Isoxazole derivatives having herbicidal action are described, for example, in US-A-5 656 573, EP-A-0 524 018 and EP-A-0 636 622. Novel isoxazole derivatives having herbicidal and growth inhibiting properties have now been found.

Accordingly, the present invention relates to compounds of formula I wherein Z is S, SO or S02; R, is hydrogen, C1-C8alkyl or C,-C8alkyl substituted by halogen, C,-C4alkoxy, C,-C4alkylthio, hydroxy,cyano,nitro,-CHO,-CO2R2,-CO2R3,-COSR4,C1-C4alkylsulf onyl,C1-C4alkylsulfinyl, -NR5R6, CONR36R37 or by phenyl which in turn may be substituted by C,-C4alkyl, C,-C6halo- alkyl, C,-C4alkoxy, C,-C4haloalkoxy, C2-C6alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyloxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, (C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C4alkylthio)-C1-C4alkyl, NHSO2-phenyl,(C1-C4alkylsuflonyl)-C1-C4alkyl,NHSO2-C1-C4alky l, N(C1-C6alkyl)SO2-C1-C4- alkyl, N (C,-C6alkyl) S02-phenyl, N (C2-C6alkenyl) S02-C,-C4alkyl, N (C2-C6alkenyl)SO2-phenyl, N(C3-C7cycloalkyl)SO2-C1-C4-N(C3-C6alkynyl)SO2-C1-C4alkyl,N( C3-C6alkynyl)SO2-phenyl, alkyl, N (C3-C7cycloalkyl) S02-phenyl, N (phenyl) S02-C,-C4alkyl, N (phenyl) S02-phenyl, OS02- <BR> <BR> C,-C4alkyl, CONR25R26, OS02-C,-C4haloalkyl, OS02-phenyl, C,-C4alkylthio, C,-C4haloalkyl- thio, phenylthio, C,-C4alkylsulfonyl, C,-C4haloalkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl,- (CH2) m-phenyl or by-NR15CO2R27 ; or R, is C2-C8alkenyl or C2-C8alkenyl substituted by halogen, C,-C4alkoxy, C,-C4alkylthio, -CONR32R33,C1-C4alkylsulfonyl,C1-C4alkylsulfinyl, cyano, -CH2R38,-COR39,-CHO, -COS-C1-C4alkyl, -NR34R35 or by phenyl which in turn may be substituted by C1-C4alkyl, C1-C6haloalkyl, C2-C6alkenyl,C3-C6alkynyl,C3-C6alkenyloxy,C1-C4haloalkoxy, <BR> <BR> <BR> <BR> C3-C6alkynyloxy, halogen, nitro, cyano,-COOH, COOC1-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C4alkylthio)-C1-C4alkyl, NHSO2-phenyl,N(C1-C6alkyl)SO2-C1-C4-(C1-C4alkylsulfonyl)-C1- C4alkyl,NHSO2-C1-C4alkyl, alkyl, N(C2-C6alkenyl)SO2-phenyl,N(C2-C6alkenyl)SO2-C1-C4alkyl, N (C3-C6alkynyl) S02-C,-C4alkyl, N (C3-C6alkynyl) SO2-phenyl, N (C3-C7cycloalkyl)SO2-C1-C4- alkyl, N (C3-C7cycloalkyl) S02-phenyl, N (phenyl) SO2-C1-C4alkyl, N (phenyl) S02-phenyl, OS02- OSO2-C1-C4haloalkyl,OSO2-phenyl,C1-C4alkylthio,C1-C4haloalky l-C1-C4alkyl,CONR40R41, thio, phenylthio, C,-C4alkylsulfonyl, C,-C4haloalkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl,- (CH2) p-phenyl or by-NR43C02R42; or R, is C3-C6alkynyl or C3-C6alkynyl substituted by halogen, C1-C4haloalkyl, cyano, -CO2R44 or by phenyl which in turn may be substituted by C1-C4alkyl, C1-C6haloalkyl, C1-C4alkoxy, C3-C6alkynyl,C3-C6alkenyloxy,C3-C6alkynyloxy,halogen,C1-C4ha loalkoxy,C2-C6alkenyl, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C1-C4alkoxy, phenoxy, (C,-C4alkoxy)- C,-C4alkyl, (C,-C4alkylthio)-C,-C4alkyl, (C,-C4alkylsulfinyl)-C,-C4alkyl, (C,-C4alkylsulfonyl)- C1-C4alkyl, NHSO2-C1-C4alkyl, NHSO2-phenyl, N (C,-C6alkyl) S02-C,-C4alkyl, N (C,-C6alkyl)- S02-phenyl, N (C2-C6alkenyl) S02-C,-C4alkyl, N (C2-C6alkenyl)SO2-phenyl, N (C3-C6alkynyl)- SO2-C1-C4alkyl, N(C3-C7cyclo-N(C3-C7cycloalkyl)SO2-C1-C4alkyl, alkyl)SO20-phenyl, OSO2-C1-C4alkyl,N(phenyl)SO2-phenyl, CONR28R29, C1-C4alkylthio,C1-C4haloalkylthio,phenyl-OSO2-phenyl, thio, C,-C4alkylsulfonyl, C,-C4haloalkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4halo- alkylsulfinyl, phenylsulfinyl,-(CH2) x-phenyl(CH2) x-phenyl or by -NR31CO2R30 ; or R, is C3-C7cycloalkyl or C3-C7cycloalkyl substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkyl- thio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl or by phenyl which in turn may be substituted by halogen, nitro, cyano, C,-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, C1-C4alkyl or byCl-C4haloalkyl; or R, is -(CH2)q-C3-C7cycloalkyl, phenyl or phenyl substituted by C,-C4alkyl, C,-C6haloalkyl, C2-C6alkenyl,C3-C6alkynyl,C3-C6alkenyloxy,C3-C6alkynyloxy,C1 -C4alkoxy,C1-C4haloalkoxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, (C,-C4- (C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C4alkyl-alkoxy)-C1-C4alk yl,(C1-C4alkylthio)-C1-C4alkyl, NHSO2-phenyl,N(C1-C6alkyl)SO2-C1-C4alkyl,sufonyl)-C1-C4alkyl ,NHSO2-C1-C4alkyl, N(C2-C6alkenyl)SO2-phenyl,N(C1-C6alkyl)SO2-phenyl,N(C2-C6alk enyl)SO2-C1-C4alkyl, N (C3-C6alkynyl) S02-C,-C4alkyl, N (C3-C6alkynyl)SO2-phenyl, N (C3-C7cycloalkyl) SO2-C,-C4- alkyl, N (C3-C7cycioalkyl) S02-phenyl, N (phenyl) S02-C,-C4alkyl, N (phenyl) SO2-phenyl, OS02- <BR> <BR> <BR> C,-C4alkyl, CONR45R46, OS02-C,-C4haloalkyl, OS02-phenyl, C,-C4alkylthio, C,-C4haloalkyl- thio, C1-C4haloalkylsulfonyl,phenylsulfonyl,C1-C4alkylsulfinyl,C1- C4alkylsulfonyl, orby-NR48CO2R47;C1-C4haloalkylsulfinyl,phenylsulfinyl or R, is -(CH2)s-phenyl, COR7 or 4-to 6-membered heterocyclyl; R2, R38, R44 and R66 are each independently of the others hydrogen, C1-C4alkyl, phenyl or phenyl substituted C1-C6haloalkyl,C1-C4alkoxy,C1-C4haloalkoxy,C2-C6-C1-C4alkyl, alkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano,-COOH, C1-C4alkoxy,phenoxy,(C1-C4alkoxy)-C1-C4alkyl,(C1-C4alkyl-COO CC1-C4alkyl,COOphenyl, <BR> <BR> <BR> thio)-C,-C4alkyl, (C,-C4alkylsulfinyl)-C,-C4alkyl, (C,-C4alkylsulfonyl)-C,-C4alkyl, NHS02-C,-C4- alkyl, NHS02-phenyl, N (C1-C6alkyl)SO2-C1-C4alklyl, N (C,-C6alkyl) S02-phenyl, N (C2-C6- alkenyl)SO2-C1-C4alkyl, N(C3-C6alkynyl)SO2-C1-C4alkyl, N(C3-C7cycloalkyl)SO2-N(C3-C6alkylnyl)SO2-phenyl,N(C3-C7cycl oalkyl)SO2-C1-C4alkyl, phenyl, N (phenyl) S02-C,-C4alkyl, N (phenyl) SO2-phenyl, OSO2-C1-C4alkyl, CONR49R50, C1-C4alkylthio,C1-C4haloalkylthio,phenylthio,C1-C4-OSO2-C1-C 4haloalkyl,OSO2-phenyl, alkylsulfonyl, C,-C4haloalkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkyl- sulfinyl, phenylsulfinyl,- (CH2) t-phenyl or by -NR52CO2R51 ; R3, R39 and R67 are each independently of the others C1-C4alkyl, phenyl or phenyl substi- tuted C1-C6haloalkyl,C1-C4alkoxy,C1-C4haloalkoxy,C2-C6alkenyl,C3-C 6-C1-C4alkyl, alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, (C,-C4alkoxy)-C,-C4alkyl, (C,-C4alkylthio)-C,-C4alkyl, NHSO2-C1-C4alkyl,NHSO2-(C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C 