Pyridine ketones useful as herbicides

[0001] The present invention relates to novel herbicidally active pyridine ketones, to processes for their preparation, to compositions which comprise these compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.

[0002] Pyridine ketones having herbicidal action are described, for example, in WO 97/46530. We have now found novel pyridine ketones having herbicidal and growth-inhibiting properties.

[0003] The present invention thus provides compounds of the formula I

[0004] in which

[0005] each R independently is C1-C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2- C6haloalkynyl, C3-C6cycloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, CC1-CC6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylamino, di-C1-C6alkylamino, C1-C6alkylaminosulfonyl, di-C1-C6alkylaminosulfonyl, —N(R1)—S—R2, —N(R3)—SO—R4, —N(R5)—SO2—R6, nitro, cyano, halogen, hydro x y, amino, formyl, hydroxy-C1-C6alkyl, CC1-C6alkoxy-C1-C6alkyl, C1-C6alkoxycarbonyloxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, thiocyanato-C1-C6alkyl, cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkoxy-C1-C6alkoxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyloxy-C1-C6alkoxy, C3C6alkynyloxy, cyano-C1-C6alkoxy, C1-C6 alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, alkoxycarbonyl-C1-C6alkylthio, alkoxycarbonyl-C1-C6alkylsulfinyl, alkoxycarbonyl-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, C1-C6haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, where the phenyl groups may be mono- or polysubstituted by halogen, methyl, ethyl, trifluoromethyl, methoxy or nitro, or R is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is either attached directly to the pyridine ring or attached to the pyridine ring via a C1-C4alkylene group, and where each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and where the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C6alkylaminosulfonyl, C1-C6dialkylaminosulfonyl, C1-C6alkylene-R7, NR8R9, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0006] m is 1, 2, 3 or 4;

[0007] p is 0 or 1;

[0008] R1, R3 and R5 independently of one another are hydrogen or C1-C6alkyl;

[0009] R2 is NR10R11, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkyl, C1-C6haloalkyl, C3-C6a lkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0010] R4 is NR12R13, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0011] R6 is NR14R15, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phpnyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0012] R7 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0013] R8, R10, R12 and R14 independently of one another are hydrogen or C1-C6alkyl;

[0014] R9, R11, R13 and R15 is independently of one another are C1-C6alkyl or C1-C6alkoxy;

[0015] Q is the group Q1

[0016] in which

[0017] R16, R17, R18 and R19 independently of one another are hydrogen, hydroxyl, C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4alkoxycarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C4alkyl-NHS(O)2, C1-C4haloalkyl, —NH—C1-C4alkyl, —N(C1-C4alkyl)2, C1-C6alkoxy, cyano, nitro, halogen or phenyl, which for its part may be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro, COOH or cyano; or two adjacent substituents from the group consisting of R16, R17, R18 and R19 form a C2-C6alkyiene bridge;

[0018] R20 is hydroxyl, O−M+, halogen, cyano, SCN, OCN, C1-C12alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C6alkoxy-C1-C6alkylthio, C1-C6alkoxy-C1-C6alkylsulfinyl, C1-C6alkoxy-C1-C6alkylsulfonyl, C2-C12alkenylthio, C2-C12alkeny isulfinyl, C2-C12alkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsultonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, (C1-C4alkoxy)2P(O)O, C1-C4alkyl-(C1-C4alkoxy)P(Q)O, H(C1-C4alkoxy)P(O)O,

[0019] R37R38N, R71R72NNH—, R21R22NC(O)O—, R73R74NC(O)NH—, C1-C4alkyl-S(O)2NR39, C1-C6haloalkyl-S(O)2NR40, C1-C6alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O, C1-C18alkylcarbonyloxy, where the alkyl group may be substituted by halogen, C1-C6alkoxy, C1-C6alkylthio or cyano, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)-NH—, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)-NH—, benzyloxy, benzylthio, benzylsulfinyl, benzyisu lfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy or benzoyloxy, where the phenyl groups for their part may each be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano,

[0020] or a group Ar1-thio, Ar2-su lfinyl, Ar3-sulfonyl, —OCO—Ar4 or NH—Ars in which Ar1, Ar2, Ar3, Ar4 and Ar5 independently of one another are a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and in which each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and in which the ring system for its part may be mono-, di- or trisubstituted by C1-C6falkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosufonyl, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R41, NR42R43, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0021] R41 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0022] R42 is hydrogen or C1-C6alkyl;

[0023] R43 is C1-C6alkyl or C1-C6alkoxy;

[0024] R21, R37, R39, R40, R71 and R73 independently of one another are hydrogen or C1-C4alkyl;

[0025] R22, R38, R72 and R74 independently of one another are hydrogen, C1-C12alkyl, hydroxyl, C1-C12alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy; or R21 and R22 together or R37 and R38 together or R71 and R72 together or R73 and R74 together are pyrrolidino, piperidino, morpholino, thiomorpholino, which may be mono- or polysubstituted by methyl groups; or are the group Q2

[0026] in which

[0027] Y is a chemical bond, an alkylene group A l, carbonyl, oxygen, sulfur, sulfinyl, sulfonyl, —NHR248 or NH(CO)R249;

[0028] A1 is C(R246R247)m01,

[0029] A is C(R244R245)r;

[0030] r and m01 independently of one another are 0, 1 or 2;

[0031] R240 is hydrogen, methyl or C1-C3alkoxycarbonyl;

[0032] R241, R242, R243, R244, R245, R246 and R247 independently of one another are hydrogen, halogen or methyl, or R243 together with an adjacent group R245 or R247 is a chemical bond;

[0033] R248 and R249 independently of one another are hydrogen or C1-C4alkyl;

[0034] R23 is hydroxyl, O−M+, halogen, cyano, SCN, OCN, C1-C12alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C6alkoxy-C1-C6alkylthio, C1-C6alkoxy-C1-C6alkylsulfinyl, C1-C6alkoxy-C1-C6alkylsulfonyl, C2-C12alkenylthio, C2-C12alkenylsulfinyl, C2-C12alkenyisulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsultonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsuflonyl, (C1-C4alkoxy)2P(O)O, C1-C4alkyl-(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O,

[0035] R44R45N, R75R76NNH—, R46R47NC(O)O—, R77R78NC(O)NH—, C1-C4alkyl-S(O)2NR48, C1-C4haloalkyl-S(O)2NR49, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O, C1-C18alkylcarbonyloxy, where the alkyl group may be substituted by halogen, C1-C6alkoxy, C1-C6alkylthio or cyano, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)-NH—, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)-NH—, benzyloxy, benzylthio, benzylsulfinyl, benzyisulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenyisulfonyl, phenylsulfonyloxy or benzoyloxy . where the phenyl groups for their part may each be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkyisulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano,

[0036] or a group Ar6-thio, Ar7-sulfinyl, Ar8-sulfonyl, —OCO—Ar9 or NH—Ar10 in which Ar6, Ar7, Ar8, Ar9 and Ar10 independently of one another are a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and in which each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and in which the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R50, NR5,R52, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0037] R50 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsultonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0038] R51 is hydrogen or C1-C6alkyl;

[0039] R52 is C1-C6alkyl or C1-C6alkoxy;

[0040] R46, R44, R48, R49, R75 and R77 independently of one another are hydrogen or C1-C4alkyl;

[0041] R47, R45, R76 and R78 independently of one another are hydrogen, C1-C12alkyl, hydroxyl, C1-C12alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy; or R44 and R45 together or R46 and R47 together or R75 and R76 together or R77 and R78 together are pyrrolidino, piperidino, morpholino, thiomorpholino, which may be mono- or polysubstituted by methyl groups; or are the group Q3

[0042] in which

[0043] R26 is hydroxyl, O−M+, halogen, cyano, SCN, OCN, C1-C12 alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C6alkoxy-C1-C6alkylthio, C1-C6alkoxy-C1-C6alkylsulfinyl, C1-C6alkoxy-C1-C6alkylsulfonyl, C2-C12alkenylthio, C2-C12alkenylsulfinyl, C2-C12alkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsulfonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, (C1-C4alkoxy)2P(O)O, C1-C4alkyl-(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O,

[0044] R53R54N, R79R80NNH—, R55R56NC()O—, R81R82NC(O)NH—, C1-C4alkyl-S(O)2NR57, C1-C4haloalkyl-S(O)2NR58, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O, C1-C18alkylcarbonyloxy, where the alkyl group may be substituted by halogen, C1-C6alkoxy, C1-C6alkylthio or cyano, C2C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)-NH—, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)-NH—, benzyloxy, benzyithio, benzylsulfinyl, benzylsultonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy or benzoyloxy, where the phenyl groups for their part may each be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano,

[0045] or a group Ar11-thio, Ar12-sulfinyl, Ar13-sulfonyl, —OCO—Ar14 or NH—Ar15 in which Ar11, Ar12, Ar13, Ar14 and Ar15 independently of one another are a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and in which each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and in which the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkyny toxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsu ffinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosu ffonyl, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R59, NR60R61, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0046] R59 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0047] R60 is hydrogen or C1-C6alkyl;

[0048] R61 is C1-C6alkyl or C1-C6alkoxy;

[0049] R55, R53, R57, R58, R79 and R81 independently of one another are hydrogen or C1-C4alkyl; R56, R54, R80 and R82 independently of one another are hydrogen, C1-C12alkyl, hydroxyl, C1-C12alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy; or R53 and R54 together or R55 and R56 together or R79 and R80 together or R81 and R82 together are pyrrolidino, piperidino, morpholino, thiomorpholino, which may be mono- or polysubstituted by methyl groups; R29 is hydrogen, C1-C6alkyl, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, (C1-C4alkyl)NHCO, phenylaminocarbonyt, benzylaminocarbonyt or (C1-C4alkyl)2NCO, where the phenyl and benzyl groups for their part may each be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), hatogen, nitro or cyano;

[0050] or is the group Q4

[0051] in which

[0052] R30 is hydroxyl, O−M+, halogen, cyano, SCN, OCN, C1-C12alkoxy, C1-C4alkoxycarbonyl-C1-C4alkoxy, C1-C12alkylthio, C1-C12alkylsulfinyl, C1-C12alky lsultonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C6alkoxy-C1-C6alkylthio, C1-C6alkoxy-C1-C6alkylsulfinyl, C1-C6alkoxy-C1-C6alkylsulfonyl, C2-C12alkenylthio, C2-C12alkenyisulfinyl, C2-C12alkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynyisulfinyl, C2-C12alkynyisulfonyl, C2-C12haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsuffonyl, C1-C4alkoxycarbonyl-C1-C4alkylthio, C1-C4alkoxycarbonyl-C1-C4alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C4alkylsulfonyl, (C1-C4alkoxy)2P(O)O, C1-C4alkyl-(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O,

[0053] R62R63N, R83R84NNH—, R64R65NC(O)O—, R85R86NC(O)NH—, C1-C4alkyl-S(O)2NR66, C1-C4haloalkyl-S(O)2NR67, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O, C1-C18alkylcarbonyloxy, where the alkyl group may be substituted by halogen, C1-C6alkoxy, C1-C6alkylthio or cyano, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)NH—, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)-NH—, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenyisulfonyloxy or benzoyloxy, where the phenyl groups for their part may each be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfony l, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C i-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano,

[0054] or a group Ar16-thio, Ar trsu lfinyl, Ar18-sulfonyl, —OCO—Ar19 or NH—Ar20 in which Ar16, Ar17, Ar18, Ar19 and Ar20 independently of one another are a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and in which each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and in which the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C ralkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acety oalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfony l, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R68, NR69R70, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0055] R68 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsu lfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0056] R70 is hydrogen or C1-C6alkyl;

[0057] R61 is C1-C6alkyl or C1-C6alkoxy;

[0058] R64, R62, R66, R67, R83 and R85 independently of one another are hydrogen or C1-C4alkyl;

[0059] R65, R63, R84 and R86 independently of one another are hydrogen, C1-C12alkyl, hydroxyl, C1-C12alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy; or R62 and R63 together or R64 and R65 together or R83 and R84 together or R85 and R86 together are pyrrolidino, piperidino, morpholino, thiomorpholino, which may be mono- or polysubstituted by methyl groups;

[0060] R33 and R34 independently of one another are hydrogen, C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4alkoxycarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsu lfonyl, C1-C4alkyl-NHS(O)2, C1-C4haloalkyl, —NH—C1-C4alkyl, —N(C1-C4alkyl)2, C1-C6alkoxy or phenyl, which for its part may be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro, COOH or cyano; or R33 and R34 together form a C2-C6alkylene bridge; and

[0061] R35 is hydrogen, C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl or benzyl, which for its part may be substituted by halogen, methyl or methoxy, or is C1-C4alkoxycarbonyl or phenyl, which for its part may be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4aikoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsuitonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro, COOH or cyano;

[0062] or is the group Q5

[0063] in which

[0064] Z is S, SO or SO2;

[0065] R01 is hydrogen, C1-C8alkyl, C1-C8alkyl substituted by halogen, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C1-C4alkylsulfinyl, —CO2R02, —COR03, —COSR04, —NR05R06, CONR036R037 or phenyl, which for its part may be substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHS)2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)S)2—C1-C4alkyl, N(C1-C6alkyI)SO2-phenyl, N(C2-C6alkenyl)S)2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)S)2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyt, N(C3-C7cycloalkyl)S)2—C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)S)2—C1-C4alkyl, N(phenyl)SO2-phenyl, OS)2—C1-C4alkyl, CONR25R26, OS)2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenytthio, C1-C4alkylsulfonyl, C1-C4haloalkylsu lfonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, C1-C4alkylene-phenyl or —NR015CO2R027;

[0066] or R01 is C2-C8alkenyl or C2-C8alkenyl substituted by halogen, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C1-C4alkylsulfinyl, —CONR032R033, cyano, nitro, —CHO, —CO2R038, —COR039, —COS—C1-C4alkyl, —NR034R035 or phenyl which for its part may be substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHS)2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)S)2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)S)2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)S)2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)S)2—C1-C4alkyl, alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2—C1-C4alkyl, CONR040R041, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsultonyl, phenylsultonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsuffinyl, C1-C4alkylene-phenyl or —NR043CO2R042;

[0067] or R01 is C3-C6alkynyl or C3-C6alkynyl substituted by halogen, C1-C4haloalkyl, cyano, —CO2R044 or phenyl, which for its part may be substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2—C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyt, OSO2—C1-C4alkyl, CONR028R029, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsu ifonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, C1-C4alkylene-phenyl or —NR031CO2R030;

[0068] or R01 is C3-C7cycloalkyl, C3-C7cycloalkyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl or phenyl, which for its part may be substituted by halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkyl and C1-C4haloalkyl; or

[0069] R01 is C1-C4alkylene-C3-C7cycloalkyl, phenyl, or phenyl which is substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2—C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2—C1-C4alkyl, CONR045R046, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfo nyl, phenylsutfonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, or —NR048CO2R047; or

[0070] R01 is C1-C4alkylene-phenyl, COR07 or 4-6-membered heterocyclyl;

[0071] R02, R038, R044 and R066 independently of one another are hydrogen, C1-C4alkyl, phenyl, or phenyl which is substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2-C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C1-C4alkyl, N(C3-C cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2—C1-C4alkyl, CONR049R050, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsuffonyl, C1-C4haloalkylsulfonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C1-C4haioalkylsulfinyl, phenylsultinyl, C1-C4alkylene phenyl or —NR052CO2R053;

[0072] R03, R039 and R067 independently of one another are C1-C4alkyl, phenyl or phenyl which is substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7 cycloalkyl)SO2—C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2—C1-C4alkyl, CONRO070R054, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, C1-C4alkylene-phenyl or —NR056CO2R055;

[0073] R04 is C1-C4alkyl;

[0074] R05 is hydrogen, C1-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl which is substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2H, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2H, N(C3-C7cycloalkyl)SO2—C1-C4alkyl, N(C3-C7cycloalkyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2-C1-C4alkyl, CONR057R058, OSO2—C1-C4haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyi, C1-C4haloalkylsulfonyl, phenylsulfonyl, C1-C4alkyisulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, C1-C4alkylenephenyl or —NR060CO2R059;

[0075] R06 is hydrogen, C1-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl which is substituted by C1-C4aikyl, C1-C6haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano, —COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, (C1-C4alkylsulfinyl)-C1-C4alkyl, (C1-C4alkylsulfonyl)-C1-C4alkyl, NHSO2—C1-C4alkyl, NHSO2-phenyl, N(C1-C6alkyl)SO2—C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl, N(C2-C6alkenyl)SO2—C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl, N(C3-C6alkynyl)SO2—C1-C4alkyl, N(C3-C6alkynyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2—C1-C4alkyl, N(C3-C7cycloaikyl)SO2-phenyl, N(phenyl)SO2—C1-C4alkyl, N(phenyl)SO2-phenyl, OSO2-C1-C4alkyl, CONR061R062, OSO2—C1-C4 haloalkyl, OSO2-phenyl, C1-C4alkylthio, C1-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkylsulfonyl, phenylsulfonyl, C1-C4alkylsulfinyl, C1-C4haloalkylsulfinyl, phenylsulfinyl, C1-C4alkylene-phenyl or —NR064CO2R063;

[0076] R07 is phenyl, substituted phenyl, C1-C4alkyl, C1-C4alkoxy or —NR08R09;

[0077] R08 and R09 independently of one another are C1-C4alkyl, phenyl or phenyl which is substituted by halogen, nitro, cyano, C1-C4alkyl, C1-C4alkoxy, C1-C4thioalkyl, —CO2R066, —COR067, C1-C4alkylsulfonyl, C1-C4alkylsulfinyl, C1-C4haloalkyl; or R08 and R09 together form a 5-6-membered ring which may be interrupted by oxygen, NR065 or S,

[0078] R015, R031, R043, R048, R052, R056, R060 and R064 independently of one another are hydrogen, C1-C4alkyl, C2-C6alkenyl, C3C6alkynyl or C3-C7cycloalkyl;

[0079] R025, R026, R027, R028, R029, R030, R032, R033, R034, R035, R036, R037, R040, R041, R042, R045, R046, R047, R049, R050, R053, R054, R055, R057, R058, R059, R061, R062, R063, R065 and R070 independently of one another are hydrogen, C1-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl, or phenyl which is substituted by halogen, nitro, cyano, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4 alkylthio, C1-C4haloalkylthio, C1-C4alkyl or C1-C4haloalkyl; and

[0080] R36 is C1-C4alkyl, C1-C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or C3-C6cycloaikyl which is substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4alkylcarbonyl, di-C1-C4alkylamino, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkyl-S(O)2O, C1-C4haloalkyl-S(O)2O or phenyl which for its part may be substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C3-C6alkenyl, C3-C6alkynyl, cyano, nitro or COOH; and agronomically acceptable salts M+ and all stereoisomers and tautomers of the compounds of the formula I.

[0081] The compounds of the formula I can be present in different isomeric forms which can be isolated in pure form. The invention therefore also embraces all stereoisomeric forms of the compound of the formula I. Examples of these isomeric forms are the formulae Ix, Ixx, Ixxx and Ixxxx below, in which Q is the group Q2.

[0082] The alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned. The alkenyl and alkynyl groups can be mono- or polyunsaturated.

[0083] Halogen is generally fluorine, chlorine, bromine or iodine. This also applies, correspondingly, to halogen in combination with other meanings, such as haloalkyl or halophenyl.

[0084] Haloalkyl groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.

[0085] Suitable haloalkenyl groups are alkenyl groups which are mono- or polysubstituted by halogen, halogen being fluorine, chlorine, bromine and iodine and in particular fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluorobut-2-en-1-yl. Among the C3-C20alkenyl groups which are mono-, di- or trisubs btuted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

[0086] Suitable haloalkynyl groups are, for example, aikynyl groups which are mono- or polysubstituted by halogen, halogen being bromine, iodine and in particular fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluorobut-2-yn-1-yl. Among the alkynyl groups which are mono- or polysubstituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

[0087] Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy and also the isomeric pentyloxy and hexyloxy radicals; preferably methoxy and ethoxy. Alkylcarbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyt, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 24luoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio. Alkylsuffinyl is, for example, methylsulfinyl, ethylsulfinyl, propyisulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfiny l, sec-butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsultonyl, sec-butylsulfonyl or tert-butylsu lfonyl; preferably methylsulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy groups are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomeric butylamines. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups have a chain length of preferably from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propylthioethyl, isopropylthiomethyl, iso-propylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Phenyl, also as part of a substituent as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl, phenoxyalkyl, may be substituted. In this case, the substituents can be in ortho, meta and/or para position. The preferred substituent positions are the ortho and para positions to the ring attachment point. Heterocyclyl is to be understood as meaning ring systems which, in addition to carbon atoms, contain at least one heteroatom, such as nitrogen, oxygen and/or sulfur. They can be saturated or unsaturated. In the context of the present invention, heterocyclyl ring systems may also be substituted. Suitable substituents are, for example, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, cyano, nitro, C1-C4alkylsulfonyl, C1-C4alkylsulfinyl, C1-C4alkylthio or C3-C6cycloalkyl.

[0088] Heterocyclyl may be, for example, furyl, thiophenyl, pyrrolidyl, piperidinyl, morpholinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, isothiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazo lyl, thiazolyl, pyrazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, tetrazolyl, pyrimidyl, pyrazinyl, sym. or unsym. triazinyl, piperazinyl, oxazolinyl (for example:

[0089] oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl, oxetanyl, in particular 2-oxetanyl, or phthalimidyl.

