Indazolesulfonylurea derivative, its use and intermediate for its production

TECHNICAL FIELD
The present invention relates to a novel indazolesulfonylurea derivative (hereinafter referred to as a compound of the present invention), an intermediate for its production and a herbicide containing it as an active ingredient.
BACKGROUND ART
Heretofore, many sulfonylurea derivatives such as sulfometuron-methyl have been known as herbicides. Japanese Unexamined Patent Publication No. 95091/1992 discloses a herbicide containing an indazolesulfonylurea as an active ingredient. However, the compound of the present invention i.e. a sulfonylurea derivative having a sulfamoyl group substituted at the 3-position of an indazole ring, has not been known. Further, the intermediate for its production i.e. an indazolesulfonamide derivative, has also not been known.
It is known that sulfonylurea derivatives have herbicidal activities, but such compounds are not necessarily practically satisfactory, for example, in that their herbicidal effects are inadequate.
Under these circumstances, the present inventors have conducted various studies, and as a result, they have found that the compound of the present invention is an excellent herbicide having a high activity and has finally accomplished the present invention.
DISCLOSURE OF THE INVENTION
Namely, the present invention provides an indazolesulfonylurea derivative represented by the general formula: ##STR2## {wherein R.sup.1 is a hydrogen atom, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkoxyalkyl group, a benzyloxyalkyl group, a benzyl group, a phenyl group, a pyridyl group, a dialkylaminocarbonyl group, an alkoxycarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, a dialkylaminosulfonyl group, a haloalkylcarbonyl group, an alkylcarbonyl group, a benzoyl group or an alkenyl group, R.sup.2 and R.sup.3 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxycarbonylalkenyl group, an alkynyl group, a haloalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an alkylcarbonylalkyl group, a cycloalkylcarbonylalkyl group, a cyanoalkyl group, a dialkylaminocarbonylalkyl group, a dialkylaminoalkyl group, a dialkylaminosulfonylalkyl group, an azidoalkyl group, a benzyl group, a phenyl group, a nitro group, a cyano group, an azide group, an amino group, a monoalkylamino group, a dialkylamino group, a benzylamino group, an alkylcarbonylamino group which may be substituted by a halogen atom, a benzoylamino group, an alkoxycarbonylamino group, a phenoxycarbonylamino group, an alkylsulfonylamino group wherein the amino group may be substituted by an alkyl group, a phenylsulfonylamino group wherein the amino group may be substituted by an alkyl group, an alkylideneamino group, a benzylideneamino group, a tetrazolyl group which may be substituted, a group represented by the formula --COR.sup.4 (wherein R.sup.4 is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a benzyl group, a phenyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkoxy group, an alkenyloxy group, a haloalkenyloxy group, an alkynyloxy group, a benzyloxy group or a phenoxy group), a group represented by the formula --C(O)NR.sup.5 R.sup.6 (wherein R.sup.5 and R.sup.6 are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a phenyl group or an alkoxy group), a group represented by the formula --SR.sup.7 (wherein R.sup.7 is a hydrogen atom, an alkyl group or a haloalkyl group), a group represented by the formula --SO.sub.2 NR.sup.5 R.sup.6 (wherein R.sup.5 and R.sup.6 have the same meanings as defined above), a group represented by the formula --S(O).sub.n R.sup.8 (wherein n represents an integer of 1 or 2, and R.sup.8 represents an alkyl group, an alkenyl group or a haloalkyl group), a group represented by the formula --OR.sup.9 �wherein R.sup.9 is a hydrogen atom, an alkyl group, a cycloalkylalkyl group, an alkenyl group, an alkynyl group, a benzyl group (said group may be substituted by a halogen atom, an alkyl group or an alkoxy group), a haloalkyl group, a haloalkenyl group, a phenyl group (said group may be substituted by a halogen atom, an alkyl group or an alkoxy group), an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a haloalkoxyalkyl group, a benzyloxyalkyl group, a phenoxyalkyl group, an alkylthioalkyl group, a dialkylaminoalkyl group, an azidoalkyl group, an alkylcarbonyl group, a haloalkylcarbonyl group, a benzoyl group, a dialkylaminocarbonyl group, a cyanoalkyl group, an alkylideneamino group, a dialkylideneamino group, a benzylideneamino group or an alkoxycarbonylalkyl group!, or the formula --C(.dbd.NOR.sup.10)R.sup.11 (wherein R.sup.10 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a haloalkyl group or a phenyl group, and R.sup.11 represents a hydrogen atom, an alkyl group, a benzyl group, a haloalkyl group or a phenyl group), R.sup.2 and R.sup.3 may together form a ring with an alkyl group which may contain a hetero atom, A and B are the same or different and represent an alkyl group, a haloalkyl group, an alkoxy group, a monoalkylamino group, a dialkylamino group, a halogen atom or a haloalkoxy group, Z represents a methine group or a nitrogen atom, X represents an oxygen atom or a sulfur atom, and Y represents a hydrogen atom, an alkyl group or an alkoxyalkyl group, as well as its intermediate represented by an indazolesulfonamide derivative represented by the formula �I-a! or �II-a!: ##STR3## {wherein R.sup.1 is a hydrogen atom, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkoxyalkyl group, a benzyloxyalkyl group, a benzyl group, a phenyl group, a pyridyl group, a dialkylaminocarbonyl group, an alkoxycarbonyl group, an alkylsulfonyl group, a phenylsulfonyl group, a dialkylaminosulfonyl group, a haloalkylcarbonyl group, an alkylcarbonyl group, a benzoyl group or an alkenyl group, R.sup.2 and R.sup.3 are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxycarbonylalkenyl group, an alkynyl group, a haloalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an alkylcarbonylalkyl group, a cycloalkylcarbonylalkyl group, a cyanoalkyl group, a dialkylaminocarbonylalkyl group, a dialkylaminoalkyl group, a dialkylaminosulfonylalkyl group, an azidoalkyl group, a benzyl group, a phenyl group, a nitro group, a cyano group, an azide group, an amino group, a monoalkylamino group, a dialkylamino group, a benzylamino group, an alkylcarbonylamino group which may be substituted by a halogen atom, a benzoylamino group, an alkoxycarbonylamino group, a phenoxycarbonylamino group, an alkylsulfonylamino group wherein the amino group may be substituted by an alkyl group, a phenylsulfonylamino group wherein the amino group may be substituted by an alkyl group, an alkylideneamino group, a benzylideneamino group, a tetrazolyl group which may be substituted, a group represented by the formula --COR.sup.4 (wherein R.sup.4 is a hydrogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a benzyl group, a phenyl group, an alkoxy group, a haloalkoxy group, an alkoxyalkoxy group, an alkenyloxy group, a haloalkenyloxy group, an alkynyloxy group, a benzyloxy group or a phenoxy group), a group represented by the formula --C(O)NR.sup.5 R.sup.6 (wherein R.sup.5 and R.sup.6 are the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a phenyl group or an alkoxy group), a group represented by the formula --SR.sup.7 (wherein R.sup.7 is a hydrogen atom, an alkyl group or a haloalkyl group), a group represented by the formula --SO.sub.2 NR.sup.5 R.sup.6 (wherein R.sup.5 and R.sup.6 have the same meanings as defined above), a group represented by the formula --S(O).sub.n R.sup.8 (wherein n represents an integer of 1 or 2, and R.sup.8 represents an alkyl group, an alkenyl group or a haloalkyl group), a group represented by the formula --OR.sup.9 �wherein R.sup.9 is a hydrogen atom, an alkyl group, a cycloalkylalkyl group, an alkenyl group, an alkynyl group, a benzyl group (said group may be substituted by a halogen atom, an alkyl group or an alkoxy group), a haloalkyl group, a haloalkenyl group, a phenyl group (said group may be substituted by a halogen atom, an alkyl group or an alkoxy group), an alkoxyalkyl group, an alkoxyalkoxyalkyl group, a haloalkoxyalkyl group, a benzyloxyalkyl group, a phenoxyalkyl group, an alkylthioalkyl group, a dialkylaminoalkyl group, an azidoalkyl group, an alkylcarbonyl group, a haloalkylcarbonyl group, a benzoyl group, a dialkylaminocarbonyl group, a cyanoalkyl group, an alkylideneamino group, a dialkylideneamino group, a benzylideneamino group or an alkoxycarbonylalkyl group!, or the formula --C(.dbd.NOR.sup.10)R.sup.11 (wherein R.sup.10 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a haloalkyl group or a phenyl group, and R.sup.11 represents a hydrogen atom, an alkyl group, a benzyl group, a haloalkyl group or a phenyl group), and R.sup.2 and R.sup.3 may form a ring with an alkyl group which may contain a hetero atom}, and a herbicide containing the indazolesulfonylurea as an active ingredient.
The compound of the present invention includes a tautomer, a geometrical isomer and an optical isomer thereof.
In the present invention, the alkyl group means a straight chain or branched chain alkyl group having from 1 to 30 carbon atoms and includes, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a n-pentyl group, an isoamyl group, a neopentyl group, a n-hexyl group, an isohexyl group, a 3,3-dimethylbutyl group, a n-heptyl group, a 5-methylhexyl group, a 4-methylhexyl group, a 3-methylhexyl group, a 4,4-dimethylpentyl group, a n-octyl group, a 6-methylheptyl group, a n-nonyl group, a 7-methyloctyl group, a n-decyl group, a 8-methylnonyl group, a n-undecyl group, a 9-methyldecyl group, a n-dodecyl group, a 10-methylundecyl group, a n-tridecyl group, a 11-methyldodecyl group, a n-tetradecyl group, a 12-methyltridecyl group, a n-pentadecyl group, a 13-methyltetradecyl group, a n-hexadecyl group, a n-heptadecyl group, a n-octadecyl group, a n-nonadecyl group, and a n-eicosyl group.
The alkoxy group and the alkylsulfonyl group mean an (alkyl)--O-- group and and (alkyl)--SO.sub.2 -- group, respectively, in which the alkyl moiety has the above-mentioned meaning.
The halogen atom includes fluorine, chlorine, bromine and iodine atoms.
The alkenyl group means a straight chain or branched chain alkenyl group having from 2 to 20 carbon atoms and includes, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a 3-methyl-1-butenyl group, and a 4-methyl-1-pentenyl group.
The alkynyl group means a straight chain or branched chain alkynyl group having from 2 to 20 carbon atoms and includes, for example, an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a 3,3-dimethyl-1-butynyl group, a 4-methyl-1-pentynyl group, a 3-methyl-1-pentynyl group, a 5-methyl-1-hexynyl group, a 4-methyl-1-hexynyl group, a 3-methyl-1-hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, a dodecynyl group, a tridecynyl group, a tetradecynyl group, a pentadecynyl group, and a hexadecynyl group.
In the above formula �I! or �II!, as a group of compounds showing preferred herbicidal effects, compounds may be mentioned wherein R.sup.1 represents a hydrogen atom, a methyl group or an ethyl group, R.sup.2 and R.sup.3 are the same or different and represent a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a dialkylaminocarbonyl group, an alkoxy group, a haloalkoxy group, an alkenyloxy group, a cyano group or a trifluoromethyl group, A and B are the same or different and represent a methoxy group, a methyl group or a haloalkoxy group, Z represents a methine group or a nitrogen atom, X represents an oxygen atom, and Y represents a hydrogen atom.
Now, typical specific examples of the compound of the present invention represented by the formula �I! or �II! will be exemplified in Tables 1 and 2. The compound numbers will be referred to in the subsequent description, and when R.sup.1 represents a hydrogen atom, the compound may take tautomers represented by the formula �I! and �II!.
The following symbols in the Tables in the present specification represent the following groups, respectively.
______________________________________Bn: Benzyl groupPen: n-Pentyl groupMe: Methyl groupEt: Ethyl groupPr: n-Propyl groupBu: n-Butyl groupPh: Phenyl group______________________________________
TABLE 1__________________________________________________________________________ ##STR4##Comp. NO. R.sup.1 R.sup.2 R.sup.3 X Y A B Z Mp.__________________________________________________________________________ (.degree.C.)I-1 Me Ph H O H OMe OMe CHI-2 Me Bn H O H OMe OMe CHI-3 Me SH H O H OMe OMe CHI-4 Me SMe H O H OMe OMe CHI-5 Me SEt H O H OMe OMe CH 189-190I-6 Me SPr H O H OMe OMe CH 162-164I-7 Me SO.sub.2 Me H O H OMe OMe CHI-8 Me SO.sub.2 Et H O H OMe 0Me CH 157-160I-9 Me SOMe H O H OMe OMe CHI-10 Me SO.sub.2 NHMe H O H OMe OMe CHI-11 Me SO.sub.2 NHOMe H O H OMe OMe CHI-12 Me SO.sub.2 NMe.sub.2 H O H OMe OMe CH 214-216I-13 Me SO.sub.2 NHBn H O H OMe OMe CHI-14 Me SO.sub.2 NHPh H O H OMe OMe CHI-15 Me SO.sub.2 NHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-16 Me SO.sub.2 NHCH.sub.2 CCH H O H OMe OMe CHI-17 H Cl H O H OMe OMe CH 191-193I-18 Me Cl H O H Me Me CH 195-198I-19 Me Cl 5-Cl O H OMe OMe CH 210-213I-20 Et Cl H O H OMe OMe CH 187-189I-21 Ph Cl H O H OMe OMe CHI-22 Bn Cl H O H OMe OMe CHI-23 Me H H O H OMe OMe CH 181-183I-24 Me H H O H Me Me CHI-25 Me H H O H OMe Me N 172-174I-26 Me F H O H OMe OMe CH 205-209I-27 Me Br H O H OMe OMe CH 276-279I-28 Me Me H O H OMe OMe CH 178-180I-29 Me CN H O H OMe OMe CH 267-269I-30 Me CF H O H OMe OMe CHI-31 Me Cl H O H OMe Me CH 243-245I-32 Me Cl H O H OMe Me N 266-267I-33 Me F H O H Me Me CH 195-197I-34 Me F H O H OMe Me N 197-200I-35 Me F H O H OMe Me CH 180-185I-36 Me H 5-Cl O H OMe OMe CHI-37 Me H 5-Cl O H Me Me CHI-38 Me H 5-Cl O H OMe Me NI-39 Me H 6-Cl O H OMe OMe CHI-40 Me H 6-Cl O H Me Me CHI-41 Me H 6-Cl O H OMe Me NI-42 Me H 7-Cl O H OMe OMe CHI-43 Me H 7-Cl O H OMe Me NI-44 Me Cl H S H OMe OMe CHI-45 Me Cl H O Me OMe OMe CH1-46 Me COH H O H OMe OMe CHI-47 Me COMe H O H OMe OMe CHI-48 Me COEt H O H OMe OMe CHI-49 Me COPh H O H OMe OMe CHI-50 Me COCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-51 Me COCH.sub.2 CCH H O H OMe OMe CHI-52 Me COBn H O H OMe OMe CHI-53 Me NO.sub.2 H O H OMe OMe CH 219-220I-54 Me NH.sub.2 H O H OMe OMe CHI-55 Me NHMe H O H OMe OMe CHI-56 Me NMe.sub.2 H O H OMe OMe CHI-57 Me NHCOMe H O H OMe OMe CHI-58 Me NHCOPh H O H OMe OMe CHI-59 Me NHCOCH.sub.2 Cl H O H OMe OMe CHI-60 Me NHSO.sub.2 CH.sub.3 H O H OMe OMe CHI-61 Me NHSO.sub.2 Ph H O H OMe OMe CHI-62 Me CO.sub.2 H H O H OMe OMe CHI-63 Me CO.sub.2 Me H O H OMe OMe CH 187-190I-64 Me CO.sub.2 Et H O H OMe OMe CH 192-193I-65 Me CO.sub.2 Pr H O H OMe OMe CH 195-197I-66 Me CO.sub.2 Pr-i H O H OMe OMe CH 168-169I-67 Me CO.sub.2 Bu H O H OMe OMe CH 169-172I-68 Me CO.sub.2 Pen H O H OMe OMe CHI-69 Me CO.sub.2 Bn H O H OMe OMe CHI-70 Me CO.sub.2 Ph H O H OMe OMe CHI-71 Me CO.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CHI-72 Me CO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-73 Me CO.sub.2 CH.sub.2 CCH H O H OMe OMe CHI-74 Me CO.sub.2 Me H O H OCHF.sub.2 OCHF.sub.2 CHI-75 Me CO.sub.2 Et H O H OCHF.sub.2 OCHF.sub.2 CHI-76 Me CO.sub.2 Me H O H OMe Cl CHI-77 Me CO.sub.2 Me H O H OMe Me CHI-78 Me CO.sub.2 Me H O H OMe Me NI-79 Me CO.sub.2 Et H O H. OMe Me N 193-196I-80 Me CO.sub.2 Me H O H OMe OCHF.sub.2 CHI-81 Me CO.sub.2 Me 5-F O H OMe OMe CHI-82 Et CO.sub.2 Me H O H OMe OMe CH 182-183I-83 Bu CO.sub.2 Me H O H OMe OMe CHI-84 Bn CO.sub.2 Me H O H OMe OMe CHI-85 Ph CO.sub.2 Me H O H OMe OMe CHI-86 H CO.sub.2 Et H O H OMe OMe CHI-87 Me CO.sub.2 Me H S H OMe OMe CHI-88 Me CO.sub.2 Et H S H OMe OMe CHI-89 Me CO.sub.2 Me H O Me OMe OMe CHI-90 Me OH H O H OMe OMe CHI-91 Me ONMe H O H OMe OMe CH 265-267I-92 Me OEt H O H OMe OMe CH 162-164I-93 Me OPr H O H OMe OMe CH 134-136I-94 Me OPr-i H O H OMe OMe CH 168-171I-95 Me OBu H O H OMe OMe CH 198-200I-96 Me OBn H O H OMe OMe CHI-97 Me OBn(4-Cl) H O H OMe OMe CHI-98 Me OBn(3-OMe) H O H OMe OMe CHI-99 Me OBn(2-Me) H O H OMe OMe CHI-100 Me OPh H O H OMe OMe CHI-101 Me OPh(4-Cl) H O H OMe OMe CH1-102 Me OPh(3-OMe) H O H OMe OMe CHI-103 Me OPh(2-Me) H O H OMe OMe CHI-104 Me OCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-105 Me OCH.sub.2 CCH H O H OMe OMe CHI-106 Me OCH.sub.2 CF.sub.3 H O H OMe OMe CHI-107 Me OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-108 Me OCH.sub.2 CH.sub.2 OPh H O H OMe OMe CHI-109 Me OCOMe H O H OMe OMe CHI-110 Me OMe H O H OMe Me CHI-111 Me OMe H O H OMe Me N 269-270I-112 Me OMe H O H Me Me CH 267-268I-113 Me OEt H O H OMe Cl CH 161-165I-114 Me OEt H O H OMe Me CH 169-170I-115 Me OEt H O H Me Me CHI-116 Me CONH.sub.2 H O H OMe OMe CHI-117 Me CONHMe H O H OMe OMe CHI-118 Me CONHEt H O H OMe OMe CHI-119 Me CONHPr H O H OMe OMe CHI-120 Me CONMe.sub.2 H O H OMe OMe CH 205-207I-121 Me COMEt H O H OMe OMe CHI-122 Me CONHBn H O H OMe OMe CHI-123 Me CONHPh H O H OMe OMe CHI-124 Me CONHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-125 Me CONHCH.sub.2 CCH H O H OMe OMe CHI-126 Me CONHOMe H O H OMe OMe CHI-127 Me H 5-F O H OMe OMe CHI-128 Me H 5-F O H Me Me CHI-129 Me H 5-F O H OMe Me CHI-130 Me H 5-F O H OMe Me NI-131 H COOMe H O H OMe OMe CH 179-180I-132 H COOMe H O H OMe Cl CH 193-194I-133 H Cl H O H OMe Cl CH 178-181I-134 Me Cl H O H OMe OMe CH 265-267I-135 Me SO.sub.22 NH.sub.2 H O H OMe OMe CHI-136 H Br H O H OMe OMe CH 190-193I-137 Me H 5-Me O H OMe OMe CHI-138 Me H 5-OEt O H OMe OMe CHI-139 Me H 5-OPr O H OMe OMe CHI-140 Me OCH(CF.sub.3)Me H O H OMe OMe CHI-141 Me OCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-142 Me OCH.sub.2 CH.sub.2 F H O H OMe OMe CHI-143 Me OCH.sub.2 CH.sub.2 OEt H O H OMe OMe CHI-144 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe OMe CHI-145 Me OCH.sub.2 CH.sub.2 OBu H O H OMe OMe CHI-146 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe CHI-147 Me OCH.sub.2 COOEt H O H OMe OMe CHI-148 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe OMe CHI-149 Me SBu H O H OMe OMe CH 165-168I-150 Me SPr-i H O H OMe OMe CH 178-180I-151 Me SO.sub.2 Pr H O H OMe OMe CH 163-167I-152 Me SO.sub.2 Bu H O H OMe OMe CH 187-189I-153 Me SO.sub.2 Pr-i H O H OMe OMe CH 279-281I-154 Me NHBn H O H OMe OMe CHI-155 Me NEt.sub.2 H O H OMe OMe CHI-156 Me OMe 5-Cl O H OMe OMe CHI-157 Me Br H O H OMe Me CH 276-279I-158 Et Cl H O H OMe Me CH 182-184I-159 Ph Cl H O H OMe Me CHI-160 Me OPr H O H OMe Me CH 178-180I-161 Me OBu H O H OMe Me CH 174-176I-162 Me OPr-i H O H OMe Me CH 184-186I-163 Me H 5-OMe O H OMe Me CHI-164 Me H 5-OEt O H OMe Me CHI-165 Me H 5-OPr O H OMe Me CHI-166 Me OCH.sub.2 CF.sub.3 H O H OMe Me CHI-167 Me OCH(CF.sub.3)Me H O H OMe Me CHI-168 Me OCH.sub.2 CH.sub.2 OMe H O H OMe Me CHI-169 Me OCH.sub.2 CH.sub.2 OEt H O H OMe Me CHI-170 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me CHI-171 Me OCH.sub.2 CH.sub.2 OBu H O H OMe Me CHI-172 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me CHI-173 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me CHI-174 Me SPr H O H OMe Me CH 155-156I-175 Me CO.sub.2 Pr H O H OMe Me CH 185-186I-176 Me CO.sub.2 Pr-i H O H OMe He CH 158-160I-177 Me CO.sub.2 Bu H O H OMe Me CH 174-175I-178 Me NO.sub.2 H O H OMe Me CH 212-214I-179 Me CN H O H OMe Me CH 180-181I-180 Me Br H O H OMe Me N 166-169I-181 Et Cl H O H OMe Me N 141-142I-182 Me OPr H O H OMe Me N 210-213I-183 Me OBu H O H OMe Me N 184-186I-184 Me OPr-i H O H OMe Me N 157-159I-185 Me H 5-OMe O H OMe Me NI-186 Me H 5-OEt O H OMe Me NI-187 Me H 5-OPr O H OMe Me NI-188 Me OCH.sub.2 CF.sub.3 H O H OMe Me NI-189 Me OCH.sub.2 CH.sub.2 OEt H O H OMe Me NI-190 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me NI-191 Me OCH.sub.2 CH.sub.2 OBu H O H OMe Me NI-192 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me NI-193 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me NI-194 Me SEt H O H OMe Me N 223-224I-195 Me SPr H O H OMe Me NI-196 Me NMe.sub.2 H O H OMe Me NI-197 Me CO.sub.2 Pr-i H O H OMe Me NI-198 Me CO.sub.2 Bu H O H OMe Me N 177-178I-199 Me CN H O H OMe Me N 255-258I-200 Me OMe 5-Cl O H OMe Me NI-201 Me Cl H O H Cl OMe CHI-202 Et Cl H O H Cl OMe CHI-203 Ph Cl H O H Cl OMe CHI-204 Me OMe H O H Cl OMe CH 268-269I-205 Me OPr H O H Cl OMe CH 168-169I-206 Me OBu H O H Cl OMe CH 171-173I-207 Me H 5-OMe O H Cl OMe CHI-208 Me OCH.sub.2 CF.sub.3 H O H Cl OMe CHI-209 Me SPr H O H Cl OMe CH 143-145I-210 Me SBu H O H Cl OMe CHI-211 Me SPr-i H O H Cl OMe CH 228-230I-212 Me SO.sub.2 Pr-i H O H Cl OMe CH 143-145I-213 Me NHBn H O H Cl OMe CHI-214 Me NMe.sub.2 H O H Cl OMe CHI-215 Et Cl H O H Me Me CHI-216 Me OPr H O H Me Me CH 149-150I-217 Me OBu H O H Me Me CH 146-149I-218 Me OPr-i H O H Me Me CH 174-176I-219 Me NMe.sub.2 H O H Me Me CHI-220 Me OMe H O H OMe OMe NI-221 Me H 5-OEt O H OMe OMe NI-222 Me H 5-OPr O H OMe OMe NI-223 Me OCH.sub.2 CH.sub.2 OBu H O H OMe OMe NI-224 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe NI-225 Me NHMe H O H OMe Me CHI-226 Me NHMe H O H OMe Me NI-227 Me OMe H O H OMe Me CHI-228 Me OMe 5-OMe O H OMe Me CHI-229 Me OCHF.sub.2 H O H OMe OMe CH 198-200I-230 Me OCHF.sub.2 H O H Me OMe CH 177-179I-231 Me OCHF.sub.2 H O H Me OMe N 165-167I-232 Me OCH.sub.2 CHF.sub.2 H O H OMe OMe CHI-233 Me OCH.sub.2 CHF.sub.2 H O H Me OMe CHI-234 Me OCH.sub.2 CHF.sub.2 H O H Me OMe NI-235 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHI-236 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe CHI-237 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe NI-238 Me OCH(CF.sub.2 CF.sub.3)Me H O H OMe OMe CHI-239 Me OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe CHI-240 Me OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe NI-241 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H OMe OMe CHI-242 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe CHI-243 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe NI-244 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H OMe OMe CHI-245 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe CHI-246 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe NI-247 Me OCH.sub.2 CHCl.sub.2 H O H OMe OMe CHI-248 Me OCH.sub.2 CHCl.sub.2 H O H Me OMe CHI-249 Me OCH.sub.2 CHCl.sub.2 H O H Me OMe NI-250 Me OCF.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-251 Me OCF.sub.2 CH.sub.2 Cl H O H Me OMe CHI-252 Me OCF.sub.2 CH.sub.2 Cl H O H Me OMe NI-253 Me OCF.sub.2 CHFCl H O H OMe OMe CHI-254 Me OCF.sub.2 CHFCl H O H Me OMe CHI-255 Me OCF.sub.2 CHFCl H O H Me OMe NI-256 Me OCF.sub.3 H O H OMe OMe CHI-257 Me OCF.sub.3 H O H Me OMe CHI-258 Me OCF.sub.3 H O H Me OMe NI-259 Me OCH.sub.2 CHCHCl H O H OMe OMe CHI-260 Me OCH.sub.2 CHCHCl H O H Me OMe CHI-261 Me OCH.sub.2 CHCHCl H O H Me OMe NI-262 Me OCH.sub.2 CHCCl.sub.2 H O H OMe OMe CHI-263 Me OCH.sub.2 CHCCl.sub.2 H O H Me OMe CHI-264 Me OCH.sub.2 CHCCl.sub.2 H O H Me OMe NI-265 Me OCH.sub.2 C(Cl)CH.sub.2 H O H OMe OMe CHI-266 Me OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe CHI-267 Me OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe NI-268 Me OCH.sub.2 C(Me)CH.sub.2 H O H OMe OMe CHI-269 Me OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe CHI-270 Me OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe NI-271 Me OCH.sub.2 CHCHMe H O H OMe OMe CHI-272 Me OCH.sub.2 CHCHMe H O H Me OMe CHI-273 Me OCH.sub.2 CHCHMe H O H Me OMe NI-274 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHI-275 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H Me OMe CHI-276 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H Me OMe NI-277 Me OCH.sub.2 OMe H O H OMe OMe CHI-278 Me OCH.sub.2 OMe H O H Me OMe CHI-279 Me OCH.sub.2 OMe H O H Me OMe NI-280 Me OCH.sub.2 OEt H O H OMe OMe CHI-281 Me OCH.sub.2 OEt H O H Me OMe CHI-282 Me OCH.sub.2 OEt H O H Me OMe NI-283 Me OCH.sub.2 OBn H O H OMe OMe CHI-284 Me OCH.sub.2 OBn H O H Me OMe CHI-285 Me OCH.sub.2 OBn H O H Me OMe NI-286 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H OMe OMe CHI-287 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe CHI-288 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe NI-289 Me OCH.sub.2 OBu-t H O H OMe OMe CHI-290 Me OCH.sub.2 OBu-t H O H Me OMe CHI-291 Me OCH.sub.2 OBu-t H O H Me OMe NI-292 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-293 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe CHI-294 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe NI-295 Me OCH.sub.2 CN H O H OMe OMe CHI-296 Me OCH.sub.2 CN H O H Me OMe CHI-297 Me OCH.sub.2 CN H O H Me OMe NI-298 Me OCH.sub.2 COOMe H O H OMe OMe CHI-299 Me OCH.sub.2 COOMe H O H Me OMe CHI-300 Me OCH.sub.2 COOMe H O H Me OMe NI-301 Me OCH.sub.2 COOPr H O H OMe OMe CHI-302 Me OCH.sub.2 COOPr H O H Me OMe CHI-303 Me OCH.sub.2 COOPr H O H Me OMe NI-304 Me OCH.sub.2 COOPr-i H O H OMe OMe CHI-305 Me OCH.sub.2 COOPr-i H O H Me OMe CHI-306 Me OCH.sub.2 COOPr-i H O H Me OMe NI-307 Me OCH.sub.2 SMe H O H OMe OMe CHI-308 Me OCH.sub.2 SMe H O H Me OMe CHI-309 Me OCH.sub.2 SMe H O H Me OMe NI-310 Me OCH.sub.2 CH.sub.2 SMe H O H OMe OMe CHI-311 Me OCH.sub.2 CH.sub.2 SMe H O H Me OMe CHI-312 Me OCH.sub.2 CH.sub.2 SMe H O H Me OMe NI-313 Me SCF.sub.3 H O H OMe OMe CHI-314 Me SCF.sub.3 H O H Me OMe CHI-315 Me SCF.sub.3 H O H Me OMe NI-316 Me SCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-317 Me SCH.sub.2 CH.sub.2 Cl H O H Me OMe CHI-318 Me SCH.sub.2 CH.sub.2 Cl H O H Me OMe NI-319 Me SCH.sub.2 CH.sub.2 F H O H OMe OMe CHI-320 Me SCH.sub.2 CH.sub.2 F H O H Me OMe CHI-321 Me SCH.sub.2 CH.sub.2 F H O H Me OMe NI-322 Me SOEt H O H OMe OMe CH 185-187I-323 Me SOEt H O H Me OMe CHI-324 Me SOEt H O H Me OMe N 136-137 (decomposed)I-325 Me SO.sub.2 NHOEt H O H OMe OMe CHI-326 Me SO.sub.2 NHOEt H O H Me OMe CHI-327 Me SO.sub.2 NHOEt H O H Me OMe NI-328 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-329 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe CHI-330 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe NI-331 Me SO.sub.2 NEt.sub.2 H O H OMe OMe CHI-332 Me SO.sub.2 NEt.sub.2 H O H Me OMe CHI-333 Me SO.sub.2 NEt.sub.2 H O H Me OMe NI-334 Me Et H O H OMe OMe CH 174-176I-335 Me Et H O H Me OMe CHI-336 Me Et H O H Me OMe NI-337 Me Pr H O H OMe OMe CH 168-171I-338 Me Pr H O H Me OMe CHI-339 Me Pr H O H Me OMe NI-340 Me Pr-i H O H OMe OMe CHI-341 Me Pr-i H O H Me OMe CHI-342 Me Pr-i H O H Me OMe NI-343 Me Bu H O H OMe OMe CHI-344 Me Bu H O H Me OMe CHI-345 Me Bu H O H Me OMe NI-346 He Bu-t H O H OMe OMe CHI-347 Me Bu-t H O H Me OMe CHI-348 Me Bu-t H O H Me OMe NI-349 Me CH.sub.2 Cl H O H OMe OMe CHI-350 Me CH.sub.2 Cl H O H Me OMe CHI-351 Me CH.sub.2 Cl H O H Me OMe NI-352 Me CH.sub.2 F H O H OMe OMe CHI-353 Me CH.sub.2 F H O H Me OMe HI-354 Me CH.sub.2 F H O H Me OMe NI-355 Me CH.sub.2 OMe H O H OMe OMe CHI-356 Me CH.sub.2 OMe H O H Me OMe CHI-357 Me CH.sub.2 OMe H O H Me OMe NI-358 Me CH.sub.2 CF.sub.3 H O H OMe OMe CHI-359 Me CH.sub.2 CF.sub.3 H O H Me OMe CHI-360 Me CH.sub.2 CF.sub.3 H O H Me OMe NI-361 Me ##STR5## H O H OMe OMe CHI-362 Me ##STR6## H O H Me OMe CHI-363 Me ##STR7## H O H Me OMe NI-364 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHI-365 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe CHI-366 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe NI-367 Me CH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-368 Me CH.sub.2 CHCH.sub.2 H O H Me OMe CHI-369 Me CH.sub.2 CHCH.sub.2 H O H Me OMe NI-370 Me CH.sub.2 CCH H O H OMe OMe CHI-371 Me CH.sub.2 CCH H O H Me OMe CHI-372 Me CH.sub.2 CCH H O H Me OMe NI-373 Me CH.sub.2 COOMe H O H OMe OMe CHI-374 Me CH.sub.2 COOMe H O H Me OMe CHI-375 Me CH.sub.2 COOMe H O H Me OMe NI-376 Me CH.sub.2 COOEt H O H OMe OMe CHI-377 Me CH.sub.2 COOEt H O H Me OMe CHI-378 Me CH.sub.2 COOEt H O H Me OMe NI-379 Me CH.sub.2 CN H O H OMe OMe CHI-380 Me CH.sub.2 CN H O H Me OMe CHI-381 Me CH.sub.2 CN H O H Me OMe NI-382 Me CH.sub.2 CONMe.sub.2 H O H OMe OMe CHI-383 Me CH.sub.2 CONMe.sub.2 H O H Me OMe CHI-384 Me CH.sub.2 CONMe.sub.2 H O H Me OMe NI-385 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H OMe OMe CHI-386 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H Me OMe CHI-387 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H Me OMe NI-388 Me CH.sub.2 NMe.sub.2 H O H OMe OMe CHI-389 Me CH.sub.2 NMe.sub.2 H O H Me OMe CHI-390 Me CH.sub.2 NMe.sub.2 H O H Me OMe NI-391 Me CHCH.sub.2 H O H OMe OMe CHI-392 Me CHCH.sub.2 H O H Me OMe CHI-393 Me CHCH.sub.2 H O H Me OMe NI-394 Me CHCHMe H O H OMe OMe CHI-395 Me CHCHMe H O H Me OMe CHI-396 Me CHCHMe H O H Me OMe NI-397 Me CCH H O H OMe OMe CHI-398 Me CCH H O H Me OMe CHI-399 Me CCH H O H Me OMe NI-400 Me CCMe H O H OMe OMe CHI-401 Me CCMe H O H Me OMe CHI-402 Me CCMe H O H Me OMe NI-403 Me CHCHCOOMe H O H OMe OMe CHI-404 Me CHCHCOOMe H O H Me OMe CHI-405 Me CHCHCOOMe H O H Me OMe NI-406 Me CH(Me)COMe H O H OMe OMe CHI-407 Me CH(Me)COMe H O H Me OMe CHI-408 Me CH(Me)COMe H O H Me OMe NI-409 Me CH(Me)COEt H O H OMe OMe CHI-410 Me CH(Me)COEt H O H Me OMe CHI-411 Me CH(Me)COEt H O H Me OMe NI-412 Me CH(Et)COMe H O H OMe OMe CHI-413 Me CH(Et)COMe H O H Me OMe CHI-414 Me CH(Et)COMe H O H Me OMe NI-415 Me CH(Et)COEt H O H OMe OMe CHI-416 Me CH(Et)COEt H O H Me OMe CHI-417 Me CH(Et)COEt H O H Me OMe NI-418 Me ##STR8## H O H OMe OMe CHI-419 Me ##STR9## H O H Me OMe CHI-420 Me ##STR10## H O H Me OMe NI-421 Me COPr H O H OMe OMe CHI-422 Me COPr H O H Me OMe CHI-423 Me COPr H O H Me OMe NI-424 Me COPr-i H O H OMe OMe CHI-425 Me COPr-i H O H Me OMe CHI-426 Me COPr-i H O H Me OMe NI-427 Me CHNOMe H O H OMe OMe CHI-428 Me CHNOMe H O H Me OMe CHI-429 Me CHNOMe H O H Me OMe NI-430 Me CHNOEt H O H OMe OMe CHI-431 Me CHNOEt H O H Me OMe CHI-432 Me CHNOEt H O H Me OMe NI-433 Me C(Me)NOMe H O H OMe OMe CHI-434 Me C(Me)NOMe H O H Me OMe CHI-435 Me C(Me)NOMe H O H Me OMe NI-436 Me C(Me)NOEt H O H OMe OMe CHI-437 Me C(Me)NOEt H O H Me OMe CHI-438 Me C(Me)NOEt H O H Me OMe NI-439 Me C(Me)NOPr H O H OMe OMe CHI-440 Me C(Me)NOPr H O H Me OMe CHI-441 Me C(Me)NOPr H O H Me OMe NI-442 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-443 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe CHI-444 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe NI-445 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H OMe OMe CHI-446 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H Me OMe CHI-447 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H Me OMe NI-448 Me NHEt H O H OMe OMe CHI-449 Me NHEt H O H Me OMe CHI-450 Me NHEt H O H Me OMe NI-451 Me NHPr H O H OMe OMe CHI-452 Me NHPr H O H Me OMe CHI-453 Me NHPr H O H Me OMe NI-454 Me NHCOOMe H O H OMe OMe CHI-455 Me NHCOOMe H O H Me OMe CHI-456 Me NHCOOMe H O H Me OMe NI-457 Me NHCOOEt H O H OMe OMe CHI-458 Me NHCOOEt H O H Me OMe CHI-459 Me NHCOOEt H O H Me OMe NI-460 Me NHCOOPh H O H OMe OMe CHI-461 Me NHCOOPh H O H Me OMe CHI-462 Me NHCOOPh H O H Me OMe NI-463 Me N(Me)SO.sub.2 Me H O H OMe OMe CHI-464 Me N(Me)SO.sub.2 Me H O H Me OMe CHI-465 Me N(Me)SO.sub.2 Me H O H Me OMe NI-466 Me N(Et)SO.sub.2 Me H O H OMe OMe CHI-467 Me N(Et)SO.sub.2 Me H O H Me OMe CHI-468 Me N(Et)SO.sub.2 Me H O H Me OMe NI-469 Me N(Me)SO.sub.2 Et H O H OMe OMe CHI-470 Me N(Me)SO.sub.2 Et H O H Me OMe CHI-471 Me N(Me)SO.sub.2 Et H O H Me OMe NI-472 Me N(Et)SO.sub.2 Et H O H OMe OMe CHI-473 Me N(Et)SO.sub.2 Et H O H Me OMe CHI-474 Me N(Et)SO.sub.2 Et H O H Me OMe NI-475 Me NHCOEt H O H OMe OMe CHI-476 Me NHCOEt H O H Me OMe CHI-477 Me NHCOEt H O H Me OMe NI-478 Me NHCOCF.sub.3 H O H OMe OMe CHI-479 Me NHCOCF.sub.3 H O H Me OMe CHI-480 Me NHCOCF.sub.3 H O H Me OMe NI-481 Me NCHMe H O H OMe OMe CHI-482 Me NCHMe H O H Me OMe CHI-483 Me NCHMe H O H Me OMe NI-484 Me NCHPh H O H OMe OMe CHI-485 Me NCHPh H O H Me OMe CHI-486 Me NCHPh H O H Me OMe NI-487 Me N.sub.3 H O H OMe OMe CHI-488 Me N.sub.3 H O H Me OMe CHI-489 Me N.sub.3 H O H Me OMe NI-490 Me I H O H OMe OMe CHI-491 Me I H O H Me OMe CHI-492 Me I H O H Me OMe NI-493 Me OCOEt H O H OMe OMe CHI-494 Me OCOEt H O H Me OMe CHI-495 Me OCOEt H O H Me OMe NI-496 Me OCOPr H O H OMe OMe CHI-497 Me OCOPr H O H Me OMe CHI-498 Me OCOPr H O H Me OMe NI-499 Me OCOPh H O H OMe OMe CHI-500 Me OCOPh H O H Me OMe CHI-501 Me OCOPh H O H Me OMe NI-502 Me OCONMe.sub.2 H O H OMe OMe CHI-503 Me OCONMe.sub.2 H O H Me OMe CHI-504 Me OCONMe.sub.2 H O H Me OMe NI-505 Me Cl H O H CF.sub.3 OMe CHI-506 Me OPr-i H O H Cl OMe CH 163-165I-507 Me SEt H O H Me OMe CH 225-227I-508 Me SEt H O H Cl OMe CH 185-187I-509 Me SEt H O H Me Me CH 220-222I-510 Me SEt H O H OMe OMe N 173-175I-511 Me SBu H O H OMe Me CH 157-160I-512 Me SBu H O H OMe Me N 155-157I-513 Me SPr-i H O H OMe Me CH 185-187I-514 Me SPr-i H O H OMe Me N 228-229I-515 Me SOEt H O H OMe OMe N 180-182I-516 Me SO.sub.2 Et H O H OMe Me CH 270-272I-517 Me SO.sub.2 Et H O H 0Me Me N 165-168I-518 Me SO.sub.2 Et H O H OMe Cl CH 272-275I-519 Me SO.sub.2 Pr H O H OMe Me CH 265-267I-520 Me SO.sub.2 Pr H O H OMe Me N 132-135I-521 Me SO.sub.2 Pr H O H OMe Cl CH 142-145I-522 Me SO.sub.2 Bu H O H OMe Me CH 243-246I-523 Me SO.sub.2 Bu H O H OMe Me N 241-243I-524 Me SO.sub.2 Bu H O H OMe Cl CH 245-247I-525 Me SO.sub.2 Pr-i H O H OMe Me CH 135-139I-526 Me SO.sub.2 Pr-i H O H OMe Me N 281-282I-527 Me COOPr H O H OMe Me N 187-189I-528 Me NO.sub.2 H O H OMe Cl CH 204-206I-529 Me CONMe.sub.2 H O H OMe Me CH 161-164I-530 Me Br H O H OMe Cl CH 276-279I-531 Me ##STR11## H O H OMe OMe CHI-532 Me OCH.sub.2Bu-t H O H OMe OMe CHI-533 Me OCH.sub.2Bu-t H O H Me OMe CHI-534 Me OCH.sub.2 CHCMe.sub.2 H O H OMe OMe CHI-535 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CHI-536 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe CHI-537 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe NI-538 Me CH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHI-539 Me ##STR12## H O H OMe OMe CHI-540 Me COCF.sub.3 H O H OMe OMe CHI-541 Me COOCH.sub.2 CHCHCl H O H OMe OMe CHI-542 Me SO.sub.2 CF.sub.3 H O H OMe OMe CHI-543 Me OCOCF.sub.3 H O H OMe OMe CHI-544 Me OCH.sub.2 OPh H O H OMe OMe CHI-545 Me CHNOH H O H OMe OMe CHI-546 Me CHNOCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-547 Me CHNOCH.sub.2 CCH H O H OMe OMe CHI-548 Me C(Me)NOBn H O H OMe OMe CHI-549 Me C(Me)NOPh H O H OMe OMe CHI-550 Me C(Bn)NOMe H O H OMe OMe CHI-551 Me C(Ph)NOMe H O H OMe OMe CHI-552 Me C(CF.sub.3)NOMe H O H OMe OMe CHI-553 Me COOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-554 Me COOCH.sub.2 CF.sub.3 H O H OMe OMe CHI-555 Me Cl 5-Cl O H OMe Me N 182-184I-556 Me Cl 5-OMe O H OMe OMe CHI-557 Me Cl 5-F O H OMe OMe CHI-558 Me F 5-Cl O H OMe OMe CHI-559 Me F 5-F O H OMe OMe CHI-560 Me COOMe 5-Cl O H OMe OMe CHI-561 Me COOEt 5-Cl O H OMe OMe CHI-562 Me COOPr 5-Cl O H OMe OMe CHI-563 Me COOPr-i 5-Cl O H OMe OMe CHI-564 Me OMe 5-COOMe O H OMe OMe CHI-565 Me COOMe 5-OMe O H OMe OMe CHI-566 Me H 5-CN O H OMe OMe CHI-567 Me H 5-CF O H OMe OMe CHI-568 Me H 5-COOMe O H OMe OMe CH 235-236I-569 Me H 5-COOEt O H OMe OMe CHI-570 Me H 5-COOPr O H OMe OMe CHI-571 Me H 5-COOPr-i O H OMe OMe CHI-572 Me H 5-COOCH.sub.2 CH.sub.2 Cl O H OMe OMe CHI-573 Me H 5-COOCH.sub.2 CH.sub.2 F O H OMe OMe CHI-574 Me H 5-COOCH.sub.2 CF.sub.3 O H OMe OMe CHI-575 Me H 5-COOCH.sub.2 OMe O H OMe OMe CHI-576 Me H 5-CONMe.sub.2 O H OMe OMe CHI-577 Me H 5-OCH.sub.2 CH.sub.2 F O H OMe OMe CHI-578 Me H 5-OCHF.sub.2 O H OMe OMe CHI-579 Me H 5-OCH.sub.2 CF.sub.3 O H OMe OMe CHI-580 Me H 5-OCH.sub.2 CH.sub.2 CH.sub.2 F O H OMe OMe CHI-581 Me H 5-OCH.sub.2 CHCH.sub.2 O H OMe OMe CHI-582 Me H 5-OCH.sub.2 CCH O H OMe OMe CHI-583 Me H 5-NO.sub.2 O H OMe OMe CHI-584 Me H 5-SMe O H OMe OMe CHI-585 Me H 5-SEt O H OMe OMe CHI-586 Me H 5-SPr O H OMe OMe CHI-587 Me H 5-SPr-i O H OMe OMe CHI-588 Me H 5-SO.sub.2 Et O H OMe OMe CHI-589 Me H 5-SO.sub.2 Pr O H OMe OMe CHI-590 Me H 5-SO.sub.2 Pr-i O H OMe OMe CHI-591 Me H 5-SOEt O H OMe OMe CHI-592 Me H 5-Me O H OMe OMe CHI-593 Me H 5-Et O H OMe OMe CHI-594 Me H 5-Pr O H OMe OMe CHI-595 Me H 5-SO.sub.2 NMe.sub.2 O H OMe OMe CHI-596 Me H 5-OCF.sub.3 O H OMe OMe CHI-597 Me H 5-CH.sub.2 CF.sub.3 O H OMe OMe CHI-598 Me H 5-CH.sub.2 CHCH.sub.2 O H OMe OMe CHI-599 Me H 5-COOMe O H OMe Me CH 134-135I-600 Me H 5-COOMe O H OMe Me N 143-144I-601 Me H 5-COOMe O H OMe OMe N 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COOEt Cl H O H OMe OMe CHI-631 COOPh Cl H O H OMe OMe CHI-632 CONMe.sub.2 Cl H O H OMe OMe CHI-633 SO.sub.2 NMe.sub.2 Cl H O H OMe OMe CHI-634 Ph Cl H O H Me OMe NI-635 CH.sub.2 OMe Cl H O H OMe 0Me CHI-636 CH.sub.2 OBn Cl H O H OMe OMe CHI-637 CH.sub.2 CH.sub.2 F Cl H O H OMe OMe CHI-638 CH.sub.2 CH.sub.2 Cl Cl H O H OMe OMe CHI-639 CF.sub.3 Cl H O H OMe OMe CHI-640 CH.sub.2 F Cl H O H OMe OMe CHI-641 CH.sub.2 CHCH.sub.2 OMe H O H OMe OMe CH 221-223I-642 COCF.sub.3 Cl H O H OMe OMe CHI-643 ##STR25## Cl H O H OMe OMe CHI-644 H Bn H O H Ome OMe CHI-645 H Br H O H OMe Me CH 183-184I-646 H Br H O H OMe Me N 154-155I-647 H Br H O H Ome OMe CHI-648 H Bu H O H Me OMe CHI-649 H Bu H O H Me OMe NI-650 H Bu H O H OMe OMe CHI-651 H Bu-t H O H Me OMe CHI-652 H Bu-t H O H Me OMe NI-653 H Bu-t H O H OMe OMe CHI-654 H C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe CHI-655 H C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe NI-656 H C(Me)NOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-657 H C(Me)NOCH.sub.2 CH.sub.2 F H O 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NI-741 H CH.sub.2 SO.sub.2 NMe.sub.2 H O H OMe OMe CHI-742 H CN H O H OMe Me CHI-743 H CN H O H OMe Me NI-744 H CN H O H OMe OMe CHI-745 H ##STR26## H O H Me OMe CHI-746 H ##STR27## H O H Me OMe NI-747 H ##STR28## H O H OMe OMe CHI-748 H CO.sub.2 Bn H O H OMe OMe CHI-749 H CO.sub.2 Bu H O H OMe Me CHI-750 H CO.sub.2 Bu H O H OMe Me NI-751 H CO.sub.2 Bu H O H OMe OMe CHI-752 H CO.sub.2 CH.sub.2 CCH H O H OMe OMe CHI-753 H CO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-754 H CO.