4alkylsulfonyl)-C1-C4alkyl, phenyl, N(C2-C6alkenyl)SO2-C1-C4-N(C1-C6alkyl)SO2-phenyl, alkyl, N(C3-C6alkynyl)SO2-N(C3-C6alkynyl)SO2-C1-C4alkyl, phenyl, N (C3-C7cycloalkyl)SO2-C1-C4alkyl, N (C3-C7cycloalkyl) S02-phenyl, N (phenyl) S02- C,-C4alkyl, N (phenyl) S02-phenyl, OSO2-C1-C4alkyl, CONR53R54, OSO2-C1-C4haloalkyl, <BR> <BR> <BR> OS02-phenyl, C,-C4alkylthio, C,-C4haloalkylthio, phenylthio, C,-C4alkylsulfonyl, C,-C4halo- alkylsulfonyl, phenylsulfonyl, phenylsulfinyl,-(CH2)t-C1-C4haloalkylsulfinyl, phenyl or by -NR56CO2R55 ; R4 is C,-C4alkyl; R5 is hydrogen, C,-C4alkyl, C2-C6alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted C1-C6haloalkyl,C1-C4alkoxy,C1-C4haloalkoxy,C2-C6alkenyl,C3-C 6-C1-C4alkyl, alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, phenoxy,(C1-C4alkoxy)-C1-C4alkyl,(C1-C4alkylthio)-C1-C4alkyl ,COOphenyl,C1-C4alkoxy, NHSO2-C1-C4alkyl,NHSO2-(C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C 4alkylsulfonyl)-C1-C4alkyl, N(C1-C6alkyl)SO2-phenyl,N(C2-C6alkenyl)SO2-C1-C4-phenyl,N(C1 -C6alkyl)SO2-C1-C4alkyl, alkyl, N (C2-C6alkenyl) S02-phenyl, N (C3-C6alkynyl)SO2H, N (C3-C6alkynyl) S02-C,-C4alkyl, N (C3-C6alkynyl) S02-phenyl, N (C3-C7cycloalkyk)SO2H, N (C3-C7cycloalkyl) S02-C,-C4alkyl, N (C3-C7cycloalkyl) S02-phenyl, N (phenyl) SO2-C1-C4alkyl, N (phenyl) S02-phenyl, OSO2-C1-C4- alkyl, OSO2-phenyl,C1-C4alkylthio,C1-C4haloalkylthio,OSO2-C1-C4halo alkyl, phenyithio, phenylsulfonyl,C1-C4alkylsulfinyl,C1-C4haloalkylsulfonyl, C,-C4haloalkylsulfinyl, phenylsulfinyl,- (CH2) u-phenyl or by -NR60CO2R59 ; R6R6is hydrogen, C1-C4alkyl, C2-C6alkenyl, phenylorphenylC3-C7cycloakyl, substituted by C,-C4alkyl, C,-C6haloalkyl, C,-C4alkoxy, C,-C4haloalkoxy, C2-C6alkenyl, C3-C6- alkynyl, C3-C6alkenyloxy, C3-C6alkynyloxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, (C1-C4alkoxy)-C1-C4alkyl, (C1-C4alkylthio)-C1-C4alkyl, NHSO2-C1-C4alkyl,NHSO2-(C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C 4alkylsulfonyl)-C1-C4alkyl, phenyl, N (C,-C6alkyl) S02-C,-C4alkyl, N (C,-C6alkyl) S02-phenyl, N (C2-C6alkenyl)SO2-C1-C4- alkyl, N (C2-C6alkenyl) S02-phenyl, N (C3-C6alkynyl) S02-C,-C4alkyl, N (C3-C6alkynyl)SO2- phenyl, N (C3-C7cycloalkyl)SO2-C1-C4alkyl, N (C3-C7cycloalkyl) S02-phenyl, N (phenyl) S02- <BR> <BR> <BR> C,-C4alkyl, N (phenyl) S02-phenyl, OSO2-C1-C4alkyl, CONR61R62, OSO2-C1-C4haloalkyl,<BR> <BR> <BR> <BR> <BR> OS02-phenyl, C,-C4alkylthio, C,-C4haloalkylthio, phenylthio, C,-C4alkylsulfonyl, C,-C4halo-<BR> <BR> <BR> <BR> <BR> <BR> alkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl, - v-phenyl or by -NR64CO2R63; R7 is phenyl, substituted phenyl, C,-C4alkyl, C,-C4alkoxy or-NR8R9; Re and Rg are each independently of the other C1-C4alkyl, phenyl or phenyl substituted by halogen, nitro, cyano, C1-C4thioalkyl,-CO2R66,-COR67,C1-C4alkyl-C1-C4alkoxy, sulfonyl, C1-C4alkylsulfinyl or by C1-C4haloalkyl ; or R8 and Rg together form a 5-or 6- membered ring which may be interrupted by oxygen, NR65 or by S; Q is C=O or CHOH; C1-C6alkyl,C1-C6alkoxy,C1-C6haloalkyl,C2-C6alkenyl,C2-C6halo alkenyl,C3-C6alkynyl,Ris C2-C6alkoxyalkenyl,C3-C6cycloalkylorC3-C6cycloalkylC3-C6halo alkynyl,C2-C6alkoxyalkynyl, substituted by C1-C4alkyl, C1-C4haloalkyl or by Ci-C4alkoxy; 3-to 6-membered, saturated heterocyclyl; or phenyl which may be substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, nitro,cyano,C1-C4alkylthio,C1-C4alkylsulfonyl,C1-C4alkyl-C1- C4alkoxy,C1-C4hloalkoxy, sulfinyl, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio; Ar is phenyl or phenyl substituted by up to four identical or different substituents selected from halogen, C1-C4haloalkoxy,(C1-C4alkoxy)-C1-C4alkoxy, (C1-C4alkylsulfonyl)-C1-C4alkyl,(C1-C4alkylsulfinyl)-C1-C4al kyl,(C1-C4alkylthio)-C1-C4alkyl, C1-C4haloalkylthio,phenylthiuo,C1-C4alkylsulfonyl,C1-C4haloa lkyl-C1-C4alkyl,C1-C4allkylthio, sulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (C,-C4alkoxy)-C,-C4alkoxy,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, -NR69SO2-C1-C4alkyl,-NR70SO2-phenyl,-NR13SO2-C1-C4alkyl, -NR71R72, C3-C6alkenyloxy, C3-C6alkynyloxy and S(O)n-C1-C4haloalkyl ; it being possible for two adjacent substituents on the aromatic ring, together with the two atoms to which they are bonded, to form a 5-to 7-membered ring; R, 3, R69, R70 and R7, are each independently of the others hydrogen, C1-C6alkyl, C2-C6- alkenyl, C3-Csalkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by C,-C4alkyl, C,-C6halo- alkyl, C,-C4alkoxy, C,-C4haloalkoxy, C2-Csalkenyl, C3-C6alkynyl, C3-C6alkenyloxy, C3-C6- alkynyloxy, halogen, nitro, cyano,-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy, phenoxy, (C1-C4alkylsulfinyl)-C1-C4alkyl,(C1-C4alkylthio)-C1-C4alkyl, NHSO2-phenyl,N(C1-C6alkyl)SO2-C1-C4-(C1-C4alkylsulfonyl)-C1- C4alkyl,NHSO2-C1-C4alkyl, alkyl, N (C,-C6alkyl) SO2-phenyl, N (C2-C6alkenyl) S02-C,-C4alkyl, N (C2-C6alkenyl) S02-phenyl, N(C3-C7cyloalkyl)SO2-C1-C4-N(C3-C6alkynyl)SO2-C1-C4alkyl,N(C 3-C6alkynyl)SO2-phenyl, alkyl, N (C3-C7cycloalkyl)SO2-phenyl, N (phenyl) S02-C,-C4alkyl, N (phenyl) S02-phenyl, OS02- <BR> <BR> <BR> C,-C4alkyl, CONR77R78, OS02-C,-C4haloalkyl, OS02-phenyl, C,-C4alkylthio, C,-C4haloalkyl- thio, phenylthio, C,-C4alkylsulfonyl, C,-C4haloalkylsulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl,- (CH2) u-phenyl or by -NR80CO2R79 ; R72 is-COOH, COOC,-C4alkyl, COOphenyl, C,-C4alkoxy or phenoxy, or COOphenyl or phenoxy each substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4halo- alkoxy, C,-C4alkylthio, nitro, cyano, phenoxy, halo-substituted phenoxy, phenylthio or by halo-substituted phenylthio; R15, R31, R43, R48, R52, R56, R60, R64, R68, and R80 are each independently of the others hydrogen, C,-C4alkyl, C2-C6alkenyl, C3-C6alkynyl or C3-C7cycloalkyl; n is 0,1 or 2; m, p, q, s, t, u, v and x are each independently of the others 1,2,3 or 4; R25, R26, R27, R28, R29, R30, R32, R33, R34, R35, R40, R41, R42, R45, R46, R47, R49, R50, R51, R53, R54, R55, R57, R61,R62,R63,R65,R77,R78,andR79,arehydrogen,C1-C4alkyl,C2-C6- R59, alkenyl, C3-C6alkynyl, C3-C7cycloalkyl, phenyl or phenyl substituted by halogen, nitro, cyano, C1-C4alkylthio,C1-C4haloalkylthio,C1-C4alkylorbyC1-C4halo-C1 -C4alkoxy,C1-C4haloalkoxy, alkyl; and agronomically acceptable salts of those compounds.