[0090] The invention also embraces the salts M+ which can be formed by the compounds of the formula 1, in particular the compounds of the formula I in which R20, R23, R26 and R30 are hydroxyl, preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal bases, the hydroxides of lithium, sodium, potassium, magnesium or calcium, in particular those of sodium or potassium, may be especially emphasized as salt formers. Examples of amines suitable for ammonium salt formation are both ammonia and primary, secondary and tertiary C1-C18alkylamines, C1-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, al iylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amiines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine: primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, naphthylamines and o,m,p-chloroanilines; but in particular triethylamine, isopropylamine and diisopropylamine. Quatemary ammonium bases which are suitable for salt formation are, for example, [N(Ra01 Rb01 Rc01 Rd01)]+ OH−, where Ra01, Rb01, Rc01 and Rd01 independently of one anotheer are C1-C4alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

[0091] Preferred compounds of the formula I correspond to the formula Ib

[0092] in which

[0093] each R independently is C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6-alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C6haloalkylsu ffinyl, C1-C6haloalkylsulfonyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylamino, di-C1-C6-alkylamino, C1-C6alkylaminosu ffonyl, di-C1-C6alkylaminosulfonyl, —N(R1)—S—R2, —N(R3)—SO—R4, —N(R5)—SO2—R6, nitro, cyano, halogen, hydroxyl, amino, or a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is either attached directly to the pyridine ring or attached via a C1-C4alkylene group to the pyridine ring, and each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-Csacetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4-cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3-alkylene-R7, NR8R9, halogen, cyano, nitro, phenyl and benzylthio where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on the nitrogen in the heterocyclic ring are different from halogen;

[0094] Q is the group Q1 in which

[0095] R20 is hydroxyl, C1-C4alkoxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyloxy, R21R22N—C(O)O, phenylthio, C1-C4alky lthio, C1-C4alkyl-S(O)2O, (C1-C4alkoxy)2P(O)O, C1-C4alkyl(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O or benzoyloxy; and

[0096] R21, and R22 independently of one another are hydrogen or C1-C4alkyl; or the group Q2a

[0097] in which R23 is hydroxyl, C1-C4alkoxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyloxy, R24R25N—C(O)O, phenylthio, C1-C4alkylthio, C1-C4alkyl-S(O)2O, (C1-C4alkoxy)2P(O)O, C1-C4-alkyl(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O or benzoyloxy; and

[0098] R24 and R25 independently of one another are hydrogen or C1-C4alkyl; and

[0099] Y is oxygen, sulfur, a chemical bond or a C1-C4alkylene bridge;

[0100] or the group Q3

[0101] in which R26 is hydroxyl, C1-C4alkoxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyloxy, R27R28N-C(O)O, phenylthio, C1-C4alkylthio, C1-C4alkyl-S(O)2O, (C1-C4alkoxy)2P(O)O, C1-C4-alkyl(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O or benzoyloxy; and

[0102] R27 and R28 independently of one another are hydrogen or C1-C4alkyl and

[0103] R29 is hydrogen, C1-C6alkyl, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, (C1-C4alkyl)NHCO or (C1-C4alkyl)2NCO; or the group Q4

[0104] in which R30 is hydroxyl, C1-C4alkoxy, C1-C4alkylcarbonyloxy, C1-C4alkoxycarbonyloxy, R31R32N-C(O)O, phenylthio, C1-C4alkylthio, C1-C4alkyl-S(O)2O, (C1-C4alkoxy)2P(O)O, C1-C4-alkyl(C1-C4alkoxy)P(O)O, H(C1-C4alkoxy)P(O)O or benzoyloxy; and

[0105] R31 and R32 independently of one another are hydrogen or C1-C4alkyl;

[0106] R33 and R34 independently of one another are hydrogen, C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C4-alkoxycarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C4alkyl-NHS(O)2, C1-C4haloalkyl, —NH—C1-C4alkyl, —N(C1-C4alkyl)2, C1-C6alkoxy, or phenyl which for its part may be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C6alkylthio, C1-C6-alkylsulfinyl, C1-C6alkylsulfonyl, C1-C4alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4-alkyl), halogen, nitro, COOH or cyano; or R33 and R34 together form a C2-C6alkylene bridge; and

[0107] R35 is hydrogen, C1-C4alkyl, C1-C4alkoxycarbonyl or phenyl which for its part may be substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, amino, C1-C4alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4-alkylsulfinyl, C1-C4alkylsulfonyl, C1-C4alkyl-S(O)2O, C0-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalkylsulfonyl, C1-C4haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4-alkyl), halogen, nitro, COOH or cyano; or the group Q5, and also agronomically acceptable salts of these compounds, the other substituents being defined as under formula I in claim 1. Among the compounds of the formula lb, preference is furthermore given to those in which the group

[0108] —C(O)—Q is located in the 3 position on the pyridine ring, or in which Q is Q2, R23 being, in particular, hydroxyl, Y being a methylene bridge and m being the number 2. Preference is further given to compounds of the formula lb in which R is C1-C6alkyl or C1-C6haloalkyl.

[0109] Preferred compounds of the formula I are characterized in that the group —C(O)Q is in the ortho position to a group R. Preference is furthermore given to compounds of the formula I in which a group R is C1-C6haloalkyl and in the ortho position to the pyridyl nitrogen. Of particular interest are furthermore compounds of the formula I in which the group —C(O)Q is in the 3 position to the pyridyl nitrogen. In the formula 1, p is preferably the number 0. Also to be emphasized are compounds of the formula I in which m is 2 and R is C1-C3alkyl, C1-C3-haloalkyl, C1-C2alkoxymethyl, C1-C2alkythiomethyl, hydroxymethyl, C1-C6alky lcarbonyloxymethyl, benzoyloxymethyl, C1-C4alkoxycarbonyloxymethyl, chlorine, cyano, C1-C3alkoxy, C1-C3haloalkoxy, allyloxy, propargyloxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl, C1-C3alkylsulfonyloxy, C1-C2alkylsulfinylmethyl or C1-C2alkylsulfonylmethyl. A further group of preferred compounds of the formula I is formed by those compounds in which at least one group R is trifluoromethyl, difluorochloromethyl, pentafluoroethyl or heptafluoro-n-propyl.

[0110] Particularly noteworthy compounds of the formula I are those in which Q is a group Q1 and R16, R18 and R19 are C1-C3alkyl and R17 is hydrogen, or Q is a group Q2 and Y is —CH2—, —CH2CH2— or oxygen, A is —CH2— and R240, R241, R242 and R243 are Mch hydrogen, or Q is a group Q3 and R29 is C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl or C1-C4alkylaminocarbonyl or di(C1-C2-alkyl)aminocarbonyl, or Q is a group Q4 in which R33, R34 and R35 are C1-C3alkyl. In these noteworthy compounds of the formula I, R20, R23, R26 and R30 independently of one another are halogen, thiocyanato, C1-C12alkoxy, C1-C4alkoxycarbonyl-C1-C2alkoxy, C1-C12-alkylthio, alkylthio, C1-C12alkylsulfinyl, C1-C12alkylsulfonyl, C1-C12haloalkylthio, C1-C12haloalkylsulfinyl, C1-C12haloalkylsulfonyl, C1-C12alkenylthio, C2-C12alkenylsulfinyl, C2-C12alkenylsulfonyl, C2-C12-haloalkenylthio, C2-C12haloalkenylsulfinyl, C2-C12haloalkenylsulfonyl, C2-C12alkynylthio, C2-C12alkynylsulfinyl, C2-C12alkynylsulfonyl, C1-C4alkoxycarbonyl-C1-C2-alkylthio, C1-C4-alkoxycarbonyl-C1-C2alkylsulfinyl, C1-C4alkoxycarbonyl-C1-C2alkylsulfonyl, C1-C4alkyl-S(O)2NH, C1-C4haloalkyl-S(O)2NH, C1-C4alkyl-S(O)2O, C1-C18alkylcarbonyloxy, C2-C18-alkenylcarbonyloxy, C3-C6cycloalkylcarbonyloxy, C1-C12alkoxycarbonyloxy, C1-C12-alkylthiocarbonyloxy, C1-C12alkylthiocarbamoyl, C1-C6alkyl-NH(CS)N(C1-C6alkyl)-NH—, di-C1-C6alkyl-N(CS)N(C1-C6alkyl)-NH—, benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy or benzoyloxy, where the phenyl groups for their part may in each case be substituted by C1-C4alkyl, C1-C4-haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4-alkylamino, di-C1-C4alkylamino, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsuonyl, C1-C4-alkyl-S(O)2O, C1-C4haloalkylthio, C1-C4haloalkylsulfinyl, C1-C4haloalky lsulfonyl, C1-C4-haloalkyl-S(O)2O, C1-C4alkyl-S(O)2NH, C1-C4alkyl-S(O)2N(C1-C4alkyl), halogen, nitro or cyano, or R20, R23, R26 and R30 independently of one another are thienylcarbonyloxy or furylcarbonyloxy which for their part may be substituted by methyl or halogen, or are pyridylcarbonyloxy which for its part may be substituted as stated in claim 1, or R20 is R37R37N, R71R72NNH—, R21R22NC(O)O— or R73R74NC(O)NH—; or R23 is R44R45N, R75R76NNH—, R46R47NC(O)O— or R77R78NC(O)NH—; or R26 is R53R54N, R79R80NNH—, R55R56NC(O)O— or R81R82NC(O)NH—; or R30 is R62R63N, R83R84NNH—, R64R65NC(O)O— or R85R86NC(O)NH—. Very particularly preferably, R20, R23, R26 or R30 are hydroxyl or O−M+.

[0111] A further preferred group is formed by those compounds of the formula I in which Q is a group Q5, R36 is C1-C4alkyl, C1-C4haloalkyl or cyclopropyl and R01 is C1-C6alkyl, C1-C4-alkoxycarbonylmethyl, C3-C8alkenyl, is benzyl or phenyl substituted by methyl, halogen, trifluoromethyl, methoxy, and at least one group R is trifluoromethyl, difluorochloromethyl, pentafluoroethyl or heptafluoro-n-propyl located in the ortho position to the pyridyl nitrogen.

[0112] The process according to the invention for preparing compounds of the formula I

[0113] in which R and m are as defined under formula 1; p is 0 and Q is the group

[0114] is carried out analogous ly to known processes (for example those desc n ibed in WO 97/46530 and EP-A-0 353 187) and comp r ises

[0115] a) reacting a compound of the formula II

[0116] in which R and m are as defined under formula I and X is a leaving group, for example halogen, in an inert organic solvent in the presence of a base with compounds of the formula III, IV,V or VI

[0117] in which R16, R17, R18, R19,R29, R33, R34, R35, R240, R243, R242, R241, A and Y are as defined under formula I to give the compounds of the formula VII, VIII, IX or X

[0118] and then isomerizing these compounds, for example in the presence of a base and a catalytic amount of dimethylaminopyridine (DMAP) or a source of cyanide; or

[0119] b) reacting a compound of the formula Xi

[0120] in which R and m are as defined under formula I with compounds of the formula III, IV, V or VI

[0121] in which R16, R17, R18, R19, R29, R33, R34, R35, R240, R243, R242, R241, A and Y are as defined under formula I in an inert organic solvent in the presence of a base and a coupling agent to give a compound of the formula VII, VIII, IX or X

[0122] and then isomerizing these compounds, for example as described under route a).

[0123] Compounds of the formula I in which R20, R23, R26 and R30 are different from hydroxyl or halogen can be prepared by converesion methods which are generally known from the literature, for example acyclations or carbamoylations with appropriate acyl chlorides, from compounds in which R20, R23, R26 or R30 is hydroxyl in the presence of a suitable base, or they can be prepared by nucleophilic substitution reactions on chlorides of the formula I in which R20, R23, R26 or R30 is halogen, which are likewise obtainable by known processes by reaction with a chlorinating agent, such as phosgene, thionyl chloride or oxalyl chloride. Here, for example, suitably substituted amines, or hydroxylamines directly, or alkylsulfonamides, mercaptans, thiophenols, phenols, Ar1—NH2 or Ar1—SH, are employed in the presence of a base, for example 5-ethyl-2-methylpyridine, diisopropylethylamine, triethylamine, sodium bicarbonate, sodium acetate or potassium carbonate.

[0124] Compounds of the formula I in which R20, R23, R26 or R30 comprise thio groups can be oxidized analogously to known standard processes, for example using peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to give the corresponding su lfones and sulfoxides of the formula I. Here, the degree of oxidation at the sulfur atom (SO— or SO2—) can be controlled by the amount of oxidizing agent.

[0125] The process according to the invention for preparing compounds of the formula I in which R and m are as defined under formula I and Q is a group

[0126] in which Z is sulfur, q is 0 and R36 and R01 are as defined under formula I is carried out analogously to known processes (for example those described in WO 97/43270) and comprises converting a compound of the formula XII

[0127] in which R36, R and m are as defined under formula I in the presence of a base, carbon disulfide and an alkylating agent of the formula XIII

R01—X1 (XIII),

[0128] in which R01 is as defined under formula I and X1 is a leaving group, for example halogen or sulfonate, into the compound of the formula XIV

[0129] in which Z is sulfur and R, R01, R36 and m are as defined above and then cyclizing this compound using hydroxylamine hydrochloride, in the presence or absence of a solvent, in the presence of a base to give the compounds of the formulae

[0130] in which Z is sulfur and R, R36, R01 and m are as defined above, and then oxidizing these compounds with an oxidizing agent, for example meta-chloroperbenzoic acid (m-CPBA). The isomers of the formulae le and If can be separated using column chromatography and a suitable mobile phase and then purified.

[0131] The preparation of the compounds of the formula I in which p is 0 is illustrated in more detail in the reaction schemes 1 and 2 below.

[0132] According to this reaction scheme, the compounds of the formula I with the group Q1 in which R20 is hydroxyl, the compounds of the formula I with the group Q2 in which R23 is hydroxyl, the compounds of the formula I with the group Q3 in which R26 is hydroxyl and the compounds of the formula I with the group Q4 in which R30 is hydroxyl can preferably be prepared.

[0133] For preparing the compounds of the formula I in which Q is the groups Q1 to Q4 and R20, R23,R26 and R30 are hydroxyl, in accordance with reaction scheme 1, route a), the carboxylic acid derivatives of the formula II in which X is a leaving group, for example halogen, for example iodine, bromine and in particular chlorine, N-oxyphthali r nide or N,O— dimethylhydroxylamino or part of an activated ester, for example

[0134] (formed from dicyclohexylcarbodiimide (DCC) and the corresponding carboxylic acid) or

[0135] (formed from N-ethyl-N′-(3-dimethyiaminopropyl)carbodiimide (EDC) and the corresponding carboxylic acid) are employed. These compounds are reacted in an inert organic solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, and in the presence of a base, for example an alkylamine, for example triethylamine, an aromatic amine, for example pyridine or 4-dimethyiaminopyridine (DMAP), with the dione derivatives of the formula III, IV, V or VI to give the isomeric enol ethers of the formulae Vl I, Vil, IX and X. This esterification is carried out at temperatures of from 0° C. to 110° C.

[0136] The isomerization of the ester derivatives of the formulae VII, VIII, IX and X to the dione derivatives of the formula I (in which R20, R23, R26 and R30 are hydroxyl) can be carried out, for example, analogously to EP 369 803 in the presence of a base, for example an alkylamine, for example triethylamine, a carbonate, for example potassium carbonate, and a catalytic amount of DMAP or a cyanide source, for example acetone cyanohydrin or potassium cyanide.

[0137] According to reaction scheme 1, route b), the desired diones of the formula I (in which R20, R23, R26 and R30 are hydroxyl) can be obtained, for example, in analogy to Chem. Lett. 1975, 1045 by esterifying the carboxylic acids of the formula Xl with the dione derivatives of the formula III, IV, V or VI in an inert solvent, for example a halogenated hydrocarbon, for example dichloromethane, a nitrile, for example acetonitrile, or an aromatic hydrocarbon, for example toluene, in the presence of a base, for example an alkylamine, for example triethylamine, and a coupling agent, for example 2-chloro-1-methylpyridinium iodide. Depending on the solvent used, this esterification is carried out at temperatures of from 0° C. to 110° C., affording initially, as described under route a), the isomeric ester of the formula I which can be isomerized as described under route a), for example in the presence of a base and a catalytic amount of DMAP, or a cyanide source, to give the desired dione derivative of the formula I (R20, R23, R26 and R30 are hydroxyl).

[0138] The preparation of the compounds of the formula I in which Q is the group Q5 can be carried out in accordance with reaction scheme 2 by reacting the β-diketone derivative of the formula XII, for example in analogy to Synthesis 1991, 301; ibid. 1988, 793; or Tetrahedron 32, 3055 (1976) with carbon disulfide in the presence of a base, for example a carbonate, for example potassium carbonate, a metal hydride, for example sodium hydride, or potassium fluoride on aluminium, and an alkylating agent of the formula XIII in which X1 is a leaving group, for example halogen, for example iodine, bromine and in particular chlorine,

[0139] This reaction is preferably carried out in the presence of a solvent, for example an amide, for example N,N-dimethylformamide (DMF), a sulfoxide, for example dimethylsulfoxide (DMSO), or a nit rle, for example acetonitrile. The ketene thioacetal of the formula XIV which is formed is cyclized with the aid of hydroxylamine hydrochloride in the presence of a base, for example sodium acetate, in a solvent, for example an alcohol, for example ethanol, or an ether, for example tetrahydrofuran, to give the compound of the formula le in which Z is sulfur. This cyclization reaction is carried out at temperatures of from 0° C. to 100° C. If appropriate, compounds of the formulae le and If (Z is sulfur) can be oxidized analogously to known standard processes, for example with peracids, for example meta-chloroperbenzoic acid (m-CPBA) or peracetic acid, to give the corresponding sulfones and sulfoxides of the formulae Ie and If (Z═SO— or SO2—). Here, the degree of oxidation at the sulfur atom (Z═SO— or SO2—) can be controlled by the amount of oxidizing agent.

[0140] Oxidations to the compounds of the formulae le and If (Z is SO— or SO2—) are carried out as described, for example, in H.O. House, “Modern Synthetic Reactions” W. A. Benjamin, Inc., Menlo Park, Calif., 1972, pages 334-335 and 353-354.

[0141] The activated carboxylic acid derivatives of the formula II in reaction scheme 1 (route a) in which X is a leaving group, for example halogen, for example bromine, iodine or in particular chlorine, can be prepared by known standard processes, as described, for example, in C. Ferri “Reaktionen der organischen Synthese” [Reactions of Organic Synthesis], Georg Thieme Verlag, Stuttgart, 1978, page 461 ff. T his is shown in reaction scheme 3 below.

[0142] According to reaction scheme 3, the compounds of the formula II (X=Ieaving group) or II (X=halogen) are prepared, for example, by employing a halogenating agent, for example a thionyl halide, for example thionyl chloride or thionyl bromide; a phosphorus halide or phosphorus oxyhalide, for example phosphorus pentachloride or phosphorus oxychloride or phosphorus pentabromide or phosphoryl bromide; or an oxalyl halide, for example oxalyl chloride, or by employing a reagent for the formation of activated esters, for example N,N′-dicyclohexylcarbodiimide (DCC) or N-ethyl-N′-(3-dimethylaminopropyli)carbodiimide (EDC) of the formula X. For the compound of the formula X used as halogenating agents, X is a leaving group, for example halogen, for example fluorine, bromine or iodine and in particular chlorine, and W1 is, for example, PCI2, SOCI, SOBr or CICOCO. The reaction is carried out in the presence or absence of an inert organic solvent, for example in aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbons, for example n-hexane, benzene, toluene, xylenes, dichloromethane, 1,2-dichloroethane or chiorobenzene, at reaction temperatures in the range of from −20° C. to the reflux temperature of the reaction mixture, preferably at 40-150° C., and in the presence of a catalytic amount of N,N-dimethylformamide. Such reactions are generally known and described in the literature in various variations with respect to the leaving group X.

[0143] The compounds of the formulae III, IV, V and VI are known and can be prepared analogously to the methods described, for example, in WO 92/07837, DE-A-3818958, EP-A-0 338 992 and DE-A-3902818.

[0144] The compounds of the formula XII in reaction scheme 2 can be obtained by standard processes, for example from the corresponding compounds of the formula II

[0145] in which R and m are as defined above and X is a leaving group, for example halogen, for example via Claisen condensation, or from the compounds of the formula II by reaction with a ketocarboxylic acid salt of the formula XV

[0146] in which R36 is as defined under formula I and M+ is an alkali metal ion (cf., for example, WO 96/26192).

[0147] The compounds of the formulae II and XI are known and can be prepared analogously to the methods described, for example, in WO 97146530, EP-A-0 353 187, Heterocycles, 48, 779 (1998), Heterocycles, 46, 129 (1997), or Tetrahedron Letters, 1749 (1998).

[0148] For preparing all other compounds of the formula I functionalized according to the definition of (R)m, there is a large number of known standard processes available, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, and the choice of the suitable preparation processes depends on the properties (reactivities) of the substituents in the intermediates in question.

[0149] All further compounds originating from the scope of the formula I can be prepared in a simple manner, taking into account the chemical properties of the pyridyl or Q moiety.

[0150] The end products of the formula I can be isolated in a customary manner by concentration or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are only sparingly soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable mobile phase.

[0151] Furthermore, it is known to the person skilled in the art in which order certain reactions have to be carried out advantageously to avoid possible side reactions. Unless a targeted synthesis is carried out for isolating pure isomers, the product may be obtained as a mixture of two or more isomers. The isomers can be separated by methods known per se.

[0152] Compounds of the formula I in which p is 1, i.e. the corresponding N-oxides of the formula I, can be prepared by reacting a compound of the formula I in which p is 0 with a suitable oxidizing agent, for example with the H2O2 urea adduct, in the presence of an acid anhydride, for example trifluoroacetic anhydride. This reaction sequence is demonstrated using the example of group Q2 below:

[0153] Compounds of the formula I in which R in the ortho position to the pyridine nitrogen is 1 -chloro-C1-C2alkyl, 1-hydroxy-C1-C2alkyl, 1-(C1-C6alkylcarbonyloxy)-C1-C2alkyl, 1 -benzoyloxy-C1-C2alkyl, 1-(C1-C4alkoxycarbonyloxy)-C1-C2alkyl, 1-(C1-C4alkylthio)-C1-C2alkyl, 1-(C1-C4-alkylsulfinyl)-C1-C2alkyl, 1-(C I-C4alkylsultonyl)-C1-C2alkyl, 1-thiocyanato-C1-C2alkyl, 1-cyano-C1-C2alkyl, can also be prepared, for example, by heating an N-oxide of the formula I under known reaction conditions, for example in the presence of tosyl chloride (see, for example, Parham, W. E.; Sloan, K. B.; Reddy, K. R.; Olson, P. E.; J Org Chem 1973, 38, 927) or in the presence of an acid anhydride (see, for example, Konno, K.; Hashimoto, K.; Shirahama, H.; Matsumoto, T.; Heterocycles 1986, 24, 2169), followed, if appropriate, by subsequent conversion.

