cl
CH
S

1-526
OCH(CH3)CH═CH2
Cl
H
CH
S

1-527
OCH(CH3)CH═CH2
H
NO2
CH
S

1-528
OCH(CH3)CH═CH2
NO2
H
CH
S

1-529
OCH2C(Cl)═CH2
H
H
CH
S

1-530
OCH2C(Cl)═CH2
H
Cl
CH
S

1-531
OCH2C(Cl)═CH2
Cl
H
CH
S

1-532
OCH2C(Cl)═CH2
H
NO2
CH
S

1-533
OCH2C(Cl)═CH2
NO2
H
CH
S

1-534
OCH2C≡CH
H
H
CH
S

1-535
OCH2C≡CH
H
Cl
CH
S

1-536
OCH2C≡CH
Cl
H
CH
S

1-537
OCH2C≡CH
H
NO2
CH
S

1-538
OCH2C≡CH
NO2
H
CH
S

1-539
OCH(CH3)C≡CH
H
H
CH
S

1-540
OCH(CH3)C≡CH
H
Cl
CH
S

1-541
OCH(CH3)C≡CH
Cl
H
CH
S

1-542
OCH(CH3)C≡CH
H
NO2
CH
S

[1492]

23

TABLE 23

Compound
R2
R3
R4
A
Y

1-543
OCH(CH3)C≡CH
NO2
H
CH
S

1-544
OCH(CH3)COOH
H
H
CH
S

1-545
OCH(CH3)COOH
H
Cl
CH
S

1-546
OCH(CH3)COOH
Cl
H
CH
S

1-547
OCH(CH3)COOH
H
NO2
CH
S

1-548
OCH(CH3)COOH
NO2
H
CH
S

1-549
OCH(CH3)COOMe
H
H
CH
S

1-550
OCH(CH3)COOMe
H
Cl
CH
S

1-551
OCH(CH3)COOMe
Cl
H
CH
S

1-552
OCH(CH3)COOMe
H
NO2
CH
S

1-553
OCH(CH3)COOMe
NO2
H
CH
S

1-554
OCH(CH3)COOEt
H
H
CH
S

1-555
OCH(CH3)COOEt
H
Cl
CH
S

1-556
OCH(CH3)COOEt
Cl
H
CH
S

1-557
OCH(CH3)COOEt
H
NO2
CH
S

1-558
OCH(CH3)COOEt
NO2
H
CH
S

1-559
OCH(CH3)COOPr
H
H
CH
S

1-560
OCH(CH3)COOPr
H
Cl
CH
S

1-561
OCH(CH3)COOPr
Cl
H
CH
S

1-562
OCH(CH3)COOPr
H
NO2
CH
S

1-563
OCH(CH3)COOPr
NO2
H
CH
S

1-564
OCH(CH3)COO-i-Pr
H
H
CH
S

1-565
OCH(CH3)COO-i-Pr
H
Cl
CH
S

1-566
OCH(CH3)COO-i-Pr
Cl
H
CH
S

1-567
OCH(CH3)COO-i-Pr
H
NO2
CH
S

[1493]

24

TABLE 24

Compound
R2
R3
R4
A
Y

1-568
OCH(CH3)COO-i-Pr
NO2
H
CH
S

1-569
OCH(CH3)COOBu
H
H
CH
S

1-570
OCH(CH3)COOBu
H
Cl
CH
S

1-571
OCH(CH3)COOBu
Cl
H
CH
S

1-572
OCH(CH3)COOBu
H
NO2
CH
S

1-573
OCH(CH3)COOBu
NO2
H
CH
S

1-574
OCH(CH3)COOPen
H
H
CH
S

1-575
OCH(CH3)COOPen
H
Cl
CH
S

1-576
OCH(CH3)COOPen
Cl
H
CH
S

1-577
OCH(CH3)COOPen
H
NO2
CH
S

1-578
OCH(CH3)COOPen
NO2
H
CH
S

1-579
OCH(CH3)COO-c-Pen
H
H
CH
S

1-580
OCH(CH3)COO-c-Pen
H
Cl
CH
S

1-581
OCH(CH3)COO-c-Pen
Cl
H
CH
S

1-582
OCH(CH3)COO-c-Pen
H
NO2
CH
S

1-583
OCH(CH3)COO-c-Pen
NO2
H
CH
S

1-584
OCH(CH3)COOHex
H
H
CH
S

1-585
OCH(CH3)COOHex
H
Cl
CH
S

1-586
OCH(CH3)COOHex
Cl
H
CH
S

1-587
OCH(CH3)COOHex
H
NO2
CH
S

1-588
OCH(CH3)COOHex
NO2
H
CH
S

1-589
OCH(CH3)COO-c-Hex
H
H
CH
S

1-590
OCH(CH3)COO-c-Hex
H
Cl
CH
S

1-591
OCH(CH3)COO-c-Hex
Cl
H
CH
S

1-592
OCH(CH3)COO-c-Hex
H
NO2
CH
S

[1494]

25

TABLE 25

Compound
R2
R3
R4
A
Y

1-593
OCH(CH3)COO-c-Hex
NO2
H
CH
S

1-594
OCH(CH3)CO2CH2CO2H
H
H
CH
S

1-595
OCH(CH3)CO2CH2CO2H
H
Cl
CH
S

1-596
OCH(CH3)CO2CH2CO2H
Cl
H
CH
S

1-597
OCH(CH3)CO2CH2CO2H
H
NO2
CH
S

1-598
OCH(CH3)CO2CH2CO2H
NO2
H
CH
S

1-599
OCH(CH3)CO2CH2CO2Me
H
H
CH
S

1-600
OCH(CH3)CO2CH2CO2Me
H
Cl
CH
S

1-601
OCH(CH3)CO2CH2CO2Me
Cl
H
CH
S

1-602
OCH(CH3)CO2CH2CO2Me
H
NO2
CH
S

1-603
OCH(CH3)CO2CH2CO2Me
NO2
H
CH
S

1-604
OCH(CH3)CO2CH2CO2Et
H
H
CH
S

1-605
OCH(CH3)CO2CH2CO2Et
H
Cl
CH
S

1-606
OCH(CH3)CO2CH2CO2Et
Cl
H
CH
S

1-607
OCH(CH3)CO2CH2CO2Et
H
NO2
CH
S

1-608
OCH(CH3)CO2CH2CO2Et
NO2
H
CH
S

1-609
OCH(CH3)CO2CH(CH3)CO2H
H
H
CH
S

1-610
OCH(CH3)CO2CH(CH3)CO2H
H
Cl
CH
S

1-611
OCH(CH3)CO2CH(CH3)CO2H
Cl
H
CH
S

1-612
OCH(CH3)CO2CH(CH3)CO2H
H
NO2
CH
S

1-613
OCH(CH3)CO2CH(CH3)CO2H
NO2
H
CH
S

1-614
OCH(CH3)CO2CH(CH3)CO2Me
H
H
CH
S

1-615
OCH(CH3)CO2CH(CH3)CO2Me
H
Cl
CH
S

1-616
OCH(CH3)CO2CH(CH3)CO2Me
Cl
H
CH
S

1-617
OCH(CH3)CO2CH(CH3)CO2Me
H
NO2
CH
S

[1495]

26

TABLE 26

Compound
R2
R3
R4
A
Y

1-618
OCH(CH3)CO2CH(CH3)CO2Me
NO2
H
CH
S

1-619
OCH(CH3)CO2CH(CH3)CO2Et
H
H
CH
S

1-620
OCH(CH3)CO2CH(CH3)CO2Et
H
Cl
CH
S

1-621
OCH(CH3)CO2CH(CH3)CO2Et
Cl
H
CH
S

1-622
OCH(CH3)CO2CH(CH3)CO2Et
H
NO2
CH
S

1-623
OCH(CH3)CO2CH(CH3)CO2Et
NO2
H
CH
S

1-624
SCH3
H
H
CH
S

1-625
SCH3
H
Cl
CH
S

1-626
SCH3
Cl
H
CH
S

1-627
SCH3
H
NO2
CH
S

1-628
SCH3
NO2
H
CH
S

1-629
SCH(CH3)CH3
H
H
CH
S

1-630
SCH(CH3)CH3
H
Cl
CH
S

1-631
SCH(CH3)CH3
Cl
H
CH
S

1-632
SCH(CH3)CH3
H
NO2
CH
S

1-633
SCH(CH3)CH3
NO2
H
CH
S

1-634
SCHCH═CH2
H
H
CH
S

1-635
SCHCH═CH2
H
Cl
CH
S

1-636
SCHCH═CH2
Cl
H
CH
S

1-637
SCHCH═CH2
H
NO2
CH
S

1-638
SCHCH═CH2
NO2
H
CH
S

1-639
SCHC≡CH
H
H
CH
S

1-640
SCHC≡CH
H
Cl
CH
S

1-641
SCHC≡CH
Cl
H
CH
S

1-642
SCHC≡CH
H
NO2
CH
S

[1496]