The alkyl groups that appear in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono-or poly-unsaturated.

Halogen is generally fluorine, chlorine, bromine or iodine. The same applies also to halogen in connection with other meanings, such as haloalkyl or halophenyl.

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

As haloalkenyl there come into consideration alkenyl groups mono-or poly-substituted by halogen, halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl and 4,4,4-trifluoro-but-2-en- 1-yl. Of the C3-C20alkenyl groups mono-, di-or tri-substituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

As haloalkynyl there come into consideration, for example, alkynyl groups mono-or poly- substituted by halogen, halogen being bromine, iodine and, especially, fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of the alkynyl groups mono-or poly-substituted by halogen, preference is given to those having a chain length of from 3 to 5 carbon atoms.

Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy. Alkyl- carbonyl is preferably acetyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy- carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxy- carbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.

Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methyjthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl- thio or tert-butylthio, preferably methylthio and ethylthio. Alkylsulfinyl is, for example, methyl- sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methyl- sulfonyl or ethylsulfonyl. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxy- propoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy. Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine. Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n- propylmethylamino, dibutylamino and diisopropylamino. Preference is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have from 1 to 8 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or iso- propoxyethyl. Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms. Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propyl- thiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butyl- thioethyl or butylthiobutyl. The cycloalkyl groups preferably have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Phenyl (also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzol, phenylthio, phenylalkyl or phenoxyalkyl) may be substituted. The substituents may be in the ortho-, meta-and/or para-position. Preferred positions for the substituents are the ortho-and para-positions with respect to the ring linkage site. Heterocyclyl is to be understood as meaning ring systems which contain, in addition to carbon atoms, at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Heterocyclyl ring systems within the scope of the present invention may also be substituted. Examples of suitable substituents are C,-C4alkyl, C,-C4haloalkyl, C,-C4- alkoxy, cyano, nitro, C,-C4alkylsulfonyl, C,-C4alkylsulfinyl, C,-C4alkylthio and C3-C6cyclo- alkyl. When the substituent Ar is heterocyclyl, two adjacent substituents on the heterocyclyl may form a 5-to 7-membered ring which may be substituted by C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, cyano, nitro, C,-C4alkylsulfonyl, C,-C4alkylsulfinyl, C,-C4alkylthio or by C3-C6- cycloalkyl.

Heterocyclyl may be, for example, furyl, thiophenyl, pyrrolidyl, piperidinyl, morpholinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, thiazolyl, pyrazolyl, 1,2,4-triazolyl, 1,2,3-triazolyl, tetrazolyl, pyrimidyl, pyrazinyl, symmetrical or asymmetrical triazinyl, piperazinyl, oxazolinyl (for example: oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl, oxetanyl, especially 2-oxetanyl, or phthalimidyl.

The invention also includes the salts which the compounds of formula I are capable of forming especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Of the alkali metal and alkaline earth metal bases, special mention is to be made, as salt-forming agents, of the hydroxides of lithium, sodium, potassium, magne- sium and calcium, especially those of sodium and potassium. There come into consider- ation as examples of amines suitable for the formation of ammonium salts both ammonia and primary, secondary and tertiary C,-C, 8alkylamines, C,-C4hydroxyalkylamines and C2-C4- alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecytamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl- nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl- heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethyl- amine, di-n-propylamine, di-isopropylamine, di-n-butylamine, di-n-amylamine, di-isoamyl- amine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso- propanolamine, N, N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allyl- amine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2- amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propyl- amine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amyl- amine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m-and p-toluidines, phenylenediamines, naphthylamines and o-, m-and p-chloroanilines; but especially triethylamine, isopropylamine and di-isopropylamine. Examples of quaternary ammonium bases suitable for the formation of salts are [N (Ra Rb R c R d)] + OH, wherein Ra, Rb, Ré and Rd are each independently of the others C,-C4alkyl. Further suitable tetraalkyl- ammonium bases containing different anions can be obtained, for example, by anion exchange reactions.

Preferred compounds of formula I are those wherein Ar is a group wherein R8"R82, R83, R84, R85, R86, R87 and R88 are each independently of the others hydrogen, halogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, C,-C4haloalkoxy, (C,-C4alkoxy)- <BR> <BR> C,-C4alkyl, (C,-C4alkylthio)-C,-C4alkyl, (C,-C4alkylsulfonyl)-C,-C4alkyl, (C-C4alkylsulfinyl)-<BR> <BR> C,-C4alkyl, C,-C4alkylthio, C,-C4haloalkylthio, phenylthio, C1-C4alkylsulfonyl, C1-C4haloalkyl- sulfonyl, phenylsulfonyl, C,-C4alkylsulfinyl, C,-C4haloalkylsulfinyl, phenylsulfinyl, nitro, cyano, (C,-C4alkoxy)-Ci-C4alkoxy,-COOH, COOC,-C4alkyl, COOphenyl, phenoxy, -C(=NOR68),-NR70SO2-phenyl,-NR71R72,C3-C6--NR69SO2-C1-C4alky l, alkenyloxy, C3-C6alkynyloxy or S (O) n-C,-C4haloalkyl;<BR> Xi, X2, X3, X4, Yi, Y2, Y3 and Y4 are each independently of the others 0, S, SO, S02, NR89, C=O, C=N-O-C1-C4alkyl, -C=N-O-C1-C4alkenyl, CR19-O-C1-C4alkyl or CRsoR20; R89 is hydrogen, C1-C4alkyl, C3-C6alkenyl, C3-C6alkylnyl or C3-C7cycloalkyl; Rig, R2o and Rgo are each independently of the others hydrogen or Ci-C4alkyl.

Preference is given also to those compounds of formula I wherein R is cyclopropyl, 1- methylcyclopropyl, tert-butyl or isopropyl.

Special preference is given to compounds of formula I wherein Q is C=O. Special mention is also to be made of compounds of formula I wherein Z is sulfur or SO.

Also of special importance are those compounds of formula I wherein R1 is hydrogen, C1-C4alkyl, C,-C4alkyl substituted by halogen, methoxy, ethoxy, cyano or by COOR2, or C3-C6alkenyl or halo-substituted C3-C6alkenyl, or C3-C6alkynyl.

Compounds of formula I can be prepared by various methods which are known per se: Preparation method 1: Scheme 1: Tx/base R T-S S-R CH2 T ll 2) alkylating agent ll Ar-COOR4 T Ar or (i) Ar T Ar-COCI PIV Plll Pll NH20H R-M _IASR (M e. g. = Mg-Hal or Li) T S-R N Ar ol Ar Y (4) Ix (T=T1 = COR) Pi (T= T2) T1,T2T= T1 = COR T2 = CN, CON (CH3)-OCH3 Tx = hydrogen, COOH or COO-C,-C4alkyl M = metal ion such as Mg (II), Zn (II), Cd (II), Li (l), K (l) Reaction step (1): Benzoic acid esters or acid chlorides are condensed with a keto compound Tx-CH2-T (T=T1=COR) or with a methylnitrile (T2=CN) or with an acetamide (T2=CON (CH3)-OCH3), in the presence of a base, such as NaH, in accordance with known methods in an inert solvent at from-100 to +100°C to form keto derivatives Poil.

Both the keto compound that is used and the nitrile may carry on the a-carbon atom an addition carboxyl or alkoxycarbonyl group Tx suitable for condensation. When Tx is COO-C,-C4alkyl, hydrolysis and decarboxylation can be carried out once the acylation is complete. Where an acid chloride ArCOCI is used, it may suitably be used with, for example, BuLi as the base at from-60 to-80°C and tetrahydrofuran as the solvent (Synthesis 1983,308; Synthesis 1984,1; J. Org. Chem. 54,4229; US 5 545 762; US 5 656 373).

Reaction step (2): The keto compound Plil is then reacted with carbon disulfide in the presence of a base, such as NaH, an alkali alkanolate (e. g. NaOEt) or an alkali carbonate, e. g. potassium carbonate, or a fluoride salt (e. g. KF) that is free or bonded, for example, to aluminium oxide, in an inert solvent at from-20 to +80°C and alkylated using an alkylating agent R,-XP1, wherein R, is as defined above and XP1 is Hal (Cl, Br, I) or OS (O) OR,, to form the ketene dithioacetal Pli (Chem. Ber. 95,2861, Z. Chem. 16,397,1976).

Reaction step (3): Cyclisation is then carried out with hydroxylamine or its hydrochloride, if desired with the addition of an alkali acetate in an inert solvent at from-20 to +120°C to form the isoxazoles of formula Ix (T=T1=COR) or PI (T=T2=CN or CON (CH3) OCH3) (J. fur prakt. Ch. 320,585).

The intermediates of formula Pi are novel and have been developed especially for the preparation of the compounds of formula 1, and the present invention therefore relates also thereto.

Reaction step (4): If the cyano-or amide-substituted isoxazoles are obtained in the cyclisation (step 3), they are subsequently reacted at from-120° to +40°C in an inert solvent, such as hexane, an ether, THF, (if required after transmetallation to, for example, potassium, zinc or cadmium salts) with Grignard (RMgHal)-or alkyl lithium (RLi) to form the compound of formula ly (J.

Het. Chem. 12,413; Tetrahedr. 31,499 (1975)).

Preparation method 2: 0 Ar Au Plll HN HNP'EG E11 (5) P2 N.H N,- N air 2s N-, Pl Piva PlVb t T , IAXT/PV PV air PVI 8) 1 HS-R1 acid acceptor 0 R-M T S-R AN 1 (M e. g. = Mg-Hal or Li) (T=T2) Ar N N Ix (T= COR) Y PI (T= T1) T=T1, T2 T1 = COR T2 = CN, CON (Me)-OCH3 M =metal ion such as Cd(II),Li(I),K(I)Zn(II), E, G = Hal (Cl, Br. I) or -SR1 Reaction steps (6) and (7) : In the manner indicated in Preparation Method 2, an aryl ketone Plil (prepared according to Scheme 1) can also be reacted either directly (Reaction step 6) or via an enamine PVI (Reaction step 7) with dihaloformaldehyde oximes (E=G=Hal) or their dithio derivatives (E=G=SR,; PVla) or their nitrile oxides (PVlb), with or without the addition of a base, such as a tertiary amine (e. g. NEt3), in inert solvents at temperatures of from-20° to +160°C, to form isoxazoles of formula I or PV (EP-A-0 503 410; EP-A-0 524 018; Heterocycles 34, 1703).

Reaction step (8): Intermediates PV wherein E is halogen can then be converted, by reaction with mercaptans HSRI, preferably in the presence of an acid acceptor (e. g. bases such as tertiary amines or oxiranes such as propylene oxide) in inert solvents at temperatures of from-20 to 150°C, into the products Ix or PI already obtainable according to Scheme 1.