[0154] The compounds of the formula XXIIa are synthesized analogously to known processes, for example those mentioned in Heterocycles, 46, 129 (1997) or Helvetica Chimica Acta 71, 596 (1988), and comprises either

[0155] a) acylating a compound of the formula XVI

[0156] in which R301 is hydrogen or C1-C6alkyl;

[0157] R401 is hydrogen, C1-C6alkyl C2-C6alkenyl, C3-C6cycloalkyl, C1-C6alkoxy, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkyl, 1-(C1-C6alkylcarbonyloxy)-C1-C6alkyl, 1-(C1-C6alkylthio)-C1-C6-alkyl, 1-(C1-C6alkylsulfinyl)-C1-C6alkyl, 1-(C1-C6alkylsulfonyl)-C1-C6alkyl, 1-thiocyanato-C1-C6-alkyl, 1-cyano-C1-C6alkyl, phenyl, where the phenyl groups may be mono- or polysubstituted by halogen, methyl, ethyl, trifluoromethyl, methoxy or nitro, or is a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is either attached directly or via a C1-C4alkylene group to the double bond, and each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms and the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxya lkyithio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R87, NR88R89, halogen, cyano, nitro, phenyi and benzylthio, where pheny l and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3-haloalkoxy, halogen, cyano or nitro and where substituents on nitrogen in the heterocyclic ring are different from halogen;

[0158] R87 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0159] R88 is hydrogen or C1-C6alkyl and

[0160] R89 is C1-C6alkyl or C1-C6alkoxy;

[0161] with a compound of the formula XVII

[0162] in which R501 is C1-C6haloalkyl and X2 is O(CO)R501 or halogen to give the compound of the formula XVIII

[0163] in which R301, R401, R501, and R14 are as defined above, in the presence of a base, for example an aromatic amine, for example pyridine, and subsequently replacing the alkoxy group by the amino group using ammonia in an organic solvent, for example a halogenated hydrocarbon, for example dichloromethane, or a nitrile, for example acetonitrile. The resulting compound of the formula XIX

[0164] is subsequently condensed with a compound of the formula XX

[0165] in which R201 is C1-C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6-haloalkynyl, C3-C6cycloalkyl, C1-C6haloalkyl, 1-(C1-C6alkylcarbonyloxy)-C1-C6alkyl, 1-(C1-C6alkylthio)-C1-C6alkyl, 1-(C1-C6alkylsulfinyl)-C1-C6alkyl, 1-(C1-C6alkylsulfonyl)C1-C6alkyl, 1-thiocyanato-C1-C6alkyl, 1-cyano-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsu ffonyl, benzyithio, benzylsulfinyl or benzylsulfonyl, where the phenyl gro y )ps may be mono- or polysubstituted at least by halogen, methyl, ethyl, trifluoromethyl, methoxy or nitro, or is a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, where the ring system is attached either directly or via a C1-C4-alkylene group and each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6a lkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalky lsulfinyl, C1-C6alkylsu lfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3-R90, NR91R92, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3-haloalkoxy, halogen, cyano or nitro, and where substituents on nitrogen in the heterocyclic ring are different from halogen;

[0166] R90 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsuffinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3-alkyl, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0167] R91 is hydrogen or C1-C6alkyl and

[0168] R92 is C1-C6alkyl or C1-C6alkoxy and

[0169] R14 is as defined above, and the resulting compound of the formula XXIa

[0170] is subsequently hydrolysed to give the compound of the formula XXIIa

[0171] in which R201, R301, R401, and R501 are as defined above, or

[0172] b) condensing a compound of the formula XXIII

[0173] in which R14 is as defined above with a compound of the formula XXIV

[0174] and chlorinating the resulting compound of the formula XXV

[0175] in which R301, R401 and R501 are as defined above and R14 is C1-C4alkyl to give compounds of the formula XXVI

[0176] in which R301, R401, R501 and R14 are as defined above (using, for example, POCI3), and subsequently reacting this compound with a nucleophile of the formula XXVII

Z—R150 (XXVII)

[0177] In which Z is SH, OH or amino and R150 is C1-C6alkyl, C3-C6alkeny4 C3-C6halogenalkenyl, C3C6alkynyl, C3-C6haloalkynyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, phenyl, benzyl, where the phenyl and benzyl groups for their part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, is C1-C1alkoxy-C1-C4alkyl or C1-C4-alkylthio-C1-C4alkyl, C1-C4alkylsulfinyl-C1-C4alkyl, C1-C4alkylsulfonyl-C1-C4alkyl, or a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and the ring system for its part may be mono-, di- or trisubstituted by C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6-alkynyl, C3-C6haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6-alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4-cyanoalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6-haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3-alkylene-R93, NR94R95, halogen, cyano, nitro, phenyl and benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3-haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro, and where substituents on nitrogen in the heterocyclic ring are different from halogen;

[0178] R93 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0179] R94 is hydrogen or C1-C6alkyl and

[0180] R95 is C1-C6alkyl or C1-C6alkoxy;

[0181] in the presence of a base to give compounds of the formula XXIb

[0182] in which R14, R150, R301, R401, and R501 are as defined above, and subsequen tly hydrolysing the resulting compound to give the compound of the formula XXIIb

[0183] in which R150, R301, R401 and R501 are as defined.

[0184] Compounds of the formula XXIb in which R l w is fluorine are prepared by reacting a compound of the formula XXVI in the presence of a polar aprotic solvent, for example acetonitrile, dimethylformamide or sulfolane, with potassium fluoride in the presence or absence of a catalytic amount of 18-crown-6. Compounds of the formula XXIc in which R150 is hydrogen are preparerd by reducing the chlorine group in the formula XXVI, for example using hydrogen in the presence of a suitable metal catalyst or using ammonium formate in a suitable solvent. The preparation of the compounds of the formula XXIIa, or XXIIb and XXIIc is illustrated in more detail in the reaction schemes 4 and 5 below.

[0185] For preparing all other compounds of the formula I which are functionalized according to the definition of R201 (R150) to R501, a large number of known standard processes is suitable, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of the suitable preparation processes depending on the properties (reactivities) of the substituents in the intermediates in question.

[0186] The novel compounds of the formula l ib in which Rf is trifluoromethyl, difluorochloromethyl, pentafluoroethyl, heptafluoro-n-propyl or trichloromethyl, RX1 is C1-C6alkyl and Q and R are as defined under formula I can be prepared by generally known processes via 3-alkoxycarbonyl-4-perhaloalkylpyridine N-oxides of the formula XXVIII according to reaction scheme 5 by preparing, using suitable chlorination conditions and separation processes, the 6-chloro-4-haloalkyl-3-nicotinic esters of the formula XXX and then converting these compounds with a nucleophile of the formula XXXI

Z01—R151 tm (XXXI)

[0187] in which Z07 is SH, hydroxyl, halogen or amino and R151 is hydrogen, C1-C6aIkyl, C3-C6-alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, halogen, C3-C6haloalkynyl, C1-C6alkylsulfonyl, C1-C6-haloalkyl, phenyl, benzyl, where the phenyl and benzyl groups for their part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C ,-C3haloalkoxy, halogen, cyano or nitro, is C1-C4alkoxy-C1-C4alkyl or C1-C ~alkylthio-C1-C4alkyl , Ct-C4alkylsulfinyl-C1-C4alkyl, C1-C4alkylsulfonyl-C1-C4alkyl, or a five- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and may contain 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and each ring system may not contain more than 2 oxygen atoms and not more than two sulfur atoms, and the ring system for its part may be mono-, di- or trisubstituted by

[0188] C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6-haloalkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C a-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C0C4cyanoalkylthio, Cl-C6-alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4dialkylaminosulfonyl, C1-C3alkylene-R96, NR97R98, halogen, cyano, nitro, phenyl or benzylthio, where phenyl and benzylthio for their part may be substituted on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3-haloalkoxy, halogen, cyano or nitro,

[0189] R96 is C1-C3alkoxy, C2-C4alkoxycarbonyl, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or phenyl, where phenyl for its part may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3-alkoxy, C1-C3haloalkoxy, halogen, cyano or nitro;

[0190] R97 is hydrogen or C1-C6alkyl and

[0191] R98 is C1-C6alkyl or C1-C6alkoxy;

[0192] and where substituents on nitrogen in the heterocyclic ring are different from halogen, using reaction processses which are generally known to the person skilled in the art, into the 6-substituted 4-perhaloalkylnicotinic acids of the formula XXXII and their subsequent products of the formulae lIb and lb as described in reaction scheme 1. This is shown in reaction scheme 6 below.

[0193] According to this reaction scheme, it is preferably possible to prepare the compounds of the formula I with the group Q1 in which R20 is hydroxyl, the compounds of the formula I with the group 02 in which R23 is hydroxyl, the compounds of the formula I with the group Q3 in which R26 is hydroxyl and the compounds of the formula I with the group Q4 in which R30 is hydroxyl.

[0194] 6-substituted 2-haloalkylnicotinic acid compounds of the formula Ic can be prepared, for example, from the corresponding 2-haloalkyl-3-alkoxycarbonyl-2-pyridines XXXIII in which Rf is trifluoromethyl, difluorochloromethyl, pentafluoroethyl, heptafluoro-n-propyl or trichioromethyl and R1x is C1-C6alkyl and R is as defined under formula I, by hydrolysis into the corresponding carboxylic acids and their subsequent activation, for example by conversion into an acylhalide (IIc). (Reaction scheme 7).

[0195] thier precursors of the formulae XXXIIIa, XXXIIIb, XXXIIIc, XXXIIId, XXXIIIe, XXXIIIf, XXXIIIg and XXXIIIh are likewise accessible by conversion processes known to the person skilled in the art (reaction shceme 7). 2-Trifluoromethyl-3-ethoxycarbonyl-2-pyridone (formula XXXIIIa in which R is hydrogen, R1X is ethyl and Rf is trifluoromethyl) in particular is known form Org. Process Research & Developmnet, 1, 370 (1997).

[0196] Intermediates of the formulae XXXIIIa to XXXIIIh can be obtained by reacting, for example for preparing a 6-halo derivative of the formula XXXIIId, a pyridone of the formula XXXIIIa (preparation according to Org. Process Research & Development, 1, 370 (1997) or scheme 8) with a halogenating agent, for example phosphorus oxychloride, phosphorus oxybromide or phenyl dichlorophosphate, in the presence or absence of added base, such as a dialkylaniline, in the presence or absence of solvent, if desired in a pressure vessel, at temperatures between 0 and 220° C. (preferably 60-200° C.). It is known to the person skilled in the art how to convert chloro derivatives by nucleophilic substitution, for example using an alkali metal iodide in an inert solvent into the corresponding iodides, or using gaseous hydrobromic acid in lower carboxylic acids, for example conc. acetic acid, into the corresponding bromo derivatives (for example according to U.S. Pat. No. 3,974,166) or using alkali metal fluoride in a dipolar solvent, such as sulfolane, into the corresponding fluoro derivatives.

[0197] The compound of the formula XXXIIIe can be prepared by reacting a halo derivative of the formula XXXIIId obtained as described above with an alcohol of the formula R151—OH in the presence of a base, such as sodium hydride, or an alkali metal oxide or carbonate, or directly with an alkali metal alkoxide, in an inert solvent such as dimethylformamide or in an excess of the alcohol of the formula R151—OH which corresponds to the group to be introduced, at temperatures between −5 and 160° C., or by reacting, to prepare a corresponding 6-thioether of the formula XXXIIIc, analogously to what was described above, either the halide of the formula XXXIIId with a thiol of the formula R151—SH in the presence of a base such as sodium hydride or with an alkali metal salt of a thiol in an inert solvent at −10-150° C., or by preparing, starting from a pyridone XXXIIIa and using a thionating agent, for example Lawesson's reagent, in an inert solvent, such as toluene or acetonitrile, a pyrithione of the formula XXXIIIb and alkylating this with an alkylating agent R r1,-X, where X is a leaving group, such as halide (Cl, Br, I) or ROSO3— or RSO2—, at 20-120° C. in an inert solvent, such as tetrahydrofuran, to give the thioether of the formula XXXIIIc, or, to prepare the corresponding sulfinyl or su lfonyl derivative of the formula XXXIIIf, reacting with an oxidizing agent, such as m-chloroperbenzoic acid or sodium periodate, or sodium perborate, under temperature control known to the person skilled in the art, depending on the degree of oxidation (for example −30° C.-+50° C. for m01=1 or −20° C.-+100° C. for m01=2) in an inert solvent, such as dichloromethane, to give XXXIIIf, or, to prepare 6-alkyl derivatives XXXIIIg according to the invention, reacting a sulfone of the formula XXXlif (m01=2) or a halo derivative of the formula XXXIIId in the presence or absence of a Pd(O) catalyst such as Pd(PPh3)2Cl2 with a tetra-C1-C6alkyltin or with a Grignard reagent C1-C6alkyl-MgHal at temperatures between −10° and 180° C., for example analogously to Synlett 1998 (1185), or as described in Organocopper Reagents, R. J. K. Taylor, Oxford University Press 1994, or in Transition Metals in Organic Synthesis, S. Gibson, Oxford Univ. Press,1997, or in Org. React. 50, 1 (Stille reaction), or, to prepare 6-cyano derivatives of the formula XXXIIIh, reacting a halide of the formula XXXIIId or a sulfone of the formula XXXIIIf (m01=2) with an alkali metal or tetraalkylammonium cyanide or copper cyanide in an inert solvent, such as dichloromethane, tetrahydrofuran or dimethylformamide, at temperatures between 0° C. and 220° C.

[0198] Some of the compounds of the formula XXXIIIe are also obtainable from the pyridone of the formula XXXIIIa by reacting them analogously to Org. React. 42, 2 with an alcohol R151OH in the presence of an azodicarboxylic ester (for example diethyl ester) and triphenylphosphine in an inert solvent, such as tetrahydrofuran or dioxane. (Scheme 9)

[0199] The intermediates of the formula XXXIIIa required in reaction scheme 8 as starting materials are obtainable according to Scheme 10 route A or route B (Org. Process Research & Development, 1, 370 (1997)) or route C.

[0200] Intermediates of the formula XXXIIIa are obtainable by route A by reacting, to prepare the 3,4-dihydro-5-alkoxycarbonyl-6-haloalkylpyridin-2-ones of the formula XXXVIII, an enamine of the formula XXXV in the presence or, preferably, in the absence of a solvent either in an excess of enamine or in the presence of a base, such as a tert-amine, with an acryloyl chloride of the formula XXXIV at temperatures between −10° and +200° C., or by reacting a keto ester of the formula XXXVII with an acrylamide of the formula XXXVI in the presence of a catalyst such as p-toluenesulfonic acid (=HOTs) in an inert solvent, such as toluene, at temperatures between 30 and 200° C., with removal of the water of reaction formed (for example azeotropic distillation), or by reacting a keto ester of the formula XXXVII in the presence of a base, such as an alkali metal alkoxide or magnesium alkoxide, with a 4-haloketo ester of the formula XXXIX in an inert solvent, such as ethanol, at 0-180° C. to give the intermediate of the formula XXXX, converting this with ammonia or an ammonium salt, such as ammonium acetate, or with a bis-silylamine such as hexamethyldisilazane, in the presence or absence of an acidic catalyst, such as sulfuric acid or p-toluenesulfonic acid or an organic carboxylic acid (for example conc. acetic acid), in an inert solvent and at temperatures between 0° and 180° C. into the corresponding enamine of the formula XXXXI, subsequently cyclizing in the presence of a catalyst, such as p-toluenesulfonic acid or sulfuric acid, if desired with continuous removal of the water of reaction formed in an inert solvent, such as toluene, to give the dihydropyridone of the formula XXXVIII, and finally treating with an oxidizing agent, such as manganese dioxide, in an inert solvent, such as chlorobenzene, at temperatures between 50 and 250° C., to prepare the pyridones XXXIIIa.

[0201] The intermediates of the formula IIa

[0202] in which Qa is hydroxyl, halogen, cyano, or a group —CH2(CO)R36 or

[0203] Rb is hydrogen, C1-C4alkyl or halogen;

[0204] R1 is trifluoromethyl, difluorochloromethyl, pentafluoroethyl, heptafluoro-n-propyl or trichloromethyl;

[0205] Ra is C1-C3alkyl, C1-C3haloalkyl, C3-C4cycloalkyl, C1-C2alkoxy-C1-C4alkyl, C1-C2-alkylthiomethyl, hydroxyl, halogen, cyano, C1-C3alkoxy, C1-C3haloalkoxy, allyloxy, propargyioxy, C1-C3alkylthio, C1-C3alkylsulfinyl, C1-C3alkylsulfonyl or C1-C3alkylsulfonyloxy, and R01 and R36 are as defined under group O5 of the formula 1, except for the compounds 2,6-bistrifluoromethyinicotinic acid, 2,6-bistrifluoromethyl-5-methoxynicotinic acid and 2-hydroxy-6-trifluoromethyinicotinic acid, are novel and therefore likewise form part of the subject matter of the present invention.

[0206] Compounds of the formula IIb

[0207] in which Qb is hydroxyl, halogen, cyano or a group —CH2(CO)R99 or

[0208] R99 is C1-C4alkyl, C1-C4haloalkyl, C3C4cycloalkyl or C1-C4alkoxy;

[0209] Rf is trifluoromethyl, difluorochloromethyl, pentafluoroethyl or heptafluoro-n-propyl; and

[0210] Rc is C1-C3alkyl, C1-C3haloalkyl, C1-C2alkoxymethyl, C1-C1alkylthiomethyl, hydroxyl, halogen, cyano, C1-C3alkoxy, C1-C3haloalkoxy, allyloxy, propargyloxy, C1-C3alkylthio, C1-C3-alkylsulfinyl, C1-C3alkylsulfonyl or C1-C3alkylsulfonyloxy and R01 is as defined under formula I are novel and therefore likewise form part of the subject matter of the present invention.

[0211] Preferred compounds of the formula Ila correspond to the formula Ia

[0212] in which Qa is hydroxyl, halogen , cyano or a group —CH2(C1)R36 or

[0213] R01 and R36 are as defined in claim 1 and Ra is C1-C3alkyl.

[0214] The compounds of the formula I or compositions comprising them can be used according to the invention in all the application methods customary in agriculture, for example pre-emergence application, postemergence application and seed dressing, and various methods and techniques, for example controlled release of active compounds. To this end, the active compound is absorbed in solution onto mineral granule carriers or polymerized granules (urea/formaldehyde) and dried. If appropriate, a coating which allows the active compound to be released in metered form over a certain period of time can additionally be applied (coated granules).

[0215] The compounds of the formula I can be employed as herbicides in unchanged form, i.e. as they are obtained in the synthesis, but they are preferably processed in a customary manner with the auxiliaries conventionally used in the art of formulation, for example to give emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485 on pages 9 to 13. The methods of application, such as spraying, atomizing, dusting, wetting, scattering or watering, in the same way as the nature of the compositions, are chosen according to the aims striven for and the given circumstances.

[0216] The formulations, i.e. the compositions, formulations or preparations comprising the active compound of the formula I or at least one active compound of the formula I and as a rule one or more solid or liquid formulation auxiliaries, are prepared in a known manner, for example by intimate mixing and/or grinding of the active compounds with the formulation auxiliaries, for example solvents or solid carriers. Surface-active compounds (surfactants) can furthermore additionally be used during the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485 on page 6. Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.

[0217] Examples of suitable anionic, nonionic and cationic surfactants are listed, for example, in WO 97/34485 on pages 7 and 8.

[0218] The surfactants conventionally used in the art of formulation and which are suitable to prepare the herbicidal compositions according to the invention are described, inter alia, in “Mc Cutcheon's Detergents and Emulsifiers Annual”, MC Publishing Corp., Ridgewood N.J., 1981, Stache, H., “Tensid-Taschenbuch” [Surfactant handbook], Carl Hanser Verag, Munich/Vienna, 1981 and M. and J. Ash, “Encyclopedia of Surfactants”, Vol I-III, Chemical Publishing Co., New York, 1980-81.

[0219] The herbicidal formulations as a rule comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant. While concentrated compositions are rather preferred as commercial goods, the end user as a rule uses dilute compositions. The compositions can also comprise further additives, such as stabilizers, for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active compounds.

[0220] The active compounds of the formula I are as a rule applied to the plants or their habitat, at application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg tha. The dosage required for the desired effect can be determined by tests. It depends on the nature of the effect, the development stage of the crop plant and the weed and on the application (location, time, process) and can, as a function of these parameters, vary within wide ranges.

[0221] The compounds of the formula I have herbicidal and growth-inhibiting properties, owing to which they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugar beet, sugar cane, plantings, rapeseed, maize and rice, and for the non-selective control of weeds. Crops include those which have been rendered tolerant towards herbicides or herbicide classes by conventional breeding methods or genetical engineering methods. The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria,Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

[0222] The examples below illustrate the invention in more detail, without limiting it.

PREPARATION EXAMPLES

Example H1

PreParation of 2-difluoromethoxy-6-trifluoromethylnicotinic acid

[0223] At 70° C., 25 g (0.106 mol ) of (3-(ethoxycarbonyl)-6-trifluoromethyl)pyrid-2-one (Helv. Chim. Acta (1988), 71(3), 596 601) in a mixture of 50 ml of dimethylformamide and 20 ml of water are treated, in the presence of 16 g (0.116 mol) of finely powdered potassium carbonate and with efficient stirring, with a continuous stream of gaseous Freon-22. After 6 hours, a further 16 g of potassium carbonate and 20 ml of dimethyl sulfoxide are added, and the mixture is stirred with continuous introduction of Freon-22 gas at a temperature of 100° C for another 4 hours. The mixture is then treated with water and ice and extracted with diethyl ether. The aqueous phase is adjusted to pH 2 using conc. HCl and extracted with ethyl acetate. Diethyl ether is added to the extract, and some (3-(carboxy)-6-trifluoromethyl)pyrid-2-one crystals which have precipitated out are removed by filtration. The filtrate is filtered through a silica gel column (mobile phase ethyl acetate/hexane 1:1) giving, as a crystalline product, pure 2-difluoromethoxy-6-trifluoromethylnicotinic acid: 1H NMR (CDCl3, ppm): 8.60, d, J=9 Hz, 1H; 7.62, d, J=9 Hz, 1H; 7.62, t, J=67 Hz, 1H.

Example H2

Preparation of 4-methyl-6-trifluoromethylnicotinic Acid

[0224] In the presence of 5.8 ml of phenyl dichlorophosphate, 7.5 g (0.03 mol) of ((3-ethoxycarbonyl)-4-methyl-6-trifluoromethyl)pyrid-2-one (Helv. Chim. Acta (1988), 71 (3), 596-601) are heated in a pressure vessel at a temperature of 170° C. for 3 hours. The cold reaction solution is filtered directly through a short silica gel column (mobile phase: ethyl acetate/hexane 1:9), giving, as an oily product, ethyl 2-chloro-4-methyl-6-trifluoromethylpyridin-3-ylcarboxylate:

[0225]

1
H NMR (CDCl3, ppm): 7.49, s, 1H; 4.48, q, 2H; 2.43, s, 3H, 1.43, t, 3H.

[0226] 3.0 g (16.8 mmol) of the above product and, in 2 portions, a total of 5 g of ammonium formate are added to a suspension of 0.55 g of 10% Pd/C in 20 ml of methanol, and the mixture is stirred at room temperature for 24 hours. The reaction mixture is then filtered through Celite and, after addition of sodium chloride solution, extracted with ethyl acetate. Chromatographic purification (mobile phase 1:9) gives the 4-methyl-6-trifluoromethylpyridin-3-yl ethyl ester as an oil: 1H NMR (CDCl3, ppm): 9.11, s, 1H; 7.56, s, 1H, 4.44, q, 2H; 2.72, s, 3H, 1.42, t, 3H. This is hydrolysed at 40° C. in the presence of aqueous potassium hydroxide solution in dioxane. Extraction with ethyl acetate gives, after acidification to pH 2.7, 4-methyl-6-trifluoromethyinicotinic acid as a crystalline product: 1H NMR (CDCl3, ppm): 7.49, s, 1H; 4.48, q, 2H; 2.43, s, 3H, 1.43, t, 3H; 9.32, s, 1 H, 7.62, s, 1 H, 2.79, s, 3H.