27

TABLE 27

Compound
R2
R3
R4
A
Y

1-643
SCHC≡CH
NO2
H
CH
S

1-644
SCH2COOH
H
H
CH
S

1-645
SCH2COOH
H
Cl
CH
S

1-646
SCH2COOH
Cl
H
CH
S

1-647
SCH2COOH
H
NO2
CH
S

1-648
SCH2COOH
NO2
H
CH
S

1-649
SCH2COOMe
H
H
CH
S

1-650
SCH2COOMe
H
Cl
CH
S

1-651
SCH2COOMe
Cl
H
CH
S

1-652
SCH2COOMe
H
NO2
CH
S

1-653
SCH2COOMe
NO2
H
CH
S

1-654
SCH2COOEt
H
H
CH
S

1-655
SCH2COOEt
H
Cl
CH
S

1-656
SCH2COOEt
Cl
H
CH
S

1-657
SCH2COOEt
H
NO2
CH
S

1-658
SCH2COOEt
NO2
H
CH
S

1-659
SCH(CH3)COOH
H
H
CH
S

1-660
SCH(CH3)COOH
H
Cl
CH
S

1-661
SCH(CH3)COOH
Cl
H
CH
S

1-662
SCH(CH3)COOH
H
NO2
CH
S

1-663
SCH(CH3)COOH
NO2
H
CH
S

1-664
SCH(CH3)COOMe
H
H
CH
S

1-665
SCH(CH3)COOMe
H
Cl
CH
S

1-666
SCH(CH3)COOMe
Cl
H
CH
S

1-667
SCH(CH3)COOMe
H
NO2
CH
S

[1497]

28

TABLE 28

Compound
R2
R3
R4
A
Y

1-668
SCH(CH3)COOMe
NO2
H
CH
S

1-669
SCH(CH3)COOEt
H
H
CH
S

1-670
SCH(CH3)COOEt
H
Cl
CH
S

1-671
SCH(CH3)COOEt
Cl
H
CH
S

1-672
SCH(CH3)COOEt
H
NO2
CH
S

1-673
SCH(CH3)COOEt
NO2
H
CH
S

1-674
SCH(CH3)COO-i-Pr
H
H
CH
S

1-675
SCH(CH3)COO-i-Pr
H
Cl
CH
S

1-676
SCH(CH3)COO-i-Pr
Cl
H
CH
S

1-677
SCH(CH3)COO-i-Pr
H
NO2
CH
S

1-678
SCH(CH3)COO-i-Pr
NO2
H
CH
S

1-679
SCH(CH3)CO2CH2CO2H
H
H
CH
S

1-680
SCH(CH3)CO2CH2CO2H
H
Cl
CH
S

1-681
SCH(CH3)CO2CH2CO2H
Cl
H
CH
S

1-682
SCH(CH3)CO2CH2CO2H
H
NO2
CH
S

1-683
SCH(CH3)CO2CH2CO2H
NO2
H
CH
S

1-684
SCH(CH3)CO2CH2CO2Me
H
H
CH
S

1-685
SCH(CH3)CO2CH2CO2Me
H
Cl
CH
S

1-686
SCH(CH3)CO2CH2CO2Me
Cl
H
CH
S

1-687
SCH(CH3)CO2CH2CO2Me
H
NO2
CH
S

1-688
SCH(CH3)CO2CH2CO2Me
NO2
H
CH
S

1-689
SCH(CH3)CO2CH2CO2Et
H
H
CH
S

1-690
SCH(CH3)CO2CH2CO2Et
H
Cl
CH
S

1-691
SCH(CH3)CO2CH2CO2Et
Cl
H
CH
S

1-692
SCH(CH3)CO2CH2CO2Et
H
NO2
CH
S

[1498]

29

TABLE 29

Compound
R2
R3
R4
A
Y

1-693
SCH(CH3)CO2CH2CO2Et
NO2
H
CH
S

1-694
SCH(CH3)CO2CH(CH3)CO2H
H
H
CH
S

1-695
SCH(CH3)CO2CH(CH3)CO2H
H
Cl
CH
S

1-696
SCH(CH3)CO2CH(CH3)CO2H
Cl
H
CH
S

1-697
SCH(CH3)CO2CH(CH3)CO2H
H
NO2
CH
S

1-698
SCH(CH3)CO2CH(CH3)CO2H
NO2
H
CH
S

1-699
SCH(CH3)CO2CH(CH3)CO2Me
H
H
CH
S

1-700
SCH(CH3)CO2CH(CH3)CO2Me
H
Cl
CH
S

1-701
SCH(CH3)CO2CH(CH3)CO2Me
Cl
H
CH
S

1-702
SCH(CH3)CO2CH(CH3)CO2Me
H
NO2
CH
S

1-703
SCH(CH3)CO2CH(CH3)CO2Me
NO2
H
CH
S

1-704
SCH(CH3)CO2CH(CH3)CO2Et
H
H
CH
S

1-705
SCH(CH3)CO2CH(CH3)CO2Et
H
Cl
CH
S

1-706
SCH(CH3)CO2CH(CH3)CO2Et
Cl
H
CH
S

1-707
SCH(CH3)CO2CH(CH3)CO2Et
H
NO2
CH
S

1-708
SCH(CH3)CO2CH(CH3)CO2Et
NO2
H
CH
S

1-709
H
NO2
H
CH
S

1-710
C≡N
H
H
CH
S

1-711
C≡N
H
Cl
CH
S

1-712
C≡N
Cl
H
CH
S

1-713
C≡N
H
NO2
CH
S

1-714
C≡N
NO2
H
CH
S

1-715
C(═O)H
H
H
CH
S

1-716
C(═O)H
H
Cl
CH
S

1-717
C(═O)H
Cl
H
CH
S

[1499]

30

TABLE 30

Compound
R2
R3
R4
A
Y

1-718
C(═O)H
H
NO2
CH
S

1-719
C(═O)H
NO2
H
CH
S

1-720
C(═O)NH2
H
H
CH
S

1-721
C(═O)NH2
H
Cl
CH
S

1-722
C(═O)NH2
Cl
H
CH
S

1-723
C(═O)NH2
H
NO2
CH
S

1-724
C(═O)NH2
NO2
H
CH
S

1-725
CO2H
H
H
CH
S

1-726
CO2H
H
Cl
CH
S

1-727
CO2H
Cl
H
CH
S

1-728
CO2H
H
NO2
CH
S

1-729
CO2H
NO2
H
CH
S

1-730
CO2Me
H
H
CH
S

1-731
CO2Me
H
Cl
CH
S

1-732
CO2Me
Cl
H
CH
S

1-733
CO2Me
H
NO2
CH
S

1-734
CO2Me
NO2
H
CH
S

1-735
CO2Et
H
H
CH
S

1-736
CO2Et
H
Cl
CH
S

1-737
CO2Et
Cl
H
CH
S

1-738
CO2Et
H
NO2
CH
S

1-739
CO2Et
NO2
H
CH
S

1-740
CO2CH2CO2H
H
H
CH
S

1-741
CO2CH2CO2H
H
Cl
CH
S

1-742
CO2CH2CO2H
Cl
H
CH
S

[1500]