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CHI-755 H CO.sub.2 Et H O H OCHF.sub.2 OCHF.sub.2 CHI-756 H CO.sub.2 Et H O H OMe Me NI-757 H CO.sub.2 Et H S H OMe OMe CHI-758 H CO.sub.2 H H O H OMe OMe CHI-759 H CO.sub.2 Me 5-F O H OMe OMe CHI-760 H CO.sub.2 Me H O H OCHF.sub.2 OCHF.sub.2 CHI-761 H CO.sub.2 Me H O H OMe Me CH 202-205I-762 H CO.sub.2 Me H O H OMe Me N 169-170I-763 H CO.sub.2 Me H O H OMe OCHF.sub.2 CHI-764 H CO.sub.2 Me H O Me OMe OMe CHI-765 H CO.sub.2 Me H S H OMe OMe CHI-766 H CO.sub.2 Pen H O H OMe OMe CHI-767 H CO.sub.2 Ph H O H OMe OMe CHI-768 H CO.sub.2 Pr H O H OMe Me CHI-769 H CO.sub.2 Pr H O H OMe OMe CHI-770 H CO.sub.2 Pr-i H O H OMe Me CHI-771 H CO.sub.2 Pr-i H O H OMe Me NI-772 H CO.sub.2 Pr-i H O H OMe OMe CHI-773 H COBn H O H OMe OMe CHI-774 H COCH.sub.2 CCH H O H OMe OMe CHI-775 H COCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-776 H COEt H O H OMe OMe CHI-777 H COH H O H OMe OMe CHI-778 H COMe H O H OMe OMe CHI-779 H CON(Et).sub.2 H O H OMe OMe CHI-780 H CON(Me).sub.2 H O H OMe OMe CHI-781 H CONH.sub.2 H O H OMe OMe CHI-782 H CONHBn H O H OMe OMe CHI-783 H CONHCH.sub.2 CCH H O H OMe OMe CHI-784 H CONHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-785 H CONHEt H O H OMe OMe CHI-786 H CONHMe H O H OMe OMe CHI-787 H CONHOMe H O H OMe OMe CHI-788 H CONHPh H O H OMe OMe CHI-789 H CONHPr H O H OMe OMe CHI-790 H COOMe H O H OMe Me CHI-791 H COOMe H O H Me OMe NI-792 H COPh H O H OMe OMe CHI-793 H COPr H O H Me OMe CHI-794 H COPr H O H Me OMe NI-795 H COPr H O H OMe OMe CHI-796 H COPr-i H O H Me OMe CHI-797 H COPr-i H O H Me OMe NI-798 H COPr-i H O H OMe OMe CHI-799 H Cl 5-Cl O H OMe OMe CHI-800 H Cl H S H Cl OMe CHI-801 H Cl H O H Me Me CHI-802 H Cl H O H OMe Me CHI-803 H Cl H O H OMe He NI-804 H Cl H S H Me Me CHI-805 H Cl H S H OMe Me CHI-806 H Cl H S H OMe Me NI-807 H Cl H O Me OMe OMe CHI-808 H Cl H S H OMe OMe CHI-809 H Et H O H Me OMe CHI-810 H Et H O H Me OMe NI-811 H Et H O H OMe OMe CHI-812 H F H O H Me Me CHI-813 H F H O H OMe Me CHI-814 H F H O H OMe Me NI-815 H F H O H OMe OMe CHI-816 H H 5-Cl O H Me Me CHI-817 H H 5-Cl O H OMe Me NI-818 H H 5-Cl O H OMe OMe CHI-819 H H 5-F O H Me Me CHI-820 H H 5-F O H OMe Me CHI-821 H H 5-F O H OMe Me NI-822 H H 5-F O H OMe OMe CHI-823 H H 5-OEt O H OMe Me CHI-824 H H 5-OEt O H OMe Me NI-825 H H 5-OEt O H OMe OMe CHI-826 H H 5-OEt O H OMe OMe NI-827 H H 5-OMe O H Cl OMe CHI-828 H H 5-OMe O H OMe Me CHI-829 H H 5-OMe O H OMe Me NI-830 H H 5-OMe O H OMe OMe CHI-831 H H 5-OPr O H OMe Me CHI-832 H H 5-OPr O H OMe Me NI-833 H H 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CHI-864 H NCHME H O H He OMe NI-865 H NCHMe H O H OMe OMe CHI-866 H N.sub.3 H O H Me OMe CHI-867 H N.sub.3 H O H Me OMe NI-868 H N.sub.3 H O H OMe OMe CHI-869 H NEt.sub.2 H O H OMe OMe CHI-870 H NH.sub.2 H O H OMe OMe CHI-871 H NHBn H O H Cl OMe CHI-872 H NHBn H O H OMe OMe CHI-873 H NHCOCF.sub.3 H O H Me OMe CHI-874 H NHCOCF.sub.3 H O H Me OMe NI-875 H NHCOCF.sub.3 H O H OMe OMe CHI-876 H NHCOCH.sub.2 Cl H O H OMe OMe CHI-877 H NHCOEt H O H Me OMe CHI-878 H NHCOEt H O H Me OMe NI-879 H NHCOEt H O H OMe OMe CHI-880 H NHCOMe H O H OMe OMe CHI-881 H NHCOOEt H O H Me OMe CHI-882 H NHCOOEt H O H Me OMe NI-883 H NHCOOEt H O H OMe OMe CHI-884 H NHCOOMe H O H Me OMe CHI-885 H NHCOOMe H O H Me OMe NI-886 H NHCOOMe H O H OMe OMe CHI-887 H NHCOOPh H O H Me OMe CHI-888 H NHCOOPh H O H Me OMe NI-889 H NHCOOPh H O H OMe OMe CHI-890 H NHCOPh H O H OMe OMe CHI-891 H NHEt H O H Me OMe CHI-892 H NHEt H O H Me OMe NI-893 H NHEt H O H OMe OMe CHI-894 H NHMe H O H OMe Me CHI-895 H NHMe H O H OMe Me NI-896 H NHMe H O H OMe OMe CHI-897 H NHPr H O H Me OMe CHI-898 H NHPr H O H Me OMe NI-899 H NHPr H O H OMe OMe CHI-900 H NHSO.sub.2 CH.sub.3 H O H OMe OMe CHI-901 H NHSO.sub.2 Ph H O H OMe OMe CHI-902 H NMe.sub.2 H O H Cl OMe CHI-903 H NMe.sub.2 H O H Me Me CHI-904 H NMe.sub.2 H O H OMe Me NI-905 H NO.sub.2 H O H OMe Me CH 208-210I-906 H NO.sub.2 H O H OMe OMe CH 184-186I-907 H OBn H O H OMe OMe CHI-908 H OBn(2-Me) H O H OMe OMe CHI-909 H OBn(3-OMe) H O H OMe OMe CHI-910 H OBn(4-Cl) H O H OMe OMe CHI-911 H OBu H O H Cl OMe CHI-912 H OBu H O H Me Me CHI-913 H OBu H O H OMe Me CHI-914 H OBu H O H OMe Me NI-915 H OBu H O H OMe OMe CHI-916 H OCF.sub.2 CH.sub.2 Cl H O H Me OMe CHI-917 H OCF.sub.2 CH.sub.2 Cl H O H Me OMe NI-918 H OCF.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-919 H OCF.sub.2 CHFCl H O H Me OMe CHI-920 H OCF.sub.2 CHFCl H O H Me OMe NI-921 H OCF.sub.2 CHFCl H O H OMe OMe CHI-922 H OCF.sub.3 H O H Me OMe CHI-923 H OCF.sub.3 H O H Me OMe NI-924 H OCF.sub.3 H O H OMe OMe CHI-925 H OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe CHI-926 H OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe NI-927 H OCH(CF.sub.2 CF.sub.3)Me H O H OMe OMe CHI-928 H OCH(CF.sub.3)Me H O H OMe Me CHI-929 H OCH(CF.sub.3)Me H O H OMe OMe CHI-930 H OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe CHI-931 H OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe NI-932 H OCH.sub.2 C(Cl)CH.sub.2 H O H OMe OMe CHI-933 H OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe CHI-934 H OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe NI-935 H OCH.sub.2 C(Me)CH.sub.2 H O H OMe OMe CHI-936 H OCH.sub.2 CCH H O H OMe OMe CHI-937 H OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe CHI-938 H OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe NI-939 H OCH.sub.2 CF.sub.2 CF.sub.3 H O H OMe OMe CHI-940 H OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe CHI-941 H OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe NI-942 H OCH.sub.2 CF.sub.2 CHF.sub.2 H O H OMe OMe CHI-943 H OCH.sub.2 CF.sub.3 H O H Cl OMe CHI-944 H OCH.sub.2 CF.sub.3 H O H OMe Me CHI-945 H OCH.sub.2 CF.sub.3 H O H OMe Me NI-946 H OCH.sub.2 CF.sub.3 H O H OMe OMe CHI-947 H OCH.sub.2 CHCCl.sub.2 H O H Me OMe CHI-948 H OCH.sub.2 CHCCl.sub.2 H O H Me OMe NI-949 H OCH.sub.2 CHCCl.sub.2 H O H OMe OMe CHI-950 H OCH.sub.2 CHCHCl H O H Me OMe CHI-951 H OCH.sub.2 CHCHCl H O H Me OMe NI-952 H OCH.sub.2 CHCHCl H O H OMe OMe CHI-953 H OCH.sub.2 CHCH.sub.2 H O H OMe OMe HI-954 H OCH.sub.2 CHCHMe H O H Me OMe CHI-955 H OCH.sub.2 CHCHMe H O H Me OMe NI-956 H OCH.sub.2 CHCHMe H O H OMe OMe CHI-957 H OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe CHI-958 H OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe NI-959 H OCH.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHI-960 H OCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-961 H OCH.sub.2 CH.sub.2 F H O H OMe OMe CHI-962 H OCH.sub.2 CH.sub.2 N.sub.3 H O H Me OMe CHI-963 H OCH.sub.2 CH.sub.2 N.sub.3 H O H He OMe NI-964 H OCH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHI-965 H OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me CHI-966 H OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me NI-967 H OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe OMe CHI-968 H OCH.sub.2 CH.sub.2 OBu H O H OMe Me CHI-969 H OCH.sub.2 CH.sub.2 OBu H O H OMe Me NI-970 H OCH.sub.2 CH.sub.2 OBu H O H OMe OMe CHI-971 H OCH.sub.2 CH.sub.2 OBu H O H OMe OMe NI-972 H OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me CHI-973 H OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me NI-974 H OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe CHI-975 H OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe NI-976 H OCH.sub.2 CH.sub.2 OEt H O H OMe Me CHI-977 H OCH.sub.2 CH.sub.2 OEt H O H OMe Me NI-978 H OCH.sub.2 CH.sub.2 OEt H O H OMe OMe CHI-979 H OCH.sub.2 CH.sub.2 OMe H O H OMe Me CHI-980 H OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-981 H OCH.sub.2 CH.sub.2 OPh H O H OMe OMe CHI-982 H OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me CHI-983 H OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me NI-984 H OCH.sub.2 CH.sub.2 OPr-i H O H OMe OMe CHI-985 H OCH.sub.2 CH.sub.2 SMe H O H Me OMe CHI-986 H OCH.sub.2 CH.sub.2 SMe H O H Me OMe NI-987 H OCH.sub.2 CH.sub.2 SMe H O H OMe OMe CHI-988 H OCH.sub.2 CHCl.sub.2 H O H Me OMe CHI-989 H OCH.sub.2 CHCl.sub.2 H O H Me OMe NI-990 H OCH.sub.2 CHCl.sub.2 H O H OMe OMe CHI-991 H OCH.sub.2 CHF.sub.2 H O H Me OMe CHI-992 H OCH.sub.2 CHF.sub.2 H O H Me OMe NI-993 H OCH.sub.2 CHF.sub.2 H O H OMe OMe CHI-994 H OCH.sub.2 CN H O H Me OMe CHI-995 H OCH.sub.2 CN H O H Me OMe NI-996 H OCH.sub.2 CN H O H OMe OMe CHI-997 H OCH.sub.2 COOEt H O H OMe OMe CHI-998 H OCH.sub.2 COOMe H O H Me OMe CHI-999 H OCH.sub.2 COOMe H O H Me OMe NI-1000 H OCH.sub.2 COOMe H O H OMe OMe CHI-1001 H OCH.sub.2 COOPr H O H Me OMe CHI-1002 H OCH.sub.2 COOPr H O H Me OMe NI-1003 H OCH.sub.2 COOPr H O H OMe OMe CHI-1004 H OCH.sub.2 COOPr-i H O H Me OMe CHI-1005 H OCH.sub.2 COOPr-i H O H Me OMe NI-1006 H OCH.sub.2 COOPr-i H O H OMe OMe CHI-1007 H OCH.sub.2 OBn H O H Me OMe CHI-1008 H OCH.sub.2 OBn H O H Me OMe NI-1009 H OCH.sub.2 OBn H O H OMe OMe CHI-1010 H OCH.sub.2 OBu-t H O H Me OMe CHI-1011 H OCH.sub.2 OBu-t H O H Me OMe NI-1012 H OCH.sub.2 OBu-t H O H OMe OMe CHI-1013 H OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe CHI-1014 H OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe NI-1015 H OCH.sub.2 OCH.sub.2 CF.sub.3 H O H OMe OMe CHI-1016 H OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe CHI-1017 H OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe NI-1018 H OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-1019 H OCH.sub.2 OEt H O H Me OMe CHI-1020 H OCH.sub.2 OEt H O H Me OMe NI-1021 H OCH.sub.2 OEt H O H OMe OMe CHI-1022 H OCH.sub.2 OMe H O H Me OMe CHI-1023 H OCH.sub.2 OMe H O H Me OMe NI-1024 H OCH.sub.2 OMe H O H OMe OMe CHI-1025 H OCH.sub.2 SMe H O H Me OMe CHI-1026 H OCH.sub.2 SMe H O H Me OMe NI-1027 H OCH.sub.2 SMe H O H OMe OMe CHI-1028 H OCHF.sub.2 H O H Me OMe CHI-1029 H OCHF.sub.2 H O H Me OMe NI-1030 H OCHF.sub.2 H O H OMe OMe CHI-1031 H OCOEt H O H Me OMe CHI-1032 H OCOEt H O H Me OMe NI-1033 H OCOEt H O H OMe OMe CHI-1034 H OCOMe H O H OMe OMe CHI-1035 H OCONMe.sub.2 H O H Me OMe CHI-1036 H OCONMe.sub.2 H O H Me OMe NI-1037 H OCONMe.sub.2 H O H OMe OMe CHI-1038 H OCOPh H O H Me OMe CHI-1039 H OCOPh H O H Me OMe NI-1040 H OCOPh H O H OMe OMe CHI-1041 H OCOPr H O H Me OMe CHI-1042 H OCOPr H O H Me OMe NI-1043 H OCOPr H O H OMe OMe CHI-1044 H OEt H O H Me Me CHI-1045 H OEt H O H OMe Me CHI-1046 H OEt H O H OMe Me NI-1047 H OEt H O H OMe OMe CHI-1048 H OH H O H OMe OMe CHI-1049 H OMe 5-Cl O H OMe Me NI-1050 H OMe 5-Cl O H OMe OMe CHI-1051 H OMe 5-OMe O H OMe Me CHI-1052 H OMe H O H Cl OMe CHI-1053 H OMe H O H OMe Me CHI-1054 H OMe H O H OMe OMe NI-1055 H OMe H O H Me Me CHI-1056 H OMe H O H OMe Me NI-1057 H OMe H O H OMe OMe CHI-1058 H OPh H O H OMe OMe CHI-1059 H OPh(2-Me) H O H OMe OMe CHI-1060 H OPh(3-OMe) H O H OMe OMe CHI-1061 H OPh(4-Cl) H O H OMe OMe CHI-1062 H OPr H O H Cl OMe CHI-1063 H OPr H O H Me Me CHI-1064 H OPr H O H OMe Me CHI-1065 H OPr H O H OMe Me NI-1066 H OPr H O H OMe OMe CHI-1067 H OPr-i H O H Me Me CHI-1068 H OPr-i H O H OMe Me CHI-1069 H OPr-i H O H OMe Me NI-1070 H OPr-i H O H OMe OMe CHI-1071 H Ph H O H OMe OMe CHI-1072 H Pr H O H Me OMe CHI-1073 H Pr H O H Me OMe NI-1074 H Pr H O H OMe OMe CHI-1075 H Pr-i H O H Me OMe CHI-1076 H Pr-i H O H Me OMe NI-1077 H Pr-i H O H OMe OMe CHI-1078 H SBu H O H Cl OMe CHI-1079 H SBu H O H OMe OMe CHI-1080 H SCF.sub.3 H O H Me OMe CHI-1081 H SCF.sub.3 H O H Me OMe NI-1082 H SCF.sub.3 H O H OMe OMe CHI-1083 H SCH.sub.2 CH.sub.2 Cl H O H Me OMe CHI-1084 H SCH.sub.2 CH.sub.2 Cl H O H Me OMe NI-1085 H SCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-1086 H SCH.sub.2 CH.sub.2 F H O H Me OMe CHI-1087 H SCH.sub.2 CH.sub.2 F H O H Me OMe NI-1088 H SCH.sub.2 CH.sub.2 F H O H OMe OMe CHI-1089 H SEt H O H OMe Me NI-1090 H SEt H O H OMe OMe CHI-1091 H SH H O H OMe OMe CHI-1092 H SMe H O H OMe OMe CHI-1093 H SO.sub.2 Bu H O H OMe OMe CHI-1094 H SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe CHI-1095 H SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe NI-1096 H SO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-1097 H SO.sub.2 Et H O H OMe OMe CHI-1098 H SO.sub.2 Me H O H OMe OMe CHI-1099 H SO.sub.2 NMe.sub.2 H O H OMe OMe CHI-1100 H SO.sub.2 NEt.sub.2 H O H Me OMe CHI-1101 H SO.sub.2 NEt.sub.2 H O H Me OMe NI-1102 H SO.sub.2 NEt.sub.2 H O H OMe OMe CHI-1103 H SO.sub.2 NH.sub.2 H O H OMe OMe CHI-1104 H SO.sub.2 NHBn H O H OMe OMe CHI-1105 H SO.sub.2 NHCH.sub.2 CCH H O H OMe OMe CHI-1106 H SO.sub.2 NHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-1107 H SO.sub.2 NHMe H O H OMe OMe CHI-1108 H SO.sub.2 NHOEt H O H Me OMe CHI-1109 H SO.sub.2 NHOEt H O H Me OMe NI-1110 H SO.sub.2 NHOEt H O H OMe OMe CHI-1111 H SO.sub.2 NHOMe H O H OMe OMe CHI-1112 H SO.sub.2 NHPh H O H OMe OMe CHI-1113 H SO.sub.2 Pr H O H OMe OMe CHI-1114 H SO.sub.2 Pr-i H O H Cl OMe CHI-1115 H SO.sub.2 Pr-i H O H OMe OMe CHI-1116 H SOEt H O H Me OMe CHI-1117 H SOEt H O H Me OMe NI-1118 H SOEt H O H OMe OMe CHI-1119 H SOMe H O H OMe OMe CHI-1120 H SPr H O H Cl OMe CHI-1121 H SPr H O H OMe Me CHI-1122 H SPr H O H OMe Me NI-1123 H SPr H O H OMe OMe CHI-1124 H SPr-i H O H Cl OMe CHI-1125 H SPr-i H O H OMe OMe CHI-1126 H NO.sub.2 H O H Me OMe N 182-184I-1127 H SEt H O H Cl OMe CHI-1128 H SEt H O H Me Me CHI-1129 H SEt H O H OMe OMe NI-1130 H SBu H O H OMe Me CHI-1131 H SBu H O H OMe Me NI-1132 H SPr-i H O H OMe Me CHI-1133 H SPr-i H O H OMe Me NI-1134 H SOEt H O H OMe OMe NI-1135 H SO.sub.2 Et H O H OMe Me CHI-1136 H SO.sub.2 Et H O H OMe Me NI-1137 H SO.sub.2 Et H O H OMe Cl CHI-1138 H SO.sub.2 Pr H O H OMe Me CHI-1139 H SO.sub.2 Pr H O H OMe Me NI-1140 H SO.sub.2 Pr H O H OMe Cl CHI-1141 H SO.sub.2 Bu H O H OMe Me CHI-1142 H SO.sub.2 Bu H O H OMe Me NI-1143 H SO.sub.2 Bu H O H OMe Cl CHI-1144 H SO.sub.2 Pr-i H O H OMe Me CHI-1145 H SO.sub.2 Pr-i H O H OMe Me NI-1146 H COOPr H O H OMe Me NI-1147 H NO.sub.2 H O H OMe Cl CHI-1148 H CONMe.sub.2 H O H OMe Me CHI-1149 H Br H O H OMe Cl CHI-1150 H ##STR29## H O H OMe OMe CHI-1151 H OCH.sub.2Bu-t H O H OMe OMe CHI-1152 H OCH.sub.2Bu-t H O H Me OMe CHI-1153 H OCH.sub.2 CHCMe.sub.2 H O H OMe OMe CHI-1154 H OCH.