Example H3

Preparation of 6-chloro-4-trifluoromethylnicotinic Acid

[0227] 9.6 g (0.047 mol) of methyl 4-trifluoromethylpyridin-3-ylcarboxylate, dissolved in 50 ml of dichloromethane, are treated with 30% hydrogen peroxide/urea adduct and 17 ml of trifluoroacetic anhydride. The reaction solution is stirred at temperature of 20° C. for 20 hours and then washed once each with dilute sodium hydroxide solution and half-saturated sodium chloride solution. The product obtained is 3-methoxycarbonyl4-trifluoromethyl-3-pyridine N-oxide; 1H NMR (CDCl3, ppm): 8.55, s, 1H; 8.31, d, 1H; 7.6, d, 1H; 3.98, s, 3H. 4.85 g (0.022 mol) of the above product are then added to a mixture of 5 ml of phosphorus oxychloride and 4.3 ml of ethyidiisopropylamine in 15 ml of 1,2dichloroethane, and the mixture is heated to a temperature of 60° C. After about 2 hours, another 2 ml of phosphorus oxychloride and 2.8 ml of ethyidiisopropylamine are added, and the mixture is stirred at this temperature for 20 hours. The reaction mixture is subsequently added to ice-water, adjusted to pH 3 using 30% NaOH and then extracted with dich ioromethane. Filtration through a little silica gel gives an approximately 5:1 product mixture of the two 6-chloro- and 2-chloro-4-trifluoromethylpyridin-3-yl methyl esters, which can be separated by HPLC into the pure components. Thus, pure methyl 6-chloro-4-trifluoromethylpyridin-3-ylcarboxylate is obtained as the main product; 1H NMR (CDCl3, ppm): 8.91, s, 1H; 7.68, s, 1H; 3.98, s, 3H, and pure methyl 2-chloro-4-trifluoromethylpyridin-3-ylcarboxylate is obtained as the byproduct; 1H NMR (CDCl3, ppm): 8.64, d, 1H; 7.52, d, 1H; 4.01, s, 3H. In the presence of 0.073 g of potassium hydroxide, 0.22 g of pure methyl 6-chloro-4-trifluoromethylpyridin-3-ylcarboxylate are hydrolysed at room temperature in a 1:1 mixture of 6 ml of dioxane/water. Recrystallization gives the pure 6-chloro-4-trifluoromethyinicotinic acid: m.p. 115-117° C.; 1H NMR (CDCl3, ppm): 9.12, s, 1H; 7.24, s, 1H.

Example H4

Preparation of 6-methylthio-4-trifluoromethyinicotinic Acid

[0228] In boiling acetone, 0.70 g (2.9 mol) of methyl 6-chloro-4-trifluoromethylpyridin-3-ylcarboxylate is treated in the presence of a catalytic amount of 18-crown-6 with methanethiolate (0.33 g) until no further conversion can be detected by gas chromatographic analysis. The mixture is then filtered through silica gel and evaporated. This gives 0.73 g of methyl 6-methylthio-4-trifluoromethylpyridin-3-yicarboxylate; 1H NMR (CDCl3, ppm): 8.98, s, 1H; 7.48, S, 1H; 3.94, s, 3H; 2.64, s, 3H. Hydrolysis under the conditions mentioned above gives 6-methylthio-4-trifluoromethylnicotinic acid: 1H NMR (CDCl3, ppm): 9.02, s, 1H; 7.46, s, 1H; 2.64, s, 3H.

Example H5

6
-Hydroxy-2-trifluoromethylpyridin-3-yl ethyl ester

[0229] Under an atmosphere of nitrogen and with stirring, 33.4 g of 3,4-dihydro-5-ethoxycarbonyl-6-trifluoromethylpyridin-2-one (Org. Res.& Devel. 1,370 (1997)) and 34 g of manganese dioxide in 250 ml of 1,2-dichlorobenzene are heated under reflux for 24 hours. In intervals of about 20 hours, manganese dioxide (total amount of MnO2 used: 213 g) is added six more times over a period of 3 days, and the mixture is in each case heated further under ref lux. The mixture is then cooled, diluted with ethyl acetate, and filtered through silica gel, the filtercake is washed with ethyl ester and the filtrate is concentrated. The solid residue (26.7 g, i.e. 80%), which may still contain about 6% of starting material, is directly reacted further. For complete purification, it is possible to purify, for example, over silica gel (hexane/ethyl acetate 7:3) (1H NMR, CDCl3, ppm): 8.02 (d, 1H); 6.85 (d, 1H); 4.86 (q, 2H); 1.37 (t, 1H).

Example H6

Preparation of ethyl 6-chloro-2-trifluoromethyl pvridin-3-ylcarboxylate

[0230] In a bomb tube, 23.5 g of ethyl 6-hydroxy-2 4rifluoromethylpyridin-3-ylcarboxylate and 23.5 ml of phenyl dichlorophosphate are heated at 170° C. for 3 hours, and the mixture is, after cooling, added to ice-water, stirred for a few minutes and subsequently taken up in ethyl acetate and made slightly alkaline using sodium bicarbonate and then washed neutral with water. The extracts are admixed with a little hexane and filtered through silica gel. The filtrate is evaporated, leaving 21.6 g (85%) of the title compound in the form of a dark oil with nD30, 1.4679. 1H NMR (CDCl3, ppm): 8.09 (d,1H); 7.60 (d,1 H); 4.43 (q, 2H); 1.43 (t,3H).

Example H7

Preparation of 6-chloro-2-trifluoromethylpyridin-3-ylcarboxylic acid

[0231] 2.5 g of the ethyl 6-chloro-2-trifluoromethylpyridin-3-ylcarboxylate obtained above are dissolved in the smallest possible amount of tetrahydrofuran, treated with approximately 20 g of ice and 11 ml of 1N lithium hydroxide and stirred at room temperature until hydrolysed completely. The mixture is then washed with a little ether and the aqueous phase is acidified using 4N hydrochloric acid and extracted with ethyl acetate. The extracts are washed with sodium chloride solution, dried and evaporated. This gives 1.8 g of the title compound of m.p. 154-156° C. The other free carboxylic acids are likewise obtained from their esters in this manner.

Example H8

Preparation of ethyl 6-methylthio-2-trifiuoromethylpyridin-3-ylcarboxylate

[0232] Under an atmosphere of nitrogen and with stirring, a solution of 1.7 g of 6-chloro-2-trifluoromethylpyridin-3-yl ethyl ester in 60 ml of dimethylformamide is treated a little at a time with 0.52 g of sodium methanethiolate and stirred at room temperature until the reaction has gone to completion. The reaction mixture is then poured into ice-water, made neutral by addition of a little dilute hydrochloric acid and extracted with ethyl acetate. The extracts are diluted with a little hexane, washed with water, dried over sodium sulfate, filtered and, after filtration through a little silica gel, evaporated. This gives 1.4 g (79%) of the title compound in the form of an oil with nD25 1.5100, 1H NMR (CDCl3, ppm): 7.90 (d, 1H); 7.40 (d, 1H); 1.40 (q, 2H); 2.60 (s, 3H); 1.49 (t, 3H).

Example H9

Preparation of ethyl 6-ethylthio-2-trifluoromethylpyridin-3-ylcarboxylate

[0233] In an apparatus previously flushed with nitrogen, a solution of 1.8 ml of ethanethiol in 40 ml of dimethy lformamide, which had been cooled to 0° C., is treated a little at a time with 0.96 g of sodium hydride oil dispersion (60%), and the mixture is stirred at room temperature. After evolution of hydrogen has ceased, the mixture is cooled to −20° C., and a solution of 5.07 g of 6-chloro-2-trifluoromethylpyridin-3-yl ethyl ester in 10 ml of dimethylformamide is added dropwise at this temperature, and the mixture is stirred slowly until room temperature has been reached. After the reaction has ended (approximately 3 hours), the reaction mixture is added to ice-water and extracted with ethyl acetate. The extracts are washed with water, dried, filtered, evaporated and dried under high vacuum. This gives 5.0 g (89%) of the title compound as a brownish oil. 1H NMR (CDCl3, ppm): 7.90 (d, 1H); 7.35 (d, 1H); 4.40 (q, 2H); 3.25 (q, 2H); 1.38 (2t, 6H).

Example H10

Preparation of ethyl 6-ethylsulfinyl-2-trifluoromethylpyridin-3-ylcarboxylate

[0234] Under an atmosphere of nitrogen and with stirring and cooling, a solution of 2.5 g of m-chloroperbenzoic acid in 40 ml of methylene chloride is added dropwise at a temperature of −20° C. to a solution of 2.8 g of ethyl 6-ethylthio-2-trifluoromethylpyridin-3-ylcarboxylate, which had been charged initially, and the mixture is stirred at a temperature of +5° C. for 20 hours. The mixture is then evaporated gently and purified over silica gel (hexanelethyl acetate 7:3). This gives 2.48 g (84%) of 6-ethylsulfinyl-2-trifluoromethylpyridin-3-yl-ethyl ester. 1H NMR (CDCl3, ppm): 8.38 (d, 1H); 8.30 (d, 1H); 4.45 (q, 2H); 3.26-3.00 (m, 2H); 1.43 (t, 3H); 1.26 (t, 3H).

[0235] Ethyl 6-methylsulfinyl-2-trifluoromethylpyridin-3-ylcarboxylate is obtained in an analogous manner.

Example H11

Preparation of ethyl 6-methylsulfonyl-2-trifluoromethylpyridin-3-ylcarboxylate

[0236] Under an atmosphere of nitrogen and with stirring and cooling, 21 g of m-chloroperbenzoic acid are introduced a little at a time over a period of 30 minutes at a temperature of −20° C. into a solution of 3.6 g of 6-methylthio-2-trifluoromethylpyridin-3-yl ethyl ester, which had been charged initially, and the reaction mixture is stirred at room temperature for 5 hours. The mixture is then evaporated and filtered through silica gel (ethyl acetate/methanol/triethylamine 85:10:5). This gives 3.95 g (97%) of ethyl 6-methylsulfonyl-2-trifluoromethylpyridin-3-ylcarboxylate as a brownish solid with m.p. 70-72° C. 1H NMR (CDCl3, ppm): 8.40 (1H,d); 8.33 (1H,d); 4.47 (2H,q); 1.43 (3H,t).

Example H12

Preparation of ethyl 6-cyano-2-trifluoromethylpyridin-3-ylcarboxylate

[0237] Under an atmosphere of nitrogen and with stirring, a solution of 0.596 g of ethyl 6-methylsulfonyl-2-trifluoromethylpyridin-3-ylcarboxylate in 5 ml of dimethylformamide is treated with 160 mg of solid potassium cyanide and a spatula tipful of 1 8-crown-6, and the mixture is heated at 80° C. for 3 hours. The mixture is cooled overnight, and the next day another 30 mg of potassium cyanide are added and the mixture is heated further until the starting material has disappeared (approximately 2 hours). The mixture is then cooled, added to ice-water and extracted with ethyl acetate. The extracts are washed with water, dried, evaporated and freed from traces of dimethylformamide under high vacuum at approximately 40° C. This gives 480 mg (yield virtually quantitative) of ethyl 6-cyano-2-trifluoromethylpyridin-3-ylcarboxylate in the form of an oil which slowly solidifies. 1H NMR (CDCl3, ppm): 8.29 (1H,d); 7.97 (1H,d); 4.48 (2H, d); 1.43 (3H,t).

Example H13

Preparation of ethyl 6-methyl-2-trifluoromethylpyridin-3-ylcarboxylate

[0238] Under an atmosphere of nitrogen and with stirring, a solution of 3.6 g of 6-chloro-2-trifluoromethylpyridin-3-yl ethyl ester in 20 ml of dimethylacetamide is treated with 4.5 ml of tetramethyltin and 200 mg of dichloro(bistriphenylphosphine)palladium, and the mixture is heated to a temperature of 80-90° C. for 24 hours. Then another 1.5 ml of tetramethyltin and 30 mg of dichloro(bistriphenylphosphine)palladium are added and the mixture is heated for another 6 hours. The reaction mixture is then freed from excess tetramethyltin using reduced pressure (destruction by passing through ethanolic sodium hydroxide solution), cooled and added to ice-water. The mixture is extracted with diethyl ether and the extract is washed with water, dried over sodium sulfate, filtered through a little silica gel, evaporated and dried under reduced pressure. This gives the title compound (2.4 g, 73%), which still contains traces of dimethylacetamide, in the form of a dark oil. 1H NMR (CDCl3, ppm): 8.00 (1H,d); 7.42 (1H,d); 4.42 (2H, d); 2.68 (3H, s); 1.41 (3H,t). Hydrolysis analogously to the description already mentioned above affords 6-methyl-2-trifluoromethylpyridin-3-ylcarboxylic acid (brown resin) which is directly converted further into the carbonyl chloride.

Example H14

Preparation of 6-methyl-2-trifluoromethyl pvridin-3-ylcarbonyl chloride

[0239] A solution of 0.45 g of 6-methyl-2-trifluoromethylpyridin-3-ylcarboxyi ic acid in 20 ml of dichloromethane is charged initially, 3 drops of dimethylformamid c are added and the mixture is subsequently treated with 1.6 ml of oxalyl chloride. After the intensive evolution of gas has ceased, the mixture is kept at a bath temperature of 40° C. for another 1.5 hours and then evaporated. The crude product (0.56 g) that remains as residue can be directly reacted further. 1H NMR (CDCl3, ppm): 8.20 (1H,d); 7.51 (1H,d); 2.65 (3H, s).

Example H15

Preparation of 4-oxobicyclo[3.2.1]oct-2-en-2-yl 6-methyl-2- trifluoromethylnicotinate

[0240] Under an atmosphere of nitrogen and with stirring and cooling, a solution of 0.56 g of 6-methyl-2-trifluoromethylpyridin-3-ylcarbonyl chloride in 10 ml of methylene chloride is added dropwise at 0° C. to a solution of 0.4 g of bicyclo[3.2.1]octane-2,4-dione and 0.72 g of triethylamine in 10 ml of methylene chloride, and the mixture is stirred for 5 hours until room temperature has been reached. The mixture is then diluted with methylene chloride, washed with cold 1N hydrochloric acid, dried and evaporated to give the desired enol ester (0 .8 9) as a brown resin which is directly reacted further. 1H NMR (CDCl3, ppm): 8.17 (1H,d); 7.51 (1H, d); 5.96 (1H, s); 3.04 (2H, m); 2.75 (3H, s);2.32-1.30 (m).

Example H16

Preparation of 4-hydroxy-3-(6-methyl-2-trifluoromethylpyridin-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one

[0241] Under an atmosphere of nitrogen and with stirring, 0.8 g of the above enol ester is dissolved in 30 ml of acetonitrile at 25° C., and the mixture is treated with 0.5 ml of triethylamine and 0.4 ml of acetone cyanohydrin and stirred at room temperature for 20 hours. The mixture is then diluted with solvent and washed with dilute hydrochloric acid, dried and evaporated, and the residue is purified through a little silica gel (ethyl acetate/methanol/triethylamine 85:10:5). This gives 371 mg (46%) of the title compound (triethylamine salt) in the form of a yellowish resin. 1H NMR (CDCl3, ppm): 7.45 (1H, d); 7.25 (1H, d); 3.80-3.43 (4H, m); 3.18 (6H, m); 2.80 (2H, s(br)); 2.62 (3H, s); 220-1.54 (m).

Example H17

Preparation of ethyl 6-methoxy-2-trifluoromethylpyridin-3-ylcarboxylate

[0242] A suspension of 5.65 g of ethyl 6-hydroxy-2-trifluoromethylpyridin-3-ylcarboxylate, 6.0 g of potassium carbonate and 2.7 ml of methyl iodide is, together with a spatula tipful of 18-crown-6, heated to a temperature of 60-70° C. until the reaction has gone to completion. The mixture is then filtered, the filtration residue is washed with acetonitrile and the filtrate is concentrated under reduced pressure. The residue is cooled, admixed with ice-water, neutralized with dilute sulfuric acid and extracted with ethyl acetate. The extracts are washed with water, dried, diluted with a little hexane and filtered through a little silica gel.

[0243] The resulting residue is the title compound (3.7 g, 65%) in the form of slightly orange crystals of m.p. 150-152° C.

[0244]

1
H NMR (CDCl3, ppm): 8.00 (1H, d); 6.83 (1H, d); 4.38 (2H, q); 4.01 (3H, s);1.39 (3H, t).

Example H18

Preparation of 4-hydroxy-3(2-methyl-6-trifluoromethylpyridin-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one

[0245] 6.68 g (0.0305 mol) of methyl 2-methyl-6-trifluoromethyinicotinate (prepared as described in Heterocycles, 46, 129 (1997)) are dissolved in 250 ml of methanovwater (3:1 mixture), and 1.92 g (0.046 mol) of lithium hydroxide hydrate are added a little at a time at 22° C. After 4 hours at 22° C, the reaction mixture is poured into ethyl acetate and 2N hydrochloric acid, the organic phase is washed three times with water, dried with sodium sulfate and evaporated and the residue is triturated with a little hexane. Filtration gives 5.69 9 (90% of theory) of the expected 2-methyl-6-trifluoromethyinicotinic acid of m.p. 147-149° C. The 2-methyl6trifluoromethyinicotinic acid obtained (2.0 g, 0.0098 mol) is dissolved in 20 ml of oxalyl chloride. Three drops of dimethylformamide are added, and the mixture is heated under reflux for 1 hour. The mixture is then concentrated using a rotary evaporator, and the residue (2-methyl-6-trifluoromethyinicotinoyl chloride) is taken up in 30 ml of methylene chloride. At I YC, 2.7 ml (0.0196 mo l) of triethylamine and 0.12 g (0.00098 mol) of dimethylaminopyridine are added. 1.49 g (0.0108 mol) of bicyclo[3.2.1]octane-2,4-dione, dissolved in 20 ml of methylene chloride, are then added dropwise. After 3 hours at 22° C., the reaction mixture is extracted with 2 N hydrochloric acid. The methylene chloride phase is separated off, washed with water and subsequently extracted with 10% aqueous sodium bicarbonate solution, dried over sodium sulfate and evaporated. This gives 3.18 g (100% of theory) of 4-oxobicyclo[3.2.1]oct-2-en-2-yl 2-methyl-6-trifluoromethyinicotinate as an oil, which can be processed further without purification.

[0246] 3.02 g (0.0093 mol) of 4-oxobicyclo [3.2.1]oct-2en-2-yl 2-methyl-6-trifluoromethyinicotinate and 1.9 ml (0.0136 mo l) of triethylamine are dissolved in 45 ml of acetonitrile. At 22° C., 0.01 ml of acetone cyanohydrin are added. After 18 hours at 22° C., the reaction mixture is poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate phase is washed with water and then with brine, dried over sodium sulfate and evaporated, and the residue is dissolved in a little warm acetone. The product crystallizes on standing. Filtration gives 0.99 g (33% of theory) of the expected 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one as white crystals (m.p. 75-77° C.).

Example H19

Preparation of 3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-4-oxo-bicyclo[3.2.1]oct-2-en-2-yl benzoate

[0247] At 0° C., a solution of 0.562 g (0.0004 mol) of benzoyl chloride in 1 ml of tetrahydrofuran is added to a solution of 1.14 g (0.0035 mol) of 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one and 0.517 g (0.004 mol) of ethyidiisopropylamine in 15 ml of tetrahydrofuran. The reaction mixture is stirred at 25° C. for 2 hours, evaporated and purified over silica gel (hexane/ethyl acetate 1:1). This gives 0.9 g (60%) of the title compound in the form of a yellowish resin. 1H NMR (CDCl3, ppm): 7.91-7.87, m, 3H; 7.64, t, J=7.5 Hz, 1 H; 7.5 0-7.40, m, 3H; 3.24, br t, J=4 Hz, 1 H; 3.14, br t, J=4 Hz, 1H; 2.70, s, 3H; 2.47, d, J=13.5 Hz, 1H; 2.40, 2.15, m, 3H; 1.95-1.8, m, 2H.

Example H20

Preparation of 4-hydroxy-3-(2-methyl-1-oxy-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one

[0248] 16.25 g (0.05 mol) of 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one and 9.4 g (0.1 mol) of urea/hydrogen peroxide complex are dissolved in 150 ml of methylene chloride, and 20.5 ml (0.15 mol) of trifluoroacetic anhydride are added dropwise at 25° C. After 14 hours at 25° C., the reaction mixture is added to ethyl acetate and water, and the organic phase is washed twice with water, dried with sodium sulfate and evaporated. The residue is chromatographed over silica gel (mobile phase: ethyl acetatelmethanol 9/1). This gives 6.8 g (40%) of the desired product as white crystals (m.p. 109-110° C.).

Example H21

Preparation of 4-chloro-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one

[0249] 20.15 g (0.062 mo l) of 4-hydroxy-3-(2-methyl-6-trifluoromethyipyridine-3carbonyl)-bicyclo[3.2.1]oct-3-en-2-one are suspended in 50 ml of oxalyl chloride, and 0.1 ml of dimethylformamide are added dropwise. After the intensive evolution of gas has ceased, the mixture is kept at a bath temperature of 45° C. for another 1.5 hours and then evaporated, and the residue is suspended in a little ethyl acetate and admixed with stirring at 0° C. with hexane. Filtration gives 19.19 g (90% of theory) of 4-chloro-3-(2-methyl-6-trifluoromethyl-pyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one of m.p. 137-138° C.

Example H22

Preparation of 4-amino-3-(2-methyl-6-trifluoronmethvlpvridine-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2one

[0250] 1.0 g (0.0029 mol) of 4-chloro-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one are dissolved in 10 ml of tetrahydrofuran and, at 25° C., treated with 2.0 ml of aqueous ammonia (30%). After 0.5 hours at 25° C., the reaction mixture is added to ethyl acetate and water, the organic phase is washed twice with water, dried with sodium sulfate and evaporated and the residue is triturated with a little ethyl acetate. Filtration gives 0.81 g (86% of theory) of 4-amino-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3en-2-one in the form of white crystals (m.p. 262-263° C). 1H NMR (CDCl3, ppm): 10.62 br s 1H; 8.223 br s 1H; 7.41, d, J=8.1 Hz, 1H; 7.35, d, J=8.1 Hz, 1H; 3.03, br t, J=4.8 Hz, 1H; 2.70, br t, J=4.8 Hz, 1H; 2.41, s, 3H; 1.97-2.14, m, 3H; 1.77-1.812, m, 1H; 1.47-1.70, m, 2H.