31

TABLE 31

Compound
R2
R3
R4
A
Y

1-743
CO2CH2CO2H
H
NO2
CH
S

1-744
CO2CH2CO2H
NO2
H
CH
S

1-745
CO2CH2CO2Me
H
H
CH
S

1-746
CO2CH2CO2Me
H
Cl
CH
S

1-747
CO2CH2CO2Me
Cl
H
CH
S

1-748
CO2CH2CO2Me
H
NO2
CH
S

1-749
CO2CH2CO2Me
NO2
H
CH
S

1-750
CO2CH2CO2Et
H
H
CH
S

1-751
CO2CH2CO2Et
H
Cl
CH
S

1-752
CO2CH2CO2Et
Cl
H
CH
S

1-753
CO2CH2CO2Et
H
NO2
CH
S

1-754
CO2CH2CO2Et
NO2
H
CH
S

1-755
CO2CH(CH3)CO2H
H
H
CH
S

1-756
CO2CH(CH2)CO2H
H
Cl
CH
S

1-757
CO2CH(CH3)CO2H
Cl
H
CH
S

1-758
CO2CH(CH3)CO2H
H
NO2
CH
S

1-759
CO2CH(CH3)CO2H
NO2
H
CH
S

1-760
CO2CH(CH3)CO2Me
H
H
CH
S

1-761
CO2CH(CH3)CO2Me
H
Cl
CH
S

1-762
CO2CH(CH3)CO2Me
Cl
H
CH
S

1-763
CO2CH(CH3)CO2Me
H
NO2
CH
S

1-764
CO2CH(CH3)CO2Me
NO2
H
CH
S

1-765
CO2CH(CH3)CO2Et
H
H
CH
S

1-766
CO2CH(CH3)CO2Et
H
Cl
CH
S

1-767
CO2CH(CH3)CO2Et
Cl
H
CH
S

[1501]

32

TABLE 32

Compound
R2
R3
R4
A
Y

1-768
CO2CH(CH3)CO2Et
H
NO2
CH
S

1-769
CO2CH(CH3)CO2Et
NO2
H
CH
S

1-770
CO2C(CH3)2CO2H
H
H
CH
S

1-771
CO2C(CH3)2CO2H
H
Cl
CH
S

1-772
CO2C(CH3)2CO2H
Cl
H
CH
S

1-773
CO2C(CH3)2CO2H
H
NO2
CH
S

1-774
CO2C(CH3)2CO2H
NO2
H
CH
S

1-775
CO2C(CH3)2CO2Me
H
H
CH
S

1-776
CO2C(CH3)2CO2Me
H
Cl
CH
S

1-777
CO2C(CH3)2CO2Me
Cl
H
CH
S

1-778
CO2C(CH3)2CO2Me
H
NO2
CH
S

1-779
CO2C(CH3)2CO2Me
NO2
H
CH
S

1-780
CO2C(CH3)2CO2Et
H
H
CH
S

1-781
CO2C(CH3)2CO2Et
H
Cl
CH
S

1-782
CO2C(CH3)2CO2Et
Cl
H
CH
S

1-783
CO2C(CH3)2CO2Et
H
NO2
CH
S

1-784
CO2C(CH3)2CO2Et
NO2
H
CH
S

1-785
CH3
H
H
CH
S

1-786
CH3
H
Cl
CH
S

1-787
CH3
Cl
H
CH
S

1-788
CH3
H
NO2
CH
S

1-789
CH3
NO2
H
CH
S

1-790
CF3
H
H
CH
S

1-791
CF3
H
Cl
CH
S

1-792
CF3
Cl
H
CH
S

[1502]

33

TABLE 33

Compound
R2
R3
R4
A
Y

1-793
CF3
H
NO2
CH
S

1-794
CF3
NO2
H
CH
S

1-795
CH═CHCO2H
H
H
CH
S

1-796
CH═CHCO2H
H
Cl
CH
S

1-797
CH═CHCO2H
Cl
H
CH
S

1-798
CH═CHCO2H
H
NO2
CH
S

1-799
CH═CHCO2H
NO2
H
CH
S

1-800
CH═CHCO2Me
H
H
CH
S

1-801
CH═CHCO2Me
H
Cl
CH
S

1-802
CH═CHCO2Me
Cl
H
CH
S

1-803
CH═CHCO2Me
H
NO2
CH
S

1-804
CH═CHCO2Me
NO2
H
CH
S

1-805
CH═CHCO2Et
H
H
CH
S

1-806
CH═CHCO2Et
H
Cl
CH
S

1-807
CH═CHCO2Et
Cl
H
CH
S

1-808
CH═CHCO2Et
H
NO2
CH
S

1-809
CH═CHCO2Et
NO2
H
CH
S

1-810
CH2CH2CO2H
H
H
CH
S

1-811
CH2CH2CO2H
H
Cl
CH
S

1-812
CH2CH2CO2H
Cl
H
CH
S

1-813
CH2CH2CO2H
H
NO2
CH
S

1-814
CH2CH2CO2H
NO2
H
CH
S

1-815
CH2CH2CO2Me
H
H
CH
S

1-816
CH2CH2CO2Me
H
Cl
CH
S

1-817
CH2CH2CO2Me
Cl
H
CH
S

[1503]

34

TABLE 34

Compound
R2
R3
R4
A
Y

1-818
CH2CH2CO2Me
H
NO2
CH
S

1-819
CH2CH2CO2Me
NO2
H
CH
S

1-820
CH2CH2CO2Et
H
H
CH
S

1-821
CH2CH2CO2Et
H
Cl
CH
S

1-822
CH2CH2CO2Et
Cl
H
CH
S

1-823
CH2CH2CO2Et
H
NO2
CH
S

1-824
CH2CH2CO2Et
NO2
H
CH
S

1-825
CH2CH(Cl)CO2H
H
H
CH
S

1-826
CH2CH(Cl)CO2H
H
Cl
CH
S

1-827
CH2CH(Cl)CO2H
Cl
H
CH
S

1-828
CH2CH(Cl)CO2H
H
NO2
CH
S

1-829
CH2CH(Cl)CO2H
NO2
H
CH
S

1-830
CH2CH(Cl)CO2Me
H
H
CH
S

1-831
CH2CH(Cl)CO2Me
H
Cl
CH
S

1-832
CH2CH(Cl)CO2Me
Cl
H
CH
S

1-833
CH2CH(Cl)CO2Me
H
NO2
CH
S

1-834
CH2CH(Cl)CO2Me
NO2
H
CH
S

1-835
CH2CH(Cl)CO2Et
H
H
CH
S

1-836
CH2CH(Cl)CO2Et
H
Cl
CH
S

1-837
CH2CH(Cl)CO2Et
Cl
H
CH
S

1-838
CH2CH(Cl)CO2Et
H
NO2
CH
S

1-839
CH2CH(Cl)CO2Et
NO2
H
CH
S

1-840
C(═O)CH3
H
H
CH
S

1-841
C(═O)CH3
H
Cl
CH
S

1-842
C(═O)CH3
Cl
H
CH
S

[1504]

35

TABLE 35

Compound
R2
R3
R4
A
Y

1-843
C(═O)CH3
H
NO2
CH
S

1-844
C(═O)CH3
NO2
H
CH
S

1-845
C(CH3)═NOH
H
H
CH
S

1-846
C(CH3)═NOH
H
Cl
CH
S

1-847
C(CH3)═NOH
Cl
H
CH
S

1-848
C(CH3)═NOH
H
NO2
CH
S

1-849
C(CH3)═NOH
NO2
H
CH
S

1-850
C(CH3)═NOMe
H
H
CH
S

1-851
C(CH3)═NOMe
H
Cl
CH
S

1-852
C(CH3)═NOMe
Cl
H
CH
S

1-853
C(CH3)═NOMe
H
NO2
CH
S

1-854
C(CH3)═NOMe
NO2
H
CH
S

1-855
F
H
H
CH
S

1-856
F
H
Cl
CH
S

1-857
F
Cl
H
CH
S

1-858
F
H
NO2
CH
S

1-859
F
NO2
H
CH
S

1-860
H
H
Cl
CH
O

1-861
H
Cl
H
CH
O

1-862
H
Cl
Cl
CH
O

1-863
H
H
Cl
CH
S

1-864
H
Cl
H
CH
S

1-865
H
Cl
Cl
CH
S

1-866
CH═NOH
H
Cl
CH
O

1-867
CH═NOH
Cl
H
CH
O

[1505]