It is also possible to carry out the reaction of PVa according to Chem. Pharm. Bull. 27, 2398; ibid. 2415. In that case, PVa (E=Hal) is converted using an alkylating agent R,-XP1 into an intermediate PVla which is quaternised at the nitrogen; that intermediate is substituted under the above-mentioned conditions by a mercaptan HSR, in the presence of an acid acceptor to form the quaternised thioether PVllb, and the latter is converted by heating at from 60 to 220°C, with the removal of R,-XP1, into the products of formula Ix or Pi. T CI T CI T S-R T S-R Rl-xpl. N N-RN-R iN 1 Ar Ar acid Ar 0'1-R Xpl Ar 0" XP1-acceptor XP1 PVa PVIa PVllb Ix (T= CO-R) Pi(T=T1) Intermediates of formula P) Va wherein E and G are halogen or S-Ri, but E and G are not simultaneously halogen, with the exception of those compounds wherein E and G are methylthio, ethylthio or benzylthio, and the intermediates of formulae PVIa and PVllb wherein Ar and R, are as defined for formula 1, T is CO-R wherein R is as defined for formula I and XP1 is halogen, are novel and have been developed especially for the preparation of the compounds of formula 1, and the present invention therefore relates also thereto.

Reaction step (5): Some enamines PVI are known (US-A-5 656 573, EP-A-0 625 505), or they are prepared according to methods known per se, for example by reaction of a keto compound Plil with a secondary amine HN (P,) P2 wherein HN (PI) P2 is an open-chained or cyclic compound such as HNEt2, pyrrolidine or morpholine, in the presence of an acid catalyst (acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins, such as Amberlyst IRA 400) and of an inert solvent, with removal of the water of reaction that forms (molecular sieve, azeotropic distillation) at temperatures of from 40 to 200°C (Tetrahedron Letters 1988,3997).

According to other variants (scheme below), enamines PVI are obtainable either (Reaction step 5a) by reacting enamines of formula PVIII with acid chlorides RCO-CI (T=T1=COR) in the presence of a base at from-30 to +80°C (US-A-5 656 573), or (Reaction step 5b) by the addition of secondary amines HN (P,) P2 (wherein HN (Pi) P2 may be open-chain or cyclic, such as HNEt2, pyrrolidine or morpholine) to acetylenes PIX: Starting materials (PIX) required therefor are in some cases known, or they can be prepared according to known methods, for example by synthesis by means of the Heck reaction of <BR> <BR> Ar-P3, wherein Ar is as defined above and P3 is halogen (Cl, Br, I), or OS02-perfluoroalkyl, such as OS02CF3, with protected acetylenes wherein Pg is a protecting group, such as Si (alkyl) 3, C (Me) 2OH, Sn (alkyl) 3, in the presence of a palladium catalyst, such as Pd (Ph3P) 4 or Pd (Ph3P) 2CI2 or Pd (OAc) 2 and Cul, and of an amine (e. g. HNEt2) at from 0 to 120°C in an inert solvent (Org. React. 27, 345; Synlett 1995,1115; WO 96/26193) to form a compound of formula PX, and subse- quent introduction of an acyl group CO-R, for example by means of a Grignard reaction, to a nitrile R-CN, or by acylation of a trialkyltin acetylide prepared as indicated above, in the presence of a palladium catalyst, such as Pd (Ph3P) 2C12 (Heterocycles 41,817 (1995); Org.

React. 50,1 (1997)) with an acid halide R-COCI: Preparation method 3: Analogously to Gazz. Chim. Ital. 91,47 (1961), 4-H-substituted isoxazoles PXla (E=Hal) or PXlb (E=S-R,) can be prepared from aryl-acetylenes PXa by metallation to corresponding Grignard or lithium compounds and direct reaction with dihalo-or dithio-formaldehyde oximes PIVa, with or without the addition of a base (e. g. NaH, tertiary amine). Gentle deprotonisation, for example with a lithium base at from-30 to-120°C, and reaction with an acid chloride RCO-CI yield the compounds of formula 1. If a suitable tin compound (e. g.

(R4) 3-SnCI) is used as the electrophile instead of an acid chloride 4-stannyl compounds XII are obtained, which can likewise be reacted with acid chlorides RCO-CI analogously to Heterocycles 43,1301 (1996) in the presence of palladium catalysts (e. g. Pd (Ph3P) 2CI2) to form the compound of formula 1.

1) metallation (e. g. BuLi) -120 to-30°C H EG H G H SR N, OH HSR,/base N bo N Ar 0 (G=Hal) Ar ol Ar o 0 PXa PXIa: G=Hal PXlb PXlb: G= SR1 1) BuLi 2) RCOCI 2) (R4) 3SnCl O + S-R RCOCI/Pd cat. (R4) 3Sn S-R 1 if required + Cul + P (Ph) 3 3 H - \\ Ar 0 0-160° C Ar O PXII Preparation method 4: Analogously to other methods of synthesis known from the literature (e. g. J. Org. Chem. 48, 1796 (1983); ibid. 45,2945, (1980); Tetrahedron 40,601 (1984); A. Katritzky, C. Rees, Compendium of Het. Chem. Vol. 6, p. 2 ff., Oxford 1984; Houben Weyl Vol. E8 a, p. 45 ff.), the compounds of formula I can be prepared also by the direct addition of nitrile oxides PIVb to unsaturated ketones of formula PIX (alkynes) or PXIII (alkenes) in accor- dance with the following scheme: SR, (Q-NCO (PXIV) tertiary N e ia'y S (O) NR '". ( oxidisingagent.. N Au e. g. with R I (PlVb) m-CPBA R SR base (e. g. s \ tertiary amine) catalyst if required/ !. i Ar (2) R S (O) nR 1 PIX Iz Hal N (KUb) Ar PO sR. t \ SR obdising agent (PIVb) PXVII e. g. Mn02 base e. g. selective tertiary amine oxidation O Ar PXV catalyst if required (4) RX SR1 Rt SR1 'Hal - Ar O (6) Ar O Au 0' PXVI PXVIII Examples of suitable oxidising agents for the selective oxidation of the compound of formula PXVIII to the compound of formula KUb, wherein Ar, R and R, are as defined for formula 1, n is 1 or 2 and'Hal is halogen, preferably chlorine or bromine, are metachloroper- benzoic acid, sodium perborate and tetrabutylammonium perruthenate. The compound of formula KUb is novel and has been developed especially for the preparation of the compounds of formula 1, and the present invention relates also thereto.

Reaction steps (1 ! (2) and (4): Alkyl-or aryl-thiomethyinitromethane derivatives of formula PXIII obtainable according to known methods (e. g. J. Org. Chem. 53,5369 (1988)) are converted into the corresponding nitrile oxides PlVb in the presence of a dehydrating agent, for example an isocyanate of formula PXIV, and of a base, for example a tertiary amine (e. g. triethylamine), in an inert solvent, such as cyclohexane, toluene, benzene, or halogenated solvents, such as dichloro- methane, and reacted with an alkyne PIX or an alkene PXV, if required in the presence of a catalyst, at temperatures of from-20°C to +80°C to form the isoxazole derivatives of formula I or the isoxazolines of formula PXVI, respectively.

The cyclisation is preferably carried out without isolation of the intermediates in a one-pot reaction in one of the mentioned solvents. Examples of suitable catalysts are Lewis acids, such as Ti (IV) salts, such as Ti (OisoPr) 4 (J. Am. Chem. Soc. 118,59; ibid. 111,5340; J. Org. Chem. 59,5687), or complexes such as Ti (OTs) 2 (TADDOL) (Helv. 77,2071); or Eu (fod) 3 (= tris 5-octanate-dionato) europium (lll)) (Heterocycles 46,95), and lanthanide complexes such as Yb (OTf) 3 (Chem. Lett. 1997, 1039).

Reaction step (5): Isoxazolines of formula PXVI can be converted into the end products of formula Iz accor- ding to methods known per se by means of aromatising oxidising agents such as, for example, Mn02 (Synthesis 1976,133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.

Reaction steps (6) and (7) : According to a further variant, the isoxazolines are first converted into the corresponding halides (preferably chlorine or bromine derivatives) PXVIII by means of a halogenating agent, such as Br2, Cri2, N-bromosuccinimide, if required with the addition of a radical initiator, such as dibenzoyl peroxide, in an inert solvent, for example carbon tetrachloride or a sulfochloride, such as thionyl chloride or trifluoromethane sulfochloride, and the halides are then reacted with a base (preferably a tertiary amine, such as triethylamine or DBU (1,8- diazabicyclo- (5.4.0)-undec-7-ene)) in an inert solvent, such as dichloromethane, at from -20°C to +80°C to form the products of formula 1. The halogenation and the subsequent reaction to form the compound of formula Iz are preferably carried out in the same reaction vessel.

Reaction step (3): The oxidation of the isoxazoles of formula Iz to the corresponding sulfoxides of formula Iw (formula I n=1) or sulfones (n=2) can be carried out, for example, analogously to WO 97/43270 using 1 or 2 equivalents of an oxidising agent such as m-chloroperbenzoic acid in an inert solvent, for example dichloromethane, at temperatures of from-20°C to +100°C.

Isoxazolines of formulae PXVI and PXVIII, wherein Ar, R and R, are as defined for formula I and'Hal is halogen, preferably chlorine or bromine, are novel and, as intermediates, the present invention relates also thereto. The compounds of formulae PXVI and PXVIII have herbicidal activity.