Example H23

Preparation of 4-(4-chlorophenylsulfanyl)-3-(2-methyl-6-trifluoromethyl-pyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one

[0251] 2.0 g (0.0058 mol) of 4-chloro-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)-bicyclo[3.2.1]oct-3-en-2-one, 0.07 g of dimethylaminopyridine (0.00058 mol) and 1.61 ml of triethylamine are dissolved in 15 ml of methylene chloride. At 25° C., 0.092 g (0.0064 mol) of 4-chlorothiophenol are added. After 2 hours at 22° C., the reaction mixture is evaporated and purified over silica gel (hexane/ethyl acetate 2:1). Recrystallization (hexane/acetic acid at −25° C.) gives pure 4-(4-chlorophenylsulfanyl)-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one: m.p. 130-131 ° C.

Example H24

Preparation of 4-(4-chlorobenzenesulfonyl)-3-(2-methyl-6-trifluoromethyl-pyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one

[0252] 0.6 g (0.00133 mol) of the 4-(4-chlorophenylsul tanyl)-3-(2-methyl-6trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one obtained above is dissolved in methylene chloride, and 0.9 ml of peracetic acid (39% in acetic acid, 0.0053 mol) are added dropwise at 25° C. After 5 hours at 25° C., the reaction mixture is added to ethyl acetate and water, the organic phase is washed with water, dried with sodium sulfate and evaporated and the residue is triturated with a little hexane. Filtration gives 0.56 g (84% of theory) of 4-(4-chlorobenzenesulfonyl)-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]oct-3-en-2-one in the form of white crystals (m.p.166-167° C.).

Example H25

Preparation of (5-cyclopropyl-3-methylsulfanylisoxazol-4-yl)-(2-methyl-6-trifluoromethylpyridin-3-yl)methanone and cyclopropyl-[3-methylsulfanyl-5-(2-methyl-6-trifluoromethylpyridin-3-yl)isoxazol4-yl)methanone

[0253] 14.8 g (0.080 mol) of tert-butyl 3-cyclopropyl-3-oxopropionic acid ester are dissolved in 25 ml of MeOH, and 1.93 g (0 .080 mol) of magnesium are added. With ice-bath cooling, 7 ml of carbon tetrachloride are added dropwise, and the reaction mixture is stirred at a temperature of 22° C. for one hour. After evaporation, the residue is suspended in 100 ml of acetonitrile, and 16.31 g (0.073 mol) of 2-methyl-6-trifluoromethyinicotinoyl chloride (prepared as described in Example H18), dissolved in 50 ml of acetonitrile, are added dropwise at a temperature of 22° C. After 6 hours, the reaction mixture is taken up in ethyl acetate and washed with saturated sodium bicarbonate solution. The ethyl acetate phase is separated off, washed with water, dried over sodium sulfate and evaporated. The residue is dissolved in 160 ml of methylene chloride, and 10 ml of trifluoroacetic acid are added dropwise at a temperature of 22° C. After 18 hours, the reaction mixture is poured into water and extracted with methylene chloride. The methylene chloride phase is washed with water and then with saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. This gives 17.3 g (88% of theory) of 1-cyclopropyl-3-(2-methyl-6-trifluoromethylpyridin-3-yl)propane-1,3-dione as an oil, which is processed further without purification. The 1-cyclopropyl-3-(2-methyl-6-trifluoromethylpyridin-3-yl)propane-1,3-dione obtained above (15.0 g, 0.055 mol) is dissolved in 150 ml of dimethylformamide, and 50 g of potassium fluoride on an aluminium oxide support (alumina) (0.0055 movg, 0.276 mol) are added a little at a time at a temperature of 0° C. After 5 minutes, 6.7 g (0.088 mol) of carbon disulfide are added dropwise. After 2 hours, 23.6 g (0.166 mol) of methyl iodide are added dropwise, and the reaction mixture is warmed to a temperature of 22° C. After a further 2 hours, the alumina is filtered off, the filtrate is added to water and the mixture is extracted with ethyl acetate. The ethyl acetate phase is washed with water and then with saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. The residue is chromatographed over silica gel (mobile phase: ethyl acetate/hexane 15/1). This gives 12.0 g (60% of theory) of 2-(bismethylsulfanylmethylene)-1-cyclopropyl-3-(2-methyl-6-trifluoromethylpyridin-3-yl)-propane-1,3-dione as a solid. 12.0 g (0.033 mol) of the product obtained above are, together with 5.4 g (0.066 mol) of anhydrous sodium acetate, suspended in 120 ml of ethanol. 4.6 g (0.066 mol) of hydroxylamine hydrochloride are added, and the reaction mixture is kept at a temperature of 22° C. for 5 hours. Another 2.7 g of anhydrous sodium acetate and 2.3 g of hydroxylamine hydrochloride are then added. After 18 hours, the reaction mixture is diluted with water and extracted with ethyl acetate. The ethyl acetate phase is washed with water and then with saturated aqueous sodium chloride solution, dried over sodium sulfate and evaporated. Trituration with a little ethyl acetate gives 9.0 g (79.5%) of the desired product as a 2:1 isomer mixture in the form of white crystals (m.p. 103-104° C.).

[0254] Main isomer: 1H NMR (CDCl3, ppm) ((5-cyclopropyl-3-methylsulfanylisoxazol-4-yl)-(2-methyl-6-trifluoromethylpyridin-3-yl)methanone) 7.98, d, J=7.8 Hz, 1H; 7.61, d, J=7.8 Hz, 1H; 2.67, s, 3H; 2.50, s, 3H; 2.02-1.93, m, 1 H; 1.34-1.28, m, 2H; 1.18-1.09, m, 2H.

[0255]

1
H NMR (CDCl3, ppm) (cyclopropyl-13-methylsulfanyl-5-(2-methy l -trifluoromethylpyridin-3-yl)isoxazol-4-yl]methane): 7.95, d, J=7.8 Hz, 1H; 7.69, d, J=7.8 Hz, 1H; 2.67, s, 3H; 2.66, s, 3H; 1.74-1.64, m, 1H; 1.28-1.18, m, 2H; 0.89 4.80, m, 2H.

Example H26

Preparation of (5-cyclopropyl-3-methylsulfinylisoxazol-4-yl)-(2-methyl-6-trifluoromethylpyridin-3-yl)methanone and cylopropyl-[3-methanesulfinyl-5-(2-methyl-6-trifluoromethylpyridin-3-yl)isoxazol-4-yl]methanone

[0256] 1.50 g (0.0043 mol) of the isomer mixture obtained above are dissolved in 30 ml of acetonelwater (2:1 mixture), and 1.02 g (0.0048 mol) of sodium metaperiodate are added a little at a time at 22° C. After 5 hours, the reaction mixture is evaporated using a rotary evaporator. The residue is taken up in water and ethyl acetate. The ethyl acetate phase is dried over sodium sulfate and evaporated. The residue is chromatographed over silica gel (mobile phase: ethyl acetate/hexane 3/1). This gives initially 0.8 g (51 % of theory) of (5-cyclopropyl-3-methylsulfinylisoxazol-4-yl)-(2-methyl-6-trifluoromethylpyridin-3-yl)methanone as white crystals (m.p. 96-97° C.). 1H NMR (CDCl3, ppm): 7.86, d, J=7.8 Hz, 1H; 7.59, d, J=7.8 Hz, 1H; 3.078, s, 3H; 2.66, s, 3H; 1.54-1A49, m, IH; 1.32-1.25, m, 2H; 1.13-1.072, m, 2H.

[0257] The second product that eiutes consists of 0.34 g (22% of theory) of cyclopropyl-[3-methanesulfinyl-5-(2-methyl-6-trifluoromethylpyridin-3yl)isoxazol4-yl]methanone as white crystals (m.p. 112-113° C.). 1H NMR (CDCl3, ppm): 7.97, d, J=7.8 Hz, 1H; 7.67, d, J=7.8 Hz, 1H; 3.128, s, 3H; 2.62, s, 3H; 1.69-1.64, m, 1H; 1.26-1.18, m, 2H; 0.90-0.85, m, 2H.

Example H27

Preparation of (5-cyclopropyl-3-methanesulfonylisoxazol-4-yl)-(2-isopropyl-6-trifluoromethylpyridin-3-yl)methanone

[0258] 0.15 g (0.0045 mol) of (5-cyclopropyl-3-methylsulfanylisoxazol-4-yl)-(2-isopropyl-6-trifluoromethylpyridin-3-yl)methanone is dissolved in methylene chloride, and 0.28 ml of peracetic acid (39% in acetic acid, 0.0016 mol) are added dropwise at a temperature of 5° C. After 15 hours at 25° C., the reaction mixture is added to ethyl acetate and water, and the organic phase is washed with water, dried with sodium sulfate and evaporated. The residue is chromatographed over silica gel (mobile phase: ethyl acetate/hexane 5/1). This gives 0.121 g (74% of theory) of the expected product as white crystals (m.p.105-106° C.).

[0259] In an analogous manner, and according to the methods shown in the general reaction schemes 1-10 and in the references mentioned therein, it is also possible to prepare the compounds listed in the tables below. In these tables, CCH is the ethynyl group, Ph is the phenyl group and Me is the methyl group.

1TABLE 1

Comp.No.R1R2R3R4R5p1.001HCF3HHOH01.002FCF3HHOH01.003ClCF3HHOH01.004BrCF3HHOH01.005CHF2CF3HHOH01.006CCl3CF3HHOH01.007CClF2CF3HHOH01.008CF3CF3HHOH01.009CH3CF3HHOH01.01CH2CH3CF3HHOH01.011CH(CH3)2CF3HHOH01.012(CH2)2CH3CF3HHOH01.013C(CH3)3CF3HHOH01.014PhCF3HHOH01.015CH2FCF3HHOH01.016CH2ClCF3HHOH01.017CH2BrCF3HHOH01.018CH2OHCF3HHOH01.019CH2OCOCH3CF3HHOH01.02CH2OCOPhCF3HHOH01.021CH2OCH3CF3HHOH01.022CH2OCH2CH3CF3HHOH01.023CH2CH2OCH3CF3HHOH01.024CH2SMeCF3HHOH01.025CH2SOMeCF3HHOH01.026CH2SO2MeCF3HHOH01.027CH2SO2PhCF3HHOH01.028SCH2PhCF3HHOH01.029SOCH2PhCF3HHOH01.03SO2CH2PhCF3HHOH01.031SCH3CF3HHOH01.032SOCH3CF3HHOH01.033SO2CH3CF3HHOH01.034SPhCF3HHOH01.035SOPhCF3HHOH01.036SO2PhCF3HHOH01.037N(CH3)2CF3HHOH01.038CH═CH2CF3HHOH01.039CH2CH═CH2CF3HHOH01.04SO2N(CH3)2CF3HHOH01.041ethynylCF3HHOH01.042cyclopropylCF3HHOH01.043OCH3CF3HHOH01.044OPhCF3HHOH01.045OCHF2CF3HHOH01.046CO2MeCF3HHOH01.0472-furylCF3HHOH01.048OCH2ethynylCF3HHOH01.0492-pyridylCF3HHOH01.053-pyridylCF3HHOH01.0514-pyridylCF3HHOH01.052HCF3HHOH11.053FCF3HHOH11.054ClCF3HHOH11.055BrCF3HHOH11.056CHF2CF3HHOH11.057CCl3CF3HHOH11.058CClF2CF3HHOH11.059CF3CF3HHOH11.06CH3CF3HHOH11.061CH2CH3CF3HHOH11.062CH(CH3)2CF3HHOH11.063(CH2)2CH3CF3HHOH11.064C(CH3)3CF3HHOH11.065PhCF3HHOH11.066CH2FCF3HHOH11.067CH2ClCF3HHOH11.068CH2BrCF3HHOH11.069CH2OHCF3HHOH11.07CH2OCOCH3CF3HHOH11.071CH2OCOPhCF3HHOH11.072CH2OCH3CF3HHOH11.073CH2OCH2CH3CF3HHOH11.074CH2CH2OCH3CF3HHOH11.075CH2SMeCF3HHOH11.076CH2SOMeCF3HHOH11.077CH2SO2MeCF3HHOH11.078CH2SO2PhCF3HHOH11.079SCH2PhCF3HHOH11.08SOCH2PhCF3HHOH11.081SO2CH2PhCF3HHOH11.082SCH3CF3HHOH11.083SOCH3CF3HHOH11.084SO2CH3CF3HHOH11.085SPhCF3HHOH11.086SOPhCF3HHOH11.087SO2PhCF3HHOH11.088N(CH3)2CF3HHOH11.089CH═CH2CF3HHOH11.09CH2CH═CH2CF3HHOH11.091SO2N(CH3)2CF3HHOH11.092ethynylCF3HHOH11.093cyclopropylCF3HHOH11.094OCH3CF3HHOH11.095OPhCF3HHOH11.096OCHF2CF3HHOH11.097CO2MeCF3HHOH11.0982-furylCF3HHOH11.099OCH2CCHCF3HHOH11.12-pyridylCF3HHOH11.1013-pyridylCF3HHOH11.1024-pyridylCF3HHOH11.103HCF2CF3HHOH01.104ClCF2CF3HHOH01.105CHF2CF2CF3HHOH01.106CCl3CF2CF3HHOH01.107CClF2CF2CF3HHOH01.108CF3CF2CF3HHOH01.109CH3CF2CF3HHOH01.11CH2CH3CF2CF3HHOH01.111CH(CH3)2CF2CF3HHOH01.112(CH2)2CH3CF2CF3HHOH01.113C(CH3)3CF2CF3HHOH01.114CH2FCF2CF3HHOH01.115CH2ClCF2CF3HHOH01.116CH2OHCF2CF3HHOH01.117CH2OCOCH3CF2CF3HHOH01.118CH2OCOPhCF2CF3HHOH01.119CH2OCH3CF2CF3HHOH01.12CH2OCH2CH3CF2CF3HHOH01.121CH2SMeCF2CF3HHOH01.122CH2SOMeCF2CF3HHOH01.123CH2SO2MeCF2CF3HHOH01.124CH2SO2PhCF2CF3HHOH01.125N(CH3)2CF2CF3HHOH01.126CH═CH2CF2CF3HHOH01.127CH2CH═CH2CF2CF3HHOH01.128SO2N(CH3)2CF2CF3HHOH01.129CCHCF2CF3HHOH01.13cyclopropylCF2CF3HHOH01.131OPhCF2CF3HHOH01.132OCH3CF2CF3HHOH01.133CO2MeCF2CF3HHOH01.134OCH2CCHCF2CF3HHOH01.1352-pyridylCF2CF3HHOH01.1363-pyridylCF2CF3HHOH01.1374-pyridylCF2CF3HHOH01.138HCF2CF3HHOH11.139ClCF2CF3HHOH11.14CHF2CF2CF3HHOH11.141CCl3CF2CF3HHOH11.142CClF2CF2CF3HHOH11.143CF3CF2CF3HHOH11.144CH3CF2CF3HHOH11.145CH2CH3CF2CF3HHOH11.146CH(CH3)2CF2CF3HHOH11.147(CH2)2CH3CF2CF3HHOH11.148C(CH3)3CF2CF3HHOH11.149CH2FCF2CF3HHOH11.15CH2ClCF2CF3HHOH11.151CH2OHCF2CF3HHOH11.152CH2OCOCH3CF2CF3HHOH11.153CH2OCOPhCF2CF3HHOH11.154CH2OCH3CF2CF3HHOH11.155CH2OCH2CH3CF2CF3HHOH11.156CH2SMeCF2CF3HHOH11.157CH2SOMeCF2CF3HHOH11.158CH2SO2MeCF2CF3HHOH11.159CH2SO2PhCF2CF3HHOH11.16N(CH3)2CF2CF3HHOH11.161CH═CH2CF2CF3HHOH11.162CH2CH═CH2CF2CF3HHOH11.163SO2N(CH3)2CF2CF3HHOH11.164CCHCF2CF3HHOH11.165cyclopropylCF2CF3HHOH11.166OPhCF2CF3HHOH11.167OCH3CF2CF3HHOH11.168CO2MeCF2CF3HHOH11.169OCH2CCHCF2CF3HHOH11.172-pyridylCF2CF3HHOH11.1713-pyridylCF2CF3HHOH11.1724-pyridylCF2CF3HHOH11.173HCF2CF2CF3HHOH01.174CHF2CF2CF2CF3HHOH01.175CF3CF2CF2CF3HHOH01.176CH3CF2CF2CF3HHOH01.177CH2CH3CF2CF2CF3HHOH01.178(CH2)2CH3CF2CF2CF3HHOH01.179CH2ClCF2CF2CF3HHOH01.18CH2OCH3CF2CF2CF3HHOH01.181HCF2CF2CF3HHOH11.182CHF2CF2CF2CF3HHOH11.183CF3CF2CF2CF3HHOH11.184CH3CF2CF2CF3HHOH11.185CH2CH3CF2CF2CF3HHOH11.186(CH2)2CH3CF2CF2CF3HHOH01.187CH2ClCF2CF2CF3HHOH11.188CH2OCH3CF2CF2CF3HHOH11.189HCF2ClHHOH01.19ClCF2ClHHOH01.191CHF2CF2ClHHOH01.192CCl3CF2ClHHOH01.193CClF2CF2ClHHOH01.194CF3CF2ClHHOH01.195CH3CF2ClHHOH01.196CH2CH3CF2ClHHOH01.197CH(CH3)2CF2ClHHOH01.198(CH2)2CH3CF2ClHHOH01.199C(CH3)3CF2ClHHOH01.2CH2FCF2ClHHOH01.201CH2ClCF2ClHHOH01.202CH2OHCF2ClHHOH01.203CH2OCOCH3CF2ClHHOH01.204CH2OCOPhCF2ClHHOH01.205CH2OCH3CF2ClHHOH01.206CH2OCH2CH3CF2ClHHOH01.207CH2SMeCF2ClHHOH01.208CH2SOMeCF2ClHHOH01.209CH2SO2MeCF2ClHHOH01.21CH2SO2PhCF2CHHOH01.211N(CH3)2CF2ClHHOH01.212CH═CH2CF2ClHHOH01.213CH2CH═CH2CF2ClHHOH01.214SO2N(CH3)2CF2ClHHOH01.215CCHCF2ClHHOH01.216cyclopropylCF2ClHHOH01.217OPhCF2ClHHOH01.218OCH3CF2ClHHOH01.219CO2MeCF2ClHHOH01.22OCH2CCHCF2ClHHOH01.2212-pyridylCF2ClHHOH01.2223-pyridylCF2ClHHOH01.2234-pyridylCF2ClHHOH01.224HCF2ClHHOH11.225ClCF2ClHHOH11.226CHF2CF2ClHHOH11.227CCl3CF2ClHHOH11.228CClF2CF2ClHHOH11.229CF3CF2ClHHOH11.23CH3CF2ClHHOH11.231CH2CH3CF2ClHHOH11.232CH(CH3)2CF2ClHHOH11.233(CH2)2CH3CF2ClHHOH11.234C(CH3)3CF2ClHHOH11.235CH2FCF2ClHHOH11.236CH2ClCF2ClHHOH11.237CH2OHCF2ClHHOH11.238CH2OCOCH3CF2ClHHOH11.239CH2OCOPhCF2ClHHOH11.24CH2OCH3CF2ClHHOH11.241CH2OCH2CH3CF2ClHHOH11.242CH2SMeCF2ClHHOH11.243CH2SOMeCF2ClHHOH11.244CH2SO2MeCF2ClHHOH11.245CH2SO2PhCF2ClHHOH11.246N(CH3)2CF2ClHHOH11.247CH═CH2CF2ClHHOH11.248CH2CH═CH2CF2ClHHOH11.249SO2N(CH3)2CF2ClHHOH11.25CCHCF2ClHHOH11.251cyclopropylCF2ClHHOH11.252OPhCF2ClHHOH11.253OCH3CF2ClHHOH11.254CO2MeCF2ClHHOH11.255OCH2CCHCF2ClHHOH11.256HCCl3HHOH01.257ClCCl3HHOH01.258CH3CCl3HHOH01.259CH2CH3CCl3HHOH01.26CH(CH3)2CCl3HHOH01.261(CH2)2CH3CCl3HHOH01.262CH2FCCl3HHOH01.263CH2ClCCl3HHOH01.264CH2OHCCl3HHOH01.265CH2OCOCH3CCl3HHOH01.266CH2OCOPhCCl3HHOH01.267CH2OCH3CCl3HHOH01.268CH2OCH2CH3CCl3HHOH01.269CH2SMeCCl3HHOH01.27CH2SOMeCCl3HHOH01.271CH2SO2MeCCl3HHOH01.272CH2SO2PhCCl3HHOH01.273cyclopropylCCl3HHOH01.274OPhCCl3HHOH01.275OCH3CCl3HHOH01.276CO2MeCCl3HHOH01.277OCH2OCHCCl3HHOH01.278HCCl3HHOH11.279ClCCl3HHOH11.28CH3CCl3HHOH11.281CH2CH3CCl3HHOH11.282CH(CH3)2CCl3HHOH11.283(CH2)2CH3CCl3HHOH11.284CH2FCCl3HHOH11.285CH2ClCCl3HHOH11.286CH2OHCCl3HHOH11.287CH2OCOCH3CCl3HHOH11.288CH2OCOPhCCl3HHOH11.289CH2OCH3CCl3HHOH11.29CH2OCH2CH3CCl3HHOH11.291CH2SMeCCl3HHOH11.292CH2SOMeCCl3HHOH11.293CH2SO2MeCCl3HHOH11.294CH2SO2PhCCl3HHOH11.295cyclopropylCCl3HHOH11.296OPhCCl3HHOH11.297OCH3CCl3HHOH11.298CO2MeCCl3HHOH11.299OCH2CCHCCl3HHOH11.3CF3CHF2HHOH01.301CH3CHF2HHOH01.302CH2OCH3CHF2HHOH01.303CH2ClCHF2HHOH01.304CH2FCHF2HHOH01.305CF3CHF2HHOH11.306CH3CHF2HHOH11.307CH2OCH3CHF2HHOH11.308CH2ClCHF2HHOH11.309CH2FCHF2HHOH11.31CH3CF3HCH3OH01.311CH3CF3HCH3OH11.312ClCF3HCH3OH01.313CH3CF3CH3HOH01.314CH3CF3PhHOH01.315CH3CF3ClHOH01.316CH3CF3CO2CH2CH3HOH01.317CH3CF3CO2CH2PhHOH01.318CH3CF3CH3HOH11.319CH3CF3PhHOH11.32CH3CF3ClHOH11.321CH3CF3CO2CH2CH3HOH11.322CH3CF3CO2CH2PhHOH11.323OCH3CF3CH3HOH01.324CH2OCH3CF3CH3HOH01.325CH2OCH3CF3PhHOH01.326CH2OCH3CF3ClHOH01.327CH2OCH3CF3CO2CH2CH3HOH01.328CH2OCH3CF3CO2CH2PhHOH01.329CH2OCH3CF3CH3HOH11.33CH2OCH3CF3PhHOH11.331CH2OCH3CF3ClHOH11.332CH2OCH3CF3CO2CH2CH3HOH11.333CH2OCH3CF3CO2CH2PhHOH11.334COOCH3HHHOH01.335CF3SCH3HHOH01.336CH3SCH3HHOH01.337CF3SOCH3HHOH01.338CH3SOCH3HHOH01.339CF3SO2CH3HHOH01.34CH3SO2CH3HHOH01.341CF3SCH2CH3HHOH01.342CH3SCH2CH3HHOH01.343CF3SOCH2CH3HHOH01.344CH3SOCH2CH3HHOH01.345CF3SO2CH2CH3HHOH01.346CH3SO2CH2CH3HHOH01.347CF3OCH3HHOH01.348CH3OCH3HHOH01.349CF3OCH2CF3HHOH01.35CH3OCH2CF3HHOH01.351CF3OCH2CCHHHOH01.352CH3OCH2CCHHHOH01.353CF3CNHHOH01.354CH3CNHHOH01.355CF3ClHHOH01.356CF3ClHHO-NEt3+01.357CH3ClHHOH01.358HClHHOH01.359CF3OCH3HHOH01.36CH3OCH3HHOH01.361CF3CH3HHOH01.362HCF3HCH3OH01.363HCF3HCF3OH01.364HCF3HCH2CH3OH01.365HCF3HCF3OH01.366HCF3HSCH3OH01.367HCF3HSOCH3OH01.368HCF3HSO2CH3OH01.369HCF3HClOH01.37HCF3HOCH3OH01.371HCH3HCF3OH01.372HClHCF3OH01.373HOCH3HCF3OH01.374HSCH3HCF3OH01.375HSOCH3HCF3OH01.376CH3CF3HHO-K+01.377CH3CF3HHS(CH2)7CH301.378CH3CF3HHS(CH2)7CH301.379CH3CF3HHSO(CH2)7CH301.38CH3CF3HHSO2(CH2)7CH301.381CH3CF3HHSPh01.382CH3CF3HHSOPh01.383CH3CF3HHSO2Ph01.384CH3CF3HHNOCH301.385CH3CF3HHNOCH2Ph01.386CH3CF3HHNOCH2CH═CH201.387CH3CF3HHNOC(CH3)301.388CH3CF3HHNOCH2CH301.389CH3CF3HHNCH2CH2SH01.39CH3CF3HHNN(CH3)201.391CH3CF3HHNN(CH3)C(S)NH201.392CH3CF3HHN-morpholino01.393CH3CF3HHNHCOCH301.394CH3CF3HHNHCO(CH2)7CH301.395CH3CF3HHNHCOPh01.396CH3CF3HHNHSO2CH301.397CH3CF3HHNH(CO)S(CH2)7CH301.398CH3CF3HHCl01.399CH3CF3HHNH201.4CH3CF3HHOCOC(CH3)301.401CH3CF3HHOCOCH301.402CH3CF3HHOCOPh01.403CH3CF3HHOCO-cyclopropyl01.404CH3CF3HHOCOCH2CH301.405CH3CF3HHOCOCH═CH201.406CH3CF3HHOCOCH═CHCH301.407CH3CF3HHO(CO)SCH301.408CH3CF3HHO(CO)S(CH2)7CH301.409CH3CF3HHO(CO)OCH2CH301.41CH3CF3HHO(CO)N(CH2CH3)201.411CH3(CF2)3CF3HHOH01.412CH3CF3HHS-(4-Cl-phenyl)01.413CH3CF3HHSO-(4-Cl-phenyl)01.414CH3CF3HHSO2-(4-Cl-phenyl)01.415CH3CF3HHS-(4-CF3-phenyl)01.416CH3CF3HHSO-(4-CF3-phenyl)01.417CH3CF3HHSO2-(4-CF3-phenyl)01.418CH3CF3HHS-(4-NO2-phenyl)01.419CH3CF3HHSO-(4-NO2-phenyl)01.42CH3CF3HHSO2-(4-NO2-phenyl)01.421CH3CF3HH