36

TABLE 36

Compound
R2
R3
R4
A
Y

1-868
CH═NOH
H
NO2
CH
O

1-869
CH═NOH
NO2
H
CH
O

1-870
CH═NOCH3
H
H
CH
O

1-871
CH═NO CH3
H
Cl
CH
O

1-872
CH═NO CH3
Cl
H
CH
O

1-873
CH═NO CH3
H
NO2
CH
O

1-874
CH═NO CH3
NO2
H
CH
O

1-875
H
H
H
N
O

1-876
H
H
Cl
N
O

1-877
H
Cl
H
N
O

1-878
H
H
NO2
N
O

1-879
H
NO2
H
N
O

1-880
OH
H
H
N
O

1-881
OH
H
Cl
N
O

1-882
OH
Cl
H
N
O

1-883
OH
H
NO2
N
O

1-884
OH
NO2
H
N
O

1-885
OCH3
H
H
N
O

1-886
OCH3
H
Cl
N
O

1-887
OCH3
Cl
H
N
O

1-888
OCH3
H
NO2
N
O

1-889
OCH3
NO2
H
N
O

1-890
OCH(CH3)CH3
H
H
N
O

1-891
OCH(CH3)CH3
H
Cl
N
O

1-892
OCH(CH3)CH3
Cl
H
N
O

[1506]

37

TABLE 37

Compound
R2
R3
R4
A
Y

1-893
OCH(CH3)CH3
H
NO2
N
O

1-894
OCH(CH3)CH3
NO2
H
N
O

1-895
OCH2C≡CH
H
H
N
O

1-896
OCH2C≡CH
H
Cl
N
O

1-897
OCH2C≡CH
Cl
H
N
O

1-898
OCH2C≡CH
H
NO2
N
O

1-899
OCH2C≡CH
NO2
H
N
O

1-900
OCH(CH3)C≡CH
H
H
N
O

1-901
OCH(CH3)C≡CH
H
Cl
N
O

1-902
OCH(CH3)C≡CH
Cl
H
N
O

1-903
OCH(CH3)C≡CH
H
NO2
N
O

1-904
OCH(CH3)C≡CH
NO2
H
N
O

1-905
OCH2CH═CH2
H
H
N
O

1-906
OCH2CH═CH2
H
Cl
N
O

1-907
OCH2CH═CH2
Cl
H
N
O

1-908
OCH2CH═CH2
H
NO2
N
O

1-909
OCH2CH═CH2
NO2
H
N
O

1-910
OCH2CO2H
H
H
N
O

1-911
OCH2CO2H
H
Cl
N
O

1-912
OCH2CO2H
Cl
H
N
O

1-913
OCH2CO2H
H
NO2
N
O

1-914
OCH2CO2H
NO2
H
N
O

1-915
OCH2CO2Et
H
H
N
O

1-916
OCH2CO2Et
H
Cl
N
O

1-917
OCH2CO2Et
Cl
H
N
O

[1507]

38

TABLE 38

Compound
R2
R3
R4
A
Y

1-918
OCH2CO2Et
H
NO2
N
O

1-919
OCH2CO2Et
NO2
H
N
O

1-920
OCH(CH3)CO2H
H
H
N
O

1-921
OCH(CH3)CO2H
H
Cl
N
O

1-922
OCH(CH3)CO2H
Cl
H
N
O

1-923
OCH(CH3)CO2H
H
NO2
N
O

1-924
OCH(CH3)CO2H
NO2
H
N
O

1-925
OCH(CH3)CO2Me
H
H
N
O

1-926
OCH(CH3)CO2Me
H
Cl
N
O

1-927
OCH(CH3)CO2Me
Cl
H
N
O

1-928
OCH(CH3)CO2Me
H
NO2
N
O

1-929
OCH(CH3)CO2Me
NO2
H
N
O

1-930
OCH(CH3)CO2Et
H
H
N
O

1-931
OCH(CH3)CO2Et
H
Cl
N
O

1-932
OCH(CH3)CO2Et
Cl
H
N
O

1-933
OCH(CH3)CO2Et
H
NO2
N
O

1-934
OCH(CH3)CO2Et
NO2
H
N
O

1-935
CO2H
H
H
N
O

1-936
CO2H
H
Cl
N
O

1-937
CO2H
Cl
H
N
O

1-938
CO2H
H
NO2
N
O

1-939
CO2H
NO2
H
N
O

1-940
CO2Me
H
H
N
O

1-941
CO2Me
H
Cl
N
O

1-942
CO2Me
Cl
H
N
O

[1508]

39

TABLE 39

Compound
R2
R3
R4
A
Y

1-943
CO2Me
H
NO2
N
O

1-944
CO2Me
NO2
H
N
O

1-945
CO2Et
H
H
N
O

1-946
CO2Et
H
Cl
N
O

1-947
CO2Et
Cl
H
N
O

1-948
CO2Et
H
NO2
N
O

1-949
CO2Et
NO2
H
N
O

1-950
CO2CH(CH3)CO2 Et
H
H
N
O

1-951
CO2CH(CH3)CO2 Et
H
Cl
N
O

1-952
CO2CH(CH3)CO2 Et
Cl
H
N
O

1-953
CO2CH(CH3)CO2 Et
H
NO2
N
O

1-954
CO2CH(CH3)CO2 Et
NO2
H
N
O

1-955
CO2C(CH3)2CO2Et
H
H
N
O

1-956
CO2C(CH3)2CO2Et
H
Cl
N
O

1-957
CO2C(CH3)2CO2Et
Cl
H
N
O

1-958
CO2C(CH3)2CO2Et
H
NO2
N
O

1-959
CO2C(CH3)2CO2Et
NO2
H
N
O

1-960
C(═O)H
H
H
N
O

1-961
C(═O)H
H
Cl
N
O

1-962
C(═O)H
Cl
H
N
O

1-963
C(═O)H
H
NO2
N
O

1-964
C(═O)H
NO2
H
N
O

1-965
CH═CHCO2Et
H
H
N
O

1-966
CH═CHCO2Et
H
Cl
N
O

1-967
CH═CHCO2Et
Cl
H
N
O

[1509]

40

TABLE 40

Compound
R2
R3
R4
A
Y

1-968
CH═CHCO2Et
H
NO2
N
O

1-969
CH═CHCO2Et
NO2
H
N
O

1-970
CH═NOH
H
H
N
O

1-971
CH═NOH
H
Cl
N
O

1-972
CH═NOH
Cl
H
N
O

1-973
CH═NOH
H
NO2
N
O

1-974
CH═NOH
NO2
H
N
O

1-975
CH═NOCH3
H
H
N
O

1-976
CH═NOCH3
H
Cl
N
O

1-977
CH═NOCH3
Cl
H
N
O

1-978
CH═NOCH3
H
NO2
N
O

1-979
CH═NOCH3
NO2
H
N
O

1-980
CH2CH2CO2Et
H
H
N
O

1-981
CH2CH2CO2Et
H
Cl
N
O

1-982
CH2CH2CO2Et
Cl
H
N
O

1-983
CH2CH2CO2Et
H
NO2
N
O

1-984
CH2CH2CO2Et
NO2
H
N
O

1-985
CH2CH(Cl)CO2Et
H
H
N
O

1-986
CH2CH(Cl)CO2Et
H
Cl
N
O

1-987
CH2CH(Cl)CO2Et
Cl
H
N
O

1-988
CH2CH(Cl)CO2Et
H
NO2
N
O

1-989
CH2CH(Cl)CO2Et
NO2
H
N
O

1-990
H
Cl
Cl
N
O

1-991
CF3
H
Cl
N
O

1-992
CF3
Cl
H
N
O

[1510] Compounds of the General Formula:

115

41TABLE 41CompoundR2R3R4AY1-2001HHHCHCH1-2002ClHHCHCH1-2003HClHCHCH1-2004HHClCHCH1-2005NO2HHCHCH1-2006HNO2HCHCH1-2007HHNO2CHCH1-2008OHHHCHCH1-2009OCH3HHCHCH1-2010OCH2CO2CH3HHCHCH1-2011OCH2CO2C2H5HHCHCH1-2012OCH(CH3)CO2CH3HHCHCH1-2013OCH(CH3)CO2C2H5HHCHCH1-2014OC(CH3)2CO2CH3HHCHCH1-2015OC(CH3)2CO2C2H5HHCHCH1-2016CO2HHHCHCH1-2017CO2CH3HHCHCH1-2018CO2C2H5HHCHCH1-2019CO2CH2CO2C2H5HHCHCH1-2020CO2CH(CH3)CO2C2H5HHCHCH1-2021CO2C(CH3)2CO2C2H5HHCHCH1-2022OHClHCHCH1-2023OCH3ClHCHCH1-2024OCH2CO2CH3ClHCHCH1-2025OCH2CO2C2H5ClHCHCH