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CHI-1155 H OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe CHI-1156 H OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe NI-1157 H CH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHI-1158 H ##STR30## H O H OMe OMe CHI-1159 H COCF.sub.3 H O H OMe OMe CHI-1160 H COOCH.sub.2 CHCHCl H O H OMe OMe CHI-1161 H SO.sub.2 CF.sub.3 H O H OMe OMe CHI-1162 H OCOCF.sub.3 H O H OMe OMe CHI-1163 H OCH.sub.2 OPh H O H OMe OMe CHI-1164 H CHNOH H O H OMe OMe CHI-1165 H CHNOCH.sub.2 CHCH.sub.2 H O H OMe OMe CHI-1166 H CHNOCH.sub.2 CCH H O H OMe OMe CHI-1167 H C(Me)NOBn H O H OMe OMe CHI-1168 H C(Me)NOPh H O H OMe OMe CHI-1169 H C(Bn)NOMe H O H OMe OMe CHI-1170 H C(Ph)NOMe H O H OMe OMe CHI-1171 H C(CF.sub.3)NOMe H O H OMe OMe CHI-1172 H COOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-1173 H COOCH.sub.2 CF.sub.3 H O H OMe OMe CHI-1174 H Cl S-Cl O H OMe Me NI-1175 H Cl 5-OMe O H OMe OMe CHI-1176 H Cl 5-F O H OMe OMe CHI-1177 H F 5-Cl O H OMe OMe CHI-1178 H F 5-F O H OMe OMe CHI-1179 H COOMe 5-Cl O H OMe OMe CHI-1180 H COOEt 5-Cl O H OMe OMe CHI-1181 H COOPr 5-Cl O H OMe OMe CHI-1182 H COOPr-i 5-Cl O H OMe OMe CHI-1183 H OMe 5-COOMe O H OMe OMe CHI-1184 H COOMe 5-OMe O H OMe OMe CHI-1185 H ONCHMe H O H OMe OMe CHI-1186 H ONCMe.sub.2 H O H OMe OMe CHI-1187 H ONCHBn H O H OMe OMe CHI-1188 H OCH.sub.2 CH.sub.2 F H O H OMe Me CHI-1189 H OCH.sub.2 CH.sub.2 F H O H OMe Me NI-1190 H H 5-CN O H OMe OMe CHI-1191 H H 5-CF.sub.3 O H OMe OMe CHI-1192 H H 5-COOMe O H OMe OMe CHI-1193 H H 5-COOEt O H OMe OMe CHI-1194 H H 5-COOPr O H OMe OMe CHI-1195 H H 5-COOPr-i O H OMe OMe CHI-1196 H H 5-COOCH.sub.2 CH.sub.2 Cl O H OMe OMe CHI-1197 H H 5-COOCH.sub.2 CH.sub.2 F O H OMe OMe CHI-1198 H H 5-COOCH.sub.2 CF.sub.3 O H OMe OMe CHI-1199 H H 5-COOCH.sub.2 OMe O H OMe OMe CHI-1200 H H 5-CONMe.sub.2 O H OMe OMe CHI-1201 H H 5-OCH.sub.2 CH.sub.2 F O H OMe OMe CHI-1202 H H 5-OCHF.sub.2 O H OMe OMe CHI-1203 H H 5-OCH.sub.2 CF.sub.3 O H OMe OMe CHI-1204 H H 5-OCH.sub.2 CH.sub.2 CH.sub.2 F O H OMe OMe CHI-1205 H H 5-OCH.sub.2 CHCH.sub.2 O H OMe OMe CHI-1206 H H 5-OCH.sub.2 CCH O H OMe OMe CHI-1207 H H 5-NO.sub.2 O H OMe OMe CHI-1208 H H 5-SMe O H OMe OMe CHI-1209 H H 5-SEt O H OMe OMe CHI-1210 H H 5-SPr O H OMe OMe CHI-1211 H H 5-SPr-i O H OMe OMe CHI-1212 H H 5-SO.sub.2 Et O H OMe OMe CHI-1213 H H 5-SO.sub.2 Pr O H OMe OMe CHI-1214 H H 5-SO.sub.2 Pr-i O H OMe OMe CHI-1215 H H 5-SOEt O H OMe OMe CHI-1216 H H 5-Me O H OMe OMe CHI-1217 H H 5-Et O H OMe OMe CHI-1218 H H 5-Pr O H OMe OMe CHI-1219 H H 5-SO.sub.2 NMe.sub.2 O H OMe OMe CHI-1220 H H 5-OCF.sub.3 O H OMe OMe CHI-1221 H H 5-CH.sub.2 CF.sub.3 O H OMe OMe CHI-1222 H H 5-CH.sub.2 CHCH.sub.2 O H OMe OMe CHI-1223 H H 5-COOMe O H OMe Me CHI-1224 H H 5-COOMe O H OMe Me NI-1225 H H 5-COOMe O H OMe OMe NI-1226 H Cl H O CH.sub.3 OCH.sub.2 OMe OMe CHI-1227 H Cl H O H OMe NMe.sub.2 NI-1228 H Cl H O H OMe NHMe NI-1229 H ##STR31## H O H Me OMe CHI-1230 H ##STR32## H O H Me OMe NI-1231 H ##STR33## H O H OMe OMe CHI-1232 H ##STR34## H O H OMe OMe CHI-1233 H ##STR35## H O H Me OMe CHI-1234 H ##STR36## H O H Me OMe NI-1235 H ##STR37## H O H OMe OMe CHI-1236 H ##STR38## H O H Me OMe CHI-1237 H ##STR39## H O H Me OMe NI-1238 H ##STR40## H O H OMe OMe CHI-1239 H ##STR41## H O H Me OMe CHI-1240 H ##STR42## H O H Me OMe NI-1241 H OC.sub.2 H.sub.4O* O H OMe OMe CHI-1242 H OC.sub.2 H.sub.4O* O H Me OMe CHI-1243 H OC.sub.2 H.sub.4O* O H Me OMe NI-1244 H SC.sub.2 H.sub.4S* O H OMe OMe CHI-1245 H SC.sub.2 H.sub.4S* O H Me OMe CHI-1246 H SC.sub.2 H.sub.4S* O H Me OMe NI-1247 H OCH.sub.2O* O H OMe OMe CHI-1248 Me Cl H O CH.sub.3 OCH.sub.2 OMe OMe CHI-1249 Me Cl H O H OMe NMe.sub.2 NI-1250 Me Cl H O H OMe NHMe NI-1251 Me ONCHMe H O H OMe OMe CHI-1252 Me ONCMe.sub.2 H O H OMe OMe CHI-1253 Me ONCHBn H O H OMe OMe CHI-1254 Me OCH.sub.2 CH.sub.2 F H O H OMe Me CHI-1255 Me OCH.sub.2 CH.sub.2 F H O H OMe Me NI-1256 Me F H O H NMe.sub.2 OCH.sub.2 CF.sub.3 N 128-130I-1257 Me CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-1258 Me CO.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHI-1259 Me CO.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-1260 H CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H OMe OMe CHI-1261 H CO.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHI-1262 H CO.sub.2 CH.sub.2 OMe H O H OMe OMe CHI-1263 Et CO.sub.2 Me H O H OMe Me CH 198-200I-1264 Et CO.sub.2 Me H O H OMe Me N 153-155I-1265 Me SO.sub.2 NMe.sub.2 H O H OMe Me CH 134-135I-1266 Me SO.sub.2 NMe.sub.2 H O H OMe Me N 253-255__________________________________________________________________________
TABLE 2__________________________________________________________________________ ##STR43##Comp. No. R.sup.1 R.sup.2 R.sup.3 X Y A B Z mp.__________________________________________________________________________ (.degree.C.)II-1 Me Ph H O H OMe OMe CHII-2 Me Bn H O H OMe OMe CHII-3 Me SH H O H OMe OMe CHII-4 Me SMe H O H OMe OMe CHII-5 Me SEt H O H OMe OMe CH 156-157II-6 Me SPr H O H OMe OMe CH 143-145II-7 Me SO.sub.2 Me H O H OMe OMe CHII-8 Me SO.sub.2 Et H O H OMe OMe CH 196-198II-9 Me SOMe H O H OMe OMe CHII-10 Me SO.sub.2 NHMe H O H OMe OMe CHII-11 Me SO.sub.2 NHOMe H O H OMe OMe CHII-12 Me SO.sub.2 NMe.sub.2 H O H OMe OMe CH 169-171II-13 Me SO.sub.2 NHBn H O H OMe OMe CHII-14 Me SO.sub.2 NHPh H O H OMe OMe CHII-15 Me SO.sub.2 NHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-16 Me SO.sub.2 NHCH.sub.2 CCH H O H OMe OMe CHII-17 H Cl H O H OMe OMe CH 191-193II-18 Me Cl H O H Me Me CH 210-213II-19 Me Cl 5-Cl O H OMe OMe CH 203-205II-20 Et Cl H O H OMe OMe CH 174-175II-21 Ph Cl H O H OMe OMe CH 221-223II-22 Bn Cl H O H OMe OMe CHII-23 Me H H O H OMe OMe CH 199-202II-24 Me H H O H Me Me CH 208-210II-25 Me H H O H OMe Me N 172-174II-26 Me F H O H OMe OMe CH 205-206II-27 Me Br H O H OMe OMe CH 179-182II-28 Me Me H O H OMe OMe CH 178-180II-29 Me CN H O H OMe OMe CH 189-191II-30 Me CF.sub.3 H O H OMe OMe CHII-31 Me Cl H O H OMe Me CH 202-204II-32 Me Cl H O H OMe Me N 170-172II-33 Me F H O H Me Me CH 207-209II-34 Me F H O H OMe Me N 178-180II-35 Me F H O H OMe Me CH 185-187II-36 Me H 5-Cl O H OMe OMe CH 215-216II-37 Me H 5-Cl O H Me Me CH 192-194II-38 Me H 5-Cl O H OMe Me N 176-178II-39 Me H 6-Cl O H OMe OMe CH 210-212II-40 Me H 6-Cl O H Me Me CH 217-220II-41 Me H 6-Cl O H OMe Me N 181-183II-42 Me H 7-Cl O H OMe OMe CH 223-225II-43 Me H 7-Cl O H OMe Me N 167-169II-44 Me Cl H S H OMe OMe CHII-45 Me Cl H O Me OMe OMe CHII-46 Me COH H O H OMe OMe CHII-47 Me COMe H O H OMe OMe CHII-48 Me COEt H O H OMe OMe CHII-49 Me COPh H O H OMe OMe CHII-50 Me COCH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-51 Me COCH.sub.2 CCH H O H OMe OMe CHII-52 Me COBn H O H OMe OMe CHII-53 Me NO.sub.2 H O H OMe OMe CH 155-157II-54 Me NH.sub.2 H O H OMe OMe CHII-55 Me NHMe H O H OMe OMe CH 143-144II-56 Me NMe.sub.2 H O H OMe OMe CH 183-185II-57 Me NHCOMe H O H OMe OMe CHII-58 Me NHCOPh H O H OMe OMe CHII-59 Me NHCOCH.sub.2 Cl H O H OMe OMe CHII-60 Me NHSO.sub.2 CH.sub.3 H O H OMe OMe CHII-61 Me NHSO.sub.2 Ph H O H OMe OMe CHII-62 Me CO.sub.2 H H O H OMe OMe CHII-63 Me CO.sub.2 Me H O H OMe OMe CH 179-181II-64 Me CO.sub.2 Et H O H OMe OMe CH 181-182II-65 Me CO.sub.2 Pr H O H OMe OMe CH 188-190II-66 Me CO.sub.2 Pr-i H O H OMe OMe CH 200-202II-67 Me CO.sub.2 Bu H O H OMe OMe CH 189-190II-68 Me CO.sub.2 Pen H O H OMe OMe CHII-69 Me CO.sub.2 Bn H O H OMe OMe CHII-70 Me CO.sub.2 Ph H O H OMe OMe CHII-71 Me CO.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CHII-72 Me CO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-73 Me CO.sub.2 CH.sub.2 CCH H O H OMe OMe CHII-74 Me CO.sub.2 Me H O H OCHF.sub.2 OCHF.sub.2 CHII-75 Me CO.sub.2 Et H O H OCHF.sub.2 OCHF.sub.2 CHII-76 Me CO.sub.2 Me H O H OMe Cl CHII-77 Me CO.sub.2 Me H O H OMe Me CHII-78 Me CO.sub.2 Me H O H OMe Me NII-79 Me CO.sub.2 Et H O H OMe Me NII-80 Me CO.sub.2 Me H O H OMe OCHF.sub.2 CHII-81 Me CO.sub.2 Me 5-F O H OMe OMe CHII-82 Et CO.sub.2 Me H O H OMe OMe CH 147-148II-83 Bu CO.sub.2 Me H O H OMe OMe CHII-84 Bn CO.sub.2 Me H O H OMe OMe CHII-85 Ph CO.sub.2 Me H O H OMe OMe CHII-86 H CO.sub.2 Et H O H OMe OMe CHII-87 Me CO.sub.2 Me H S H OMe OMe CHII-88 Me CO.sub.2 Et H S H OMe OMe CHII-89 Me CO.sub.2 Me H O Me OMe OMe CHII-90 Me OH H O H OMe OMe CH 179-181II-91 Me OMe H O H OMe OMe CH 162-165II-92 Me OEt H O H OMe OMe CH 153-154II-93 Me OPr H O H OMe OMe CH 119-120II-94 Me OPr-i H O H OMe OMe CH 176-179II-95 Me OBu H O H OMe OMe CH 184-186II-96 Me OBn H O H OMe OMe CH 200-203II-97 Me OBn(4-Cl) H O H OMe OMe CHII-98 Me OBn(3-OMe) H O H OMe OMe CHII-99 Me OBn(2-Me) H O H OMe OMe CHII-100 Me OPh H O H OMe OMe CHII-101 Me OPh(4-Cl) H O H OMe OMe CHII-102 Me OPh(3-OMe) H O H OMe OMe CHII-103 Me OPh(2-Me) H O H OMe OMe CHII-104 Me OCH.sub.2 CHCH.sub.2 H O H OMe OMe CH 133-136II-105 Me OCH.sub.2 CCH H O H OMe OMe CH 182-183II-106 Me OCH.sub.2 CF.sub.3 H O H OMe OMe CH 165-170II-107 Me OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CH 139-141II-108 Me OCH.sub.2 CH.sub.2 OPh H O H OMe OMe CHII-109 Me OCOMe H O H OMe OMe CHII-110 Me OMe H O H OMe Me CH 206-208II-111 Me OMe H O H OMe Me N 198-201II-112 Me OMe H O H Me Me CH 193-196II-113 Me OEt H O H OMe Me N 179-181II-114 Me OEt H O H OMe Me CH 174-175II-115 Me OEt H O H Me Me CH 182-183II-116 Me CONH.sub.2 H O H OMe OMe CHII-117 Me CONHMe H O H OMe OMe CHII-118 Me CONHEt H O H OMe OMe CHII-119 Me CONHPr H O H OMe OMe CHII-120 Me CONMe.sub.2 H O H OMe OMe CH 150-151II-121 Me CONEt.sub.2 H O H OMe OMe CHII-122 Me CONHBn H O H OMe OMe CHII-123 Me CONHPh H O H OMe OMe CHII-124 Me CONHCH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-125 Me CONHCH.sub.2 CCH H O H OMe OMe CHII-126 Me CONHOMe H O H OMe OMe CHII-127 Me H 5-F O H OMe OMe CH 205-208II-128 Me H 5-F O H Me Me CH 203-206II-129 Me H 5-F O H OMe Me CH 186-189II-130 Me H 5-F O H OMe Me N 175-179II-131 H COOMe H O H OMe OMe CH 179-180II-132 H COOMe H O H OMe Cl CH 193-194II-133 H Cl H O H OMe Cl CH 178-181II-134 Me Cl H O H OMe OMe CH 171-172II-135 Me SO.sub.2 NH.sub.2 H O H OMe OMe CHII-136 H Br H O H OMe OMe CH 190-193II-137 Me H 5-OMe O H OMe OMe CH 178-181II-138 Me H 5-OEt O H OMe OMe CH 188-189II-139 Me H 5-OPr O H OMe OMe CH 197-198II-140 Me OCH(CF.sub.3)Me H O H OMe OMe CH 129-130II-141 Me OCH.sub.2 CH.sub.2 Cl H O H OMe OMe CH 182-186II-142 Me OCH.sub.2 CH.sub.2 F H O H OMe OMe CH 162-165II-143 Me OCH.sub.2 CH.sub.2 OEt H O H OMe OMe CH 138-139II-144 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe OMe CH 185-187II-145 Me OCH.sub.2 CH.sub.2 OBu H O H OMe OMe CH 120-121II-146 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe CH 169-171II-147 Me OCH.sub.2 COOEt H O H OMe OMe CH 163-165II-148 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe OMe CH 126-129II-149 Me SBu H O H OMe OMe CH 156-158II-150 Me SPr-i H O H OMe OMe CH 183-184II-151 Me SO.sub.2 Pr H O H OMe OMe CH 202-204II-152 Me SO.sub.2 Bu H O H OMe OMe CH 201-203II-153 Me SO.sub.2 Pr-i H O H OMe OMe CH 185-187II-154 Me NHBn H O H OMe OMe CH 167-168II-155 Me NEt.sub.2 H O H OMe OMe CH 173-175II-156 Me OMe 5-Cl O H OMe OMe CH 211-212II-157 Me Br H O H OMe Me CH 187-189II-158 Et Cl H O H OMe Me CH 205-206II-159 Ph Cl H O H OMe Me CH 215-217II-160 Me OPr H O H OMe Me CH 174-175II-161 Me OBu H O H OMe Me CH 169-171II-162 Me OPr-i H O H OMe Me CH 157-159II-163 Me H 5-OMe O H OMe Me CH 206-208II-164 Me H 5-OEt O H OMe Me CH 174-176II-165 Me H 5-OPr O H OMe Me CH 176-178II-166 Me OCH.sub.2 CF.sub.3 H O H OMe Me CH 150-153II-167 Me OCH(CF.sub.3)Me H O H OMe Me CH 112-114II-168 Me OCH.sub.2 CH.sub.2 OMe H O H OMe Me CH 138-139II-169 Me OCH.sub.2 CH.sub.2 OEt H O H OMe Me CH 160-163II-170 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me CH 130-132II-171 Me OCH.sub.2 CH.sub.2 OBu H O H OMe Me CH 104-106II-172 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me CH 148-149II-173 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me CH 126-129II-174 Me SPr H O H OMe Me CH 164-165II-175 Me CO.sub.2 Pr H O H OMe Me CH 179-181II-176 Me CO.sub.2 Pr-i H O H OMe Me CH 187-190II-177 Me CO.sub.2 Bu H O H OMe Me CH 189-192II-178 Me NO.sub.2 H O H OMe Me CH 161-163II-179 Me CN H O H OMe Me CH 195-197II-180 Me Br H O H OMe Me N 172-174II-181 Et Cl H O H OMe Me N 192-194II-182 Me OPr H O H OMe Me N 176-177II-183 Me OBu H O H OMe Me N 143-145II-184 Me OPr-i H O H OMe Me N 155-156II-185 Me H 5-OMe O H OMe Me N 171-174II-186 Me H 5-OEt O H OMe Me N 180-182II-187 Me H 5-OPr O H OMe Me N 168-170II-188 Me OCH.sub.2 CF.sub.3 H O H OMe Me N 168-170II-189 Me OCH.sub.2 CH.sub.2 OEt H O H OMe Me N 168-170II-190 Me OCH.sub.2 CH.sub.2 OPr-i H O H OMe Me N 153-155II-191 Me OCH.sub.2 CH.sub.2 OBu H O H OMe Me N 121-123II-192 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe Me N 161-162II-193 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H O H OMe Me N 119-121II-194 Me SEt H O H OMe Me N 160-162II-195 Me SPr H O H OMe Me N 129-131II-196 Me NMe.sub.2 H O H OMe Me N 131-133II-197 Me CO.sub.2 Pr-i H O H OMe Me N 190-191II-198 Me CO.sub.2 Bu H O H OMe Me N 179-181II-199 Me CN H O H OMe Me N 196-197II-200 Me OMe 5-Cl O H OMe Me N 201-203II-201 Me Cl H O H Cl OMe CH 187-189II-202 Et Cl H O H Cl OMe CH 206-208II-203 Ph Cl H O H Cl OMe CH 202-204II-204 Me OMe H O H Cl OMe CH 220-223II-205 Me OPr H O H Cl OMe CH 140-141II-206 Me OBu H O H Cl OMe CH 153-154II-207 Me H 5-OMe O H Cl OMe CH 174-177II-208 Me OCH.sub.2 CF.sub.3 H O H Cl OMe CH 175-179II-209 Me SPr H O H Cl OMe CH 165-167II-210 Me SBu H O H Cl OMe CH 156-157II-211 Me SPr-i H O H Cl OMe CH 177-179II-212 Me SO.sub.2 Pr-i H O H Cl OMe CH 184-186II-213 Me NHBn H O H Cl OMe CH 160-163II-214 Me NMe.sub.2 H O H Cl OMe CH 197-199II-215 Et Cl H O H Me Me CH 229-231II-216 Me OPr H O H Me Me CH 172-173II-217 Me OBu H O H Me Me CH 148-149II-218 Me OPr-i H O H Me Me CH 187-190II-219 Me NMe.sub.2 H O H Me Me CH 174-176II-220 Me OMe H O H OMe OMe N 193-195II-221 Me H 5-OEt O H OMe OMe N 169-170II-222 Me H 5-OPr O H OMe OMe N 168-169II-223 Me OCH.sub.2 CH.sub.2 OBu H O H OMe OMe N 132-133II-224 Me OCH.sub.2 CH.sub.2 OBu-t H O H OMe OMe N 162-163II-225 Me NHMe H O H OMe Me CH 164-165II-226 Me NHMe H O H OMe Me N 173-175II-227 Me OMe 5-Cl O H OMe Me CH 222-225II-228 Me OMe 5-OMe O H OMe OMe CH 168-170II-229 Me OCHF.sub.2 H O H OMe OMe CH 179-181II-230 Me OCHF.sub.2 H O H Me OMe CH 195-197II-231 Me OCHF.sub.2 H O H Me OMe N 165-167II-232 Me OCH.sub.2 CHF.sub.2 H O H OMe OMe CH 178-180II-233 Me OCH.sub.2 CHF.sub.2 H O H Me OMe CH 180-182II-234 Me OCH.sub.2 CHF.sub.2 H O H Me OMe N 164-166II-235 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHII-236 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe CHII-237 Me OCH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe NII-238 Me OCH(CF.sub.2 CF.sub.3)Me H O H OMe OMe CHII-239 Me OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe CHII-240 Me OCH(CF.sub.2 CF.sub.3)Me H O H Me OMe NII-241 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H OMe OMe CHII-242 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe CHII-243 Me OCH.sub.2 CF.sub.2 CHF.sub.2 H O H Me OMe NII-244 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H OMe OMe CHII-245 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe CHII-246 Me OCH.sub.2 CF.sub.2 CF.sub.3 H O H Me OMe NII-247 Me OCH.sub.2 CHCl.sub.2 H O H OMe OMe CHII-248 Me OCH.sub.2 CHCl.sub.2 H O H Me OMe CHII-249 Me OCH.sub.2 CHCl.sub.2 H O H Me OMe NII-250 Me OCF.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-251 Me OCF.sub.2 CH.sub.2 Cl H O H Me OMe CHII-252 Me OCF.sub.2 CH.sub.2 Cl H O H Me OMe NII-253 Me OCF.sub.2 CHFCl H O H OMe OMe CHII-254 Me OCF.sub.2 CHFCl H O H Me OMe CHII-255 Me OCF.sub.2 CHFCl H O H Me OMe NII-256 Me OCF.sub.3 H O H OMe OMe CHII-257 Me OCF.sub.3 H O H Me OMe CHII-258 Me OCF.sub.3 H O H Me OMe NII-259 Me OCH.sub.2 CHCHCl H O H OMe OMe CH 160-162II-260 Me OCH.sub.2 CHCHCl H O H Me OMe CHII-261 Me OCH.sub.2 CHCHCl H O H Me OMe NII-262 Me OCH.sub.2 CHCCl.sub.2 H O H OMe OMe CHII-263 Me OCH.sub.2 CHCCl.sub.2 H O H Me OMe CHII-264 Me OCH.sub.2 CHCCl.sub.2 H O H Me OMe NII-265 Me OCH.sub.2 C(Cl)CH.sub.2 H O H OMe OMe CH 160-162II-266 Me OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe CHII-267 Me OCH.sub.2 C(Cl)CH.sub.2 H O H Me OMe NII-268 Me OCH.sub.2 C(Me)CH.sub.2 H O H OMe OMe CH 163-164II-269 Me OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe CHII-270 Me OCH.sub.2 C(Me)CH.sub.2 H O H Me OMe NII-271 Me OCH.sub.2 CHCHMe H O H OMe OMe CHII-272 Me OCH.sub.2 CHCHMe H O H Me OMe CHII-273 Me OCH.sub.2 CHCHMe H O H Me OMe NII-274 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHII-275 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H Me OMe CHII-276 Me OCH.sub.2 CH.sub.2 N.sub.3 H O H Me OMe NII-277 Me OCH.sub.2 OMe H O H OMe OMe CH 165-167II-278 Me OCH.sub.2 OMe H O H Me OMe CHII-279 Me OCH.sub.2 OMe H O H Me OMe NII-280 Me OCH.sub.2 OEt H O H OMe OMe CH 154-155II-281 Me OCH.sub.2 OEt H O H Me OMe CHII-282 Me OCH.sub.2 OEt H O H Me OMe NII-283 Me OCH.sub.2 OBn H O H OMe OMe CH 162-164II-284 Me OCH.sub.2 OBn H O H Me OMe CHII-285 Me OCH.sub.2 OBn H O H Me OMe NII-286 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H OMe OMe CHII-287 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe CHII-288 Me OCH.sub.2 OCH.sub.2 CF.sub.3 H O H Me OMe NII-289 Me OCH.sub.2 OBu-t H O H OMe OMe CHII-290 Me OCH.sub.2 OBu-t H O H Me OMe CHII-291 Me OCH.sub.2 OBu-t H O H Me OMe NII-292 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H OMe OMe CHII-293 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe CHII-294 Me OCH.sub.2 OCH.sub.2 CH.sub.2 OMe H O H Me OMe NII-295 Me OCH.sub.2 CN H O H OMe OMe CHII-296 Me OCH.sub.2 CN H O H Me OMe CHII-297 Me OCH.sub.2 CN H O H Me OMe NII-298 Me OCH.sub.2 COOMe H O H OMe OMe CHII-299 Me OCH.sub.2 COOMe H O H Me OMe CHII-300 Me OCH.sub.2 COOMe H O H Me OMe NII-301 Me OCH.sub.2 COOPr H O H OMe OMe CHII-302 Me OCH.sub.2 COOPr H O H Me OMe CHII-303 Me OCH.sub.2 COOPr H O H Me OMe NII-304 Me OCH.sub.2 COOPr-i H O H OMe OMe CHII-305 Me OCH.sub.2 COOPr-i H O H Me OMe CHII-306 Me OCH.sub.2 COOPr-i H O H Me OMe NII-307 Me OCH.sub.2 SMe H O H OMe OMe CHII-308 Me OCH.sub.2 SMe H O H Me OMe CHII-309 Me OCH.sub.2 SMe H O H Me OMe NII-310 Me OCH.sub.2 CH.sub.2 SMe H O H OMe OMe CHII-311 Me OCH.sub.2 CH.sub.2 SMe H O H Me OMe CHII-312 Me OCH.sub.2 CH.sub.2 SMe H O H Me OMe NII-313 Me SCF.sub.3 H O H OMe OMe CHII-314 Me SCF.sub.3 H O H Me OMe CHII-315 Me SCF.sub.3 H O H Me OMe NII-316 Me SCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-317 Me SCH.sub.2 CH.sub.2 Cl H O H Me OMe CHII-318 Me SCH.sub.2 CH.sub.2 Cl H O H Me OMe NII-319 Me SCH.sub.2 