01.422CH3CF3HH

01.423CH3CF3HH

01.424CH3CF3HH

01.425CF2HSCH3HHOH01.426CF2ClSCH3HHOH01.427CF2HSOCH3HHOH01.428CF2ClSOCH3HHOH01.429CF2HSO2CH3HHOH01.43CF2ClSO2CH3HHOH01.431CF2HSCH2CH3HHOH01.432CF2ClSCH2CH3HHOH01.433CF2HSOCH2CH3HHOH01.434CF2ClSOCH2CH3HHOH01.435CF2HSO2CH2CH3HHOH01.436CF2ClSO2CH2CH3HHOH01.437CF2HOCH3HHOH01.438CF2ClOCH3HHOH01.439CF2HOCH2CF3HHOH01.44CF2ClOCH2CF3HHOH01.441CF2HOCH2CCHHHOH01.442CF2ClOCH2CCHHHOH01.443CF2HCNHHOH01.444CF2ClCNHHOH01.445CF2HClHHOH01.446CF2ClClHHOH01.447CF2HOCH3HHOH01.448CF2ClOCH3HHOH01.449CF3CH2OCH3HHOH01.45CF3CH2OCH3HHOH11.451CF2ClCH2OCH3HHOH01.452CF2ClCH2OCH3HHOH11.453CF2HCH2OCH3HHOH01.454CF2HCH2OCH3HHOH11.455CNCF3HHOH0

[0260]

2

TABLE 2

Comp. No.
R1
R2
R3
R4

2.001
H
CF3
H
H

2.002
F
CF3
H
H

2.003
Cl
CF3
H
H

2.004
Br
CF3
H
H

2.005
CHF2
CF3
H
H

2.006
CCl3
CF3
H
H

2.007
CClF2
CF3
H
H

2.008
CF3
CF3
H
H

2.009
CH3
CF3
H
H

2.01
CH2CH3
CF3
H
H

2.011
CH(CH3)2
CF3
H
H

2.012
(CH2)2CH3
CF3
H
H

2.013
Ph
CF3
H
H

2.014
CH2F
CF3
H
H

2.015
CH2Cl
CF3
H
H

2.016
CH2Br
CF3
H
H

2.017
CH2OH
CF3
H
H

2.018
CH2OCOCH3
CF3
H
H

2.019
CH2OCOPh
CF3
H
H

2.02
CH2OCH3
CF3
H
H

2.021
CH2OCH2CH3
CF3
H
H

2.022
CH2CH2OCH3
CF3
H
H

2.023
CH2SMe
CF3
H
H

2.024
CH2SOMe
CF3
H
H

2.025
CH2SO2Me
CF3
H
H

2.026
CH2SO2Ph
CF3
H
H

2.027
SCH2ph
CF3
H
H

2.028
SOCH2Ph
CF3
H
H

2.029
SO2CH2Ph
CF3
H
H

2.03
SCH3
CF3
H
H

2.031
SOCH3
CF3
H
H

2.032
SO2CH3
CF3
H
H

2.033
N(CH3)2
CF3
H
H

2.034
CH═CH2
CF3
H
H

2.035
CH2CH═CH2
CF3
H
H

2.036
SO2N(CH3)2
CF3
H
H

2.037
CCH
CF3
H
H

2.038
OCH3
CF3
H
H

2.039
OPh
CF3
H
H

2.04
OCHF2
CF3
H
H

2.041
CO2Me
CF3
H
H

2.042
OCH2CCH
CF3
H
H

2.043
OCH2CF3
CF3
H
H

2.044
H
CF3
H
Cl

2.045

F
H
Cl

2.046
CN
CF3
H
H

2.047
H
CHF2
H
H

2.048
CH3
CHF2
H
H

2.049
CH2CH3
CHF2
H
H

2.05
CH2OCH3
CHF2
H
H

2.051
H
CF2Cl
H
H

2.052
CH3
CF2Cl
H
H

2.053
CH2CH3
CF2Cl
H
H

2.054
CH2OCH3
CF2Cl
H
H

[0261]

3

TABLE 3

Comp. No.
R1
R2
R3
R4

3.001
H
CF3
H
H

3.002
F
CF3
H
H

3.003
Cl
CF3
H
H

3.004
Br
CF3
H
H

3.005
CHF2
CF3
H
H

3.006
CCl3
CF3
H
H

3.007
CClF2
CF3
H
H

3.008
CF3
CF3
H
H

3.009
CH3
CF3
H
H

3.01
CH2CH3
CF3
H
H

3.011
CH(CH3)2
CF3
H
H

3.012
(CH2)2CH3
CF3
H
H

3.013
Ph
CF3
H
H

3.014
CH2F
CF3
H
H

3.015
CH2Cl
CF3
H
H

3.016
CH2Br
CF3
H
H

3.017
CH2OH
CF3
H
H

3.018
CH2OCOCH3
CF3
H
H

3.019
CH2OCOPh
CF3
H
H

3.02
CH2OCH3
CF3
H
H

3.021
CH2OCH2CH3
CF3
H
H

3.022
CH2CH2OCH3
CF3
H
H

3.023
CH2SMe
CF3
H
H

3.024
CH2SOMe
CF3
H
H

3.025
CH2SO2Me
CF3
H
H

3.026
CH2SO2Ph
CF3
H
H

3.027
SCH2Ph
CF3
H
H

3.028
SOCH2Ph
CF3
H
H

3.029
SO2CH2Ph
CF3
H
H

3.03
SCH3
CF3
H
H

3.031
SOCH3
CF3
H
H

3.032
SO2CH3
CF3
H
H

3.033
N(CH3)2
CF3
H
H

3.034
CH═CH2
CF3
H
H

3.035
CH2CH═CH2
CF3
H
H

3.036
SO2N(CH3)2
CF3
H
H

3.037
CCH
CF3
H
H

3.038
OCH3
CF3
H
H

3.039
OPh
CF3
K
H

3.04
OCHF2
CF3
H
H

3.041
CO2Me
CF3
H
H

3.042
OCH2CCH
CF3
H
H

3.043
OCH2CF3
CF3
H
H

3.044
H
CF3
H
H

3.045
CN
CF3
H
H

3.046
H
CHF2
H
H

3.047
CH3
CHF2
H
H

3.048
CH2CH3
CHF2
H
H

3.049
CH2OCH3
CHF2
H
H

3.05
H
CF2Cl
H
H

3.051
CH3
CF2Cl
H
H

3.052
CH2CH3
CF2Cl
H
H

3.053
CH2OCH3
CF2Cl
H
H

3.054
Cl
CH3
H
H

3.055
CN
SCH3
H
H

3.056
CN
SO2CH3
H
H

[0262]

4

TABLE 4

Comp.