Startinq materials (Details regarding acetylene ketones of formula PIX are given above.) Enones of formula PXV are either known or can be prepared according to known methods, for example by Wittig or Wittig-Horner condensation of an aldehyde of formula PXXI with a phosphorane PXX obtained from a halide PXIX, in an inert solvent, such as tetrahydrofuran, dioxane or acetonitrile, at temperatures of from 20°C to 160°C (analogously to Tetrahedron Lett. 1974,2491, scheme below). According to another process, enones of formula PXV are obtainable by condensation of aldehydes of formula PXXI with a methyl ketone of formula XXII T-CH3 (XXII) or with an activated keto ester XXIII T-CH2-COOalkyl (XXIII), in the presence of a bifunctional catalyst, such as ammonium acetate, a pyridine/piperidine mixture (analogously to Synthesis 1980,806), an alkali fluoride (KF, Synthesis 1983,173), and subsequent removal of the activating group (customary hydrolysis and decarboxylation (-COOalkyl) in the case of a 1,3-keto ester). Ph ) P (Ph) 3 I Pu "-Ph 2)base t PXX PXIX (Hal = Cl, Br, I) Ar-CHO (PXXI) Ar-COR PXV A further process for the preparation of unsaturated ketones of formula PXV comprises the Heck reaction of an aryl halide of formula PXXllla Ar-Hal (Hal = Cl, Br, I) (PXXllla) or of a trifluoromethylsulfonate PXXlllb Ar-OTf (PXXlllb) with an unsaturated vinyl ketone PXXIV in the presence of a palladium catalyst, for example Pd (OAc) 2, and of a base, such as triethylamine, in an inert solvent, such as acetonitrile or N, N-dimethylformamide, at temperatures of from 0°C to 180°C (analogously to R. Heck in Org. React. 27,345 ff (1982)).

The arylaldehydes (PXXI) required for the above-mentioned condensation reactions are either known or can be prepared according to known methods, for example by catalytic reduction of appropriate carboxylic acid halides according to Rosenmund or an analogous variant in the presence of a catalyst, for example Pd/BaS04, and of a pyridine base, such as lutidine.

According to a further variant, known carboxylic acid esters (US-A-5 656 573, EP-A-0 625 505) of the formula Ar COOalkyl can be reduced by means of complex hydrides, for example NaBH4, in a short-chain aliphatic alcohol as solvent (for example analogously to Angew. 92,1067 (1980)) to form the primary alcohol PXXV Ar-CH20H (PXXV) and then oxidised with an oxidising agent, such as cerium (IV)-ammonium nitrate (J. prakt.

Chem. 336,470 (1994)) or phenyl dichlorophosphate/DMSO/NEt3 (J. Org. Chem. 59,7704 (1994)) or oxalyl chloride/DMSO (Synth. 1990,857), to the aldehyde PXXI Ar-CHO (PXXI).

Preparation method 5: Finally, the isoxazoles of formula I are also obtainable from the dihaloformaldoximes P) Va, as shown below, by means of addition to olefins PXV via isoxazolines of formula PXVI. In that reaction, the 3-halo-isoxazoline of formula PXVII may also be isolated. To that end, in reaction step (1) there are added to the olefin PXV in an inert solvent, such as 1,2- dimethoxyethane, at a temperature of from 0°C to +60°C, a base, for example an alkali hydrogen carbonate, as well as a small amount of water and the oxime P) Va and then the thiolate R, SM, is introduced in small portions over a prolonged period of about from 1 to 6 hours. Han han 0 il Hal lial HA HO if required and Ar R SMr/base Ar O Ar O ( PXV PXVII sélective R S (O) NR oxidation N (KUa) Ar N O base (e. g. tertiary amine) P"n R SR n R SR AXo/N oxidising agent o) ddising agent N N iror 0 halogenating agent base Iz M, is an alkali metal, preferably lithium. Examples of suitable oxidising agents for the selective oxidation of the compound of formula PXVI to the compound of formula KUa, wherein Ar, R and R, are as defined for formula I and n is 1 or 2, are metachloroperbenzoic acid, sodium perborate and tetrabutylammonium perruthenate. The compound of formula KUa is novel and has been developed especially for the preparation of the compounds of formula 1, and the present invention relates also thereto.

Other starting materials: Dihaloformaldehyde oximes and dithioalkylformaldehyde oximes of formula P) Va are known or can be prepared according to known methods, for example Chem. Ber. 43,3362; Synth.

Comm. 12,601 or according to CH-A-563 967, Chem. and Industry 1979,826.

Dithio-substituted formaldehyde oximes can also be obtained from the dihalo compounds and appropriate thiols in the presence of a base.

Substituted aryl derivatives (Ar-P3, Ar-COOR4) are for the most part also known or can be prepared according to known methods (as described, for example, in US-A-5 658 858, US-A-5 656 573, EP-A-0 524 018, EP-A-0 527 037, EP-A-0 609 797, EP-A-0 588 357, WO 97/19076, WO 97/09324, WO 97/09327, WO 97/19071, WO 96/26192, EP-A-0 768 033, WO 96/26206, WO 97/12885, WO 96/26200 and US-A-0 5 607 898).

The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N, N-dimethylformamide, diethylformamide or N- methylpyrrolidinone. The reaction temperatures are preferably from-20°C to +120°C. The reactions are generally slightly exothermic and can usually be carried out at room tempera- ture. In order to shorten the reaction time or to initiate the reaction, the reaction mixture may if required be heated for a short time up to its boiling point. The reaction times may also be shortened by adding a few drops of a base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diaza- bicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] non-5-ene or 1,5-diazabicyclo [5.4.0] undec-7- ene. However, it is also possible to use as bases inorganic bases, for example hydrides, such as sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate. The compounds of formula I may be isolated in customary manner by concentration and/or evaporation of the solvent, and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.

For the use, according to the invention, of the compounds of formula I or of compositions comprising them there come into consideration any methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose, a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, a coating may addition be applied (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.

The compounds of formula I may be used as herbicides in unmodified form, i. e. as they are formed in the synthesis. Preferably, however, they are processed in customary manner together with the adjuvants conventionally employed in formulation technology e. g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wet- table powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485, pages 9 to 13. As with the nature of the compo- sitions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i. e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and generally one or more solid or liquid formulation adjuvants, are prepared in known manner, e. g. by homoge- neously mixing and/or grinding the active ingredients with the formulation adjuvants, e. g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97/34485, page 6.

Depending on the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97/34485, pages 7 and 8.

Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, interalia, in"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, MunichNienna, 1981, and M. and J. Ash,"Encyclopedia of Surfactants", Vol. 1-111, Chemical Publishing Co., New York, 1980-1981.

The herbicidal formulations usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise other auxiliaries, such as stabilisers, e. g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e. g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients.

The compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the type of action, on the stage of development of the cultivated plant and of the weed, and also on the application (place, time, method) and, in dependence on those parameters, may vary within wide limits.

The compounds of formula I are distinguished by herbicidal and growth inhibiting properties, which render them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, as well as for non-selective weed control. Crops are also to be understood as meaning crops that have been rendered tolerant to herbicides or classes of herbicide by conventional cultivation or genetic engineering methods. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The Examples which follow further illustrate, but do not limit, the invention.

Preparation Examples: Example P1: Preparation of dithiomethylformaldehyde oxime: A solution of 2.03 g of dibromoformaldehyde oxime in 10 ml of anhydrous tetrahydrofuran is <BR> <BR> <BR> added dropwise at room temperature to a stirred suspension of 1.4 g of sodium methane- thiolate in 15 mi of tetrahydrofuran, and stirring is carried out for 16 hours. The reaction mixture is then poured into ice-water, adjusted to pH 5 by the addition of 1 N HCI and extracted with ethyl acetate, and the extracts are then dried over sodium sulfate, filtered and concentrated by evaporation in vacuo. The yellow residue that remains is filtered over silica gel (hexane/ethyl acetate 8: 2). Dithiomethylformaldehyde oxime having a melting point of 71-73°C is obtained.

Example P2: Preparation of 2-chloro-4-trifluoromethylbenzoic acid ethyl ester by carbonylation: 68.3 mg of palladium acetate, 125.5 mg of 1,1-bis (diphenylphosphino) ferrocene and 1.87 ml of triethylamine which has been dried over KOH are added to 2.0 g of 3-chloro-4-tri- fluorosulfonyloxy benzotrifluoride in an autoclave in a mixture of 25 ml of DMF and 10 ml of ethanol, and the mixture is then heated overnight (about 20 hours) at 82°C in the presence of carbon monoxide, the carbon monoxide pressure being 8 bar. The mixture is then concentrated by evaporation in vacuo, and the residue is partitioned between ethyl acetate and water; the organic extract is washed with saturated sodium chloride solution, dried over sodium sulfate and filtered, and concentration by evaporation is carried out. The residue (1.1 g), which according to NMR is already pure, is rapidly distilled in a bulb tube, yielding a virtually colourless oil having a refractive index (nD20) of 1.4664.

Example 3: Preparation of 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester: A solution of 1.27 g of 2-chloro-4-trifluoromethyl-benzoic acid ethyl ester in 3.5 ml of DMF is <BR> <BR> <BR> added at room temperature to a suspension of 0.39 g of sodium ethanethiolate in 3 ml of DMF, and the mixture is heated for 4 hours at a temperature of 50°C. The reaction mixture is then cooled, poured into ice-water and extracted with toluene; the extracts are washed with water and dried. Filtration over a small amount of silica gel and concentration by evaporation in vacuo yield 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester having a refractive index (nD20) of 1.5052 in a yield of 85 % of the theoretical yield.

Example P4: Preparation of 2- luoromethvl)-benzoylacetonitrile: Under a nitrogen atmosphere and with stirring, 54 mg of acetonitrile are added at a temperature of 0°C to 87 mg of sodium hydride (60 % dispersion in oil) in 3 ml of dimethyl sulfoxide, and stirring is carried out for 10 minutes. 264 mg of 2-methylthio-4-trifluoromethyl- benzoic acid ethyl ester are then added, and the reaction mixture is stirred for a further 4 hours at a temperature of 20°C, whereupon dissolution takes place. The reaction mixture is then poured into ice-water, acidified with 0.1 N HCI and extracted with ethyl acetate, and the extracts are washed with water and brine. The solid residue that remains after drying and concentration by evaporation is purified on silica gel (hexane/ethyl acetate 9: 1). The 2- (2-methylthio-4-trifluoromethyl)-benzoylacetonitrile so obtained has a melting point of 149-150°C. Example P5: Preparation of 2- (2-methylthio-4-trifluorobenzoyl)-3, 3-dimethvldithio-acrylo- nitrile: To a mixture of 130 mg of 2-methylthio-4-trifluoromethyl-benzoic acid ethyl ester in 2 ml of absolute DMF there are added, under a nitrogen atmosphere and with stirring at a tempera- ture of 0°C, 360 mg of potassium fluoride (40 %) on aluminium oxide and, after stirring for a further 10 minutes, 0.05 ml of carbon disulfide. Stirring is then carried out for 2 hours at a temperature of 0°C; 0.1 ml of methyl iodide is then added and the yellow suspension is stirred for 4 hours at a temperature of 20°C. The solid precipitate is then filtered off, washed <BR> <BR> <BR> <BR> with DMF and concentrated by evaporation in vacuo, and the residue is partitioned between water and dichloromethane. The organic phase is washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. 2- (2-Methyl- thio-4-trifluorobenzoyl)-3, 3-dimethyidithio-acrylonitrile having a melting point of 91-92°C is obtained.