CH.sub.2 F H O H OMe OMe CHII-320 Me SCH.sub.2 CH.sub.2 F H O H Me OMe CHII-321 Me SCH.sub.2 CH.sub.2 F H O H Me OMe NII-322 Me SOEt H O H OMe OMe CHII-323 Me SOEt H O H Me OMe CHII-324 Me SOEt H O H Me OMe NII-325 Me SO.sub.2 NHOEt H O H OMe OMe CHII-326 Me SO.sub.2 NHOEt H O H Me OMe CHII-327 Me SO.sub.2 NHOEt H O H Me OMe NII-328 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-329 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe CHII-330 Me SO.sub.2 CH.sub.2 CHCH.sub.2 H O H Me OMe NII-331 Me SO.sub.2 NEt.sub.2 H O H OMe OMe CHII-332 Me SO.sub.2 NEt.sub.2 H O H Me OMe CHII-333 Me SO.sub.2 NEt.sub.2 H O H Me OMe NII-334 Me Et H O H OMe OMe CHII-335 Me Et H O H Me OMe CHII-336 Me Et H O H Me OMe NII-337 Me Pr H O H OMe OMe CHII-338 Me Pr H O H Me OMe CHII-339 Me Pr H O H Me OMe NII-340 Me Pr-i H O H OMe OMe CHII-341 Me Pr-i H O H Me OMe CHII-342 Me Pr-i H O H Me OMe NII-343 Me Bu H O H OMe OMe CHII-344 Me Bu H O H Me OMe CHII-345 Me Bu H O H Me OMe NII-346 Me Bu-t H O H OMe OMe CHII-347 Me Bu-t H O H Me OMe CHII-348 Me Bu-t H O H Me OMe NII-349 Me CH.sub.2 Cl H O H OMe OMe CHII-350 Me CH.sub.2 Cl H O H Me OMe CHII-351 Me CH.sub.2 Cl H O H Me OMe NII-352 Me CH.sub.2 F H O H OMe OMe CHII-353 Me CH.sub.2 F H O H Me OMe CHII-354 Me CH.sub.2 F H O H Me OMe NII-355 Me CH.sub.2 OMe H O H OMe OMe CHII-356 Me CH.sub.2 OMe H O H Me OMe CHII-357 Me CH.sub.2 OMe H O H Me OMe NII-358 Me CH.sub.2 CF.sub.3 H O H OMe OMe CHII-359 Me CH.sub.2 CF.sub.3 H O H Me OMe CHII-360 Me CH.sub.2 CF.sub.3 H O H Me OMe NII-361 Me ##STR44## H O H OMe OMe CHII-362 Me ##STR45## H O H Me OMe CHII-363 Me ##STR46## H O H Me OMe NII-364 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHII-365 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe CHII-366 Me CH.sub.2 CH.sub.2 CF.sub.3 H O H Me OMe NII-367 Me CH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-368 Me CH.sub.2 CHCH.sub.2 H O H Me OMe CHII-369 Me CH.sub.2 CHCH.sub.2 H O H Me OMe NII-370 Me CH.sub.2 CCH H O H OMe OMe CHII-371 Me CH.sub.2 CCH H O H Me OMe CHII-372 Me CH.sub.2 CCH H O H Me OMe NII-373 Me CH.sub.2 COOMe H O H OMe OMe CHII-374 Me CH.sub.2 COOMe H O H Me OMe CHII-375 Me CH.sub.2 COOMe H O H Me OMe NII-376 Me CH.sub.2 COOEt H O H OMe OMe CHII-377 Me CH.sub.2 COOEt H O H Me OMe CHII-378 Me CH.sub.2 COOEt H O H Me OMe NII-379 Me CH.sub.2 CN H O H OMe OMe CHII-380 Me CH.sub.2 CN H O H Me OMe CHII-381 Me CH.sub.2 CN H O H Me OMe NII-382 Me CH.sub.2 CONMe.sub.2 H O H OMe OMe CHII-383 Me CH.sub.2 CONMe.sub.2 H O H Me OMe CHII-384 Me CH.sub.2 CONMe.sub.2 H O H Me OMe NII-385 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H OMe OMe CHII-386 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H Me OMe CHII-387 Me CH.sub.2 SO.sub.2 NMe.sub.2 H O H Me OMe NII-388 Me CH.sub.2 NMe.sub.2 H O H OMe OMe CHII-389 Me CH.sub.2 NMe.sub.2 H O H Me OMe CHII-390 Me CH.sub.2 NMe.sub.2 H O H Me OMe NII-391 Me CHCH.sub.2 H O H OMe OMe CHII-392 Me CHCH.sub.2 H O H Me OMe CHII-393 Me CHCH.sub.2 H O H Me OMe NII-394 Me CHCHMe H O H OMe OMe CHII-395 Me CHCHMe H O H Me OMe CHII-396 Me CHCHMe H O H Me OMe NII-397 Me CCH H O H OMe OMe CHII-398 Me CCH H O H Me OMe CHII-399 Me CCH H O H Me OMe NII-400 Me CCMe H O H OMe OMe CHII-401 Me CCMe H O H Me OMe CHII-402 Me CCMe H O H Me OMe NII-403 Me CHCHCOOMe H O H OMe OMe CHII-404 Me CHCHCOOMe H O H Me OMe CHII-405 Me CHCHCOOMe H O H Me OMe NII-406 Me CH(Me)COMe H O H OMe OMe CHII-407 Me CH(Me)COMe H O H Me OMe CHII-408 Me CH(Me)COMe H O H Me OMe NII-409 Me CH(Me)COEt H O H OMe OMe CHII-410 Me CH(Me)COEt H O H Me OMe CHII-411 Me CH(Me)COEt H O H Me OMe NII-412 Me CH(Et)COMe H O H OMe OMe CHII-413 Me CH(Et)COMe H O H Me OMe CHII-414 Me CH(Et)COMe H O H Me OMe NII-415 Me CH(Et)COEt H O H OMe OMe CHII-416 Me CH(Et)COEt H O H Me OMe CHII-417 Me CH(Et)COEt H O H Me OMe NII-418 Me ##STR47## H O H OMe OMe CHII-419 Me ##STR48## H O H Me OMe CHII-420 Me ##STR49## H O H Me OMe NII-421 Me COPr H O H OMe OMe CHII-422 Me COPr H O H Me OMe CHII-423 Me COPr H O H Me OMe NII-424 Me COPr-i H O H OMe OMe CHII-425 Me COPr-i H O H Me OMe CHII-426 Me COPr-i H O H Me OMe NII-427 Me CHNOMe H O H OMe OMe CHII-428 Me CHNOMe H O H Me OMe CHII-429 Me CHNOMe H O H Me OMe NII-430 Me CHNOEt H O H OMe OMe CHII-431 Me CHNOEt H O H Me OMe CHII-432 Me CHNOEt H O H Me OMe NII-433 Me C(Me)NOMe H O H OMe OMe CHII-434 Me C(Me)NOMe H O H Me OMe CHII-435 Me C(Me)NOMe H O H Me OMe NII-436 Me C(Me)NOEt H O H OMe OMe CHII-437 Me C(Me)NOEt H O H Me OMe CHII-438 Me C(Me)NOEt H O H Me OMe NII-439 Me C(Me)NOPr H O H OMe OMe CHII-440 Me C(Me)NOPr H O H Me OMe CHII-441 Me C(Me)NOPr H O H Me OMe NII-442 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-443 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe CHII-444 Me C(Me)NOCH.sub.2 CH.sub.2 Cl H O H Me OMe NII-445 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H OMe OMe CHII-446 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H Me OMe CHII-447 Me C(Me)NOCH.sub.2 CH.sub.2 F H O H Me OMe NII-448 Me NHEt H O H OMe OMe CHII-449 Me NHEt H O H Me OMe CHII-450 Me NHEt H O H Me OMe NII-451 Me NHPr H O H OMe OMe CHII-452 Me NHPr H O H Me OMe CHII-453 Me NHPr H O H Me OMe NII-454 Me NHCOOMe H O H OMe OMe CHII-455 Me NHCOOMe H O H Me OMe CHII-456 Me NHCOOMe H O H Me OMe NII-457 Me NHCOOEt H O H OMe OMe CHII-458 Me NHCOOEt H O H Me OMe CHII-459 Me NHCOOEt H O H Me OMe NII-460 Me NHCOOPh H O H OMe OMe CHII-461 Me NHCOOPh H O H Me OMe CHII-462 Me NHCOOPh H O H Me OMe NII-463 Me N(Me)SO.sub.2 Me H O H OMe OMe CHII-464 Me N(Me)SO.sub.2 Me H O H Me OMe CHII-465 Me N(Me)SO.sub.2 Me H O H Me OMe NII-466 Me N(Et)SO.sub.2 Me H O H OMe OMe CHII-467 Me N(Et)SO.sub.2 Me H O H Me OMe CHII-468 Me N(Et)SO.sub.2 Me H O H Me OMe NII-469 Me N(Me)SO.sub.2 Et H O H OMe OMe CHII-470 Me N(Me)SO.sub.2 Et H O H Me OMe CHII-471 Me N(Me)SO.sub.2 Et H O H Me OMe NII-472 Me N(Et)SO.sub.2 Et H O H OMe OMe CHII-473 Me N(Et)SO.sub.2 Et H O H Me OMe CHII-474 Me N(Et)SO.sub.2 Et H O H Me OMe NII-475 Me NHCOEt H O H OMe OMe CHII-476 Me NHCOEt H O H Me OMe CHII-477 Me NHCOEt H O H Me OMe NII-478 Me NHCOCF.sub.3 H O H OMe OMe CHII-479 Me NHCOCF.sub.3 H O H Me OMe CHII-480 Me NHCOCF.sub.3 H O H Me OMe NII-481 Me NCHMe H O H OMe OMe CHII-482 Me NCHMe H O H Me OMe CHII-483 Me NCHMe H O H Me OMe NII-484 Me NCHPh H O H OMe OMe CHII-485 Me NCHPh H O H Me OMe CHII-486 Me NCHPh H O H Me OMe NII-487 Me N.sub.3 H O H OMe OMe CHII-488 Me N.sub.3 H O H Me OMe CHII-489 Me N.sub.3 H O H Me OMe NII-490 Me I H O H OMe OMe CHII-491 Me I H O H Me OMe CHII-492 Me I H O H Me OMe NII-493 Me OCOEt H O H OMe OMe CHII-494 Me OCOEt H O H Me OMe CHII-495 Me OCOEt H O H Me OMe NII-496 Me OCOPr H O H OMe OMe CHII-497 Me OCOPr H O H Me OMe CHII-498 Me OCOPr H O H Me OMe NII-499 Me OCOPh H O H OMe OMe CHII-500 Me OCOPh H O H Me OMe CHII-501 Me OCOPh H O H Me OMe NII-502 Me OCONMe.sub.2 H O H OMe OMe CHII-503 Me OCONMe.sub.2 H O H Me OMe CHII-504 Me OCONMe.sub.2 H O H Me OMe NII-505 Me Cl H O H CF.sub.3 OMe CHII-506 Me OPr-i H O H Cl OMe CHII-507 Me SEt H O H Me OMe CHII-508 Me SEt H O H Cl OMe CHII-509 Me SEt H O H Me Me CHII-510 Me SEt H O H OMe OMe NII-511 Me SBu H O H OMe Me CHII-512 Me SBu H O H OMe Me NII-513 Me SPr-i H O H OMe Me CHII-514 Me SPr-i H O H OMe Me NII-515 Me SOEt H O H OMe OMe NII-516 Me SO.sub.2 Et H O H OMe Me CHII-517 Me SO.sub.2 Et H O H OMe Me NII-518 Me SO.sub.2 Et H O H OMe Cl CHII-519 Me SO.sub.2 Pr H O H OMe Me CHII-520 Me SO.sub.2 Pr H O H OMe Me NII-521 Me SO.sub.2 Pr H O H OMe Cl CHII-522 Me SO.sub.2 Bu H O H OMe Me CHII-523 Me SO.sub.2 Bu H O H OMe Me NII-524 Me SO.sub.2 Bu H O H OMe Cl CHII-525 Me SO.sub.2 Pr-i H O H OMe Me CHII-526 Me SO.sub.2 Pr-i H O H OMe Me NII-527 Me COOPr H O H OMe Me NII-528 Me NO.sub.2 H O H OMe Cl CHII-529 Me CONMe.sub.2 H O H OMe Me CHII-530 Me Br H O H OMe Cl CHII-531 Me ##STR50## H O H OMe OMe CH 156-158II-532 Me OCH.sub.2Bu-t H O H OMe OMe CH 144-146II-533 Me OCH.sub.2Bu-t H O H Me OMe CH 126-128II-534 Me OCH.sub.2 CHCMe.sub.2 H O H OMe OMe CH 164-166II-535 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H OMe OMe CH 136-138II-536 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe CH 173-175II-537 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H O H Me OMe N 160-163II-538 Me CH.sub.2 CH.sub.2 N.sub.3 H O H OMe OMe CHII-539 Me ##STR51## H O H OMe OMe CHII-540 Me COCF.sub.3 H O H OMe OMe CHII-541 Me COOCH.sub.2 CHCHCl H O H OMe OMe CHII-542 Me SO.sub.2 CF.sub.3 H O H OMe OMe CHII-543 Me OCOCF.sub.3 H O H OMe OMe CHII-544 Me OCH.sub.2 OPh H O H OMe OMe CHII-545 Me CHNOH H O H OMe OMe CHII-546 Me CHNOCH.sub.2 CHCH.sub.2 H O H OMe OMe CHII-547 Me CHNOCH.sub.2 CCH H O H OMe OMe CHII-548 Me C(Me)NOBn H O H OMe OMe CHII-549 Me C(Me)NOPh H O H OMe OMe CHII-550 Me C(Bn)NOMe H O H OMe OMe CHII-551 Me C(Ph)NOMe H O H OMe OMe CHII-552 Me C(CF.sub.3)NOMe H O H OMe OMe CHII-553 Me COOCH.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-554 Me COOCH.sub.2 CF.sub.3 H O H OMe OMe CHII-555 Me Cl 5-Cl O H OMe Me NII-556 Me Cl 5-OMe O H OMe OMe CH 197-199II-557 Me Cl 5-F O H OMe OMe CHII-558 Me F 5-Cl O H OMe OMe CHII-559 Me F 5-F O H OMe OMe CHII-560 Me COOMe 5-Cl O H OMe OMe CHII-561 Me COOEt 5-Cl O H OMe OMe CHII-562 Me COOPr 5-Cl O H OMe OMe CHII-563 Me COOPr-i 5-Cl O H OMe OMe CHII-564 Me OMe 5-COOMe O H OMe OMe CHII-565 Me COOMe 5-OMe O H OMe OMe CHII-566 Me H 5-CN O H OMe OMe CHII-567 Me H 5-CF.sub.3 O H OMe OMe CHII-568 Me H 5-COOMe O H OMe 0Me CHII-569 Me H 5-COOEt O H OMe OMe CHII-570 Me H 5-COOPr O H OMe OMe CHII-571 Me H 5-COOPr-i O H OMe OMe CHII-572 Me H 5-COOCH.sub.2 CH.sub.2 Cl O H OMe OMe CHII-573 Me H 5-COOCH.sub.2 CH.sub.2 F O H OMe OMe CHII-574 Me H 5-COOCH.sub.2 CF.sub.3 O H OMe OMe CHII-575 Me H 5-COOCH.sub.2 OMe O H OMe OMe CHII-576 Me H 5-CONMe.sub.2 O H OMe OMe CHII-577 Me H 5-OCH.sub.2 CH.sub.2 F O H OMe OMe CHII-578 Me H 5-OCHF.sub.2 O H OMe OMe CHII-579 Me H 5-OCH.sub.2 CF.sub.3 O H OMe OMe CHII-580 Me H 5-OCH.sub.2 CH.sub.2 CH.sub.2 F O H OMe OMe CHII-581 Me H 5-OCH.sub.2 CHCH.sub.2 O H OMe OMe CHII-582 Me H 5-OCH.sub.2 CCH O H OMe OMe CHII-583 Me H 5-NO.sub.2 O H OMe OMe CHII-584 Me H 5-SMe O H OMe OMe CHII-585 Me H 5-SEt O H OMe OMe CHII-586 Me H 5-SPr O H OMe OMe CHII-587 Me H 5-SPr-i O H OMe OMe CHII-588 Me H 5-SO.sub.2 Et O H OMe OMe CHII-589 Me H 5-SO.sub.2 Pr O H OMe OMe CHII-590 Me H 5-SO.sub.2 Pr-i O H OMe OMe CHII-591 Me H 5-SOEt O H OMe OMe CHII-592 Me H 5-Me O H OMe OMe CHII-593 Me H 5-Et O H OMe OMe CHII-594 Me H 5-Pr O H OMe OMe CHII-595 Me H 5-SO.sub.2 NMe.sub.2 O H OMe OMe CHII-596 Me H 5-OCF.sub.3 O H OMe OMe CHII-597 Me H 5-CH.sub.2 CF.sub.3 O H OMe OMe CHII-598 Me H 5-CH.sub.2 CHCH.sub.2 O H OMe OMe CHII-599 Me H 5-COOMe O H OMe Me CHII-600 Me H 5-COOMe O H OMe Me NII-601 Me H 5-COOMe O H OMe OMe NII-602 Me ##STR52## H O H OMe OMe CHII-603 Me ##STR53## H O H Me OMe CHII-604 Me ##STR54## H O H Me OMe NII-605 Me ##STR55## H O H OMe OMe CHII-606 Me ##STR56## H O H Me OMe CHII-607 Me ##STR57## H O H Me OMe NII-608 Me ##STR58## H O H OMe OMe CHII-609 Me ##STR59## H O H Me OMe CHII-610 Me ##STR60## H O H Me OMe NII-611 Me OC.sub.2 H.sub.4O* O H OMe OMe CHII-612 Me OC.sub.2 H.sub.4O* O H Me OMe CHII-613 Me OC.sub.2 H.sub.4O* O H Me OMe NII-614 Me SC.sub.2 H.sub.4S* O H OMe OMe CHII-615 Me SC.sub.2 H.sub.4S* O H Me OMe CHII-616 Me SC.sub.2 H.sub.4S* O H Me OMe NII-617 Me OCH.sub.2O* O H OMe OMe CHII-618 ##STR61## Cl H O H OMe OMe CHII-619 ##STR62## Cl H O H OMe OMe CHII-620 ##STR63## Cl H O H OMe OMe CHII-621 COMe Cl H O H OMe OMe CHII-622 COEt Cl H O H OMe OMe CHII-623 COPr Cl H O H OMe OMe CHII-624 COPr-i Cl H O H OMe OMe CHII-625 COPh Cl H O H OMe OMe CHII-626 SO.sub.2 Me Cl H O H OMe OMe CHII-627 SO.sub.2 Et Cl H O H OMe OMe CHII-628 SO.sub.2 Ph Cl H O H OMe OMe CHII-629 COOMe Cl H O H OMe OMe CHII-630 COOEt Cl H O H OMe OMe CHII-631 COOPh Cl H O H OMe OMe CHII-632 CONMe.sub.2 Cl H O H OMe OMe CHII-633 SO.sub.2 NMe.sub.2 Cl H O H OMe OMe CHII-634 Ph Cl H O H Me OMe NII-635 CH.sub.2 OMe Cl H O H OMe OMe CHII-636 CH.sub.2 OBn Cl H O H OMe OMe CHII-637 CH.sub.2 CH.sub.2 F Cl H O H OMe OMe CHII-638 CH.sub.2 CH.sub.2 Cl Cl H O H OMe OMe CHII-639 CF.sub.3 Cl H O H OMe OMe CHII-640 CH.sub.2 F Cl H O H OMe OMe CHII-641 CH.sub.2 CHCH.sub.2 OMe H O H OMe OMe CHII-642 COCF.sub.3 Cl H O H OMe OMe CHII-643 ##STR64## Cl H O H OMe OMe CHII-644 Me Cl H O CH.sub.3 OCH.sub.2 OMe OMe CHII-645 Me Cl H O H OMe NMe.sub.2 NII-646 Me Cl H O H OMe NHMe NII-648 Me ONCHMe H O H OMe OMe CHII-649 Me ONCMe.sub.2 H O H OMe OMe CHII-650 Me ONCHBn H O H OMe OMe CHII-651 Me OCH.sub.2 CH.sub.2 F H O H OMe Me CH 167-170II-652 Me OCH.sub.2 CH.sub.2 F H O H OMe Me N 167-169II-653 Me F H O H NMe.sub.2 OCH.sub.2 CF.sub.3 N 108-112II-654 Me SO.sub.2 NMe.sub.2 H O H OMe Me N 191-193II-655 Me CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-656 Me CO.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHII-657 Me CO.sub.2 CH.sub.2 OMe H O H OMe OMe CHII-658 H CO.sub.2 CH.sub.2 CH.sub.2 Cl H O H OMe OMe CHII-659 H CO.sub.2 CH.sub.2 CF.sub.3 H O H OMe OMe CHII-660 H CO.sub.2 CH.sub.2 OMe H O H OMe OMe CH__________________________________________________________________________ *R.sup.3 represents the 5position.
The following processes may, for example, be mentioned as the processes for producing the compounds of the present invention. However, the processes are not limited to such specific processes.
Common processes for producing the compound �I! or �II! of the present invention are shown by the following Processes 1 to 3.
PROCESS 1 ##STR65## (wherein R.sup.1, R.sup.2, R.sup.3, A, B, Z, X and Y have the same meanings as defined above.)
Namely, the compound of the present invention represented by the formula �I! or �II! can be produced by reacting an intermediate for its production of the present invention represented by the formula �I-a! or �II-a! (hereinafter referred to as an intermediate, and the process for its production will be described hereinafter) and a compound represented by the formula �III!.
This reaction is usually conducted in a solvent or without solvent, if necessary, in the presence of a base. The range of the reaction temperature is a range from -20.degree. C. to the boiling point of the solvent, and the range of the reaction time is a range of from 0.5 hour to 24 hours. With respect to the amounts of the compounds to be subjected to the reaction, the amounts of the compound represented by the formula �III! and the base are respectively independently from 1 to 1.5 equivalent relative to one equivalent of the intermediate represented by the formula �I-a! or �II-a!.
As the solvent, an aromatic hydrocarbon such as benzene, xylene or toluene, a halogenated hydrocarbon such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene or dichlorobenzene, an ether such as diethyl ether, dioxane, tetrahydrofuran (THF), isopropyl ether (IPE) or diethylene glycol dimethyl ether, an alcohol such as methanol, ethanol or 2-propanol, an ester such as ethyl acetate or butyl acetate, a nitro compound such as nitromethane or nitrobenzene, a nitrile such as acetonitrile or isobutyronitrile, or an aprotic polar solvent such as formamide, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO) or N-methylpyrrolidone (NMP), may, for example, be mentioned.
As the base, an organic base such as pyridine, triethylamine, 1,4-diazabicyclo�2.2.2!octane, 1,8-diazabicyclo�5.4.0!-7-undecene (DBU), N,N-diethylaniline or diethyl-methylamine, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride, or an alkali metal alkoxide such as sodium methoxide or sodium ethoxide, may, for example, be mentioned.
Further, the compound represented by the formula �III! can be produced by reacting a compound represented by the formula �IV! in Process 2 with phenyl chloroformate, phenyl chlorothio-O-formate or phenyl chlorodithioformate, in a proper solvent in the presence of a base.
PROCESS 2 ##STR66## (wherein R.sup.1, R.sup.2, R.sup.3, A, B, X, Y and Z have the same meanings as defined above.)
The compound of the present invention represented by the formula �I! or �II! can be produced by reacting a compound represented by the formula �I-b! or �II-b! and a compound represented by the formula �IV!. The compound represented by the formula �I-b! or �II-b! can be produced by reacting an intermediate represented by the formula �I-a! or �II-a! with phosgene or thiophosgene in a suitable solvent.
This reaction is usually conducted in a solvent or without solvent, if necessary, in the presence of a base. The range of the reaction temperature, the range of the reaction time, and the solvent and the base to be used in the reaction are the same as in Process 1. With respect to the amounts of the compounds to be subjected to the reaction, the amounts of the compounds represented by the formula �IV! and the base are respectively independently from 1 to 1.5 equivalent relative to one equivalent of the compound represented by the formula �I-b! or �II-b!.
PROCESS 3 ##STR67## (wherein R.sup.1, R.sup.2, R.sup.3, A, B, X, Y and Z have the same meanings as defined above.)
The compound of the present invention represented by the formula �I! or �II! can be produced by reacting a compound represented by the formula �I-c! or �II-c! and a compound of the formula �IV!. The compound represented by the formula �I-c! or �II-c! can be produced by reacting an intermediate represented by the formula �I-a! or �II-a! with phenyl chloroformate, phenyl chlorothio-O-formate or phenyl chlorodithioformate, in a suitable solvent in the presence of a base. It may also be produced by reacting a compound represented by the formula �I-b! or �II-b! with phenol or thiophenol.