[1511]

42

TABLE 42

Compound
R2
R3
R4
A
Y

1-2026
OCH(CH3)CO2CH3
Cl
H
CH
CH

1-2027
OCH(CH3)CO2C2H5
Cl
H
CH
CH

1-2028
OC(CH3)2CO2CH3
Cl
H
CH
CH

1-2029
OC(CH3)2CO2C2H5
Cl
H
CH
CH

1-2030
CO2H
Cl
H
CH
CH

1-2031
CO2CH3
Cl
H
CH
CH

1-2032
CO2C2H5
Cl
H
CH
CH

1-2033
CO2CH2CO2C2H5
Cl
H
CH
CH

1-2034
CO2CH(CH3)CO2C2H5
Cl
H
CH
CH

1-2035
CO2C(CH3)2CO2C2H5
Cl
H
CH
CH

1-2036
OH
NO2
H
CH
CH

1-2037
OCH3
NO2
H
CH
CH

1-2038
OCH2CO2CH3
NO2
H
CH
CH

1-2039
OCH2CO2C2H5
NO2
H
CH
CH

1-2040
OCH(CH3)CO2CH3
NO2
H
CH
CH

1-2041
OCH(CH3)CO2C2H5
NO2
H
CH
CH

1-2042
OC(CH3)2CO2CH3
NO2
H
CH
CH

1-2043
OC(CH3)2CO2C2H5
NO2
H
CH
CH

1-2044
CO2H
NO2
H
CH
CH

1-2045
CO2CH3
NO2
H
CH
CH

1-2046
CO2C2H5
NO2
H
CH
CH

1-2047
CO2CH2CO2C2H5
NO2
H
CH
CH

1-2048
CO2CH(CH3)CO2C2H5
NO2
H
CH
CH

1-2049
CO2C(CH3)2CO2C2H5
NO2
H
CH
CH

1-2050
Cl
H
Cl
CH
CH

[1512]

43

TABLE 43

Compound
R2
R3
R4
A
Y

1-2051
H
H
H
N
CH

1-2052
Cl
H
H
N
CH

1-2053
H
Cl
H
N
CH

1-2054
H
H
Cl
N
CH

1-2055
NO2
H
H
N
CH

1-2056
H
NO2
H
N
CH

1-2057
H
H
NO2
N
CH

1-2058
OH
H
H
N
CH

1-2059
OCH3
H
H
N
CH

1-2060
OCH2CO2CH3
H
H
N
CH

1-2061
OCH2CO2C2H5
H
H
N
CH

1-2062
OCH(CH3)CO2CH3
H
H
N
CH

1-2063
OCH(CH3)CO2C2H5
H
H
N
CH

1-2064
OC(CH3)2CO2CH3
H
H
N
CH

1-2065
OC(CH3)2CO2C2H5
H
H
N
CH

1-2066
CO2H
H
H
N
CH

1-2067
CO2CH3
H
H
N
CH

1-2068
CO2C2H5
H
H
N
CH

1-2069
CO2CH2CO2C2H5
H
H
N
CH

1-2070
CO2CH(CH3)CO2C2H5
H
H
N
CH

1-2071
CO2C(CH3)2CO2C2H5
H
H
N
CH

1-2072
OH
Cl
H
N
CH

1-2073
OCH3
Cl
H
N
CH

1-2074
OCH2CO2CH3
Cl
H
N
CH

1-2075
OCH2CO2C2H5
Cl
H
N
CH

[1513]

44

TABLE 44

Compound
R2
R3
R4
A
Y

1-2076
OCH(CH3)CO2CH3
Cl
H
N
CH

1-2077
OCH(CH3)CO2C2H5
Cl
H
N
CH

1-2078
OC(CH3)2CO2CH3
Cl
H
N
CH

1-2079
OC(CH3)2CO2C2H5
Cl
H
N
CH

1-2080
CO2H
Cl
H
N
CH

1-2081
CO2CH3
Cl
H
N
CH

1-2082
CO2C2H5
Cl
H
N
CH

1-2083
CO2CH2CO2C2H5
Cl
H
N
CH

1-2084
CO2CH(CH3)CO2C2H5
Cl
H
N
CH

1-2085
CO2C(CH3)2CO2C2H5
Cl
H
N
CH

1-2086
OH
NO2
H
N
CH

1-2087
OCH3
NO2
H
N
CH

1-2088
OCH2CO2CH3
NO2
H
N
CH

1-2089
OCH2CO2C2H5
NO2
H
N
CH

1-2090
OCH(CH3)CO2CH3
NO2
H
N
CH

1-2091
OCH(CH3)CO2C2H5
NO2
H
N
CH

1-2092
OC(CH3)2CO2CH3
NO2
H
N
CH

1-2093
OC(CH3)2CO2C2H5
NO2
H
N
CH

1-2094
CO2H
NO2
H
N
CH

1-2095
CO2CH3
NO2
H
N
CH

1-2096
CO2C2H5
NO2
H
N
CH

1-2097
CO2CH2CO2C2H5
NO2
H
N
CH

1-2098
CO2CH(CH3)CO2C2H5
NO2
H
N
CH

1-2099
CO2C(CH3)2CO2C2H5
NO2
H
N
CH

1-2100
Cl
H
Cl
N
CH

[1514]

45

TABLE 45

Compound
R2
R3
R4
A
Y

1-2101
H
H
H
CH
N

1-2102
Cl
H
H
CH
N

1-2103
H
Cl
H
CH
N

1-2104
H
H
Cl
CH
N

1-2105
NO2
H
H
CH
N

1-2106
H
NO2
H
CH
N

1-2107
H
H
NO2
CH
N

1-2108
OH
H
H
CH
N

1-2109
OCH3
H
H
CH
N

1-2110
OCH2CO2CH3
H
H
CH
N

1-2111
OCH2CO2C2H5
H
H
CH
N

1-2112
OCH(CH3)CO2CH3
H
H
CH
N

1-2113
OCH(CH3)CO2C2H5
H
H
CH
N

1-2114
OC(CH3)2CO2CH3
H
H
CH
N

1-2115
OC(CH3)2CO2C2H5
H
H
CH
N

1-2116
CO2H
H
H
CH
N

1-2117
CO2CH3
H
H
CH
N

1-2118
CO2C2H5
H
H
CH
N

1-2119
CO2CH2CO2C2H5
H
H
CH
N

1-2120
CO2CH(CH3)CO2C2H5
H
H
CH
N

1-2121
CO2C(CH3)2CO2C2H5
H
H
CH
N

1-2122
OH
Cl
H
CH
N

1-2123
OCH3
Cl
H
CH
N

1-2124
OCH2CO2CH3
Cl
H
CH
N

1-2125
OCH2CO2C2H5
Cl
H
CH
N

[1515]

46

TABLE 46

Compound
R2
R3
R4
A
Y

1-2126
OCH(CH3)CO2CH3
Cl
H
CH
N

1-2127
OCH(CH3)CO2C2H5
Cl
H
CH
N

1-2128
OC(CH3)2CO2CH3
Cl
H
CH
N

1-2129
OC(CH3)2CO2C2H5
Cl
H
CH
N

1-2130
CO2H
Cl
H
CH
N

1-2131
CO2CH3
Cl
H
CH
N

1-2132
CO2C2H5
Cl
H
CH
N

1-2133
CO2CH2CO2C2H5
Cl
H
CH
N

1-2134
CO2CH(CH3)CO2C2H5
Cl
H
CH
N

1-2135
CO2C(CH3)2CO2C2H5
Cl
H
CH
N

1-2136
OH
NO2
H
CH
N

1-2137
OCH3
NO2
H
CH
N

1-2138
OCH2CO2CH3
NO2
H
CH
N

1-2139
OCH2CO2C2H5
NO2
H
CH
N

1-2140
OCH(CH3)CO2CH3
NO2
H
CH
N

1-2141
OCH(CH3)CO2C2H5
NO2
H
CH
N

1-2142
OC(CH3)2CO2CH3
NO2
H
CH
N

1-2143
OC(CH3)2CO2C2H5
NO2
H
CH
N

1-2144
CO2H
NO2
H
CH
N

1-2145
CO2CH3
NO2
H
CH
N

1-2146
CO2C2H5
NO2
H
CH
N

1-2147
CO2CH2CO2C2H5
NO2
H
CH
N

1-2148
CO2CH(CH3)CO2C2H5
NO2
H
CH
N

1-2149
CO2C(CH3)2CO2C2H5
NO2
H
CH
N

1-2150
Cl
H
Cl
CH
N

[1516]