No.
R1
R2
R3
R4
R5
P

4.001
H
CF3
H
H
OH
0

4.002
F
CF3
H
H
OH
0

4.003
Cl
CF3
H
H
OH
0

4.004
Br
CF3
H
H
OH
0

4.005
CHF2
CF3
H
H
OH
0

4.006
CCl3
CF3
H
H
OH
0

4.007
CClF2
CF3
H
H
OH
0

4.008
CF3
CF3
H
H
OH
0

4.009
CH3
CF3
H
H
OH
0

4.01
CH2CH3
CF3
H
H
OH
0

4.011
CH(CH3)2
CF3
H
H
OH
0

4.012
(CH2)2CH3
CF3
H
H
OH
0

4.013
C(CH3)3
CF3
H
H
OH
0

4.014
Ph
CF3
H
H
OH
0

4.015
CH2F
CF3
H
H
OH
0

4.016
CH2Cl
CF3
H
H
OH
0

4.017
CH2Br
CF3
H
H
OH
0

4.018
CH2OH
CF3
H
H
OH
0

4.019
CH2OCOCH3
CF3
H
H
OH
0

4.02
CH2OCOPh
CF3
H
H
OH
0

4.021
CH2OCH3
CF3
H
H
OH
0

4.022
CH2OCH2CH3
CF3
H
H
OH
0

4.023
CH2CH2OCH3
CF3
H
H
OH
0

4.024
CH2SMe
CF3
H
H
OH
0

4.025
CH2SOMe
CF3
H
H
OH
0

4.026
CH2SO2Me
CF3
H
H
OH
0

4.027
CH2SO2Ph
CF3
H
H
OH
0

4.028
N(CH3)2
CF3
H
H
OH
0

4.029
CH═CH2
CF3
H
H
OH
0

4.03
CH2CH═CH2
CF3
H
H
OH
0

4.031
SO2N(CH3)2
CF3
H
H
OH
0

4.032
CCH
CF3
H
H
OH
0

4.033
cyclopropyl
CF3
H
H
OH
0

4.034
OCH3
CF3
H
H
OH
0

4.035
OPh
CF3
H
H
OH
0

4.036
OCHF2
CF3
H
H
OH
0

4.037
CO2Me
CF3
H
H
OH
0

4.038
OCH2CCH
CF3
H
H
OH
0

4.039
H
CF3
H
H
OH
1

4.04
F
CF3
H
H
OH
1

4.041
Cl
CF3
H
H
OH
1

4.042
Br
CF3
H
H
OH
1

4.043
CHF2
CF3
H
H
OH
1

4.044
Cl3
CF3
H
H
OH
1

4.045
CClF2
CF3
H
H
OH
1

4.046
CF3
CF3
H
H
OH
1

4.047
CH3
CF3
H
H
OH
1

4.048
CH2CH3
CF3
H
H
OH
1

4.049
CH(CH3)2
CF3
H
H
OH
1

4.05
(CH2)2CH3
CF3
H
H
OH
1

4.051
C(CH3)3
CF3
H
H
OH
1

4.052
Ph
CF3
H
H
OH
1

4.053
CH2F
CF3
H
H
OH
1

4.054
CH2Cl
CF3
H
H
OH
1

4.055
CH2Br
CF3
H
H
OH
1

4.056
CH2OH
CF3
H
H
OH
1

4.057
CH2OCOCH3
CF3
H
H
OH
1

4.058
CH2OCOPh
CF3
H
H
OH
1

4.059
CH2OCH3
CF3
H
H
OH
1

4.06
CH2OCH2CH3
CF3
H
H
OH
1

4.061
CH2CH2OCH3
CF3
H
H
OH
1

4.062
CH2SMe
CF3
H
H
OH
1

4.063
CH2SOMe
CF3
H
H
OH
1

4.064
CH2SO2Me
CF3
H
H
OH
1

4.065
CH2SO2Ph
CF3
H
H
OH
1

4.066
N(CH3)2
CF3
H
H
OH
1

4.067
CH═CH2
CF3
H
H
OH
1

4.068
CH2CH═CH2
CF3
H
H
OH
1

4.069
SO2N(CH3)2
CF3
H
H
OH
1

4.07
CCH
CF3
H
H
OH
1

4.071
cyclopropyl
CF3
H
H
OH
1

4.072
OCH3
CF3
H
H
OH
1

4.073
OPh
CF3
H
H
OH
1

4.074
OCHF2
CF3
H
H
OH
1

4.075
CO2Me
CF3
H
H
OH
1

4.076
2-furyl
CF3
H
H
OH
1

4.077
OCH2CCH
CF3
H
H
OH
1

4.078
H
CF2CF3
H
H
OH
0

4.079
Cl
CF2CF3
H
H
OH
0

4.08
CHF2
CF2CF3
H
H
OH
0

4.081
CCl3
CF2CF3
H
H
OH
0

4.082
CClF2
CF2CF3
H
H
OH
0

4.083
CF3
CF2CF3
H
H
OH
0

4.084
CH3
CF2CF3
H
H
OH
0

4.085
CH2CH3
CF2CF3
H
H
OH
0

4.086
CH(CH3)2
CF2CF3
H
H
OH
0

4.087
(CH2)2CH3
CF2CF3
H
H
OH
0

4.088
C(CH3)3
CF2CF3
H
H
OH
0

4.089
CH2F
CF2CF3
H
H
OH
0

4.09
CH2Cl
CF2CF3
H
H
OH
0

4.091
CH2OH
CF2CF3
H
H
OH
0

4.092
CH2OCOCH3
CF2CF3
H
H
OH
0

4.093
CH2OCOPh
CF2CF3
H
H
OH
0

4.094
CH2OCH3
CF2CF3
H
H
OH
0

4.095
CH2OCH2CH3
CF2CF3
H
H
OH
0

4.096
CH2SMe
CF2CF3
H
H
OH
0

4.097
CH2SOMe
CF2CF3
H
H
OH
0

4.098
CH2SO2Me
CF2CF3
H
H
OH
0

4.099
CH2SO2Ph
CF2CF3
H
H
OH
0

4.1
N(CH3)2
CF2CF3
H
H
OH
0

4.101
CH═CH2
CF2CF3
H
H
OH
0

4.102
CH2CH═CH2
CF2CF3
H
H
OH
0

4.103
SO2N(CH3)2
CF2CF3
H
H
OH
0

4.104
CCH
CF2CF3
H
H
OH
0

4.105
cyclopropyl
CF2CF3
H
H
OH
0

4.106
OPh
CF2CF3
H
H
OH
0

4.107
OCH3
CF2CF3
H
H
OH
0

4.108
CO2Me
CF2CF3
H
H
OH
0

4.109
OCH2CCH
CF2CF3
H
H
OH
0

4.11
H
CF2CF2CF3
H
H
OH
0

4.111
CHF2
CF2CF2CF3
H
H
OH
0

4.112
CF3
CF2CF2CF3
H
H
OH
0

4.113
CH3
CF2CF2CF3
H
H
OH
0

4.114
CH2CH3
CF2CF2CF3
H
H
OH
0

4.115
(CH2)2CH3
CF2CF2CF3
H
H
OH
0

4.116
CH2Cl
CF2CF2CF3
H
H
OH
0

4.117
CH2OCH3
CF2CF2CF3
H
H
OH
0

4.118
H
CF2Cl
H
H
OH
0

4.119
Cl
CF2Cl
H
H
OH
0

4.12
CHF2
CF2Cl
H
H
OH
0

4.121
CCl3
CF2Cl
H
H
OH
0

4.122
CClF2
CF2Cl
H
H
OH
0

4.123
CF3
CF2Cl
H
H
OH
0

4.124
CH3
CF2Cl
H
H
OH
0

4.125
CH2CH3
CF2Cl
H
H
OH
0

4.126
CH(CH3)2
CF2Cl
H
H
OH
0

4.127
(CH2)2CH3
CF2Cl
H
H
OH
0

4.128
C(CH3)3
CF2Cl
H
H
OH
0

4.129
CH2F
CF2Cl
H
H
OH
0

4.13
CH2Cl
CF2Cl
H
H
OH
0

4.131
CH2OH
CF2Cl
H
H
OH
0

4.132
CH2OCOCH3
CF2Cl
H
H
OH
0

4.133
CH2OCOPh
CF2Cl
H
H
OH
0

4.134
CH2OCH3
CF2Cl
H
H
OH
0

4.135
CH2OCH2CH3
CF2Cl
H
H
OH
0

4.136
CH2SMe
CF2Cl
H
H
OH
0

4.137
CH2SOMe
CF2Cl
H
H
OH
0

4.138
CH2SO2Me
CF2Cl
H
H
OH
0

4.139
CH2SO2Ph
CF2Cl
H
H
OH
0

4.14
N(CH3)2
CF2Cl
H
H
OH
0

4.141
CH═CH2
CF2Cl
H
H
OH
0

4.142
CH2CH═CH2
CF2Cl
H
H
OH
0

4.143
SO2N(CH3)2
CF2Cl
H
H
OH
0

4.144
CCH
CF2Cl
H
H
OH
0

4.145
cyclopropyl
CF2Cl
H
H
OH
0

4.146
OPh
CF2Cl
H
H
OH
0

4.147
OCH3
CF2Cl
H
H
OH
0

4.148
CO2Me
CF2Cl
H
H
OH
0

4.149
OCH2CCH
CF2Cl
H
H
OH
0

4.15
CH3
CF2Cl
H
H
OH
1

4.151
CH2OCH3
CF2Cl
H
H
OH
1

4.152
H
CCl3
H
H
OH
0

4.153
Cl
CCl3
H
H
OH
0

4.154
CH3
CCl3
H
H
OH
0

4.155
CH2CH3
CCl3
H
H
OH
0

4.156
CH(CH3)2
CCl3
H
H
OH
0

4.157
(CH2)2CH3
CCl3
H
H
OH
0

4.158
CH2F
CCl3
H
H
OH
0

4.159
CH2Cl
CCl3
H
H
OH
0

4.16
CH2OH
CCl3
H
H
OH
0

4.161
CH2OCOCH3
CCl3
H
H
OH
0

4.162
CH2OCOPh
CCl3
H
H
OH
0

4.163
CH2OCH3
CCl3
H
H
OH
0

4.164
CH2OCH2CH3
CCl3
H
H
OH
0

4.165
CH2SMe
CCl3
H
H
OH
0

4.166
CH2SOMe
CCl3
H
H
OH
0

4.167
CH2SO2Me
CCl3
H
H
OH
0

4.168
CH2SO2Ph
CCl3
H
H
OH
0

4.169
cyclopropyl
CCl3
H
H
OH
0

4.17
OPh
CCl3
H
H
OH
0

4.171
OCH3
CCl3
H
H
OH
0

4.172
CO2Me
CCl3
H
H
OH
0

4.173
OCH2CCH
CCl3
H
H
OH
0

4.174
CF3
CHF2
H
H
OH
0

4.175
CH3
CHF2
H
H
OH
0

4.176
CH2OCH3
CHF2
H
H
OH
0

4.177
CH2Cl
CHF2
H
H
OH
0

4.178
CH2F
CHF2
H
H
OH
0

4.179
CF3
CHF2
H
H
OH
1

4.18
CH3
CHF2
H
H
OH
1

4.181
CH2OCH3
CHF2
H
H
OH
1

4.182
CH2Cl
CHF2
H
H
OH
1

4.183
CH2F
CHF2
H
H
OH
1

4.184
CH3
CF3
H
CH3
OH
0

4.185
CH3
CF3
H
CH3
OH
1

4.186
Cl
CF3
H
CH3
OH
0

4.187
CH3
CF3
CH3
H
OH
0

4.188
CH3
CF3
Ph
H
OH
0

4.189
CH3
CF3
Cl
H
OH
0

4.19
CH3
CF3
CO2CH2CH3
H
OH
0

4.191
CH3
CF3
CO2CH2Ph
H
OH
0

4.192
CH3
CF3
CH3
H
OH
1

4.193
CH3
CF3
Ph
H
OH
1

4.194
CH3
CF3
Cl
H
OH
1

4.195
CH3
CF3
CO2CH2CH3
H
OH
1

4.196
CH3
CF3
OC2CH2Ph
H
OH
1

4.197
OCH3
CF3
CH3
H
OH
0

4.198
CH2OCH3
CF3
CH3
H
OH
0

4.199
CH2OCH3
CF3
Ph
H
OH
0

4.2
CH2OCH3
CF3
Cl
H
OH
0

4.201
CH2OCH3
CF3
CO2CH2CH3
H
OH
0

4.202
CH2OCH3
CF3
CO2CH2Ph
H
OH
0

4.203
CH2OCH3
CF3
CH3
H
OH
1

4.204
CH2OCH3
CF3
Ph
H
OH
1

4.205
CH2OCH3
CF3
Cl
H
OH
1

4.206
CH2OCH3
CF3
CO2CH2CH3
H
OH
1

4.207
CH2OCH3
CF3
CO2CH2Ph
H
OH
1

4.208
COOCH3
H
H
H
OH
0

4.209
CF3
SCH3
H
H
OH
0

4.21
CH3
SCH3
H
H
OH
0

4.211
CF3
SOCH3
H
H
OH
0

4.212
CH3
SOCH3
H
H
OH
0

4.213
CF3
SO2CH3
H
H
OH
0

4.214
CH3
SO2CH3
H
H
OH
0

4.215
CF3
SCH2CH3
H
H
OH
0

4.216
CH3
SCH2CH3
H
H
OH
0

4.217
CF3
SOCH2CH3
H
H
OH
0

4.218
CH3
SOCH2CH3
H
H
OH
0

4.219
CF3
SO2CH2CH3
H
H
OH
0

4.22
CH3
SO2CH2CH3
H
H
OH
0

4.221
CF3
OCH3
H
H
OH
0

4.222
CH3
OCH3
H
H
OH
0

4.223
CF3
OCH2CF3
H
H
OH
0

4.224
CH3
OCH2CF3
H
H
OH
0

4.225
CF3
OCH2CCH
H
H
OH
0

4.226
CH3
OCH2CCH
H
H
OH
0

4.227
CF3
CN
H
H
OH
0

4.228
CH3
CN
H
H
OH
0

4.229
CF3
Cl
H
H
OH
0

4.23
CH3
Cl
H
H
OH
0

4.231
H
Cl
H
H
OH
0

4.232
CF3
OCH3
H
H
OH
0

4.233
CH3
OCH3
H
H
OH
0

4.234
CF3
CH3
H
H
OH
0

4.235
H
CF3
H
CH3
OH
0

4.236
H
CF3
H
CF3
OH
0

4.237
H
CF3
H
CH2CH3
OH
0

4.238
H
CF3
H
CF3
OH
0

4.239
H
CF3
H
SCH3
OH
0

4.24
H
CF3
H
SOCH3
OH
0

4.241
H
CF3
H
SO2CH3
OH
0

4.242
H
CF3
H
Cl
OH
0

4.243
H
CF3
H
OCH3
OH
0

4.244
H
CH3
H
CF3
OH
0

4.245
H
Cl
H
CF3
OH
0

4.246
H
OCH3
H
CF3
OH
0

4.247
H
SCH3
H
CF3
OH
0

4.248
H
SOCH3
H
CF3
OH
0

4.249
CH3
CF3
H
H
S(CH2)7CH3
0

4.25
CH3
CF3
H
H
S(CH2)7CH3
0

4.251
CH3
CF3
H
H
SO(CH2)7CH3
0

4.252
CH3
CF3
H
H
SO2(CH2)7CH3
0

4.253
CH3
CF3
H
H
SPh
0

4.254
CH3
CF3
H
H
SOPh
0

4.255
CH3
CF3
H
H
SO2Ph
0

4.256
CH3
CF3
H
H
NOCH3
0

4.257
CH3
CF3
H
H
NOCH2Ph
0

4.258
CH3
CF3
H
H
NOCH2CH═CH2
0

4.259
CH3
CF3
H
H
NOC(CH3)3
0

4.26
CH3
CF3
H
H
NOCH2CH3
0

4.261
CH3
CF3
H
H
NCH2CH2SH
0

4.262
CH3
CF3
H
H
NN(CH3)2
0

4.263
CH3
CF3
H
H
NN(CH3)C(S)NH2
0

4.264
CH3
CF3
H
H
N-morpholino
0

4.265
CH3
CF3
H
H
NHCOCH3
0

4.266
CH3
CF3
H
H
NHCO(CH2)7CH3
0

4.267
CH3
CF3
H
H
NHCOPh
0

4.268
CH3
CF3
H
H
NHSO2CH3
0

4.269
CH3
CF3
H
H
NH(CO)S(CH2)7CH3
0

4.27
CH3
CF3
H
H
Cl
0

4.271
CH3
CF3
H
H
NH2
0

4.272
CH3
CF3
H
H
OCOC(CH3)3
0

4.273
CH3
CF3
H
H
OCOCH3
0

4.274
CH3
CF3
H
H
OCOPh
0

4.275
CH3
CF3
H
H
OCO-cyclopropyl
0

4.276
CH3
CF3
H
H
OCOCH2CH3
0

4.277
CH3
CF3
H
H
OCOCH═CH2
0

4.278
CH3
CF3
H
H
OCOCH═CHCH3
0

4.279
CH3
CF3
H
H
O(CO)SCH3
0

4.28
CH3
CF3
H
H
O(CO)S(CH2)7CH3
0

4.281
CH3
CF3
H
H
O(CO)OCH2CH3
0

4.282
CH3
CF3
H
H
O(CO)N(CH2CH3)2
0

4.283
CH3
(CF2)3CF3
H
H
OH
0

4.284
CH3
CF3
H
H
S-(4-Cl-phenyl)
0

4.285
CH3
CF3
H
H
SO-(4-Cl-phenyl)
0

4.286
CH3
CF3
H
H
SO2-(4-Cl-phenyl)
0

4.287
CH3
CF3
H
H
S-(4-CF3-phenyl)
0

4288
CH3
CF3
H
H
SO-(4-CF3-phenyl)
0

4.289
CH3
CF3
H
H
SO2-(4-CF3-phenyl)
0

4.29
CH3
CF3
H
H
S-(4-NO2-phenyl)
0

4.291
CH3
CF3
H
H
SO-(4-NO2-phenyl)
0

4.292
CH3
CF3
H
H
SO2-(4-NO2-phenyl)
0

4.293
CH3
CF3
H
H

0

4.294
CH3
CF3
H
H

0

4.295
CH3
CF3
H
H

0

4.296
CH3
CF3
H
H

0

4.297
CF2H
SCH3
H
H
OH
0

4.298
CF2Cl
SCH3
H
H
OH
0

4.299
CF2H
SOCH3
H
H
OH
0

4.3
CF2Cl
SOCH3
H
H
OH
0

4.301
CF2H
SO2CH3
H
H
OH
0

4.302
CF2Cl
SO2CH3
H
H
OH
0

4.303
CF2H
SCH2CH3
H
H
OH
0

4.304
CF2Cl
SCH2CH3
H
H
OH
0

4.305
CF2H
SOCH2CH3
H
H
OH
0

4.306
CF2Cl
SOCH2CH3
H
H
OH
0

4.307
CF2H
SO2CH2CH3
H
H
OH
0

4.308
CF2Cl
SO2CH2CH3
H
H
OH
0

4.309
CF2H
OCH3
H
H
OH
0

4.31
CF2Cl
OCH3
H
H
OH
0

4.311
CF2H
OCH2CF3
H
H
OH
0

4.312
CF2Cl
OCH2CF3
H
H
OH
0

4.313
CF2H
OCH2CCH
H
H
OH
0

4.314
CF2Cl
OCH2CCH
H
H
OH
0

4.315
CF2H
CN
H
H
OH
0

4.316
CF2Cl
CN
H
H
OH
0

4.317
CF2H
Cl
H
H
OH
0

4.318
CF2Cl
Cl
H
H
OH
0

4.319
CF2H
OCH3
H
H
OH
0

4.32
CF2Cl
OCH3
H
H
OH
0

4.321
CF3
CH2OCH3
H
H
OH
0

4.322
CF3
CH2OCH3
H
H
OH
1

4.323
CF2Cl
CH2OCH3
H
H
OH
0

4.324
CF2Cl
CH2OCH3
H
H
OH
1

4.325
CF2H
CH2OCH3
H
H
OH
0

4.326
CF2H
CH2OCH3
H
H
OH
1

4.327
CN
CF3
H
H
OH
0

4.328
SCH3
H
H
H
OH
0

[0263]

5

TABLE 5

Comp. No.
R1
R2
R3
R4
R5

5.001
H
CF3
H
H
CH3

5.002
F
CF3
H
H
CH3

5.003
Cl
CF3
H
H
CH3

5.004
CHF2
CF3
H
H
CH3

5.005
CCl3
CF3
H
H
CH3

5.006
CClF2
CF3
H
H
CH3

5.007
CF3
CF3
H
H
CH3

5.008
CH3
CF3
H
H
CH3

5.009
CH2CH3
CF3
H
H
CH3

5.01
CH(CH3)2
CF3
H
H
CH3

5.011
(CH2)2CH3
CF3
H
H
CH3

5.012
CH2F
CF3
H
H
CH3

5.013
CH2Cl
CF3
H
H
CH3

5.014
CH2Br
CF3
H
H
CH3

5.015
CH2OCOCH3
CF3
H
H
CH3

5.016
CH2OCH3
CF3
H
H
CH3

5.017
CH2CH2OCH3
CF3
H
H
CH3

5.018
CH2SMe
CF3
H
H
CH3

5.019
CH2SOMe
CF3
H
H
CH3

5.02
CH2SO2Me
CF3
H
H
CH3

5.021
N(CH3)2
CF3
H
H
CH3

5.022
CH═CH2
CF3
H
H
CH3

5.023
CH2CH═CH2
CF3
H
H
CH3

5.024
SO2N(CH3)2
CF3
H
H
CH3

5.025
CCH
CF3
H
H
CH3

5.026
cyclopropyl
CF3
H
H
CH3

5.027
OCH3
CF3
H
H
CH3

5.028
OPh
CF3
H
H
CH3

5.029
OCHF2
CF3
H
H
CH3

5.03
CO2Me
CF3
H
H
CH3

5.031
OCH2CCH
CF3
H
H
CH3

5.032
CF3
SCH3
H
H
CH3

5.033
CH3
SCH3
H
H
CH3

5.034
CF3
SOCH3
H
H
CH3

5.035
CH3
SOCH3
H
H
CH3

5.036
CF3
SO2CH3
H
H
CH3

5.037
CH3
SO2CH3
H
H
CH3

5.038
CF3
OCH3
H
H
CH3

5.039
CH3
OCH3
H
H
CH3

5.04
CF3
OCH2CF3
H
H
CH3

5.041
CH3
OCH2CF3
H
H
CH3

5.042
CF3
OCH2CCH
H
H
CH3

5.043
CH3
OCH2CCH
H
H
CH3

5.044
CF3
CN
H
H
CH3

5.045
CH3
CN
H
H
CH3

5.046
CF3
Cl
H
H
CH3

5.047
CH3
Cl
H
H
CH3

5.048
H
Cl
H
H
CH3

5.049
CF3
OCH3
H
H
CH3

5.05
CH3
OCH3
H
H
CH3

5.051
CF3
CH3
H
H
CH3

5.052
H
CF3
H
CH3
CH3

5.053
H
CF3
H
CF3
CH3

5.054
H
CF3
H
CH2CH3
CH3

5.055
H
CF3
H
CF3
CH3

5.056
H
CF3
H
SCH3
CH3

5.057
H
CF3
H
SOCH3
CH3

5.058
H
CF3
H
SO2CH3
CH3

5.059
H
CF3
H
Cl
CH3

5.06
H
CF3
H
OCH3
CH3

5.061
H
CH3
H
CF3
CH3

5.062
H
Cl
H
CF3
CH3

5.063
H
OCH3
H
CF3
CH3

5.064
H
SCH3
H
CF3
CH3

5.065
H
SOCH3
H
CF3
CH3

5.066
CF2Cl
CH3
H
H
CH3

5.067
CF2Cl
CH2CH3
H
H
CH3

5.068
CF2Cl
SCH3
H
H
CH3

5.069
CF2Cl
SOCH3
H
H
CH3

5.07
CF2Cl
SO2CH3
H
H
CH3

5.071
CF2Cl
OCH3
H
H
CH3

5.072
CF2Cl
OCH2CF3
H
H
CH3

5.073
CF2Cl
OCH2CCH
H
H
CH3

5.074
CF2Cl
CN
H
H
CH3

5.075
CF2Cl
Cl
H
H
CH3

5.076
CF2Cl
OCH3
H
H
CH3

5.077
CF3
CH2OCH3
H
H
CH3

5.078
CF2Cl
CH2OCH3
H
H
CH3

5.079
CF2H
CH2OCH3
H
H
CH3

5.08
CN
CF3
H
H
CH3

5.081
CH3
CF3
H
H
CH2CH3

5.082
CH3
CF3
H
H
SCH3

5.083
CH3
CF3
H
H
SOCH3

5.084
CH3
CF3
H
H
SO2CH3

5.085
CH3
CF3
H
H
H

[0264]

6

TABLE 6

Comp. No.
R1
R2
R3
R4
R5

6.001
Cl
CF3
H
H
CH2CH3

6.002
CHF2
CF3
H
H
CH2CH3

6.003
CCl3
CF3
H
H
CH2CH3

6.004
CClF2
CF3
H
H
CH2CH3

6.005
CF3
CF3
H
H
CH2CH3

6.006
CH3
CF3
H
H
CH2CH3

6.007
CH2CH3
CF3
H
H
CH2CH3

6.008
(CH2)2CH3
CF3
H
H
CH2CH3

6.009
CH2F
CF3
H
H
CH2CH3

6.01
CH2Cl
CF3
H
H
CH2CH3

6.011
CH2OCH3
CF3
H
H
CH2CH3

6.012
CH2SMe
CF3
H
H
CH2CH3

6.013
CH2SO2Me
CF3
H
H
CH2CH3

6.014
CH═CH2
CF3
H
H
CH2CH3

6.015
CH2CH═CH2
CF3
H
H
CH2CH3

6.016
CCH
CF3
H
H
CH2CH3

6.017
CF3
SCH3
H
H
CH2CH3

6.018
CF3
SOCH3
H
H
CH2CH3

6.019
CF3
SO2CH3
H
H
CH2CH3

6.02
CF3
OCH3
H
H
CH2CH3

6.021
CF3
CN
H
H
CH2CH3

6.022
CF3
Cl
H
H
CH2CH3

6.023
CF3
OCH3
H
H
CH2CH3

6.024
CF3
CH3
H
H
CH2CH3

6.025
H
CF3
H
CH3
CH2CH3

6.026
H
CF3
H
CF3
CH2CH3

6.027
H
CF3
H
SCH3
CH2CH3

6.028
H
CF3
H
SOCH3
CH2CH3

6.029
H
CF3
H
SO2CH3
CH2CH3

6.03
H
CF3
H
Cl
CH2CH3

6.031
H
CF3
H
OCH3
CH2CH3

6.032
H
CH3
H
CF3
CH2CH3

6.033
H
Cl
H
CF3
CH2CH3

6.034
H
OCH3
H
CF3
CH2CH3

6.035
CN
CF3
H
H
CH2CH3

6.036
Cl
CF3
H
H
CH(CH3)2

6.037
CHF2
CF3
H
H
CH(CH3)2

6.038
CCl3
CF3
H
H
CH(CH3)2

6.039
CClF2
CF3
H
H
CH(CH3)2

6.04
CF3
CF3
H
H
CH(CH3)2

6.041
CH3
CF3
H
H
CH(CH3)2

6.042
CH2CH3
CF3
H
H
CH(CH3)2

6.043
(CH2)2CH3
CF3
H
H
CH(CH3)2

6.044
CH2F
CF3
H
H
CH(CH3)2

6.045
CH2Cl
CF3
H
H
CH(CH3)2

6.046
CH2OCH3
CF3
H
H
CH(CH3)2

6.047
CH2SMe
CF3
H
H
CH(CH3)2

6.048
CH2SO2Me
CF3
H
H
CH(CH3)2

6.049
CH═CH2
CF3
H
H
CH(CH3)2

6.05
CH2CH═CH2
CF3
H
H
CH(CH3)2

6.051
CCH
CF3
H
H
CH(CH3)2

6.052
CF3
SCH3
H
H
CH(CH3)2

6.053
CF3
SOCH3
H
H
CH(CH3)2

6.054
CF3
SO2CH3
H
H
CH(CH3)2

6.055
CF3
OCH3
H
H
CH(CH3)2

6.056
CF3
CN
H
H
CH(CH3)2

6.057
CF3
Cl
H
H
CH(CH3)2

6.058
CF3
OCH3
H
H
CH(CH3)2

6.059
CF3
CH3
H
H
CH(CH3)2

6.06
H
CF3
H
CH3
CH(CH3)2

6.061
H
CF3
H
CF3
CH(CH3)2

6.062
H
CF3
H
SCH3
CH(CH3)2

6.063
H
CF3
H
SOCH3
CH(CH3)2

6.064
H
CF3
H
SO2CH3
CH(CH3)2

6.065
H
CF3
H
Cl
CH(CH3)2

6.066
H
CF3
H
OCH3
CH(CH3)2

6.067
H
CH3
H
CF3
CH(CH3)2

6.068
H
Cl
H
CF3
CH(CH3)2

6.069
H
OCH3
H
CF3
CH(CH3)2

6.07
CN
CF3
H
H
CH(CH3)2

6.071
Cl
CF3
H
H
HNPh

6.072
CHF2
CF3
H
H
HNPh

6.073
CCl3
CF3
H
H
HNPh

6.074
CClF2
CF3
H
H
HNPh

6.075
CF3
CF3
H
H
HNPh

6.076
CH3
CF3
H
H
HNPh

6.077
CH2CH3
CF3
H
H
HNPh

6.078
(CH2)2CH3
CF3
H
H
HNPh

6.079
CH2F
CF3
H
H
HNPh

6.08
CH2Cl
CF3
H
H
HNPh

6.081
CH2OCH3
CF3
H
H
HNPh

6.082
CH2SMe
CF3
H
H
HNPh

6.083
CH2SO2Me
CF3
H
H
HNPh

6.084
CH═CH2
CF3
H
H
HNPh

6.085
CH2CH═CH2
CF3
H
H
HNPh

6.086
CCH
CF3
H
H
HNPh

6.087
CF3
SCH3
H
H
HNPh

6.088
CF3
SOCH3
H
H
HNPh

6.089
CF3
SO2CH3
H
H
HNPh

6.09
CF3
OCH3
H
H
HNPh

6.091
CF3
CN
H
H
HNPh

6.092
CF3
Cl
H
H
HNPh

6.093
CF3
OCH3
H
H
HNPh

6.094
CF3
CH3
H
H
HNPh

6.095
H
CF3
H
CH3
HNPh

6.096
H
CF3
H
CF3
HNPh

6.097
H
CF3
H
SCH3
HNPh

6.098
H
CF3
H
SOCH3
HNPh

6.099
H
CF3
H
SO2CH3
HNPh

6.1
H
CF3
H
Cl
HNPh

6.101
H
CF3
H
OCH3
HNPh

6.102
H
CH3
H
CF3
HNPh

6.103
H
Cl
H
CF3
HNPh

6.104
H
OCH3
H
CF3
HNPh

6.105
CN
CF3
H
H
HNPh

6.106
Cl
CF3
H
H
HNC(CH3)3

6.107
CHF2
CF3
H
H
HNC(CH3)3

6.108
CCl3
CF3
H
H
HNC(CH3)3

6.109
CClF2
CF3
H
H
HNC(CH3)3

6.11
CF3
CF3
H
H
HNC(CH3)3

6.111
CH3
CF3
H
H
HNC(CH3)3

6.112
CH2CH3
CF3
H
H
HNC(CH3)3

6.113
(CH2)2CH3
CF3
H
H
HNC(CH3)3

6.114
CH2F
CF3
H
H
HNC(CH3)3

6.115
CH2Cl
CF3
H
H
HNC(CH3)3

6.116
CH2OCH3
CF3
H
H
HNC(CH3)3

6.117
CH2SMe
CF3
H
H
HNC(CH3)3

6.118
CH2SO2Me
CF3
H
H
HNC(CH3)3

6.119
CH═CH2
CF3
H
H
HNC(CH3)3

6.12
CH2CH═CH2
CF3
H
H
HNC(CH3)3

6.121
CCH
CF3
H
H
HNC(CH3)3

6.122
CF3
SCH3
H
H
HNC(CH3)3

6.123
CF3
SOCH3
H
H
HNC(CH3)3

6.124
CF3
SO2CH3
H
H
HNC(CH3)3

6.125
CF3
OCH3
H
H
HNC(CH3)3

6.126
CF3
CN
H
H
HNC(CH3)3

6.127
CF3
Cl
H
H
HNC(CH3)3

6.128
CF3
OCH3
H
H
HNC(CH3)3

6.129
CF3
CH3
H
H
HNC(CH3)3

6.13
H
CF3
H
CH3
HNC(CH3)3

6.131
H
CF3
H
CF3
HNC(CH3)3

6.132
H
CF3
H
SCH3
HNC(CH3)3

6.133
H
CF3
H
SOCH3
HNC(CH3)3

6.134
H
CF3
H
SO2CH3
HNC(CH3)3

6.135
H
CF3
H
Cl
HNC(CH3)3

6.136
H
CF3
H
OCH3
HNC(CH3)3

6.137
H
CH3
H
CF3
HNC(CH3)3

6.138
H
Cl
H
CF3
HNC(CH3)3

6.139
H
OCH3
H
CF3
HNC(CH3)3

6.14
CN
CF3
H
H
HNC(CH3)3

[0265]