This reaction is usually conducted in a solvent or without solvent, if necessary, in the presence of a base. The range of the reaction temperature, the range of the reaction time, and the solvent and the base to be used in the reaction are the same as in Process 1. With respect to the amounts of the compounds to be subjected to the reaction, the amounts of the compound represented by the formula �IV! and the base are respectively independently from 1 to 1.5 equivalent relative to one equivalent of the compound represented by the formula �I-c! or �II-c!. A process for producing an intermediate of the formula �I-a! useful for the production of the compound of the present invention will be shown by Process 1 For Producing An Intermediate, and a process for producing an intermediate of the formula �II-a! will be shown by Process 2 For Producing An Intermediate. However, the processes are not limited to such specific examples.
Process 1 For Producing An Intermediate Production of the formula �I-a! ##STR68## (wherein R.sup.1 represents a hydrogen atom, an alkyl group, a benzyl group or a phenyl group, R.sup.2 and R.sup.3 represent a hydrogen atom, an alkyl group, a halogen atom, a nitro group, an alkoxy group, a haloalkoxy group or a haloalkyl group, and L represents a halogen atom.)
Namely, a compound represented by the formula �V! is reacted with the corresponding hydrazine derivative, for example, in DMSO, to obtain a compound represented by the formula �VI!. Further, in concentrated hydrochloric acid, a diazonium salt is formed, and this is reacted with sulfurous acid gas in a solvent such as acetic acid in the presence of copper chloride to obtain a compound represented by the formula �VII!. This is reacted with excess t-butylamine to produce a compound represented by the formula �I-d!. Then, the t-butyl group is removed with excess trifluoroacetic acid to obtain an intermediate represented by the formula �I-a!.
Process 2 For Producing An Intermediate Production of the formula �II-a! ##STR69## (wherein R.sup.1 represents an alkyl group, a haloalkyl group, a benzyl group or a phenyl group, and R.sup.2 and R.sup.3 represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a phenyl group, a benzyl group or a haloalkoxy group.)
Namely, a compound represented by the formula �IX! can be produced by reacting a compound represented by the formula �VIII! with n-butyl lithium, for example, in ethyl ether, within a temperature range of from -40.degree. to -20.degree. C., followed by blowing in sulfurous acid gas. An intermediate represented by the formula �II-a! can be produced by adding an aqueous solution of the compound represented by the formula �IX! to an aqueous solution of a mixture of hydroxylamine-O-sulfonic acid and a base under cooling with ice.
In this reaction formula, the compound of the formula �VIII! can be produced by a method disclosed in a known literature such as �Liebigs Ann. Chem., 908 (1980)!, �Org. Synth. Coll. Vol. V, 650!, �J. Chem. Soc. Perkin Trans. II, 1695, (1975)!, or �Org. Synth, Coll. Vol. V, 941!.
The intermediate represented by the formula �I-a! or �II-a! can be produced also by the following process.
Process 3 For Producing An Intermediate Production of the formula �I-a! or �II-a! ##STR70## (wherein R.sup.1 represents an alkyl group, a cycloalkyl group, a haloalkyl group, an alkoxyalkyl group, a benzyloxyalkyl group, a benzyl group, a dialkylaminocarbonyl group, an alkoxycarbonyl group, a alkylsulfonyl group, a phenylsulfonyl group, a dialkylaminosulfonyl group, a haloalkylcarbonyl group, an alkylcarbonyl group, a benzoyl group or an alkenyl group, R.sup.2 or R.sup.3 represents a hydrogen atom, a halogen atom, an alkoxy group, a haloalkoxy group, a haloalkyl group, an alkoxycarbonyl group, a phenyl group or a benzyl group, L represents a halogen atom, and M represents a bromine atom or a chlorine atom.)
Namely, a compound represented by the formula �X! is reacted with N-bromosuccinimide, N-chlorosuccinimide, or bromine or chlorine in carbon tetrachloride in the presence of a light and a radical reaction initiating agent to obtain a compound represented by the formula �XI!. The compound represented by the formula �XI! is reacted with thiourea to obtain a compound represented by the formula �XII!. The compound represented by the formula �XII! is reacted with chlorine or bromine in a mixed solution of acetic acid and water to obtain a compound represented by the formula �XIII!. Then, this compound is reacted with t-butylamine to obtain a compound represented by the formula �XIV!. The compound represented by the formula �XIV! is reduced to obtain a compound represented by the formula �XV!. The compound represented by the formula �XV! and isoamylnitrous acid are reacted, followed by reaction with hydrochloric acid to obtain a compound represented by the formula �XVI!. The compound represented by the formula �XVI! is reacted with e.g. an alkyl halide or a benzyl halide to obtain a compound represented by the formula �I-d! or �II-d!.
The compound represented by the formula �XVI!, �I-d! or �II-d! can be converted to a compound represented by the formula �XVII! and an intermediate represented by the formula �I-a! or �II-a!, respectively, by removing the t-butyl group with trifluoroacetic acid, as shown in Process 1 For Producing An Intermediate.
Further, the compound represented by the formula �XVII! is reacted with R.sup.1 L (wherein R.sup.1 and L have the same meanings as defined above) to obtain intermediates of the formulas �I-a! and �II-a!.
The intermediate represented by the formula �I-a! may be prepared by various processes depending upon the types of the substituents. However, it can be produced by the processes represented by the following Process 4 For Producing An Intermediate and Processes 5-1 to 5-3 For Producing An Intermediate.
Process 4 For Producing An Intermediate ##STR71## (wherein R.sup.1 represents a hydrogen atom, an alkyl group, a benzyl group or a phenyl group, R.sup.2 represents a halogen atom, preferably a fluorine atom, R.sup.3 has the same meaning as defined above, and R.sup.4 represents an alkoxy group, an alkoxyalkoxy group, a benzyloxy group, a cycloalkylalkoxy group, a haloalkoxy group, a dialkylaminoalkoxy group, an alkylthio group, an alkylamino group, a dialkylamino group or a benzylamino group.)
Namely, in this reaction, an intermediate represented by the formula �I-a! or �II-a! is reacted with a compound represented by the formula R.sup.4 -H (wherein R.sup.4 has the same meaning as defined above) in a polar solvent such as DMSO, DMF, DMAC or NMP in the presence of a base such as sodium hydride, potassium hydride, potassium carbonate, potassium t-butoxide, sodium hydroxide or potassium hydroxide, to obtain an intermediate represented by the formula �I-e! or �II-e!, respectively.
Process 5-1 For Producing An Intermediate ##STR72## (wherein R.sup.1 represents an alkyl group, a benzyl group or a phenyl group, R.sup.3 has the same meaning as defined above, R.sup.5 represents an alkyl group, a benzyl group, an alkenyl group, an alkynyl group, a haloalkenyl group, a haloalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a cyanoalkyl group, and L.sup.1 represents a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group or a benzenesulfonyloxy group which may be substituted.)
Namely, in this reaction formula, an intermediate represented by the formula �I-f! or �II-f! is reacted with a compound represented by the formula R.sup.5 -L.sup.1 (wherein R.sup.5 and L.sup.1 have the same meanings as defined above) in a suitable solvent in the presence of a base, to obtain an intermediate represented by the formula �I-g! or �II-g!, respectively.
The intermediate represented by the formula �I-f! or �II-f! can be produced by the following process. ##STR73## (wherein R.sup.1 represents an alkyl group, a benzyl group or a phenyl group, R.sup.2 represents a halogen atom, preferably a fluorine atom, R.sup.3 represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, a haloalkoxy group or an alkoxy group, and R.sup.8 represents an alkyl group, a benzyl group or a cycloalkyl group, preferably a cyclopropylmethyl group.)
Namely, in this reaction formula, an intermediate represented by the formula �I-a! or �II-a! is reacted with a compound of the formula R.sup.8 -OH (wherein R.sup.8 has the same meaning as defined above) in a suitable solvent in the presence of a base, to obtain an intermediate represented by the formula �I-h! or �II-h!, which is further subjected to removal of the protecting group to obtain an intermediate of the formula �I-f! or �II-f!, respectively.
Process 5-2 For Producing An Intermediate ##STR74## (wherein R.sup.1 represents an alkyl group, a benzyl group or a phenyl group, and R.sup.3 and R.sup.5 have the same meanings as defined above.)
Namely, in this reaction formula, an intermediate represented by the formula �I-f! or �II-f! is subjected to a Mitsunobu reaction (as disclosed in Organic Reactions Vol. 42, p-335) using a compound represented by the formula R.sup.5 -OH (wherein R.sup.5 has the same meaning as defined above) in a suitable solvent, to obtain an intermediate of the formula �I-g! or �II-g!, respectively.
Process 5-3 For Producing an Intermediate ##STR75## (wherein R.sup.1 represents an alkyl group, a benzyl group or a phenyl group, R.sup.3, R.sup.5 and L.sup.1 have the same meanings as defined above, and R.sup.6 represents an alkyl group, preferably a methyl group.)
Namely, in this reaction formula, an intermediate represented by the formula �I-f! or �II-f! is reacted with acetal of DMF to obtain a compound represented by the formula �I-i! or �II-i!, which is then reacted with a compound represented by the formula R.sup.5 -L.sup.1 (wherein R.sup.5 and L.sup.1 have the same meanings as defined above) in a suitable solvent in the presence of a base to obtain a compound represented by the formula �I-j! or �II-j!, which is then hydrolyzed with an acid or alkali to obtain an intermediate represented by the formula �I-g! or �II-g!.
Now, specific compounds of the intermediate represented by the formula �I-a! or �II-a! will be listed in Table 3.
TABLE 3______________________________________IntermediateNo. R.sup.1 R.sup.2 R.sup.3 mp. (.degree.C.)______________________________________ ##STR76## 1 Me Ph H 2 Me Bn H 3 Me SH H 4 Me SMe H 5 Me SEt H 223-225 6 Me SPr H 208-209 7 Me SO.sub.2 Me H 8 Me SO.sub.2 Et H 271-273 9 Me SOMe H 10 Me SO.sub.2 NHMe H 11 Me SO.sub.2 NHOMe H 12 Me SO.sub.2 NMe.sub.2 H 248-252 13 Me SO.sub.2 NHBn H 14 Me SO.sub.2 NHPh H 15 Me SO.sub.2 NHCH.sub.2 CHCH.sub.2 H 16 Me SO.sub.2 NHCH.sub.2 CCH H 17 H Cl H 215-217 18 Me Cl H 268-270 19 Me Cl 5-Cl 283-285 20 Et Cl H 180-182 21 Ph Cl H 22 Bn Cl H 23 Me H H 178-180 24 Me F H 221-223 25 Me Br H 285-287 26 Me Me H 27 Me CN H 274-281 28 Me CF.sub.3 H 29 Me H 5-Cl 30 Me H 6-Cl 31 Me H 7-Cl 32 Me COH H 33 Me COMe H 34 Me COEt H 35 Me COPh H 36 Me CO.sub.2 CH.sub.2 CHCH.sub.2 H 37 Me CO.sub.2 CH.sub.2 CCH H 38 Me COBn H 39 Me NO.sub.2 H 249-251 40 Me NH.sub.2 H 41 Me NHMe H 42 Me NMe.sub.2 H 43 Me NHCOMe H 44 Me NHCOPh H 45 Me NHCOCH.sub.2 Cl H 46 Me NHSO.sub.2 CH.sub.3 H 47 Me NHSO.sub.2 Ph H 48 Me CO.sub.2 H H 49 Me CO.sub.2 Me H 233-234 50 Me CO.sub.2 Et H 193-195 51 Me CO.sub.2 Pr H 185-188 52 Me CO.sub.2 Pr-i H 219-220 53 Me CO.sub.2 Bu H 167-168 54 Me CO.sub.2 Pen H 55 Me CO.sub.2 Bn H 56 Me CO.sub.2 Ph H 57 Me CO.sub.2 CH.sub.2 CH.sub.2 F H 58 Me CO.sub.2 Me 5-F 59 Et CO.sub.2 Me H 60 Bu CO.sub.2 Me H 61 Bn CO.sub.2 Me H 62 Ph CO.sub.2 Me H 63 H CO.sub.2 Et H 64 Me OH H 65 Me OMe H 268-270 66 Me OEt H 230-233 67 Me OPr H 210-212 68 Me OPr-i H 200-201 69 Me OBu H 203-205 70 Me OBn H 71 Me OBn(4-Cl) H 72 Me OBn(3-OMe) H 73 Me OBn(2-Me) H 74 Me OPh H 75 Me OPh(4-Cl) H 76 Me OPh(3-OMe) H 77 Me OPh(2-Me) H 78 Me OCH.sub.2 CHCH.sub.2 H 79 Me OCH.sub.2 CCH H 80 Me OCH.sub.2 CF.sub.3 H 81 Me OCH.sub.2 CH.sub.2 OMe H 82 Me OCH.sub.2 CH.sub.2 OPh H 83 Me OCOMe H 84 Me CONH.sub.2 H 85 Me CONHMe H 86 Me CONHEt H 87 Me CONHPr H 88 Me CONMe.sub.2 H 274-275 89 Me CONEt.sub.2 H 90 Me CONHBn H 91 Me CONHPh H 92 Me CONHCH.sub.2 CHCH.sub.2 H 93 Me CONHCH.sub.2 CCH H 94 Me CONHOMe H 95 Me H 5-F 96 Me SO.sub.2 NH.sub.2 H 97 Me SPr-i H 228-231 98 Me OCH.sub.2 CH.sub.2 OEt H 99 Me OCH.sub.2 CH.sub.2 OPr-i H100 Me OCH.sub.2 CH.sub.2 OBu H101 Me OCH.sub.2 CH.sub.2 OBu-t H102 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H103 Me OCH.sub.2 COOEt H104 Me OCH.sub.2 CH.sub.2 Cl H105 Me OCH.sub.2 CH.sub.2 F H106 Me OCH.sub.2 OCH.sub.3 H107 Me OCH(CF.sub.3)Me H108 Me H 5-OMe109 Me H 5-OEt110 Me H 5-OPr111 Et CO.sub.2 Me H112 Et Br H113 Me OCHF.sub.2 H114 Me SO.sub.2 Pr H 270-272115 Me SO.sub.2 Pr-i H 260-263116 Me SO.sub.2 Bu H 287-290117 Me SBu H 187-189118 Me OMe 5-Cl119 Me NHBn H120 Me OCH.sub.2 Bu-t H121 Me OCH.sub.2 CHF.sub.2 H122 H NO.sub.2 H >300123 H Br H 183-186124 H COOCH.sub.3 H 243-247125 Me H 5-CO.sub.2 Me 238-241______________________________________ ##STR77##126 Me Ph H127 Me Bn H128 Me SH H129 Me SMe H130 Me SEt H 145-147131 Me SPr H132 Me SO.sub.2 Me H133 Me SO.sub.2 Et H 167-169134 Me SOMe H135 Me SO.sub.2 NHMe H136 Me SO.sub.2 NHOMe H137 Me SO.sub.2 NMe.sub.2 H 218-220138 Me SO.sub.2 NHBn H139 Me SO.sub.2 NHPh H140 Me SO.sub.2 NHCH.sub.2 CHCH.sub.2 H141 Me SO.sub.2 NHCH.sub.2 CCH H142 H Cl H 215-217143 Me Cl H 173-175144 Me Cl 5-Cl145 Et Cl H 182-184146 Ph Cl H 220-221147 Bn Cl H148 Me H H 181-183149 Me F H 151-152150 Me Br H 182-183151 Me Me H 149-151152 Me CN H 227-228153 Me CF.sub.3 H154 Me H 5-Cl 186-188155 Me H 6-Cl 206-207156 Me H 7-Cl 175-177157 Me COH H158 Me COMe H159 Me COEt H160 Me COPh H161 Me CO.sub.2 CH.sub.2 CHCH.sub.2 H162 Me CO.sub.2 CH.sub.2 CCH H163 Me COBn H164 Me NO.sub.2 H 193-194165 Me NH.sub.2 H166 Me NHMe H 179-181167 Me NMe.sub.2 H 197-200168 Me NHCOMe H169 Me NHCOPh H170 Me NHCOCH.sub.2 Cl H171 Me NHSO.sub.2 CH.sub.3 H172 Me NHSO.sub.2 Ph H173 Me CO.sub.2 H H174 Me CO.sub.2 Me H 160-163175 Me CO.sub.2 Et H 135-137176 Me CO.sub.2 Pr H 130-132177 Me CO.sub.2 Pr-i H 145-147178 Me CO.sub.2 Bu H 113-114179 Me CO.sub.2 Pen H180 Me CO.sub.2 Bn H181 Me CO.sub.2 Ph H182 Me CO.sub.2 CH.sub.2 CH.sub.2 F H183 Me CO.sub.2 Me 5-F184 Et CO.sub.2 Me H185 Bu CO.sub.2 Me H186 Bn CO.sub.2 Me H187 Ph CO.sub.2 Me H188 H CO.sub.2 Et H189 Me OH H 180-181190 Me OMe H 265-268191 Me OEt H 184-185192 Me OPr H 186-188193 Me OPr-i H 205-206194 Me OBu H 152-154195 Me OBn H196 Me OBn(4-Cl) H197 Me OBn(3-OMe) H198 Me OBn(2-Me) H199 Me OPh H200 Me OPh(4-Cl) H201 Me OPh(3-OMe) H202 Me OPh(2-Me) H203 Me OCH.sub.2 CHCH.sub.2 H 143-144204 Me OCH.sub.2 CCH H 180-181205 Me OCH.sub.2 CF.sub.3 H 182-183206 Me OCH.sub.2 CH.sub.2 OMe H 174-176207 Me OCH.sub.2 CH.sub.2 OPh H208 Me OCOMe H209 Me CONH.sub.2 H210 Me CONHMe H211 Me CONHEt H212 Me CONHPr H213 Me CONMe.sub.2 H 267-270214 Me CONEt.sub.2 H215 Me CONHBn H216 Me CONHPh H217 Me CONHCH.sub.2 CHCH.sub.2 H218 Me CONHCH.sub.2 CCH H219 Me CONHOMe H220 Me H 5-F 174-175221 Me SO.sub.2 NH.sub.2 H222 Me SPr-i H 134-135223 Me OCH.sub.2 CH.sub.2 OEt H 116-120224 Me OCH.sub.2 CH.sub.2 OPr-i H 118-119225 Me OCH.sub.2 CH.sub.2 OBu H 144-145226 Me OCH.sub.2 CH.sub.2 OBu-t H 183-184227 Me OCH.sub.2 CH.sub.2 NMe.sub.2 H 184-187228 Me OCH.sub.2 COOEt H 116-120229 Me OCH.sub.2 CH.sub.2 Cl H 177-179230 Me OCH.sub.2 CH.sub.2 F H 178-180231 Me OCH.sub.2 OCH.sub.3 H 163-165232 Me OCH(CF.sub.3)Me H 165-167233 Me H 5-OMe 169-172234 Me H 5-OEt 152-153235 Me H 5-OPr 149-151236 Et CO.sub.2 Me H 123-125237 Et Br H238 Me OCHF.sub.2 H 164-166239 Me SO.sub.2 Pr H 176-178240 Me SO.sub.2 Pr-i H 220-221241 Me SO.sub.2 Bu H 156-158242 Me SBu H 162-164243 Me OMe 5-Cl 161-163244 Me NHBn H 189-191245 Me OCH.sub.2 Bu-t H 207-208246 Me OCH.sub.2 CHF.sub.2 H 186-188247 Me OCH.sub.2 CH.sub.2 CH.sub.2 F H 139-140248 Me OMe H 138-140249 Me Cl H 176-178250 Me OCH.sub.2 OEt H 148-150251 Me OCH.sub.2 C(CH.sub.3)CH.sub.2 H 132-134252 Me OCH.sub.2 CHC(Me).sub.2 H 141-143253 Me OCH.sub.2 CHCHCl H 164-166254 Me ##STR78## H 139-141255 Me OCH.sub.2 OBn H 156-158______________________________________

BEST MODE FOR CARRYING OUT THE INVENTION
Now, the present invention will be specifically explained by describing the process for producing the intermediate and the process for producing the compound of the present invention as Preparation Examples.
PREPARATION EXAMPLE 1
Preparation of 1-methyl-4-fluoro-1H-indazole-3-sulfonamide (Intermediate No. 24)
75 g (539 mmol) of 2,6-difluorobenzonitrile was added to 300 ml of DMSO, and 33 g (716 mmol) of methylhydrazine was dropwise added thereto with stirring. The reaction proceeded exothermically, and the dropwise addition was continued while maintaining the temperature at a level of from 80.degree. to 100.degree. C. After returning to room temperature, the mixture was poured into a large excess amount of cool water, whereupon crystals were collected by filtration and dried in air to obtain 72 g (yield: 81%) of 3-amino-1-methyl-4-fluoro-1H-indazole (compound represented by the formula �VI! (slightly yellow crystals).
Then, 70 g (424 mmol) of 3-amino-1-methyl-4-fluoro-1H-indazole was dissolved in 200 ml of acetic acid, and 140 ml of concentrated hydrochloric acid was added thereto. The mixture was vigorously stirred, and a solution having 33 g (478 mmol) of sodium nitrite dissolved in 60 ml of water, was gradually dropwise added thereto within a range of from -5.degree. to -10.degree. C. The diazonium salt solution thus obtained, was gradually dropwise added to a mixture having 17 g (100 mmol) of cupric chloride dihydrate added to a solution obtained by blowing sulfurous acid gas into 370 ml of acetic acid until saturation (120 g). After completion of the dropwise addition, stirring was continued for one hour at a temperature of not higher than 0.degree. C., and then the mixture was poured into a large excess amount of cold water, whereupon crystals were collected by filtration and dried in air to obtain 70 g (yield: 66%) of 1-methyl-4-fluoro-1H-indazole-3-sulfonylchloride (compound represented by the formula �VII!) (slightly purple crystals).
Further, 13.9 g (56 mmol) of 1-methyl-4-fluoro-1H-indazole-3-sulfonylchloride in 50 ml of THF, was added to 12.9 g (177 mmol) of t-butylamine in 100 ml of THF, and the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was poured into a large excess amount of water, whereupon the crystals were collected by filtration and dried in air to obtain 15.9 g (yield: 99.6%) of 3-(N-t-butylsulfamoyl)-1-methyl-4-fluoro-1H-indazole (compound represented by the formula �I-d!) (slightly purple crystals).
15 g (53 mmol) of 3-(N-t-butylsulfamoyl)-1-methyl-4-fluoro-1H-indazole was added to 50 ml of trifluoroacetic acid, and the mixture was stirred overnight. After completion of the reaction, trifluoroacetic acid was distilled off under reduced pressure, and the residue was washed with n-hexane to obtain 10.5 g (yield: 86.8%) of 1-methyl-4-fluoro-1H-indazole-3-sulfonamide (slightly purple crystals). Melting point: 221.degree.-223.degree. C.
PREPARATION EXAMPLE 2
Preparation of 1-(1-methyl-4-fluoro-1H-indazole-3-sulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (Compound No. I-26)
0.35 g (2.3 mmol) of DBU was added to a solution containing 0.5 g (2.3 mmol) of 1-methyl-4-fluoro-1H-indazole-3-sulfonamide obtained in Preparation Example 1 and 0.62 g (2.3 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate in 20 ml of acetonitrile, and the mixture was stirred at room temperature for 12 hours. The mixture was poured into ice water and acidified with citric acid, whereupon the formed crystals were collected by filtration and washed with ice water, IPE and ethyl ether to obtain 0.49 g (yield: 52%) of the desired product (colorless needle like crystals). Melting point: 205.degree.-209.degree. C.
PREPARATION EXAMPLE 3-1
Preparation of methyl 2-bromomethyl-3-nitrobenzoate (compound represented by the formula �XI!)
A suspension containing 98 g (0.5 mol) of methyl 2-methyl-3-nitrobenzoate, 100 g (0.56 mol) of N-bromosuccinimide and 1 g of benzoyl peroxide in carbon tetrachloride (800 ml), was refluxed for 3 days under irradiation with 500W. The suspension was cooled to room temperature and subjected to filtration, whereupon the filtrate was concentrated. To the residue, ethyl ether (200 ml) and IPE (200 ml) were added, whereupon the formed crystals were collected by filtration to obtain 121 g (yield: 88.3%) of the desired product. Melting point: 65.degree.-67.degree. C.
PREPARATION EXAMPLE 3-2
Preparation of S-(2-methoxycarbonyl-6-nitrobenzyl)thiouronium bromide (compound represented by the formula �XII!