Example P6: Preparation of 5-(2-methylthio-4-trifluoromethylphenyl)-4-cyano-3-methylthi o- isoxazole: 90 mg of 2- (2-methylthio-4-trifluoromethylbenzoyl)-3, 3-dimethyldithio-acrylonitrile are added to a stirred suspension of 27 mg of hydroxylamine hydrochloride and 31 mg of sodium acetate, and stirring is carried out for 6 hours at room temperature. The mixture is then poured into ice-water and extracted with ethyl acetate. The extracts are washed with saturated sodium chloride solution, dried and filtered; a small amount of hexane is added to the filtrate, and filtration is carried out over silica gel. The 5- (2-methylthio-4-trifluoromethyl- phenyl)-4-cyano-3-methylthioisoxazole that remains after concentration by evaporation and drying in vacuo has a melting point of 85-86°C.

Example P7: Preparation of 3-cyclopropyl-2- (methylthio) methylene)-1-(2. 4-dichloro- phenvl)-propane-1.3-dione: 4.9 g (0.019 mol) of 3-cyclopropyl-1- (2, 4-dichlorophenyl)-propane-1,3-dione are dissolved at 20°C in 50 ml of DMF. The clear solution is cooled to-3°C. 17.3 g (0.095 mol) of KF/AI203 (20 %) are then added in portions in the course of 5 minutes. 1.8 ml of CS2 are added dropwise with cooling (0°C), and stirring is carried out for 3 hours at 0°C. 3.4 mi (0.055 mol) of methyl iodide are pipette into the resulting suspension. The mixture is heated to a temperature of 20°C and stirred for 18 hours. When the reaction is complete, excess KF/AtzOs is filtered off and the solvent is distille off in vacuo. The oily residue is subjected to flash chromatography on silica gel with ethyl acetate/hexane (1: 8) as eluant. 2.2 g of 3- cyclopropyl-2-(bis (methylthio) methylene)-1-(2, 4-dichlorophenyl)-propane-1, 3-dione(bis (methylthio) methylene)-1-(2, 4-dichlorophenyl)-propane-1, 3-dione are isolated in the form of a yellow oil.

'H-NMR (CDCI3): 0.9-1.0 (m, 2H); 1.1-1.2 (m, 2H); 2.2-2.4 (m, 1 H); (s, 6H); 7.3 (d, 1 H); 7.4 (s, 1 H); 7.6 (d, 1 H).

Example P8: Preparation of 4-cyciopropylcarbonvl-3-thiomethyl-5-(2 4-dichlorophenyl !- isoxazole: 0.52 g (7.5 mmol) of hydroxylamine hydrochloride and 0.55 g (6.7 mmol) of anhydrous sodium acetate are added to a solution of 2.2 g (6.1 mmol) of 3-cyclopropyl-2- (bis (methyl- thio)-methylene)-1-(2, 4-dichlorophenyl)-propane-1,(2, 4-dichlorophenyl)-propane-1, 3-dione in 50 ml of ethanol. The reaction mixture is stirred for 48 hours at 20°C. Insoluble portions are then filtered off and the filtrate is concentrated to dryness by evaporation. The partially crystalline crude product is pre- purified on silica gel with ethyl acetate/hexane (1: 9) as eluant. The pre-purified product is then chromatographed again by means of preparative HPLC. 60 mg of 4-cyclopropyl- carbonyl-3-thiomethyl-5- (2, 4-dichlorophenyl)-isoxazole are obtained.

M. p.: 105-107°C.

'H-NMR (CDCI3): 0.78-0.83 (m, 2H); 1.18-1.2 (m, 2H); 1.7-1.75 (m, 1H); 2.6 (s, 3H); 7.42-7.46 (dd, 1 H); 7.48-7.51 (d, 1 H); 7.59-7.6 (d, 1 H).

Preparation of the preliminary products: Example P9: Preparation of 1-cyclopropyl-2-triphenylphosphoranylidene-ethanone: A solution of 32.6 g of bromomethyl cyclopropyl ketone in 30 ml of toluene is added dropwise at a temperature of 20°C to a suspension of 52.3 g of triphenylphosphine in 300 ml of toluene, and the reaction mixture is then stirred at the same temperature for 15 hours. Filtration is then carried out, and the precipitate is washed with toluene and taken up in dichloromethane; the solution is washed twice with 2N sodium hydroxide solution, concentrated sodium carbonate solution and concentrated sodium chloride solution. After drying over sodium sulfate, filtration is carried out and the filtrate is then concentrated by evaporation. 1-Cyclopropyl-2-triphenylphosphoranylidene-ethanone having a melting point of 170-172°C is obtained.

Example P10: Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehyde: 8.6 g of phenyl dichlorophosphate are added dropwise at a temperature of-60°C to a<BR> <BR> <BR> suspension of 6 g of 4-hydroxymethyl-2-methylsulfonyl benzotrifluoride, 12.1 g of triethyl- amine and 7.5 g of dimethyl sulfoxide in 120 mi of ethyl acetate, and the mixture is cooled, with stirring, to a temperature of 0°C. After 1.5 hours, 13.5 ml of concentrated hydrochloric acid are added to the brownish suspension, with cooling. After extraction with ethyl acetate and water, the organic extract is washed twice with sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated by evaporation; there remain 5.8 g of unpurified 2-methylsulfonyl-4-trifluoromethyl-benzaldehyde, which is used further in the next reaction step in that form.

The product purified on silica gel (hexane/ethyl acetate) is a white solid having a melting point of 86-88°C. Example P11: Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehyde via catalytic hydroaenation: Hydrogen is introduced at 20°C, under reduced pressure, into a solution of 4.4 g of 2-methylsulfonyl-4-trifluoromethyl-benzoic acid chloride in 80 ml of tetrahydrofuran, with the addition of 1.74 g of 2,6-lutidine and 3.5 g of palladium-BaS04 (5 %), until the reaction is complete. The catalyst is then filtered off, and ethyl acetate is added; the lutidine hydro- chloride that has precipitated is filtered off, and the filtrate is washed with water and concentrated sodium chloride solution, dried and filtered over a small amount of silica gel (hexane/ethyl acetate). 2-Methylsulfonyl-4-trifluoromethyl-benzaldehyde having a melting point of 66-88°C is obtained.

Example P12: Preparation of 1-cyclopropyl-3- (2-methylsulfonyl-4-trifluoromethyl)-phenyl-2- propen-1-one: A solution of 1.26 g of 2-methylsulfonyl-4-trifluoromethylbenzaldehyde and 1.9 g of 1-cyclo- propyl-2-triphenylphosphoranylidene-ethanone in 15 mi of dioxane is stirred for 15 hours overnight under a nitrogen atmosphere at a temperature of 70°C. The mixture is then concentrated by evaporation, digested with ethyl acetate and a small amount of hexane and filtered, and the filtrate is purified over silica gel (hexane/ethyl acetate). 1-Cyclopropyl-3- (2- methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1-one having a melting point of 114-116°C is obtained.

Example P13 : Preparation of methylthiomethvl-nitromethane : A solution of 12.3 ml of nitromethane in 200 ml of chloroform is added dropwise at a <BR> <BR> <BR> temperature of-5°C, in the course of 25 minutes, to a solution of 5.7 g of sodium in 200 ml of absolute methanol, whereupon a white suspension forms. After 30 minutes'stirring at that temperature, a solution of 12.3 mi of nitromethane in 200 ml of chloroform is added to the reaction mixture at a temperature of-5°C, and stirring is carried out for a further 30 minutes. There are then added dropwise in succession, at the same temperature, a solution of 23.5 g of S-methylmethanethiosulfone in 100 ml of chloroform, and 13 ml of concentrated acetic acid, and the mixture is stirred until the reaction is complete. The reaction mixture is then poured into ice-water, the resulting mixture is extracted with chloro- form, and the extracts are washed with water and then dried. After filtration, concentration by evaporation is carried out and the residue is purified on silica gel (hexane/ethyl acetate 7: 3). Methylthiomethyl-nitromethane is obtained in the form of a yellow oil.

Example P14: Preparation of 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methyl- sulfanyl-4,5-dihydro-isoxazol-4-yl-cyclopropyl-methanone: a) via methylthiomethylnitromethane 0.5 ml of triethylamine is added in the course of 15 minutes, with stirring and under a <BR> <BR> <BR> nitrogen atmosphere, at a temperature of 20°C to a solution of 1.59 g of 1-cyclopropyl-3- (2- methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1-one, 0.643 g of methylthiomethyinitro- methane and 1.3 ml of phenyl isocyanate in 40 ml of benzene. Stirring is then carried out for 3 hours at a temperature of 20°C, for one hour at a temperature of 40°C and for 15 hours at a temperature of 20°C. The brownish red suspension is then filtered over a small amount of Hyflo (commercially available) and washed with diethyl ether, and the filtrate is concentrated by evaporation. The residue is filtered first over silica gel (hexane/- ethyl acetate 7: 3) and then purified by means of HPLC chromatography (Lichrospher Si60 12R*m; hexane/ethyl acetate 9: 1 with increasing gradients in respect of the more polar <BR> <BR> <BR> <BR> component). 0.50 g of 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 190 to 191 °C is obtained. b) via dibromoformaidehyde oxime 2.2 g of potassium hydrogen carbonate and 10 drops of water are added, with stirring, to a solution of 1.59 g of 1-cyclopropyl-3-(2-methylsulfonyl-4-trifluoromethyl)-phenyl- 2-propen-1- one in 25 ml of 1,2-dimethoxyethane. There are then introduced at hourly intervals a total of 425 mg of dibromoformaldehyde oxime and, at the same time, 158 mg of sodium methane- thiolate, and the yellowish suspension is stirred for 15 hours at a temperature of 20°C.