47

TABLE 47

Compound
R2
R3
R4
A
Y

1-2151
H
H
H
N
N

1-2152
Cl
H
H
N
N

1-2153
H
Cl
H
N
N

1-2154
H
H
Cl
N
N

1-2155
NO2
H
H
N
N

1-2156
H
NO2
H
N
N

1-2157
H
H
NO2
N
N

1-2158
OH
H
H
N
N

1-2159
OCH3
H
H
N
N

1-2160
OCH2CO2CH3
H
H
N
N

1-2161
OCH2CO2C2H5
H
H
N
N

1-2162
OCH(CH3)CO2CH3
H
H
N
N

1-2163
OCH(CH3)CO2C2H5
H
H
N
N

1-2164
OC(CH3)2CO2CH3
H
H
N
N

1-2165
OC(CH3)2CO2C2H5
H
H
N
N

1-2166
CO2H
H
H
N
N

1-2167
CO2CH3
H
H
N
N

1-2168
CO2C2H5
H
H
N
N

1-2169
CO2CH2CO2C2H5
H
H
N
N

1-2170
CO2CH(CH3)CO2C2H5
H
H
N
N

1-2171
CO2C(CH3)2CO2C2H5
H
H
N
N

1-2172
OH
Cl
H
N
N

1-2173
OCH3
Cl
H
N
N

1-2174
OCH2CO2CH3
Cl
H
N
N

1-2175
OCH2CO2C2H5
Cl
H
N
N

[1517]

48

TABLE 48

Compound
R2
R3
R4
A
Y

1-2176
OCH(CH3)CO2CH3
Cl
H
N
N

1-2177
OCH(CH3)CO2C2H5
Cl
H
N
N

1-2178
OC(CH3)2CO2CH3
Cl
H
N
N

1-2179
OC(CH3)2CO2C2H5
Cl
H
N
N

1-2180
CO2H
Cl
H
N
N

1-2181
CO2CH3
Cl
H
N
N

1-2182
CO2C2H5
Cl
H
N
N

1-2183
CO2CH2CO2C2H5
Cl
H
N
N

1-2184
CO2CH(CH3)CO2C2H5
Cl
H
N
N

1-2185
CO2C(CH3)2CO2C2H5
Cl
H
N
N

1-2186
OH
NO2
H
N
N

1-2187
OCH3
NO2
H
N
N

1-2188
OCH2CO2CH3
NO2
H
N
N

1-2189
OCH2CO2C2H5
NO2
H
N
N

1-2190
OCH(CH3)CO2CH3
NO2
H
N
N

1-2191
OCH(CH3)CO2C2H5
NO2
H
N
N

1-2192
OC(CH3)2CO2CH3
NO2
H
N
N

1-2193
OC(CH3)2CO2C2H5
NO2
H
N
N

1-2194
CO2H
NO2
H
N
N

1-2195
CO2CH3
NO2
H
N
N

1-2196
CO2C2H5
NO2
H
N
N

1-2197
CO2CH2CO2C2H5
NO2
H
N
N

1-2198
CO2CH(CH3)CO2C2H5
NO2
H
N
N

1-2199
CO2C(CH3)2CO2C2H5
NO2
H
N
N

1-2200
Cl
H
Cl
N
N

[1518] Compounds of the General Formula:

116

49TABLE 49CompoundR2R3R4AY2-1 HHHCHO2-2 ClHClCHO2-3 HHHCHS2-4 HHHNO2-5 ClHClNO2-6 HHHNS2-7 OCH3HHCHO2-8 OCH3HHNO2-9 NHCH3HHCHO2-10NHCH3HHNO2-11OCH2CH═CH2HHCHO2-12OCH2CH═CH2HHNO2-13CO2CH2CO2EtHHCHO2-14CO2CH2CO2EtHHNO2-15OCH2CO2C2H5HHCHO2-16OCH2CO2C2H5HHNO2-17OCH(CH3)CH═CH2HHCHO2-18OCH(CH3)CH═CH2HHNO2-19CO2CH(CH3)CO2EtHHCHO2-20CO2CH(CH3)CO2EtHHNO2-21OCH(CH3)CO2C2H5HHCHO2-22OCH(CH3)CO2C2H5HHNO2-23OCH(CH3)C≡CHHHCHO2-24OCH(CH3)C≡CHHHNO2-25OCH2C≡CHHHCHO

[1519]

50

TABLE 50

Compound
R2
R3
R4
A
Y

2-26
OCH2C≡CH
H
H
N
O

2-27
OCH3
NO2
H
CH
O

2-28
OCH3
NO2
H
N
O

2-29
OCH3
H
Cl
CH
O

2-30
OCH3
H
Cl
N
O

2-31
CH2CO2CH3
H
H
CH
O

2-32
CH2CO2CH3
H
H
N
O

2-33
CH2CO2CH3
NO2
H
CH
O

2-34
CH2CO2CH3
NO2
H
N
O

2-35
CH2CO2CH3
H
Cl
CH
O

2-36
CH2CO2CH3
H
Cl
N
O

2-37
OCH(CH3)CO2C2H5
NO2
H
CH
O

2-38
OCH(CH3)CO2C2H5
NO2
H
N
O

2-39
OCH(CH3)CO2C2H5
H
Cl
CH
O

2-40
OCH(CH3)CO2C2H5
H
Cl
N
O

2-41
OCH2C≡CH
NO2
H
CH
O

2-42
OCH2C≡CH
NO2
H
N
O

2-43
OCH2C≡CH
H
Cl
CH
O

2-44
OCH2C≡CH
H
Cl
N
O

2-45
OCH(CH3)C≡CH
NO2
H
N
O

2-46
OCH(CH3)C≡CH
NO2
H
CH
O

2-47
OCH(CH3)C≡CH
H
Cl
N
O

2-48
OCH(CH3)C≡CH
H
Cl
CH
O

2-49
SCH(CH3)CO2C2H5
NO2
H
CH
O

2-50
SCH(CH3)CO2C2H5
NO2
H
N
O

[1520] Compounds of the General Formula:

117

51TABLE 51CompoundR2R3R4AY2-2001HHHCHCH2-2002HHHCHN2-2003HHHNCH2-2004HHHNN2-2005OCH3HHCHCH2-2006OCH3HHCHN2-2007OCH3HHNCH2-2008OCH3HHNN2-2009CO2EtHHCHCH2-2010CO2EtHHCHN2-2011CO2EtHHNCH2-2012CO2EtHHNN2-2013OCH2CO2C2H5HHCHCH2-2014OCH2CO2C2H5HHCHN2-2015OCH2CO2C2H5HHNCH2-2016OCH2CO2C2H5HHNN2-2017OCH(CH3)CO2C2H5HHCHCH2-2018OCH(CH3)CO2C2H5HHCHN2-2019OCH(CH3)CO2C2H5HHNCH2-2020OCH(CH3)CO2C2H5HHNN2-2021OCH2C≡CHHHCHCH2-2022OCH2C≡CHHHCHN2-2023OCH2C≡CHHHNCH2-2024OCH2C≡CHHHNN2-2025OCH(CH3)C≡CHHHNN

[1521] Compounds of the Formula:

118

52TABLE 52CompoundR2R3R4AY3-1HHHCHO3-2ClHClCHO3-3HHHCHS3-4HHHNO3-5ClHClNO3-6HHHNS3-7OCH3HHCHO3-8OCH3HHNO3-9NHCH3HHCHO3-10NHOH3HHNO3-11OCH2CH═CH2HHCHO3-12OCH2CH═CH2HHNO3-13CO2CH2CO2EtHHCHO3-14CO2CH2CO2EtHHNO3-15OCH2CO2C2H5HHCHO3-16OCH2CO2C2H5HHNO3-17OCH(CH3)CH═CH2HHCHO3-18OCH(CH3)CH═CH2HHNO3-19CO2CH(CH3)CO2EtHHCHO3-20CO2CH(CH3)CO2EtHHNO3-21OCH(CH3)CO2C2H5HHCHO3-22OCH(CH3)CO2C2H5HHNO3-23OCH(CH3)O≡CHHHCHO3-24OCH(CH3)C≡CHHHNO3-25OCH2C≡OHHHCHO

[1522]

53

TABLE 53

Compound
R2
R3
R4
A
Y

3-26
OCH2C≡CH
H
H
N
O

3-27
OCH3
NO2
H
CH
O

3-28
OCH3
NO2
H
N
O

3-29
OCH3
H
Cl
CH
O

3-30
OCH3
H
Cl
N
O

3-31
CH2CO2CH3
H
H
CH
O

3-32
CH2CO2CH3
H
H
N
O

3-33
CH2CO2CH3
NO2
H
CH
O

3-34
CH2CO2CH3
NO2
H
N
O

3-35
CH2CO2CH3
H
Cl
CH
O

3-36
CH2CO2CH3
H
Cl
N
O

3-37
OCH(CH3)CO2C2H5
NO2
H
CH
O

3-38
OCH(CH3)CO2C2H5
NO2
H
N
O

3-39
OCH(CH3)CO2C2H5
H
Cl
CH
O

3-40
OCH(CH3)CO2C2H5
H
Cl
N
O

3-41
OCH2C≡CH
NO2
H
CH
O

3-42
OCH2C≡CH
NO2
H
N
O

3-43
OCH2C≡CH
H
Cl
CH
O

3-44
OCH2C≡CH
H
Cl
N
O

3-45
OCH(CH3)C≡CH
NO2
H
N
O

3-46
OCH(CH3)C≡CH
NO2
H
CH
O

3-47
OCH(CH3)C≡CH
H
Cl
N
O

3-48
OCH(CH3)C≡CH
H
Cl
CH
O

3-49
SCH(CH3)CO2C2H5
NO2
H
CH
O

3-50
SCH(CH3)CO2C2H5
NO2
H
N
O

[1523] Compounds of the General Formula:

119

54TABLE 54CompoundR2R3R4AY3-2001HHHCHCH3-2002HHHCHN3-2003HHHNCH3-2004HHHNN3-2005OCH3HHCHCH3-2006OCH3HHCHN3-2007OCH3HHNCR3-2008OCH3HHNN3-2009CO2EtHHCHCH3-2010CO2EtHHCHN3-2011CO2EtHHNCH3-2012CO2EtHHNN3-2013OCH2CO2C2H6HHCHCR3-2014OCH2CO2C2H5HHCHN3-2015OCH2CO2C2H5HHNCR3-2016OCH2CO2C2H5HHNN3-2017OCH(CH3)CO2C2H5HHCHCR3-2018OCH(CH3)CO2C2H5HHCHN3-2019OCH(CH3)CO2C2H5HHNCR3-2020OCH(CH3)CO2C2H5HHNN3-2021OCH2C≡CHHHCHCH3-2022OCH2C≡CHHHCHN3-2023OCH2C≡CHHHNCR3-2024OCH2C≡CHHHNN3-2025OCH(CH3)C≡CHHHNN

[1524] For some of the present compounds, melting points or 1H-NMR data as their physical properties are shown below.

[1525] The present compound 1-4

[1526] m.p.: 132.1° C.

[1527] The present compound 1-11

[1528]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.20 (3H, t, J=7.14 Hz), 1.44 (3H, d, J=6.92 Hz), 3.56 (3H, m), 4.06-4.20 (4H, m), 6.38 (1H, s), 6.42 (1H, d, J=2.33 Hz), 6.67 (1H, dd, J=8.87 Hz, 2.33 Hz), 7.32 (1H, d, J=8.87 Hz), 7.72 (1H, s)

[1529] The present compound 1-76

[1530]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.60 (3H, s), 6.40 (1H, s), 7.39 (1H, d, J=1.52 Hz), 7.51 (1H, d, J=1.52 Hz), 7.91 (1H, s)

[1531] The present compound 1-77

[1532]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59 (3H, s), 6.40 (1H, s), 7.61 (1H, s), 7.69 (1H, s), 7.84 (1H, s)

[1533] The present compound 1-80

[1534]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.58-3.60 (3H, m), 5.47 (1H, s), 6.40 (1H, s), 6.92 (1H, s), 7.56 (1H, s), 7.80 (1H, s)

[1535] The present compound 1-82

[1536]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.60-3.61 (3H, m), 6.41 (1H, s), 7.02 (1H, s), 8.05 (1H, s), 8.35 (1H, s), 10.46 (1H, s)

[1537] The present compound 1-83

[1538]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59 (3H, s), 3.80 (3H, s), 6.39 (1H, s), 6.64 (1H, d, J=2.19 Hz), 7.00 (1H, d, J=2.19 Hz), 7.85 (1H, s)

[1539] The present compound 1-84

[1540]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 3.60-3.61 (3H, m), 3.91 (3H, s), 6.41 (1H, s), 6.75 (1H, s), 7.61 (1H, s), 7.80 (1H, s)

[1541] The present compound 1-86

[1542]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61 (3H, m), 3.95 (3H, s), 6.42 (1H, s), 6.89 (1H, s), 8.00 (1H, s), 8.09 (1H, s)

[1543] The present compound 1-128

[1544]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.22 (3H, t, J=7.08 Hz), 1.60 (3H, d, J=6.76 Hz), 3.58 (3H, m), 4.15-4.24 (2H, m), 4.71 (1H, q, J=6.78 Hz), 6.39 (1H, s), 6.66 (1H, d, J=2.33 Hz), 7.03 (1H, d, J=2.33 Hz), 7.86 (1H, s)

[1545] The present compound 1-129

[1546]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.20 (3H, t, J=7.17 Hz), 1.66 (3H, d, J=6.76 Hz), 3.57 (3H, s), 4.18 (2H, q, J=7.10 Hz), 4.72 (1H, q, J=6.85 Hz), 6.38 (1H, s), 6.83 (1H, s), 7.60 (1H, s), 7.80 (1H, s)

[1547] The present compound 1-131

[1548]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.20 (3H, t, J=7.20 Hz), 1.67 (3H, d, J=6.90 Hz), 3.60 (3H, m), 4.18 (2H, q, J=7.09 Hz), 4.80 (1H, q, J=6.80 Hz), 6.40 (1H, s), 6.92 (1H, s), 8.02 (1H, s), 8.09 (1H, s)

[1549] The present compound 1-246

[1550]

1
H-NMR (250 MHz, CDCl3, TMS, δ (ppm)): 1.13 (3H, t, J=7.07 Hz), 1.55 (3H, d, J=7.25 Hz), 3.61-3.62 (3H, m), 3.96 (1H, q, J=7.14 Hz), 4.08-4.15 (2H, m), 6.42 (1H, s), 8.10 (1H, s), 8.28 (1H, s)

[1551] The present compound 1-285

[1552]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61 (3H, m), 6.42 (1H, s), 7.72 (1H, s), 7.73 (1H, s), 7.98 (1H, s)

[1553] The present compound 1-289

[1554]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61-3.62 (3H, m), 6.43 (1H, s), 7.81 (1H, d, J=1.26 Hz), 7.93 (1H, d, J=1.44 Hz), 8.02 (1H, s), 10.00 (1H, s)

[1555] The present compound 1-304

[1556]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.60 (3H, s), 3.94 (3H, s), 6.41 (1H, s), 7.97 (1H, s), 7.98 (1H, d, J=1.35 Hz), 8.09 (1H,d, J=1.35 Hz)

[1557] The present compound 1-305

[1558]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59 (3H, m), 3.93 (3H, s), 6.40 (1H, s), 7.67 (1H, s), 7.87 (1H, s), 7.89 (1H, s)

[1559] The present compound 1-358

[1560]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 2.40 (3H, s), 3.59 (3H, m), 6.40 (1H, s), 7.01 (1H, s), 7.19 (1H, s), 7.85 (1H, s)

[1561] The present compound 1-361

[1562]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 2.67 (3H, s), 3.61 (3H, m), 6.42 (1H, s), 7.27 (1H, s), 8.03 (1H, s), 8.27 (1H, s)

[1563] The present compound 1-378

[1564] m.p.: 208.2° C.