In methanol (2 l), 207 g (0.76 mol) of the product from Preparation Example 3-1 and 57.6 g (0.76 mol) of thiourea were refluxed for 12 hours. After cooling, methanol was distilled off, and ethyl acetate (1 l) was added to the residue. The product was subjected to filtration. This product was used for the subsequent reaction without purification. The obtained amount: 246 g (yield: 93%)
PREPARATION EXAMPLE 3-3
Preparation of methyl 2-(t-butylaminosulfonylmethyl)-3-nitrobenzoate (compounds represented by the formulas �XIII! and �XIV!)
110 g (0.32 mol) of the product from Preparation Example 3-2 in water (2 l) and acetic acid (1 l), was cooled to 5.degree. C. and chlorine was blown thereto for 4 hours at a temperature of from 5.degree. to 10.degree. C. And, the mixture was stirred at room temperature for one hour. Then, the product was collected by filtration and washed with ice water and then dissolved in 1 l of dichloromethane. To this solution, 54 g (0.74 mol) of t-butylamine was dropwise added at a temperature of from 0.degree. to 5.degree. C. Then, the mixture was stirred at room temperature for 2 hours. The organic layer was washed with water and then concentrated. IPE was added to the residue, followed by filtration to obtain 63 g (yield: 60.1%) of the desired product. This product was used for the subsequent reaction without purification.
PREPARATION EXAMPLE 3-4
Preparation of methyl 3-amino-2-(t-butylaminosulfonylmethyl)benzoate (compound represented by the formula �XV!)
A solution containing 48 g (0.145 mol) of the product from Preparation Example 3-3 and 164 g (0.73 mol) of stannous chloride dihydrate in 300 ml of ethanol, was refluxed for 2 hours. After cooling, it was added to 2 l of ethyl acetate, and powdery sodium hydrogencarbonate (500 g) was gradually added thereto. The formed salt was collected by filtration and thoroughly washed with ethyl acetate. The organic layer was concentrated to obtain 35.9 g (yield: 82.4%) of the desired product. Melting point: 123.degree.-125.degree. C.
PREPARATION EXAMPLE 3-5
Preparation of methyl 3-(t-butylaminosulfonyl)-1H-indazole-4-carboxylate (compound represented by the formula �XVI!)
A suspension containing 30 g (0.1 mol) from Preparation Example 3-4, 30.6 g (0.3 mol) of acetic anhydride and 10 g (0.102 mol) of potassium acetate in benzene (500 ml), was heated to 80.degree. C., and at the same temperature, 17.6 g (0.15 mol) of isoamyl nitrite was dropwise added thereto. Further, the mixture was refluxed for 12 hours and then cooled, and the salt was filtered. The organic layer was concentrated, and methanol (500 ml) and 10% hydrochloric acid (20 ml) were added to the residue, and the mixture was refluxed for one hour. After distilling off methanol, water was added thereto, and the mixture was neutralized with an aqueous sodium hydrogencarbonate solution. The formed crystals were collected by filtration to obtain 29.3 g (yield: 94.1%) of the desired product. Melting point: 218.degree.-220.degree. C.
PREPARATION EXAMPLE 3-6
Preparation of methyl 3-(t-butylaminosulfonyl)-1-methyl-1H-indazole-4-carboxylate and methyl 3-(t-butylaminosulfonyl) 2-methyl-2H-indazole-4-carboxylate (compounds represented by the formulas �I-d! and �II-d!)
6.8 g (48 mmol) of methyl iodide was added to a solution containing 10 g (32 mmol) of the product from Preparation Example 3-5 and 6.6 g (48 mmol) of potassium carbonate in methanol (200 ml), and the mixture was refluxed for 3 hours. Methanol was distilled off, and water was added to the residue, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, then concentrated and purified by silica gel column chromatography to obtain 5.9 g (yield: 56.8%; melting point: 189.degree.-190.degree. C.) of methyl 3-(t-butylaminosulfonyl)-1-methyl-1H-indazole-4-carboxylate and 2.1 g (yield: 19.8%; melting point: 147.degree.-148.degree. C.) of methyl 3-(t-butylaminosulfonyl) 2-methyl-2H-indazole-4-carboxylate.
PREPARATION EXAMPLE 4
Preparation of 2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 148)
A solution containing 9.5 g (72 mmol) of 2-methyl-2H-indazole in 200 ml of ethyl ether, was cooled to -30.degree. C., and 61.4 g (144 mmol) of n-butyl lithium (a 15% hexane solution) was dropwise added thereto. The mixture was stirred for one hour at the same temperature, and then an excess amount of sulfurous acid gas was blown thereinto for 3 hours at a temperature of not higher than -20.degree. C. After completion of the reaction, the mixture was returned to room temperature, stirred for 12 hours and then diluted with ethyl ether. The product was subjected to filtration. The crystals were dried to obtain crude lithium 2-methyl-2H-indazole-3-sulfinate. This product was used for the subsequent reaction without purification. 48.8 g (430 mmol) of hydroxylamine-O-sulfonic acid was gradually added to a solution containing 17.2 g (430 mmol) of sodium hydroxide in water (300 ml) under cooling with ice (not higher than 10.degree. C.). This solution was added all at once to a solution containing the crude lithium 2-methyl-2H-indazole-3-sulfinate previously prepared in water (100 ml), and then the mixture was stirred for 12 hours at room temperature. Formed crystals were collected by filtration to obtain 8.8 g (yield: 58%) of 2-methyl-2H-indazole-3-sulfonamide (slightly yellow granular crystals). Melting point: 181.degree.-183.degree. C.
PREPARATION EXAMPLE 5
Preparation of 1-(2-methyl-2H-indazole-3-sulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (Compound No. II-23)
2.3 g (15 mmol) of DBU was added to a solution containing 3.2 g (15 mmol) of 2-methyl-2H-indazole-3-sulfonamide obtained in Preparation Example 4 and 4.1 g (15 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate in acetonitrile (50 ml), and the mixture was stirred at room temperature for 12 hours. The mixture was poured into ice water and acidified with citric acid. Formed crystals were collected by filtration and washed with ice water, IPE and ethyl ether, to obtain 4.0 g (yield: 68%) of the desired product (colorless needle like crystals). Melting point: 199.degree.-202.degree. C.
PREPARATION EXAMPLE 6
Preparation of 4-methoxy-1-methyl-1H-indazole-3-sulfonamide (Intermediate No. 65)
A solution containing 5 g (21.8 mmol) of 4-fluoro-1-methyl-1H-indazole-3-sulfonamide and 12.6 g of sodium methoxide (a 28% methanol solution) (65 mmol) in DMSO (50 ml), was stirred at 130.degree. C. for one hour. After confirming the disappearance of the starting material by thin layer chromatography (TLC), the mixture was poured into ice water and acidified with citric acid. Formed crystals were collected by filtration and washed with water and IPE to obtain 3.2 g (yield: 60.9%) of the desired product. Melting point: 268.degree.-270.degree. C.
PREPARATION EXAMPLE 7
Preparation of 4-ethylthio-2-methyl-2H-indazole-3-sulfonamide (Intermediate-No. 130)
4.8 g (77 mmol) of ethanethiol was added to a solution containing 8.6 g (77 mmol) of potassium t-butoxide in DMSO (70 ml), under cooling with ice, and 8 g (35 mmol) of 4-fluoro-2-methyl-2H-indazole-3-sulfonamide was further added thereto. This mixture was stirred at 120.degree. C. for 2 hours. After confirming the disappearance of the starting material by TLC, treatment was conducted in the same manner as in Preparation Example 6 to obtain 6.8 g (yield: 72.5%) of the desired product. Melting: 145.degree.-147.degree. C.
PREPARATION EXAMPLE 8-1
Preparation of 4-cyclopropylmethoxy-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 254)
2.8 g (70 mmol) of 60% sodium hydride was suspended in 50 ml of DMSO, and 6 g (83 mmol) of cyclopropane methanol was dropwise added thereto. The mixture was stirred at room temperature for one hour, and then 5.4 g (24 mmol) of 4-fluoro-2-methyl-2H-indazole-3-sulfonamide was added thereto. The mixture was stirred at 130.degree. C. for 3 hours. After the reaction, the mixture was poured into ice water, acidified with citric acid and extracted with ethyl acetate. The organic layer was washed with water and then concentrated. Formed crystals were collected by filtration, washed with IPE and then dried to obtain 5.8 g (yield: 90%) of the desired product. Melting point: 139.degree.-141.degree. C.
PREPARATION EXAMPLE 8-2
Preparation of 4-hydroxy-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 189)
A mixture comprising 62 g (221 mmol) of 4-cyclopropylmethoxy-2-methyl-2H-indazole-3-sulfonamide, 120 ml of acetic acid and 120 ml of concentrated hydrochloric acid, was stirred at 80.degree. C. for one hour. After concentrating acetic acid.hydrochloric acid, the mixture was poured into ice water. Crystals were collected by filtration and washed with water. Further, the crystals were washed with IPE and dried to obtain 35.1 g (yield: 70%) of the desired product. Melting point: 180.degree.-181.degree. C.
PREPARATION EXAMPLE 8-3
Preparation of 4-allyloxy-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 203)
1.3 g of allyl bromide was added to a mixture comprising 5 g (22 mmol) of 4-hydroxy-2-methyl-2H-indazole-3-sulfonamide and 50 ml of a DMF solution of 1.9 g (22 mmol) of sodium hydrogencarbonate, and the mixture was stirred at room temperature for 12 hours. The mixture was poured into ice water, acidified with citric acid and extracted with ethyl acetate. The organic layer was washed, then concentrated and purified by column chromatography (hexane/ethyl acetate=2/1) to obtain 1.9 g (yield: 32.5%) of the desired product. Melting point: 143.degree.-144.degree. C.
PREPARATION EXAMPLE 9
Preparation of 4-(2-chloroethoxy-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 229) (Mitsunobu reaction)
3.8 g (22 mmol) of diethylazo dicarboxylate was added to a solution containing 5 g (22 mmol) of 4-hydroxy-2-methyl-2H-indazole-3-sulfonamide, 1.8 g (22 mmol) of 2-chloroethanol and 5.8 g (22 mmol) of triphenylphosphine in 50 ml of THF, and the mixture was stirred at room temperature for 20 hours. The mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, then concentrated and purified by column chromatography (hexane/ethyl acetate=2/1) to obtain 1.66 g (yield: 26%) of the desired product. Melting point: 177.degree.-179.degree. C.
PREPARATION EXAMPLE 10-1
Preparation of N.sup.1, N.sup.1 -dimethyl-N.sup.2 -�(4-hydroxy-2-methyl-2H-indazol-3-yl)sulfonyl!formamidine (compound represented by the formula �II-i!)
21.3 g (174 mmol) of dimethylformamide dimethylacetal was dropwise added to a solution containing 33 g (145 mmol) of 4-hydroxy-2-methyl-2H-indazole-3-sulfonamide in 200 ml of acetonitrile, at room temperature. The mixture was stirred for one hour, then poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, then concentrated and purified by column chromatography to obtain 35.2 g (yield: 86.3%) of the desired product. Melting point: 118.degree.-119.degree. C.
PREPARATION EXAMPLE 10-2
Preparation of N.sup.1,N.sup.1 -dimethyl-N.sup.2 -{�4-(2-fluoroethoxy)-2-methyl-2H-indazol-3-yl!sulfonyl}formamidine (compound represented by the formula �II-j!)
4.2 g (15 mmol) of N.sup.1,N.sup.1 -dimethyl-N.sup.2 -�(4-hydroxy-2-methyl-2H-indazol-3-yl)sulfonyl!formamidine was added to a suspension containing 0.6 g (15 mmol) of 60% sodium hydride in 50 ml of DMF, and the mixture was stirred at room temperature for one hour. Further, 2 g (16 mmol) of 1-bromo-2-fluoroethane was added thereto, and the mixture was stirred at room temperature for 12 hours. The mixture was poured into ice water, and the formed crystals were collected by filtration and washed with water and IPE to obtain the desired product. This product was used for the subsequent reaction without purification. Obtained amount: 3.4 g (yield: 69.5%)
PREPARATION EXAMPLE 10-3
Preparation of 4-(2-fluoroethoxy)-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 230)
A mixture comprising 3.4 g of N.sup.1,N.sup.1 -dimethyl-N.sup.2 -{�4-(2-fluoroethoxy)-2-methyl-2H-indazol-3-yl!sulfonyl}formamidine, 5 ml of concentrated hydrochloric acid and 50 ml of ethanol, was refluxed for 12 hours. Disappearance of the starting material was confirmed by TLC, and then ethanol was distilled off. Water was added to the residue, whereupon the formed crystals were collected by filtration and washed with water and IPE to obtain 2.4 g (yield: 85%) of the desired product. Melting point: 178.degree.-180.degree. C.
PREPARATION EXAMPLE 11
Preparation of 4-chloro-2-methyl-2H-indazole-3-sulfonamide (Intermediate No. 143)
36.1 g (0.24 mol) of 4-chloro-1H-indazole was added to a solution containing 28.4 g (0.7 mol) of sodium hydroxide in 500 ml of methanol, and 85.2 g (0.6 mol) of methyl iodide was dropwise added thereto. The mixture was heated and refluxed for 4 hours. Then, methanol was distilled off, and water was added to the residue, followed by extraction with dichloromethane. The organic layer was washed with water, dried and concentrated to obtain a mixture of 4-chloro-1-methyl-1H-indazole and 4-chloro-2-methyl-2H-indazole. This mixture was separated by silica gel column chromatography (ethyl acetate/hexane=4/1) to obtain 17.4 g (yield: 43.6%) of 4-chloro-2-methyl-2H-indazole (yellow liquid, refractive index (20.degree. C.): 1.6095).
A solution containing 16 g (0.1 mol) of 4-chloro-2-methyl-2H-indazole in 300 ml of ethyl ether, was cooled to -30.degree. C., and 85.4 g (0.2 mol) of n-butyl lithium (15% hexane solution) was dropwise added thereto. The mixture was stirred for one hour at the same temperature. Then, an excess amount of sulfurous acid gas was blown thereinto at a temperature of not higher than -20.degree. C. for 3 hours. After completion of the reaction, the mixture was returned to room temperature and diluted with ethyl ether, and the product was subjected to filtration. Crystals were dried to obtain crude lithium 4-chloro-2-methyl-2H-indazole-3-sulfinate. This product was used for the subsequent reaction without purification.
45.2 g (0.4 mol) of hydroxylamine-O-sulfonic acid was gradually added to a solution containing 16 g (0.4 mol) of sodium hydroxide in water (300 ml) under cooling with ice (<10.degree. C.). This solution was added all at once to a solution of the previously prepared crude lithium 4-chloro-2-methyl-2H-indazole-3-sulfinate in water (100 ml). The mixture was stirred at room temperature for 12 hours. Formed crystals were collected by filtration to obtain 17.1 g (yield: 69.8%) of the desired 4-chloro-2-methyl-2H-indazole-3-sulfonamide (slightly yellow granular crystals). Melting point: 173.degree.-175.degree. C.
PREPARATION EXAMPLE 12
Preparation of 1-(4-chloro-2-methyl-2H-indazole-3-sulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl)urea (Compound No. II-134)
0.5 g (3.3 mmol) of DBU was added to a solution containing 0.8 g (3.3 mmol) of 4-chloro-2-methyl-2H-indazole-3-sulfonamide obtained in Preparation Example 11 and 0.9 g (3.3 mmol) of phenyl (4,6-dimethoxypyrimidin-2-yl)carbamate in acetonitrile (50 ml), and the mixture was stirred at room temperature for 12 hours. The mixture was poured into ice water and acidified with citric acid. Formed crystals were collected by filtration and sequentially washed with water, isopropyl ether and ethyl ether, to obtain 1.2 g (yield: 85%) of the desired product (colorless needle-like crystals). Melting point: 171.degree.-172.degree. C.
The herbicide of the present invention contains an indazolesulfonylurea derivative represented by the general formula �I! or �II! as an active ingredient.
For the compound of the present invention to be used as a herbicide, the compound of the present invention may be used by itself. However, it may be used in the form of a formulation such as a dust, a wettable powder, an emulsifiable concentrate, a microgranule or a granule by blending it with a carrier, a surfactant, a dispersant or an adjuvant which is commonly used for formulations.
The carrier to be used for such formulations, may, for example, be a solid carrier such as Zeeklite, talc, bentonite, clay, kaolin, diatomaceous earth, fine silica, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate or urea, or a liquid carrier such as isopropyl alcohol, xylene, cyclohexane or methylnaphthalene.
As the surfactant and dispersant, a metal salt of alkylbenzenesulfonic acid, a metal salt of dinaphthylmethane disulfonic acid, a salt of alcohol-sulfuric acid ester, an alkylaryl sulfonate, a lignin sulfonate, a polyoxyethylene glycol ether, a polyoxyethylene alkylaryl ether or a polyoxyethylene sorbitol monoalkylate may, for example, be mentioned.
The adjuvant may, for example, be carboxymethyl cellulose, polyethylene glycol or gum arabic.
In practical use, the herbicide may be diluted to a suitable concentration before application, or may be directly applied.
The herbicide of the present invention may be used for application to foliage, soil or water surface. The blending proportion of the active ingredient is suitably selected as the case requires. However, in a case of a dust or a granule, the proportion of the active ingredient is selected suitably within a range of from 0.01 to 10% (by weight), preferably from 0.05 to 5% (by weight). In a case of an emulsifiable concentrate or a wettable powder, the proportion is selected suitably within a range of from 1 to 50% (by weight), preferably from 5 to 30% (by weight).
The dose of the herbicide of the present invention varies depending upon the type of the compound, the weeds to be controlled, the germination tendency, the environmental conditions and the type of the formulation to be used. However, in the case of a dust or a granule which is used by itself, the dose of the active ingredient is selected suitably within a range of from 0.1 g to 5 kg, preferably from 1 g to 1 kg, per 10 ares. In a case of an emulsifiable concentrate or a wettable powder which is used in a liquid state, the dose of the active ingredient is selected suitably within a range of from 0.1 to 50,000 ppm, preferably from 10 to 10,000 ppm.
Further, the compound of the present invention may be used in combination with an insecticide, a fungicide, other herbicide, a plant growth controlling agent, a fertilizer or the like, as the case requires.
Now, the formulation method will be described with reference to typical Formulation Examples. The compounds, types of the additives and blending ratios are not limited to such specific Examples and may be changed within wide ranges. In the following description, "parts" means "parts by weight".
FORMULATION EXAMPLE 1
(Wettable powder)
To 10 parts of Compound No. I-9 or II-26, 0.5 part of polyoxyethyleneoctylphenyl ether, 0.5 part of sodium .beta.-naphthalene sulfonate-formalin condensate, 20 parts of diatomaceous earth and 69 parts of clay were mixed and pulverized to obtain a wettable powder.
FORMULATION EXAMPLE 2
(Wettable powder)
To 10 parts of Compound No. I-63 or II-134, 0.5 part of polyoxyethyleneoctylphenyl ether, 0.5 part of sodium .beta.-naphthalene sulfonate-formalin condensate, 20 parts of diatomaceous earth, 5 parts of fine silica and 64 parts of clay were mixed and pulverized to obtain a wettable powder.
FORMULATION EXAMPLE 3
(Wettable powder)
To 10 parts of Compound No. I-134 or II-104, 0.5 part of polyoxyethyleneoctylphenyl ether, 0.5 part of sodium .beta.-naphthalene sulfonate-formalin condensate, 20 parts of diatomaceous earth, 5 parts of fine silica and 64 parts of calcium carbonate, were mixed and pulverized to obtain a wettable powder.
FORMULATION EXAMPLE 4
(Emulsifiable concentrate)
To parts of Compound No. I-92 or II-64, 60 parts of a mixture comprising equal amounts of xylene and isophorone and 10 parts of a mixture comprising a polyoxyethylene sorbitol alkylate surfactant, a polyoxyethylenealkylaryl polymer and an alkylaryl sulfonate, were added, and the mixture was thoroughly stirred to obtain an emulsifiable concentrate.
FORMULATION EXAMPLE 5
(Granule)
10 Parts of Compound No. I-64 or II-142, 80 parts of a bulking agent comprising a 1:3 mixture of talc and bentonite, 5 parts of fine silica, 5 parts of a mixture comprising a polyoxyethylene sorbitol alkylate surfactant, a polyoxyethylenealkylaryl polymer and an alkylaryl sulfonate and 10 parts of water were mixed and thoroughly kneaded to obtain a paste, which was extruded from sieve apertures with a diameter of 0.7 mm. The extruded product was dried and then cut into a length of from 0.5 to 1 mm to obtain granules.
The compound of the present invention represented by the general formula �I! or �II! is capable of controlling annual weeds such as barnyardgrass (Echinochloa oryzicola), smallflower umbrella-plant (Cyperus difformis) and monochoria (Monochoria vaginalis) as well as perennial weeds such as Japanese ribbon wapato (Sagittaria pygmaea), arrowhead (Sagittaria trifolia), water nutgrass (Cyperus serotinus), water chestnut (Eleocharis kuroguwai), bulrush (Scirpus juncoides) and narrow-leaved arrowhead (Alisma canaliculatum), which germinate in paddy fields. Further, it exhibits excellent herbicidal effects against various weeds problematic in upland fields, including broadleaf weeds such as smartweed (Polygonum lapathifolium), green amaranth (Amaranthus viridis), lambsquater (Chenopodium album), goose grass (Galium aparine), chickweed (Stellaria media), velvetleaf (Abtilon theophrasti), prickly sida (Sida spinosa), hemp sesbania (Sesbania exaltata), morningglory (Ipomoea spp) and common cocklebur (Xanthium strumarium), perennial and annual syperaceous weeds such as purple nutsedge (Cyperus rotundus), yellow nutsedge (Cyperus esculentus), himekugu (Cyperus brevifolius var. leiolepis), annual sedge (Cyperus microiria) and rice flatsedge (Cyperus iria), and gramineous weeds such as barnyardgrass (Echinochloa crus-galli), goosegrass (Eleusine indica), greenfoxtail (Setaria viridis), annual bluegrass (Poa annua), johnsongrass (Sorghum halepense), water foxtail (Alopecurus aequalis) and wild oat (Avena fatua), over a wide range from the preemergence stage to the growing stage.
On the other hand, the herbicide of the present invention is highly safe to crop plants and exhibits particularly high safety to e.g. rice, wheat, barley, corn, grain sorghum and sugar beat.
Now, the effects of the compounds of the present invention will be described with reference to Test Examples.
TEST EXAMPLE 1
(Test on herbicidal effects by paddy field soil treatment)
In a plastic pot (surface area: 100 cm.sup.2) filled with paddy field soil, barnyardgrass (Ec), monochoria (Mo) and bulrush (Sc) were sown after puddling and leveling, and flooded to a water depth of 3 cm. Next day, a wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied dropwise to the water surface. The dose was 100 g of the active ingredient per 10 ares. The plants were then cultured in a green house, and the evaluation of the herbicidal effects was conducted on the 21st day after the application in accordance with the standards as identified in Table 4. The results are shown in Table 5.