7

TABLE 7

Comp. No.
R1
R2
R3
R4
p

7.001
H
CF3
H
H
0

7.002
F
CF3
H
H
0

7.003
Cl
CF3
H
H
0

7.004
Br
CF3
H
H
0

7.005
CHF2
CF3
H
H
0

7.006
CCl3
CF3
H
H
0

7.007
CClF2
CF3
H
H
0

7.008
CF3
CF3
H
H
0

7.009
CH3
CF3
H
H
0

7.01
CH2CH3
CF3
H
H
0

7.011
CH(CH3)2
CF3
H
H
0

7.012
(CH2)2CH3
CF3
H
H
0

7.013
C(CH3)3
CF3
H
H
0

7.014
Ph
CF3
H
H
0

7.015
CH2F
CF3
H
H
0

7.016
CH2Cl
CF3
H
H
0

7.017
CH2Br
CF3
H
H
0

7.018
CH2OH
CF3
H
H
0

7.019
CH2OCOCH3
CF3
H
H
0

7.02
CH2OCOPh
CF3
H
H
0

7.021
CH2OCH3
CF3
H
H
0

7.022
CH2OCH2CH3
CF3
H
H
0

7.023
CH2CH2OCH3
CF3
H
H
0

7.024
CH2SMe
CF3
H
H
0

7.025
CH2SOMe
CF3
H
H
0

7.026
CH2SO2Me
CF3
H
H
0

7.027
CH2SO2Ph
CF3
H
H
0

7.028
SCH3
CF3
H
H
0

7.029
SOCH3
CF3
H
H
0

7.03
SO2CH3
CF3
H
H
0

7.031
N(CH3)2
CF3
H
H
0

7.032
CH═CH2
CF3
H
H
0

7.033
CH2CH═CH2
CF3
H
H
0

7.034
SO2N(CH3)2
CF3
H
H
0

7.035
CCH
CF3
H
H
0

7.036
cyclopropyl
CF3
H
H
0

7.037
OCH3
CF3
H
H
0

7.038
OCHF2
CF3
H
H
0

7.039
OCH2CCH
CF3
H
H
0

7.04
H
CF2CF3
H
H
0

7.041
Cl
CF2CF3
H
H
0

7.042
CHF2
CF2CF3
H
H
0

7.043
CCl3
CF2CF3
H
H
0

7.044
CClF2
CF2CF3
H
H
0

7.045
CF3
CF2CF3
H
H
0

7.046
CH3
CF2CF3
H
H
0

7.047
CH2CH3
CF2CF3
H
H
0

7.048
CH(CH3)2
CF2CF3
H
H
0

7.049
(CH2)2CH3
CF2CF3
H
H
0

7.05
C(CH3)3
CF2CF3
H
H
0

7.051
CH2F
CF2CF3
H
H
0

7.052
CH2Cl
CF2CF3
H
H
0

7.053
CH2OH
CF2CF3
H
H
0

7.054
CH2OCOCH3
CF2CF3
H
H
0

7.055
CH2OCOPh
CF2CF3
H
H
0

7.056
CH2OCH3
CF2CF3
H
H
0

7.057
CH2OCH2CH3
CF2CF3
H
H
0

7.058
CH2SMe
CF2CF3
H
H
0

7.059
CH2SOMe
CF2CF3
H
H
0

7.06
CH2SO2Me
CF2CF3
H
H
0

7.061
CH2SO2Ph
CF2CF3
H
H
0

7.062
N(CH3)2
CF2CF3
H
H
0

7.063
CH═CH2
CF2CF3
H
H
0

7.064
CH2CH═CH2
CF2CF3
H
H
0

7.065
SO2N(CH3)2
CF2CF3
H
H
0

7.066
CCH
CF2CF3
H
H
0

7.067
cyclopropyl
CF2CF3
H
H
0

7.068
OCH3
CF2CF3
H
H
0

7.069
CO2Me
CF2CF3
H
H
0

7.07
OCH2CCH
CF2CF3
H
H
0

7.071
H
CF2Cl
H
H
0

7.072
Cl
CF2Cl
H
H
0

7.073
CHF2
CF2Cl
H
H
0

7.074
CCl3
CF2Cl
H
H
0

7.075
CClF2
CF2Cl
H
H
0

7.076
CF3
CF2Cl
H
H
0

7.077
CH3
CF2Cl
H
H
0

7.078
CH2CH3
CF2Cl
H
H
0

7.079
CH(CH3)2
CF2Cl
H
H
0

7.08
(CH2)2CH3
CF2Cl
H
H
0

7.081
C(CH3)3
CF2Cl
H
H
0

7.082
CH2F
CF2Cl
H
H
0

7.083
CH2Cl
CF2Cl
H
H
0

7.084
CH2OH
CF2Cl
H
H
0

7.085
CH2OCOCH3
CF2Cl
H
H
0

7.086
CH2OCOPh
CF2Cl
H
H
0

7.087
CH2OCH3
CF2Cl
H
H
0

7.088
CH2OCH2CH3
CF2Cl
H
H
0

7.089
CH2SMe
CF2Cl
H
H
0

7.09
CH2SOMe
CF2Cl
H
H
0

7.091
CH2SO2Me
CF2Cl
H
H
0

7.092
CH2SO2Ph
CF2Cl
H
H
0

7.093
N(CH3)2
CF2Cl
H
H
0

7.094
CH═CH2
CF2Cl
H
H
0

7.095
CH2CH═CH2
CF2Cl
H
H
0

7.096
SO2N(CH3)2
CF2Cl
H
H
0

7.097
CCH
CF2Cl
H
H
0

7.098
cyclopropyl
CF2Cl
H
H
0

7.099
OCH3
CF2Cl
H
H
0

7.1
OCH2CCH
CF2Cl
H
H
0

7.101
CF3
CHF2
H
H
0

7.102
CH3
CHF2
H
H
0

7.103
CH2OCH3
CHF2
H
H
0

7.104
CH2Cl
CHF2
H
H
0

7.105
CH2F
CHF2
H
H
0

7.106
CH3
CF3
H
CH3
0

7.107
Cl
CF3
H
CH3
0

7.108
CH3
CF3
CH3
H
0

7.109
CH3
CF3
Cl
H
0

7.11
OCH3
CF3
CH3
H
0

7.111
CH2OCH3
CF3
CH3
H
0

7.112
CH2OCH3
CF3
Cl
H
0

7.113
COOCH3
H
H
H
0

7.114
CF3
SCH3
H
H
0

7.115
CH3
SCH3
H
H
0

7.116
CF3
SOCH3
H
H
0

7.117
CH3
SOCH3
H
H
0

7.118
CF3
SO2CH3
H
H
0

7.119
CH3
SO2CH3
H
H
0

7.12
CF3
OCH3
H
H
0

7.121
CH3
OCH3
H
H
0

7.122
CF3
OCH2CF3
H
H
0

7.123
CH3
OCH2CF3
H
H
0

7.124
CF3
OCH2CCH
H
H
0

7.125
CH3
OCH2CCH
H
H
0

7.126
CF3
CN
H
H
0

7.127
CH3
CN
H
H
0

7.128
CF3
Cl
H
H
0

7.129
CF3
Cl
H
H
0

7.13
CH3
Cl
H
H
0

7.131
H
Cl
H
H
0

7.132
CF3
OCH3
H
H
0

7.133
CH3
OCH3
H
H
0

7.134
CF3
CH3
H
H
0

7.135
H
CF3
H
CH3
0

7.136
H
CF3
H
CF3
0

7.137
H
CF3
H
CH2CH3
0

7.138
H
CF3
H
CF3
0

7.139
H
CF3
H
SCH3
0

7.14
H
CF3
H
SOCH3
0

7.141
H
CF3
H
SO2CH3
0

7.142
H
CF3
H
Cl
0

7.143
H
CF3
H
OCH3
0

7.144
H
CH3
H
CF3
0

7.145
H
Cl
H
CF3
0

7.146
H
OCH3
H
CF3
0

7.147
H
SCH3
H
CF3
0

7.148
H
SOCH3
H
CF3
0

7.149
CH3
(CF2)3CF3
H
H
0

7.15
CF2H
SCH3
H
H
0

7.151
CF2Cl
SCH3
H
H
0

7.152
CF2H
SOCH3
H
H
0

7.153
CF2Cl
SOCH3
H
H
0

7.154
CF2H
SO2CH3
H
H
0

7.155
CF2Cl
SO2CH3
H
H
0

7.156
CF2H
OCH3
H
H
0

7.157
CF2Cl
OCH3
H
H
0

7.158
CF2H
OCH2CF3
H
H
0

7.159
CF2Cl
OCH2CF3
H
H
0

7.16
CF2H
OCH2CCH
H
H
0

7.161
CF2Cl
OCH2CCH
H
H
0

7.162
CF2H
CN
H
H
0

7.163
CF2Cl
CN
H
H
0

7.164
CF2H
Cl
H
H
0

7.165
CF2Cl
Cl
H
H
0

7.166
CF2H
OCH3
H
H
0

7.167
CF2Cl
OCH3
H
H
0

7.168
CF3
CH2OCH3
H
H
0

7.169
CF2Cl
CH2OCH3
H
H
0

7.17
CF2H
CH2OCH3
H
H
0

7.171
CN
CF3
H
H
0

7.172
H
CF3
H
H
2

7.173
F
CF3
H
H
2

7.174
Cl
CF3
H
H
2

7.175
Br
CF3
H
H
2

7.176
CHF2
CF3
H
H
2

7.177
CCl3
CF3
H
H
2

7.178
CClF2
CF3
H
H
2

7.179
CF3
CF3
H
H
2

7.18
CH3
CF3
H
H
2

7.181
CH2CH3
CF3
H
H
2

7.182
CH(CH3)2
CF3
H
H
2

7.183
(CH2)2CH3
CF3
H
H
2

7.184
C(CH3)3
CF3
H
H
2

7.185
Ph
CF3
H
H
2

7.186
CH2F
CF3
H
H
2

7.187
CH2Cl
CF3
H
H
2

7.188
CH2Br
CF3
H
H
2

7.189
CH2OH
CF3
H
H
2

7.19
CH2OCOCH3
CF3
H
H
2

7.191
CH2OCOPh
CF3
H
H
2

7.192
CH2OCH3
CF3
H
H
2

7.193
CH2OCH2CH3
CF3
H
H
2

7.194
CH2CH2OCH3
CF3
H
H
2

7.195
CH2SMe
CF3
H
H
2

7.196
CH2SOMe
CF3
H
H
2

7.197
CH2SO2Me
CF3
H
H
2

7.198
CH2SO2Ph
CF3
H
H
2

7.199
SCH3
CF3
H
H
2

7.2
SOCH3
CF3
H
H
2

7.201
SO2CH3
CF3
H
H
2

7.202
N(CH3)2
CF3
H
H
2

7.203
CH═CH2
CF3
H
H
2

7.204
CH2CH═CH2
CF3
H
H
2

7.205
SO2N(CH3)2
CF3
H
H
2

7.206
CCH
CF3
H
H
2

7.207
cyclopropyl
CF3
H
H
2

7.208
OCH3
CF3
H
H
2

7.209
OCHF2
CF3
H
H
2

7.21
OCH2CCH
CF3
H
H
2

[0266]

8

TABLE 8

Comp. No.
R1
R2
R3
R4

8.001
H
CF3
H
H

8.002
F
CF3
H
H

8.003
Cl
CF3
H
H

8.004
Br
CF3
H
H

8.005
CHF2
CF3
H
H

8.006
CCl3
CF3
H
H

8.007
CClF2
CF3
H
H

8.008
CF3
CF3
H
H

8.009
CH3
CF3
H
H

8.01
CH2CH3
CF3
H
H

8.011
CH(CH3)2
CF3
H
H

8.012
(CH2)2CH3
CF3
H
H

8.013
C(CH3)3
CF3
H
H

8.014
Ph
CF3
H
H

8.015
CH2F
CF3
H
H

8.016
CH2Cl
CF3
H
H

8.017
CH2Br
CF3
H
H

8.018
CH2OH
CF3
H
H

8.019
CH2OCOCH3
CF3
H
H

8.02
CH2OCOPh
CF3
H
H

8.021
CH2OCH3
CF3
H
H

8.022
CH2OCH2CH3
CF3
H
H

8.023
CH2CH2OCH3
CF3
H
H

8.024
CH2SMe
CF3
H
H

8.025
CH2SOMe
CF3
H
H

8.026
CH2SO2Me
CF3
H
H

8.027
CH2SO2Ph
CF3
H
H

8.028
SCH3
CF3
H
H

8.029
SOCH3
CF3
H
H

8.03
SO2CH3
CF3
H
H

8.031
N(CH3)2
CF3
H
H

8.032
CH═CH2
CF3
H
H

8.033
CH2CH═CH2
CF3
H
H

8.034
SO2N(CH3)2
CF3
H
H

8.035
CCH
CF3
H
H

8.036
cyclopropyl
CF3
H
H

8.037
OCH3
CF3
H
H

8.038
OCHF2
CF3
H
H

8.039
OCH2CCH
CF3
H
H

[0267]

9

TABLE 9

Comp. No.
R1
R2
R3
R4

9.001
H
CF3
H
H

9.002
F
CF3
H
H

9.003
Cl
CF3
H
H

9.004
Br
CF3
H
H

9.005
CHF2
CF3
H
H

9.006
CCl3
CF3
H
H

9.007
CClF2
CF3
H
H

9.008
CF3
CF3
H
H

9.009
CH3
CF3
H
H

9.01
CH2CH3
CF3
H
H

9.011
CH(CH3)2
CF3
H
H

9.012
(CH2)2CH3
CF3
H
H

9.013
C(CH3)3
CF3
H
H

9.014
Ph
CF3
H
H

9.015
CH2F
CF3
H
H

9.016
CH2Cl
CF3
H
H

9.017
CH2Br
CF3
H
H

9.018
CH2OH
CF3
H
H

9.019
CH2OCOCH3
CF3
H
H

9.02
CH2OCOPh
CF3
H
H

9.021
CH2OCH3
CF3
H
H

9.022
CH2OCH2CH3
CF3
H
H

9.023
CH2CH2OCH3
CF3
H
H

9.024
CH2SMe
CF3
H
H

9.025
CH2SOMe
CF3
H
H

9.026
CH2SO2Me
CF3
H
H

9.027
CH2SO2Ph
CF3
H
H

9.028
SCH3
CF3
H
H

9.029
SOCH3
CF3
H
H

9.03
SO2CH3
CF3
H
H

9.031
N(CH3)2
CF3
H
H

9.032
CH═CH2
CF3
H
H

9.033
CH2CH═CH2
CF3
H
H

9.034
SO2N(CH3)2
CF3
H
H

9.035
CCH
CF3
H
H

9.036
cyclopropyl
CF3
H
H

9.037
OCH3
CF3
H
H

9.038
OCHF2
CF3
H
H

9.039
OCH2CCH
CF3
H
H

[0268]

10

Physical data (melting points in ° C.):

Comp.

No.

1.001
resin

1.005
crystals m.p. 61-62

1.008
oil

1.009
crystals m.p. 75-77

1.01
oil

1.011
crystals m.p. 111-112

1.012
crystals m.p. 87-88

1.013
crystals m.p. 112-114

1.014
oil

1.021
crystals m.p. 128-129

1.023
crystals m.p. 91-92

1.024
oil

1.026
amorphous

1.028
amorphous

1.03
resin

1.031
crystals m.p. 145-146

1.042
oil

1.043
crystals m.p. 107-110

1.047
crystals m.p. 155-156

1.048
viscous

1.05
crystals m.p. 51-53

1.06
crystals m.p. >220

1.109
oil

1.195
oil

1.258
crystals m.p. 119-121

1.31
crystals m.p. 92-94

1.312
viscous

1.313
crystals m.p. 137-138

1.314
oil

1.316
resin

1.323
oil

1.334
resin

1.335
crystals m.p. 140-142

1.339
crystals m.p. 137-139

1.341
resin

1.343
crystals m.p. 97-99

1.347
crystals m.p. 135-137

1.349
oil, nD 1.4965

1.351
crystals m.p. 125-127

1.353
resin, nD 1.5289

1.355
crystals m.p. 90-92

1.356
resin

1.358
resin

1.361
oil

1.362
crystals m.p. 139-142

1.371
crystals m.p. 96-97

1.372
resin

1.373
resin

1.374
crystals m.p. 116-1199

1.375
resin

1.376
crystals m.p. >270

1.381
crystals m.p. 117-118

1.383
crystals m.p. 172-173

1.384
resin

1.385
resin

1.386
resin

1.387
resin

1.388
crystals m.p. 102-104

1.389
crystals m.p. 143-145

1.39
crystals m.p. 195-197

1.391
solid

1.392
crystals m.p. 202-206

1.398
crystals m.p. 137-138

1.399
crystals m.p. 262-263

1.4
oil

1.401
oil

1.402
oil

1.403
oil

1.404
oil

1.405
viscous

1.406
oil

1.408
oil

1.409
oil

1.41
oil

1.411
crystals m.p. 98-100

1.412
crystals m.p. 130-131

1.413
crystals m.p. 167-170

1.414
crystals m.p. 166-167

1.415
crystals m.p. 91-93

1.418
crystals m.p. 149-150

1.421
crystals m.p. 88-89

1.422
crystals m.p. 175-177

1.423
crystals m.p. 45-47

1.424
crystals m.p. 102-104

2.001
resin

2.003
oil

2.03
crystals m.p. 107-110

2.038
crystals m.p. 111-113

2.043
resin

2.044
crystals m.p. 105-106

2.045
amorphous

3.001
crystals m.p. 95-97

3.054
oil

3.055
crystals m.p. 108-110

3.056
resin, DD 1.5509

4.009
crystals m.p. 107-109

4.01
oil

4.011
oil

4.014
crystals m.p. 148-149

4.021
crystals m.p. 44-45

4.033
crystals m.p. 46-48

4.124
crystals m.p. 46-48

4.328
oil

5.008
resin

5.081
resin

5.083
crystals m.p. 161-162

5.084
crystals m.p. 215-216

5.085
resin

6.006
crystals m.p. 176-177

6.041
crystals m.p. 186-187

6.076
crystals m.p. 195-196

6.111
crystals m.p. 163-164

7.009
ratio A: B = 2:1. H-NMR(CDCl3,ppm) SCH3: A: 2.50; B: 2.66.

7.01
ratio A: B = 5:1. H-NMR(CDCl3,ppm) SCH3: A: 2.50; B: 2.64.

7.011
ratio A: B = 9:1. H-NMR(CDCl3,ppm) SCH3: A: 2.46; B: 2.59.

7.021
ratio A: B = 3:1. H-NMR(CDCl3,ppm) SCH3: A: 2.50; B: 2.62.

7.18
ratio A: B = 2:. H-NMR(CDCl3,ppm) SO2CH3: A: 3.40;

B: 3.58.

7.182
ratio A: B = 9:1. H-NMR(CDCl3,ppm) SO2CH3: A: 3.32;

B: 3.50.

7.192
ratio A: B = 3:1. H-NMR(CDCl3,ppm) SO2CH3: A: 3.40;

B: 3.58.

8.009
crystals m.p. 96-97

8.01
amorphous

8.011
oil

8.021
oil

9.009
crystals m.p. 112-113

9.01
amorphous

9.011
amorphous

9.021
oil

Biological Examples

Example B1

Herbical action before emergence of the plants (pre-emergence action)

[0269] Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on (500 l of water/ha) as an aqueous suspension (prepared from a 25% wettable powder (Example F3, b) according to WO 97/34485) or emulsion (prepared from a 25% emulsion concentrate (Example F1, c)), corresponding to a dosage of 2 kg of AS/ha. The test plants are then grown under optimum conditions in a greenhouse. After a test period of 3 weeks, the test is evaluated with a nine-level scale of ratings (1=complete damage, 9=no effect). Ratings of 1 to 4 (in particular 1 to 3) mean good to very good herbicidal action.

11TABLE B1pre-emergence action:ActivecompoundTest plantNo.AvenaCyperusSetariaSinapisSolanumStellaria1.0092112121.3762112124.0091212137.0094213121.3814122111.0112111115.0082112124.0212122121.0102111121.0214211131.3982111111.1952111124.1242122121.4113212121.0424221141.0232221121.1092222131.3133121121.4012112121.4042112121.4002112121.4032111121.4052111121.4062111121.4022112121.0054111111.0434212121.4091111111.41 2111111.06 2112117.1924223227.021111111

[0270] The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8 according to WO 97/34485.

Example B2

Post-emeroence Herbicidal Action

[0271] Monocotyledonous and dicotyledonous test plants are grown in plastic pots with standard soil in a greenhouse and, in the 4- to 6-leaf stage, are sprayed with an aqueous suspension of the test substances of the formula 1, prepared from a 25% wettable powder (Example F3, b) according to WO 97134485) or with an emulsion of the test substances of the formula I, prepared from a 25% emulsion concentrate (Example F1, c) according to WO 97/34485), corresponding to a dosage of 2 kg of AS/ha (500 l of water/ha). The test plants are then grown further under optimum conditions in a greenhouse. After a test period of about 18 days, the test is evaluated with a nine-level scale of rating (1=complete damage, 9=no effect). Ratings of 1 to 4 (in particular 1 to 3) mean good to very good herbicidal action. In this test, the compounds of the formula I show strong herbicidal action.

12TABLE B2post-emergence action:Active compoundTest plantNo.AvenaSetariaSolanumSinapisStellaria1.009111121.376122124.009111111.026311127.009321111.381222221.011222225.008231125.085322124.021221121.012322121.010222144.010332221.021242121.398222121.195222124.124221121.411222121.008222126.006252225.081321121.042222121.023222121.109222121.313222121.401222221.404221121.400222121.403222121.403222121.405222121.406221121.402222121.001322121.005222121.362322121.043222121.409211121.410111111.060211127.192233227.021121121.04821112

[0272] The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8 according to WO 97/34485.

Example B3

Herbicidal action before emergence of the plants (pre-emergence action)

[0273] Monocotyledonous and dicotyledonous test plants are sown in pots in standard soil. Immediately after sowing, the test substances are sprayed on (500 l of spray liquorlha) as an aqueous suspension, prepared from a wettable powder WP10 corresponding to the desired dosage (250 g of a.i./ha).

[0274] The test plants are then grown under optimum conditions in a greenhouse. After a test period of 3 weeks, the test is evaluated with a nine -evel scale of ratings (1=complete damage, 9=no effect). Ratings of 1 to 4 (in particular 1 to 3) mean good to very good herbicidal action, 7-9 mean good tolerance.

13TABLE B3Pre-emergence action:Test plantActiveDosecompoundAbut-Amar-Cheno-[g ofNo.ilonanthuspodiumKochiaSidaStellariaAS/ha]1.3551111222501.3472211412501.3351215272501.3491314252501.3392117212501.3413919412501.343141935250

[0275] The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8 according to WO 97/34485.

Example B4

Herbicidal action after the emergence of the plants ( post-emer gence action)

[0276] Monocotyledonous and dicotyledonous test plants are sown in pots in standard soil. In the 2-3- leaf stage of the test plants, the test substances are sprayed on (500 l of spray liquor/ha) as an aqueous suspension, prepared from a wettable powder WP10 according to the desired dosage (250 g of a.i./ha). 0.2% of X77 is added as wetting agent to the spray liquor. The test plants are then grown under optimum conditions in a greenhouse.

[0277] After a test period of 3 weeks, the test is evaluated with a nine4evel scale of ratings (1=complete damage, 9=no effect). Ratings of 1 to 4 (in particular 1 to 3) mean good to very good herbicidal action, 7-9 mean good tolerance.

14TABLE B4Post-emergence action:Test plantActiveDosecompoundAbut-Amar-Cheno-[g ofNo.ilonanthuspodiumKochiaSidaStellariaAS/ha]1.3552223232501.3473222332501.3353222232501.3492222232501.3392231432501.3515233332501.3415234542501.3433223932501.361222223250

[0278] The same results are obtained when the compounds of the formula I are formulated according to Examples F2 and F4 to F8 according to WO 97/34485.

Pyridine ketones useful as herbicides

Information

Publication Number

Date Filed

Date Published

Inventors

CPC

US Classifications

International Classifications

Abstract

Description

Claims

Priority Claims (1)