[1565] The present compound 1-861

[1566] m.p.: 135.9° C.

[1567] The present compound 1-864

[1568] m.p.: 183.8° C.

[1569] The present compound 1-871

[1570] m.p.: 193.2° C.

[1571] The present compound 1-882

[1572]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.59-3.61 (3H, m), 6.42 (1H, s), 6.98 (1H, s), 7.85 (1H, s)

[1573] The present compound 1-887

[1574]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 3.61 (3H, s), 3.96 (1H, s), 6.44 (1H, s), 6.91 (1H, s), 7.94 (1H, s)

[1575] The present compound 1-892

[1576]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.41 (6H, d, J=6.3 Hz), 3.60 (3H, d, J=1.1 Hz), 4.56-4.68 (1H, m), 6.43 (1H, s), 6.91 (1H, s), 7.91 (1H, s)

[1577] The present compound 1-932

[1578]

1
H-NMR (300 MHz, CDCl3, TMS, δ (ppm)): 1.19 (3H, t, J=7.1 Hz), 1.73 (3H, d, J=7.0), 3.59-3.61 (3H, m), 4.14-4.23 (2H, m), 4.81 (1H, q, J=7.1 Hz), 6.42 (1H, s), 6.87 (1H, s), 7.96 (1H, s)

[1579] The following are Formulation Examples in which the present compounds are indicated by their compound numbers in Tables 1 to 54 and parts are by weight.

Formulation Example 1

[1580] Fifty parts of each of the present compounds 1-1 to 1-992, 1-2001 to 1-2200, 2-1 to 2-50, 2-2001 to 2-2025, 3-1 to 3-50 and 3-2001 to 3-2025, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrated silicon oxide are well pulverized and mixed to give a wettable powder for each compound.

Formulation Example 2

[1581] Ten parts of each of the present compounds 1-1 to 1-992, 1-2001 to 1-2200, 2-1 to 2-50, 2-2001 to 2025,3-1 to 3-50 and 3-2001 to 3-2025, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone are well mixed to an emulsifiable concentrate for each compound.

Formulation Example 3

[1582] Two parts of each of the present compounds 1-1 to 1-992, 1-2001 to 1-2200, 2-1 to 2-50, 2-2001 to 2025, 3-1 to 3-50 and 3-2001 to 3-2025, 2 parts of synthetic hydrated silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite, and 64 parts of kaolin clay are well pulverized and mixed, and the mixture is well kneaded with water, followed by granulation and drying, to give a granule for each compound.

Formulation Example 4

[1583] Twenty-five parts of each of the present compounds 1-1 to 1-992, 1-2001 to 1-2200, 2-1 to 2-50, 2-2001 to 2025, 3-1 to 3-50 and 3-2001 to 3-2025, 50 parts of 10% aqueous polyvinyl alcohol solution, and 25 parts of water are mixed and pulverized until the mean particle size reaches 5 μm or smaller to give a flowable for each compound.

Formulation Example 5

[1584] Five parts of each of the present compounds 1-1 to 1-992, 1-2001 to 1-2200, 2-1 to 2-50, 2-2001 to 2-2025, 3-1 to 3-50 and 3-2001 to 3-2025 is added to 40 parts of 10% aqueous polyvinyl alcohol solution, and the mixture is emulsified by dispersion with a homogenizer until the mean particle size reaches 10 μm or smaller, followed by addition of 55 parts of water, to give a concentrated emulsion for each compound

[1585] The following are Test Examples for demonstrating that the present compounds are useful as active ingredients of herbicides. In Test Examples, the present compounds are designated by their compound numbers in Tables 1 to 54.

Test Example 1

[1586] Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, seeded with velvetleaf (Abutilon theophrasti), and kept in a greenhouse for 14 days. After that, according to Formulation Example 2, compound 1-1,1-2, 1-3,1-4, 1-5,1-8, 1-9,1-10, 1-11, 1-24, 1-28, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-871, 1-877, 1-892, 1-2068, 2-4 or 2-2011 was formulated into an emulsifiable concentrate, which was diluted in a prescribed amount with water containing a spreading agent and then uniformly sprayed over the foliage of the plants with a sprayer at a ratio of 1000 liters per hectare. The pots were further kept in the greenhouse for 8 days and examined for herbicidal activity. As a result, it was found that compounds 1-1,1-2, 1-3,1-4, 1-5,1-8, 1-9,1-10, 1-11, 1-24, 1-28, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-871, 1-877, 1-892, 1-2068, 2-4 and 2-2011 completely inhibited the growth of velvetleaf at a dosage of 2000 g/ha.

Test Example 2

[1587] Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil, seeded with velvetleaf (Abutilon theophrasti), and kept in a greenhouse for 14 days. After that, according to Formulation Example 2, compound 2-2001 or 3-2001 was formulated into an emulsifiable concentrate, which was diluted in a prescribed amount with water containing a spreading agent and then uniformly sprayed over the foliage of the plants with a sprayer at a ratio of 1000 liters per hectare. The pots were further kept in the greenhouse for 5 days and examined for herbicidal activity. As a result, it was found that compounds 2-2001 and 3-2001 completely killed velvetleaf at a dosage of 8000 g/ha.

Test Example 3

[1588] Cylindrical plastic pots of 10 cm in diameter and 10 cm in depth were filled with soil and seeded with velvetleaf (Abutilon theophrasti). According to Formulation Example 2, compound 1-1,1-2, 1-3,1-4, 1-5,1-8, 1-9,1-10, 1-11, 1-24, 1-28, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-877 or 1-892 was formulated into an emulsifiable concentrate, which was diluted in a prescribed amount with water and then uniformly sprayed over the surface of the soil in the pots with a sprayer at a ratio of 1000 liters per hectare. The pots were kept in a greenhouse for 9 days and examined for herbicidal activity. As a result, it was found that compounds 1-1,1-2, 1-3, 1-4,1-5, 1-8,1-9, 1-10, 1-11, 1-24, 1-28, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-877 and 1-892 completely inhibited the germination of velvetleaf at a dosage of 2000 g/ha.

Test Example 4

[1589] Cylindrical plastic pots of 9 cm in diameter and 11 cm of depth were filled with soil, seeded with barnyardgrass (Echinochloa oryzicola), flooded into a paddy field, and kept in a greenhouse for 12 days. According to Formulation Example 2, compound 1-1,1-2, 1-3,1-4, 1-5,1-8, 1-9,1-10, 1-11, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-864, 1-877 or 1-892 was formulated into an emulsifiable concentrate, which was diluted in a prescribed amount with water and then applied on the water surface in the pots at a ratio of 50 liters per are. The pots were further kept in the greenhouse for 9 days and examined for herbicidal activity. As a result, it was found that compounds 1-1,1-2, 1-3,1-4, 1-5,1-8, 1-9,1-10, 1-11, 1-75, 1-82, 1-84, 1-86, 1-127, 1-129, 1-131, 1-201, 1-246, 1-282, 1-283, 1-289, 1-293, 1-303, 1-358, 1-361, 1-378, 1-407, 1-431, 1-861, 1-864, 1-877 and 1-892 completely inhibited the growth of barnyardgrass at a dosage of 1000 g/ha.

INDUSTRIAL APPLICABILITY

[1590] The condensed heterocyclic compounds of the present invention are useful as active ingredients of herbicides because of their excellent herbicidal activity.

Number	Date	Country
257237/1998	Sep 1998	JP
004373/1999	Jan 1999	JP
143300/1999	May 1999	JP

	Number	Date	Country
Parent	09762479	Feb 2001	US
Child	10422720	Apr 2003	US

Condensed heterocylic compounds and herbicides containing them as active ingredients

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