TABLE 4______________________________________Index Herbicidal effectsNo. (growth-controlling degree) or phytotoxicity______________________________________5 Herbicidal effect or phytotoxicity: at least 90%4 Herbicidal effect or phytotoxicity: at least 70% and less than 90%3 Herbicidal effect or phytotoxicity: at least 50% and less than 70%2 Herbicidal effect or phytotoxicity: at least 30% and less than 50%1 Herbicidal effect or phytotoxicity: at least 10 and less than 30%0 Herbicidal effect or phytotoxicity: 0 to less than______________________________________ 10%
TABLE 5______________________________________Compound Herbicidal effectsNo. Ec Mo Sc______________________________________I-5 5 5 5I-6 5 5 5I-8 5 5 5I-17 5 5 5I-18 5 5 5I-19 5 5 5I-20 5 5 5I-23 5 5 5I-25 5 5 5I-26 5 5 5I-27 5 5 5I-28 5 5 5I-29 5 5 5I-31 5 5 5I-32 5 5 5I-33 5 5 5I-34 5 5 5I-35 5 5 5I-63 5 5 5I-64 5 5 5I-65 5 5 5I-66 5 5 5I-67 5 5 5I-79 5 5 5I-91 5 5 5I-92 5 5 5I-93 5 5 5I-94 5 5 5I-95 5 5 5I-111 5 5 5I-114 5 5 5I-120 5 5 5I-131 5 5 5I-134 5 5 5I-136 5 5 5I-149 5 5 5I-150 5 5 5I-151 5 5 4I-153 5 5 5I-157 5 5 5I-158 5 5 5I-160 5 5 5I-161 5 5 5I-162 5 5 5I-174 5 5 5I-175 5 5 5I-176 5 5 5I-179 5 5 5I-180 5 5 5I-181 5 5 5I-182 5 5 5I-183 5 5 5I-184 5 5 5I-194 5 5 5I-204 5 5 5I-205 5 5 5I-216 5 5 5I-218 5 5 4I-322 5 5 5I-334 5 5 5I-337 5 5 5I-506 5 5 5I-507 5 5 5I-508 4 5 4I-513 5 5 5I-514 5 5 5I-516 5 5 5I-517 5 5 5I-518 5 5 5I-519 5 5 4I-520 3 5 5I-527 3 5 5I-530 5 5 5I-555 5 5 4I-641 5 5 5I-645 3 5 5I-906 3 5 5II-5 5 5 5II-6 5 5 5II-8 5 5 5II-17 5 5 5II-18 4 5 4II-19 5 5 5II-20 5 5 5II-23 5 5 5II-25 5 5 5II-26 5 5 5II-27 5 5 5II-28 5 5 5II-29 5 5 5II-31 5 5 5II-32 5 5 5II-33 5 5 5II-34 5 5 5II-35 5 5 5II-36 5 5 5II-38 5 5 5II-42 4 5 5II-53 5 5 5II-55 5 5 5II-63 5 5 5II-64 5 5 5II-65 5 5 5II-66 5 5 5II-67 5 5 5II-91 5 5 5II-92 5 5 5II-93 5 5 5II-94 5 5 5II-95 5 5 5II-104 5 5 5II-106 5 5 5II-107 5 5 5II-110 5 5 5II-111 5 5 5II-112 5 5 5II-113 5 5 5II-114 5 5 5II-115 5 5 5II-120 5 5 5II-127 5 5 5II-129 4 5 5II-130 5 5 5II-131 5 5 5II-132 3 5 5II-134 5 5 5II-136 3 5 5II-137 5 5 5II-141 5 5 5II-142 5 5 5II-143 5 5 5II-149 5 5 5II-150 5 5 5II-151 5 5 5II-153 5 5 5II-155 5 5 5II-156 5 5 5II-157 5 5 5II-158 5 5 5II-159 5 5 5II-160 5 5 5II-161 5 5 5II-162 5 5 5II-163 5 5 5II-166 5 5 5II-168 5 5 5II-169 5 5 5II-174 5 5 5II-175 5 5 5II-176 5 5 5II-177 5 5 5II-178 5 5 5II-179 5 5 5II-180 5 5 5II-181 5 5 5II-182 5 5 5II-183 5 5 5II-184 5 5 5II-185 5 5 5II-188 5 5 5II-189 5 5 5II-194 5 5 5II-195 5 5 5II-197 5 5 5II-198 5 5 5II-199 5 5 5II-200 5 5 5II-202 4 5 5II-204 5 5 5II-208 5 5 5II-215 5 5 5II-220 5 5 5II-225 5 5 5II-227 5 5 5II-531 5 5 5______________________________________
TEST EXAMPLE 2
(Test on herbicidal effects by upland field soil treatment)
In a plastic pot (surface area: 120 cm.sup.2) filled with upland field soil, pale smartweed (Pc), slender amaranth (Am), common lambsquarters (Ch) and rice flatsedge (Ci) were sown and covered with soil. A wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied uniformly to the soil surface by a small-sized sprayer in an amount of 100 l/10 ares so as to apply 100 g of the active ingredient per 10 ares. The plants were then cultured in a green house, and the evaluation of the herbicidal effects was conducted on the 21st day after the application in accordance with the standards as identified in Table 4. The results are shown in Table 6.
TABLE 6______________________________________Compound Herbicidal effectsNo. Po Am Ch Ci______________________________________I-5 5 5 5 5I-6 5 5 5 5I-8 5 5 5 5I-17 5 5 5 5I-18 5 5 5 5I-19 5 5 5 5I-20 5 5 5 5I-23 5 5 5 5I-25 5 5 5 --I-26 5 5 5 --I-27 5 5 5 5I-28 5 5 5 5I-29 5 5 5 --I-31 5 5 5 --I-32 5 5 5 5I-33 5 5 5 5I-34 5 5 5 5I-35 5 5 5 5I-53 5 5 5 5I-63 5 5 5 5I-64 5 5 5 5I-65 5 5 5 5I-66 5 5 5 5I-67 5 5 5 5I-79 5 5 5 5I-91 5 5 5 5I-92 5 5 5 5I-93 5 5 5 5I-94 5 5 5 5I-95 5 5 5 5I-110 5 5 5 5I-111 5 5 5 5I-112 5 5 5 5I-113 5 5 5 5I-114 5 5 5 5I-120 5 5 5 5I-131 5 5 5 5I-134 5 5 5 5I-136 5 5 5 5I-149 5 5 5 5I-150 5 5 5 5I-151 5 5 5 5I-152 5 5 4 5I-153 5 5 5 5I-157 5 5 5 5I-158 5 5 5 5I-160 5 5 5 5I-161 5 5 5 5I-162 5 5 5 5I-174 5 5 5 5I-175 5 5 5 5I-176 5 5 5 --I-177 5 5 5 --I-178 5 5 5 5I-179 5 5 5 --I-180 5 5 5 5I-181 5 5 5 5I-182 5 5 5 5I-183 5 5 4 5I-184 5 5 5 5I-194 5 5 5 5I-198 5 5 5 5I-199 5 5 5 5I-204 5 5 5 5I-205 5 5 4 5I-209 5 5 4 5I-212 5 5 5 5I-216 5 5 5 5I-218 4 5 4 5I-322 5 5 5 --I-334 5 5 5 --I-337 5 5 5 --I-506 5 5 5 5I-507 5 5 5 5I-508 5 5 5 5I-509 5 5 4 5I-511 5 5 5 4I-513 5 5 5 5I-514 5 5 5 4I-516 5 5 5 5I-517 4 5 4 5I-518 5 5 5 5I-519 5 5 5 5I-520 5 5 5 5I-521 5 5 5 5I-525 5 5 5 5I-526 4 5 4 5I-527 5 5 5 5I-528 5 5 5 5I-529 4 5 5 5I-530 5 5 5 5I-555 5 5 5 5I-641 5 5 5 5I-645 5 5 5 5I-761 4 5 4 --I-905 5 5 5 --I-906 5 5 5 --II-5 5 5 5 5II-6 5 5 4 5II-8 5 5 5 5II-17 5 5 5 5II-19 5 5 5 5II-20 5 5 5 5II-23 5 5 5 5II-25 5 5 4 5II-26 5 5 5 5II-27 5 5 5 5II-28 5 5 5 5II-29 5 5 5 --II-31 5 5 5 5II-32 5 5 5 5II-34 5 5 5 5II-35 5 5 5 5II-36 5 5 5 5II-38 5 5 4 5II-53 5 5 5 --II-55 5 5 4 5II-56 5 5 5 5II-63 5 5 5 5II-64 5 5 5 5II-65 5 5 5 --II-66 5 5 5 --II-67 5 5 5 --II-90 4 5 5 --II-91 5 5 5 5II-92 5 5 5 5II-93 5 5 4 5II-95 4 5 4 5II-96 5 5 4 5II-104 5 5 5 --II-105 4 5 5 --II-106 5 5 5 5II-107 5 5 5 5II-110 5 5 5 5II-111 5 5 5 5II-113 5 5 5 5II-114 5 5 5 5II-115 5 5 4 4II-120 5 5 5 5II-127 5 5 5 5II-130 5 5 4 5II-131 5 5 5 5II-134 5 5 5 5II-136 5 5 5 5II-137 5 5 5 --II-138 5 5 5 --II-139 5 5 5 --II-140 5 5 4 --II-141 5 5 5 --II-142 5 5 5 --II-143 5 5 5 --II-144 5 5 5 --II-145 5 5 5 --II-146 5 5 5 5II-149 5 5 4 5II-150 5 5 5 5II-155 5 5 5 5II-156 4 5 5 5II-157 5 5 5 5II-158 5 5 5 5II-160 5 5 5 5II-161 4 5 5 5II-162 5 5 5 5II-163 5 5 4 5II-164 5 5 5 5II-166 5 5 5 5II-167 4 5 5 5II-168 5 5 5 5II-169 5 5 5 5II-170 4 5 5 5II-172 5 5 5 5II-174 5 5 5 5II-175 5 5 5 --II-176 5 5 5 --II-177 5 5 5 --II-178 5 5 5 --II-179 5 5 5 --II-180 5 5 5 5II-181 5 5 5 5II-182 5 5 5 5II-183 5 5 4 5II-184 5 5 5 5II-185 5 5 5 --II-188 5 5 5 5II-189 5 5 5 5II-191 5 5 5 --II-195 5 5 5 4II-197 5 5 5 --II-198 5 5 5 --II-199 5 5 5 --II-200 5 5 5 --II-204 5 5 4 5II-207 5 5 4 --II-219 4 5 5 5II-220 5 5 5 --II-223 5 5 5 --II-225 5 5 5 5II-226 5 5 5 5II-227 5 5 5 --II-531 5 5 5 --______________________________________
TEST EXAMPLE 3
(Test on herbicidal effects by upland field foliage treatment)
In a plastic pot (surface area: 120 cm.sup.2) filled with upland field soil, pale smartweed (Po), slender amaranth (Am), common lambsquarters (Ch) and rice flatsedge (Ci) were sown and covered with soil and were cultured in a green house for 2 weeks. A wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied onto the entire foliages of the plants from above by a small-sized sprayer in an amount of 100 l/10 ares so as to apply 100 g of the active ingredient per 10 ares. The plants were then cultured in the green house, and the evaluation of the herbicidal effects was conducted on the 14th day after the treatment in accordance with the standards as identified in Table 4. The results are shown in Table 7.
TABLE 7______________________________________Compound Herbicidal effectsNo. Po Am Ch Ci______________________________________I-5 5 5 5 5I-6 5 5 5 5I-8 5 5 5 5I-17 5 5 5 5I-18 5 5 5 5I-19 5 5 5 5I-20 5 5 5 5I-23 5 5 5 5I-25 5 5 5 5I-26 5 5 5 5I-27 5 5 5 5I-28 5 5 5 5I-29 5 5 5 5I-31 5 5 5 5I-32 5 5 5 5I-33 5 5 5 5I-34 5 5 5 5I-35 5 5 5 5I-53 5 5 5 5I-63 5 5 5 5I-64 5 5 5 5I-65 5 5 5 5I-66 5 5 5 5I-67 5 5 5 5I-79 5 5 5 5I-91 5 5 5 5I-92 5 5 5 5I-93 5 5 5 5I-94 5 5 5 5I-95 5 5 5 5I-111 5 5 5 5I-112 5 5 5 5I-113 5 5 5 5I-114 5 5 5 5I-120 5 5 5 5I-131 5 5 5 5I-134 5 5 5 5I-136 5 5 4 4I-149 4 5 4 5I-150 5 5 5 5I-151 5 5 5 5I-157 5 5 5 5I-158 5 5 5 5I-160 5 5 5 5I-161 5 5 5 5I-162 5 5 5 5I-174 5 5 5 5I-175 5 5 5 5I-176 5 5 5 5I-177 4 4 5 5I-178 5 5 5 5I-179 5 5 5 5I-180 5 5 5 5I-181 5 5 5 5I-182 5 5 5 5I-183 5 5 5 4I-184 5 5 5 5I-194 5 5 5 5I-204 5 5 5 5I-205 5 5 5 5I-206 5 5 5 4I-209 4 5 5 4I-211 4 5 5 4I-212 4 5 5 4I-216 5 5 5 5I-218 5 5 4 4I-322 5 5 5 5I-324 4 5 4 5I-334 5 5 4 5I-337 5 5 5 5I-506 4 5 4 5I-507 5 5 5 5I-508 5 5 5 5I-509 5 5 5 5I-511 4 5 5 4I-513 5 5 5 5I-514 5 5 5 4I-516 5 5 5 5I-517 5 5 4 5I-518 5 5 5 5I-520 5 5 5 5I-525 5 5 5 5I-526 5 5 5 4I-527 5 5 5 5I-528 5 5 5 5I-530 5 5 5 5I-555 5 5 5 5I-641 5 5 5 5II-5 5 5 5 5II-6 4 5 5 5II-8 5 5 4 5II-17 5 5 4 5II-19 5 5 5 5II-20 5 5 5 5II-23 5 5 5 5II-25 5 5 5 5II-26 5 5 5 5II-27 5 5 5 5II-28 5 5 5 5II-29 5 5 5 5II-31 5 5 4 5II-32 5 5 5 5II-34 5 5 5 5II-35 5 5 5 5II-38 5 5 4 5II-53 5 5 5 5II-55 5 5 5 5II-56 5 5 5 5II-63 5 5 5 5II-64 5 5 5 5II-65 5 5 5 5II-66 5 5 5 5II-67 5 5 5 5II-91 5 5 5 5II-92 5 5 5 5II-93 5 5 5 5II-94 5 5 5 5II-104 5 5 5 5II-105 5 5 5 5II-106 5 5 5 5II-107 5 5 5 5II-110 5 5 5 5II-111 5 5 5 5II-112 5 5 5 5II-113 5 5 5 5II-114 5 5 5 5II-115 5 5 4 5II-120 5 5 5 5II-129 5 5 5 5II-130 5 5 5 5II-131 5 5 5 5II-134 5 5 5 5II-136 5 5 4 4II-140 5 5 5 5II-141 4 5 4 5II-142 5 5 5 5II-143 5 5 5 5II-146 5 5 4 5II-149 5 5 5 5II-150 5 5 5 5II-153 5 5 4 4II-154 5 5 5 4II-155 5 5 5 5II-157 5 5 5 5II-158 5 5 4 5II-160 5 5 5 5II-162 5 5 5 5II-166 5 5 5 5II-167 5 5 5 5II-168 5 5 5 5II-169 5 5 5 5II-170 4 5 5 5II-174 5 5 4 5II-175 5 4 5 5II-176 5 5 5 5II-178 5 5 5 5II-179 5 5 5 5II-180 5 5 5 5II-181 5 5 5 5II-182 5 5 5 5II-183 5 5 4 5II-184 5 5 5 5II-188 5 5 5 5II-189 5 5 4 5II-192 4 5 4 5II-194 5 5 5 5II-195 5 5 5 5II-196 4 5 4 5II-197 5 5 5 5II-199 5 5 5 5II-204 5 5 5 5II-218 5 5 5 4II-219 4 5 5 4II-220 5 5 4 5II-225 5 5 5 5II-226 5 5 5 5II-531 5 5 5 5______________________________________
TEST EXAMPLE 4
(Test on crop plant selectivity by paddy field soil treatment)
In a 1/10,000a plastic pot, paddy field soil was filled, irrigated, paddled and leveled. Then, barnyardgrass (Ec), monochoria (Mo) and bulrush (Sc) were sown at a depth of 0.5 cm. Further, two seedlings of rice (Or) of 2 leaf stage was transplanted at a transplantation depth of 2 cm. Then, the pot was flooded to a water depth of 3 cm. Next day, a prescribed amount of the active ingredient (g.sup.ai /10a) of a wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied dropwise to the water surface. The plants were then cultured in a green house, and the evaluation of the herbicidal effects and phytotoxicity was conducted on the 28th day after the application in accordance with the standards as identified in Table 4. The results are shown in Table 8.
TABLE 8______________________________________Compound Dose Herbicidal effects PhytotoxicityNo. (gai 10a) Eo Mo Sc Or______________________________________I-17 25 4 5 5 0I-157 6.3 5 5 5 1I-161 25 5 5 5 0I-174 25 5 5 4 1I-216 25 4 5 4 2II-19 25 5 5 5 0 6.3 5 5 5 0II-23 25 4 5 5 0II-26 25 5 5 5 1 6.3 5 5 5 0 1.6 5 5 4 0II-27 25 5 5 5 0 6.3 5 5 5 0II-29 6.3 5 5 5 1 1.6 3 5 5 0II-31 6.3 5 5 5 1 1.6 5 5 5 0II-35 25 5 5 5 1 6.3 5 5 5 0II-36 25 5 5 5 0II-53 25 5 5 5 0II-64 25 5 5 5 0 6.3 5 5 5 0II-65 25 5 5 5 0 6.3 5 5 5 0II-66 25 5 5 5 1 6.3 5 5 5 0II-92 25 5 5 5 2 6.3 5 5 5 0 1.6 5 5 5 0II-93 25 5 5 5 1 6.3 5 5 5 0II-94 25 5 5 5 1 6.3 5 5 5 0II-104 25 5 5 5 0 6.3 5 5 5 0II-114 6.3 5 5 5 1 1.6 5 5 5 0II-127 25 5 5 5 1 6.3 3 5 5 0II-134 25 5 5 5 0 6.3 5 5 5 0II-137 25 5 5 5 2 6.3 5 5 5 0 1.6 5 5 5 0II-141 25 5 5 5 1 6.3 5 5 4 0II-142 6.3 5 5 5 0 1.6 5 5 5 0II-157 25 5 5 5 0 6.3 5 5 5 0II-160 25 5 5 5 0 6.3 5 5 5 0II-162 25 5 5 5 1 6.3 5 5 5 0II-166 1.6 5 5 5 0II-178 25 5 5 5 0 6.3 4 5 4 0II-208 25 5 5 5 0 6.3 4 5 4 0II-531 25 5 5 5 0 6.3 5 5 4 0Comparative 25 5 5 5 5compound 6.3 5 5 4 5A 1.6 3 4 2 5______________________________________ Comparative compound A: Disclosed in Japanese Unexamined Patent Publication No. 95091/1992 (Compound No. 1)
TEST EXAMPLE 5
(Test on crop plant selectivity by upland field soil treatment)
In a plastic pot (surface area: 600 cm.sup.2) filled with upland field soil, seeds or tubers of wheat (Tr), corn (Ze), grain sorghum (Gs), pale smartweed (Po), slender amaranth (Am), common lambsquarters (Ch), velvetleaf (Ab), morningglory (Ip), cocklebur (Xa) and purple nutsedge (CR) were planted and covered with soil. Next day, a prescribed amount of the active ingredient (g.sup.ai /10a) of a wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied uniformly to the soil surface by a small-sized sprayer in an amount of 100 l per 10 ares. The plants were then cultured in a green house, and the evaluation of the herbicidal effects was conducted on the 21st day after the application in accordance with the standards as identified in Table 4. The results are shown in Table 9.
TABLE 9______________________________________Com-pound Dose Herbicidal effects PhytotoxicityNo. (gai 10a) Po Am Ch Ab Ip Xa CR Tr Ze Gs______________________________________II-19 25 5 5 5 5 5 5 2 0 1 0II-23 25 5 5 5 5 5 5 5 0 3 1 6.3 4 5 4 5 4 5 5 0 3 0II-26 25 5 5 5 5 5 5 -- 1 4 3 6.3 5 5 4 4 4 4 4 0 3 1II-28 25 5 5 5 5 5 5 -- 0 1 0 6.3 5 5 4 4 4 4 4 0 0 0II-29 25 5 5 5 5 5 5 5 0 3 3 6.3 5 5 5 5 5 5 5 0 1 1II-35 6.3 5 5 5 4 4 4 5 0 1 0II-53 25 5 5 5 5 5 5 5 1 2 1 6.3 5 5 5 5 5 5 4 0 0 0II-63 25 5 5 5 5 5 5 5 0 5 3 6.3 5 5 5 5 5 5 5 0 3 2II-64 6.3 5 5 5 5 5 5 5 0 1 3 1.6 5 5 5 3 5 5 5 0 0 0II-65 25 5 5 5 5 5 5 5 1 1 4 6.3 5 5 5 4 4 5 5 0 0 3II-66 25 5 5 5 5 5 5 5 0 4 4 6.3 5 5 5 5 4 5 5 0 1 3II-91 6.3 5 5 5 5 5 5 5 0 4 1II-104 25 5 5 5 5 5 5 5 0 4 3 6.3 5 5 5 4 4 5 5 0 1 3II-107 25 5 5 5 5 5 5 5 0 4 4 6.3 5 5 5 4 3 5 5 0 3 3II-134 25 5 5 5 5 5 5 5 1 1 1 6.3 5 5 5 5 5 5 5 0 0 0II-137 25 5 5 5 5 5 5 5 0 4 2 6.3 5 5 5 5 4 5 5 0 3 1II-142 25 5 5 5 5 5 5 5 1 4 4 6.3 5 5 5 5 5 5 5 0 3 3II-157 25 5 5 5 5 5 5 4 2 4 0 6.3 5 5 5 5 3 5 3 0 1 0II-168 25 5 5 5 5 5 5 4 1 4 4 6.3 5 5 5 4 4 5 3 0 3 3II-215 25 5 5 5 4 5 5 5 1 2 1______________________________________
TEST EXAMPLE 5
(Test on crop plant selectivity by upland field foliage treatment)
In a plastic pot (surface area: 600 cm.sup.2) filled with upland field soil, seeds or tubers of wheat (Tr), corn (Ze), grain sorghum (Gs), pale smartweed (Po), slender amaranth (Am), common lambsquarters (Ch), velvetleaf (Ab), morningglory (Ip), cocklebur (Xa) and purple nutsedge (CR) were planted, covered with soil and cultured in a green house for 2 weeks. Then, a prescribed amount of the active ingredient (g.sup.ai /10a) of a wettable powder prepared in accordance with Formulation Example 1 was diluted with water and applied onto the entire foliages of the plants from above by a small-sized sprayer in an amount of 100 l per 10 ares. The plants were then cultured in a green house, and the evaluation of the herbicidal effects was conducted on the 14th day after the treatment in accordance with the standards as identified in Table 4. The results are shown in Table 10.
TABLE 10______________________________________Com-pound Dose Herbicidal effects PhytotoxicityNo. (gai 10a) Po Am Ch Ab Ip Xa CR Tr Ze Gs______________________________________I-20 6.3 5 5 5 5 5 5 3 1 3 3I-23 25 5 5 5 5 5 5 2 0 4 3 6.3 5 5 5 5 5 5 0 0 3 3I-26 1.6 5 5 5 5 5 5 5 1 4 4I-27 6.3 5 5 5 5 5 5 3 1 3 3 1.6 5 5 4 5 5 5 1 0 3 3I-28 25 5 5 5 5 5 5 2 1 3 3 6.3 5 5 4 5 4 5 1 0 3 3I-53 25 5 5 5 5 5 5 3 1 3 3 6.3 5 5 5 5 5 5 1 0 3 2I-66 25 5 5 5 5 5 5 2 1 3 --I-176 25 5 5 5 5 5 5 3 1 3 3 6.3 5 5 5 5 5 4 2 0 3 3I-194 25 5 5 4 5 5 5 3 0 4 4I-204 25 5 5 4 5 5 5 -- 1 4 4 6.3 4 5 4 5 5 5 -- 0 4 3I-337 25 5 5 5 5 5 5 4 1 4 3 6.3 4 5 5 5 5 5 4 0 3 3I-516 25 4 5 5 5 5 5 2 0 4 3II-20 25 5 5 5 5 5 5 5 0 4 3 6.3 5 5 5 5 5 5 5 0 4 3II-26 25 5 5 5 5 5 5 5 0 3 1 6.3 5 5 5 5 5 5 5 0 2 1II-27 25 5 5 5 5 5 5 2 0 0 0 6.3 5 5 5 5 5 5 1 0 0 0II-28 25 5 5 5 5 5 5 -- 1 3 3 6.3 5 5 5 5 5 5 5 0 2 2II-31 25 5 5 5 5 5 5 5 1 1 1 6.3 5 5 4 5 5 5 5 0 1 1II-64 25 5 5 5 5 5 5 4 0 0 3 6.3 5 5 5 5 5 5 4 0 0 2II-93 25 5 5 5 5 5 5 5 1 1 3 6.3 5 5 5 5 5 5 5 0 1 3II-104 100 5 5 5 5 5 5 5 0 0 3 25 5 5 5 5 5 5 4 0 0 3II-127 25 5 5 4 5 5 5 5 0 4 1II-134 25 5 5 5 5 5 5 5 0 0 0 6.3 5 5 4 5 5 5 5 0 0 0II-150 25 5 5 4 5 5 5 -- 0 1 3II-157 25 5 5 5 5 5 5 -- 0 0 2 6.3 5 5 4 5 5 5 -- 0 0 1II-168 25 5 5 5 5 5 5 4 1 4 3 6.3 5 5 4 5 5 5 3 0 2 3II-180 25 5 5 5 5 5 5 -- 0 0 1 6.3 5 5 4 5 5 5 -- 0 0 1II-181 25 5 5 5 5 5 5 5 1 3 2 6.3 5 5 5 5 5 5 4 0 1 1______________________________________

Number	Date	Country
5-180809	Jun 1993	JPX
5-180810	Jun 1993	JPX
5-341772	Dec 1993	JPX

Number	Name	Date	Kind
4465505	Wolf	Aug 1984
4622062	Wexler	Nov 1986

Indazolesulfonylurea derivative, its use and intermediate for its production

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