Filtration over Hyflo and intensive washing with dimethoxyethane are then carried out; the filtrate is dried over sodium sulfate and concentrated by evaporation. The resin that remains is separated by means of HPLC chromatography (Lichrospher Si60 1 2, u*m; hexane/ethyl acetate 85: 15 to 50: 50). In addition to unreacted starting material and 5- (2-methanesulfonyl- 4-trifluoromethyl-phenyl)-3-bromo-4, 5-dihydroisoxazol-4-yl-cyclopropyl-methanone of nD (40°C) = 1.5191, there is obtained 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3- methylsulfanyl-4,5-dihydro-isoxazol-4-yl-cyclopropyl-methano ne having a melting point of from 190 to 191°C.

Example P15: Preparation of 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methyl- sulfanyl-isoxazol-4-yl-cyclopropyl-methanone: (a) via 1- (4-bromo-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-4,5- dihydroisoxazol-4-yl-cyclopropyl-methanone A solution of 6 ml of 0.1 M DBU (1,8-diazabicyclo (5.4.0) undec-7-ene) in dioxane is added <BR> <BR> <BR> <BR> dropwise, with stirring, to a solution of 1.0 g of 1- (4-bromo-5- (2-methanesulfonyl-4-trifluoro- methyl-phenyl)-3-methyisulfanyl-4, 5-dihydroisoxazol-4-yl-cyclopropyl-methanone in 60 ml of dioxane, and stirring is carried out for a short time at a temperature of 20°C. A further 3 ml of 0.1 M DBU solution are then added, and stirring is carried out for one hour. The mixture is then diluted with ethyl acetate, washed with ice-water and dried over sodium sulfate. Filtra- tion over a small amount of silica gel, concentration by evaporation and purification yield 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-isoxazol-4-yl-cyclopropyl- methanone having a melting point of from 160 to 161°C. <BR> <BR> <P>(b) via 1- (4-chloro-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-4,5-<BR> dihydroisoxazol-4-yl-cyclopropyl-methanone A solution of 41 mg of 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone in 2 ml of dichloromethane is cooled to-16°C, with stirring and under a nitrogen atmosphere, and 2.4 ml of a 0.1 M solution of 1,8-diaza- bicyclo (5.4.0) undec-7-ene (1.5-5) (=DBU) are added. 1.2 mi of a 0.1 M solution of trifluoro- methane sulfochloride in dichloromethane are then added dropwise, the supply of nitrogen is cut off, the cooling bath is removed, and the still slightly yellowish solution is stirred at a temperature of 20°C. After about 20 minutes TLC analysis indicates almost complete conversion into the slightly less polar 4-chloro compound which, in the course of a total of 5 hours and with the further addition of a small amount of DBU solution, is converted into 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-isoxazol-4-yl-cyclopropyl- methanone. For working up, the reaction mixture is cooled, neutralised with a few drops of dilute aqueous acetic acid and extracted between dichloromethane and a small amount of water. The extracts are washed with a small amount of water, dried over sodium sulfate and filtered over a small amount of silica gel. The filtrate is concentrated by evaporation and dried in vacuo. 20 mg of 5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 161 to 162°C are obtained. <BR> <BR> <P> (c) via 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfa nyl-4, 5-dihydroisoxazol- 4-yl-cyclopropyl-methanone A solution of 41 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfa nyl-4,5- dihydro-isoxazol-4-yl-cyclopropyl-methanone in 10 ml of benzene is heated for 15 hours, under reflux and under a nitrogen atmosphere, with 48 mg of manganese dioxide. After cooling and filtration over a small amount of Hyflo, concentration by evaporation is carried out and the residue is purified by means of HPLC chromatography (Lichrospher Si60, hexane/ethyl acetate). 5-(2-Methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfa nyl- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 159 to 161°C is obtained.

Example P16: Preparation of 3.4-dibromo-5- (2-methanesulfonyl-4-trifluoromethyl-phenvl)- 4.5-dihydroisoxazol-4-yl-cyclopropyl-methanone: 393 mg of potassium hydrogen carbonate and 0.2 ml of water are added to a solution of 318 mg of 1-cyclopropyl-3- (2-methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1-one in 5 ml of 1,2-dimethoxyethane. In the course of 2 hours, 255 mg of dibromoformaldehyde oxime in 15 mi of dimethoxyethane are added dropwise thereto, with stirring. When the addition is complete, stirring is carried out for 2 hours; the suspension is filtered over a small amount of Hyflo and washed with ethyl acetate. The filtrate is dried over sodium sulfate and concentrated by evaporation, and the residue is purified by means of HPLC chromato- graphy (Lichrospher Si60, hexane/ethyl acetate). 3,4-Dibromo-5- (2-methanesulfonyl-4-tri- fluoromethyl-phenyl)-4, 5-dihydroisoxazol-4-yl-cyclopropyl-methanone is obtained in the form of a slightly yellowish resin of nD (40°C) = 1.5319.

3,4-Dibromo-5- (2, 4-dichloro-phenyl)-4, 5-dihydroisoxazol-4-yl-cyclopropyl-methanone having a melting point of from 88 to 90°C is obtained in an analogous manner.

Example P17: Preparation of 3-methanesulfinyl-5- (2-methanesulfonyl-4-trifluoromethyl- phenyl)-isoxazol-4-yl-cyclopropyl-methanone: A solution of 166 mg of m-chloroperbenzoic acid in 2 ml of dichloromethane is added drop- wise, while cooling and with stirring at a temperature of from-15 to-18°C, to a solution of 256 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfa nyl-isoxazol-4-yl- cyclopropyl-methanone in 10 ml of dichloromethane, and stirring is carried out for 4 hours at the same temperature. A further 30 mg of m-chloroperbenzoic acid are then added; after 20 minutes, the mixture is diluted with dichloromethane and washed with sodium hydrogen carbonate solution and water. Filtration over a small amount of silica gel, concentration by evaporation and purification by chromatography (silica gel, ethyl acetate/hexane 1: 1o 2: 1) are then carried out. 3-Methanesulfinyl-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 143 to 145°C is obtained.

Example P18: Preparation of 3-methanesulfonyl-5-(2-methanesulfonyl-4-trifluorormethVl- phenyl)-isoxazol-4-yl-cyclopropyl-methanone: 100 mg of 3-methanesulfinyl-5-(2-methanesulfonyl-4-trifluoromethyl-phe nyl)-isoxazol-4-yl- cyclopropyl-methanone that already contains small amounts of 3-methanesulfonyl-5- (2- methanesulfonyl-4-trifluoromethyl-phenyl)-isoxazol-4-yl-cycl opropyl-methanone is placed in 5 ml of dichloromethane at 0°C; a solution of 65 mg of 70 % m-chloroperbenzoic acid in 2 ml of dichloromethane is added dropwise, and stirring is carried out for 15 hours at a temperature of 20°C. The mixture is then diluted with dichloromethane, washed with sodium hydrogen carbonate solution, dried over sodium sulfate and concentrated by evaporation; the residue is purified on silica gel (hexane/ethyl acetate). 3-Methanesulfonyl-5- (2-methane- sulfonyl-4-trifluoromethyl-phenyl)-isoxazol-4-yl-cyclopropyl -methanone having a melting point of from 178 to 180°C is obtained. Example P19: Preparation of 1- (4-bromo-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-<BR> methylsulfanyl-4. 5-dihydroisoxazol-4-vl-cyclopropyl-methanone: 10 mg of sodium hydrogen carbonate are added to a solution of 41 mg of 5- (2-methane- sulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-4, 5-dihydroisoxazol-4-yl-cyclopropyl- methanone in 20 ml of carbon tetrachloride, and then 1 ml of 0.1 M bromine in carbon tetra- chloride is added dropwise thereto. After in each case one hour or two hours, a further 10 mg of sodium hydrogen carbonate and 0.5 ml of 0.1 M bromine solution are added. The reaction mixture is then heated for 2 hours under reflux and subsequently left to stand for 15 hours. The residue that remains after washing with ice-water, drying over sodium sulfate, filtering over a small amount of silica gel and concentrating by evaporation is purified by means of HPLC chromatography (Lichrospher Si60, hexane/ethyl acetate). 1- (4-Bromo-5- (2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfany l-4, 5-dihydroisoxazol-4-yl- cyclopropyl-methanone is obtained in the form of a viscous resin of nD (40°C) = 1.5399.

The compounds listed in the following Tables 1 to 19 can be prepared analogously to the above Examples and the information given in the description. In the Tables, Ph represents the phenyl group and Cp represents cyclopropyl: Table 1: Compounds of formula la: No. R92R93R94R95M.p.(°C)z /ND35 0ClHClH105-1071.001CH3 0NO2HSOCH3H1.002CH3 0NO2HOCHF2H1.003CH3 0NO2HOSO2CH3H1.004CH3 0NO2HClH1.005CH3 1.006 CH3 0 N02 H SCH3 H 1.007 CH3 0 N02 H S02CH3 H 0NO2HOCF2-CHCIFH1.008CH3 1.009 CH3 0 N02 H OCF2-CH2F-CF3 H 1.010 CH3 0 N02 H OCF3 H 0NO2HHH1.011CH3 1.012 CH3 1 N02 H CF3 H 1.013 CH3 1 N02 H SOCH3 H 1NO2HOCHF2H1.014CH3 1NO2HOSO2CH3H1.015CH3 1NO2HCIH1.016CH3 1NO2HSCH3H1.017CH3 1NO2HSO2CH3H1.018CH3 1NO2HOCF2-CHCIFH1.019CH3 1NO2HOCF2-CH2F-CF3H1.020CH3 1.021 CH3 1 N02 H OCF3 H 0SO2CH3HBrH1.022CH3 NO. R92R93R94R95M.p.(°C)z /nD35 0SO2CH3HCF3H1.023CH3 159-161 0SO2CH3CICIH1.024CH3 0SO2CH3HCIH1.025CH3 1.026 CH3 0 S02CH3 H N02 H 1.027 CH3 0 S02CH3 H S02CH3 H 0SO2C2H5HCIH1.028CH3 0SO2-iSoC3H7HCIH1.029CH3 1.030 CH3 0 S02Ph H CF3 H 0SO2-iSoC3H7HOCF2-CH2FH1.031CH3 0SO2-iSoC3H7HOCF2-CHBr2H1.032CH3 1.033 CH3 2 N02 H CF3 H 1.034 CH3 2 N02 H SOCH3 H 1.035 CH3 2 N02 H OCHF2 H 2NO2HOSO2CH3H1.036CH3 2NO2HCIH1.037CH3 1.038 CH3 2 N02 H SCH3 H 2NO2HSO2CH3H1.039CH3 1.040 CH3 0 N02 H CF3 H 0CIHFH1.041CH3 0CIHSO2CH3H154-1551.042CH3 0CIHOCHF2H1.043CH3 0CIHSCH3H1.044CH3 0CIHBrH1.045CH3 0CIHNO2H1.046CH3 0CIHSC2H5H1.047CH3 0CIHOSO2CH3H1.048CH3 0CIHSOCH3H1.049CH3 0CIHS-nC3H7H1.050CH3 0CIHSO2nC3H71.051CH3 1.052 C2H5 0 CF3 H SCH3 H 0CF3HCIH1.053C2H5 NO. R92R93R94R95M.p.(°C)z <BR> <BR> <BR> /n 35<BR> <BR> ALE 0CF3HFH1.054C2H5 1.055 C2H5 0 CF3 H Br H 0CF3HSO2CH3H1.056C2H5 1.057 C2H5 0 CF3 H CF3 H 0NO2HSO2CF3H1.058CH3 0NO2HSO2CHF2H1.059CH3 1.060 CH3 0 N02 H F H 1.061 CH3 0 N02 H Br H 0NO2CIHH1.062CH3 1.063 CH3 0 N02 CH3 H H 1.064 CH3 0 N02 H SC2H5 H 0NO2HCH3H1.065CH3 1.066 CH3 0 N02 H S02C2H5 H 1SO2CH3HBrH1.067CH3 1.068 CH3 1 S02CH3 H CF3 H 143-145 1SO2CH3CICIH1.069CH3 1SO2CH3HCIH1.070CH3 1.071 CH3 1 S02CH3 H N02 H 1.072 CH3 1 S02CH3 H S02CH3 H 1SO2C2H5HCIH1.073CH3 1SO2-iSoC3H7HCIH1.074CH3 1SO2PhHCF3H1.075CH3 1SO2-iSoC3H7HOCF2-CH2FH1.076CH3 1SO2-iSoC3H7HOCF2-CHBr2H1.077CH3 1.078 CH3 0 CF3 H SCH3 H 0CF3HCIH1.079CH3 1.080 CH3 0 CF3 H F H 1.081 CH3 0 CF3 H Br H OCF3HSO2CH3H1.082CH3 1.083 CH3 0 CF3 H CF3 H 145-146 0NO2HNO2H1.084CH3 NO. R92R93R94R95M.p.(°C)z /nD35 0NO2HOHH1.085CH3 1.086 CH3 0 N02 H OCH3 H 1.087 CH3 0 N02 H OS02Ph H 0NO2HOSO2C2H5H1.088CH3 0NO2HOSO2-iSoC3H7H1.089CH3 1.090 CH3 0 N02 CH3 H H 1.091 CH3 0 N02 H OS02CF3 H 0NO2HSO2CH2-CF3H1.092CH3 1.093 CH3 0 N02 H S02CF2-CF3 H 0NO2HS-nC4H9H1.094CH3 0NO2HS-nC3H7H1.095CH3 0NO2HOSO2CF3H1.096C2H5 0NO2HSO2CH2-CF3H1.097C2H5 1.098 C2H5 0 N02 H S02CF2-CF3 H 0NO2HS-nC4H9H1.099C2H5 1.100 C2H5 0 NO2 H S-nC3H7 H 1.101 CH3 1 CF3 H SCH3 H 1CF3HCIH1.102CH3 1.103 CH3 1 CF3 H F H 1.104 CH3 1 CF3 H Br H 1CF3HSO2CH3H1.105CH3 1.106 CH3 1 CF3 H CF3 H 127-128 1.107 CH3 2 CF3 CH3 H H 1.108 CH3 2 CF3 H SC2H5 H 1.109 CH3 2 CF3 H CH3 H 1.110 CH3 2 CF3 H S02C2H5 H 1.111 CH3 2 CF3 H Br H 1.112 CH3 2 CF3 H CF3 H 1CIHCIH1.113CH3 1CIHFH1.114CH3 1CIHSO2CH3H186-1881.115CH3 NO. R92R93R94R95M.p.(°C)z /nD35 1CIHOCHF2H1.116CH3 1CIHSCH3H1.117CH3 1CIHBrH1.118CH3 1CIHNO2H1.119CH3 1CIHSC2H5H1.120CH3 1CIHOSO2CH3H1.121CH3 1CIHSOCH3H1.122CH3 1CIHS-nC2H7H1.123CH3 1CIHSO2nC3H7H1.124CH3 1.125 CH3 0 F H Br H 0FHCIH1.126CH3 1.127 CH3 0 F H CF3 H 0CH3CISO2CH3H1.128CH3 1.129 CH3 0 CH3 OCH3 S02CH3 H 146-148 1.130 CH3 0 CH3 OC2H5 S02CH3 H 1.131 CH3 0 CH3 H S02CH3 CH3 1.132 CH3 0 CH3 CH3 OS02CH3 CH3 1.133 CH3 0 CH3 OC2H5 Br H 1.134 CH3 0 CH3 OC2H5 S02CH2CI H 0CH3CISCH3H1.135CH3 1.136 CH3 0 CH3 OCH2CF3 Br H 1.137 CH3 0 CH3 OCH3 Br H 0CH3OC2H4OCH3BrH1.138CH3 1.139 CH3 0 CH3 C02CH3 S02CH3 H 0CH3OCH3CIH1.140CH3 1.141 CH3 0 CH3 OCH3 Br CH3 1.142 CH3 0 CH3 OCH3 S02CH3 CH3 1.143 CH3 0 CH3 OCH2CCH Br H 1.144 CH3 0 CH3 OCH2Ph Br H 1.145 CH3 0 CH3 OCH2CH=CH2 Br H 1.146 CH3 0 CH3 C (CH3) =NOCH3 S02CH3 H No. R92R93R94R95M.p.(°C)z <BR> <BR> <BR> /n 35<BR> /nid 0CH3O-C2H4-SCH3BrH1.137CH3 0CH3O-isoC3H7BrH1.148CH3 1.149 CH3 0 CH3 OCH2-SCH3 Br H 1.150 CH3 0 CH3 CH20CH3 S02CH3 H 1.151 CH3 0 CH3 C02CH3 SCH3 H 0ClClSO2CH3H1.152CH3 0ClOCH3SO2CH3H1.153CH3 0ClOC2H5SO2C2H5H1.154CH3 0ClOC2H5SO2CH3H1.155CH3 0ClCH2OPhClH1.156CH3 0ClCOPhClH1.157CH3 0ClCO2CH3SO2CH3H1.158CH3 0ClClClH1.159CH3 0ClClOCH3H1.160CH3 0ClClOSO2CH3H1.161CH3 0ClHOSO2C2H5H1.162CH3 0ClHOCH3H1.163CH3 0ClHClH1.164CH3 0ClHSO2CH3H1.165CH3 0ClHSO2CH3H1.166CH3 0ClHSO2CH3H1.167CH3 0SCH3ClClH1.168CH3 1.169 CH3 0 SCH3 COCH3 SCH3 H 1.170 CH3 0 SCH3 CH20Ph SCH3 H 1.171 CH3 0 SCH3 COCH3 S2CH5 H 0CH3ClSO2CH3H1.172C2H5 1.173 C2H5 0 CH3 OCH3 S02CH3 H 1.174 C2H5 0 CH3 OC2H5 S02CH3 H 1.175 C2H5 0 CH3 H S02CH3 CH3 1.176 C2H5 0 CH3 CH3 OS02CH3 CH3 1.177 C2H5 0 CH3 OC2H5 Br H No. R91 z R92 R93 R94 R95 M. p. (°C) 0CH3OC2H5SO2CH2Cl1.178C2H5 H 0CH3ClSCH3H1.179C2H5 1.180 C2H5 0 CH3 OCH2CF3 Br H 1.181 C2H5 0 CH3 OCH3 Br H 0CH3OC2H4OCH3BrH1.182C2H5 1.183 C2H5 0 CH3 C02CH3 S02CH3 H 1.184 C2H5 0 CH3 OCH3 Cl H 1.185 C2H5 0 CH3 OCH3 Br CH3 1.186 C2H5 0 CH3 OCH3 S02CH3 CH3 1.187 C2H5 0 CH3 OCH2CCH Br H 1.188 C2H5 0 CH3 OCH2Ph Br H 1.189 C2H5 0 CH3 OCH2CH=CH2 Br H 1.190 C2H5 0 CH3 C (CH3) =NOCH3 S02CH3 H 1.191 C2H5 0 CH3 O-C2H4-SCH3 Br H 1.192 C2H5 0 CH3 O-isoC3H7 Br H 1.193 C2H5 0 CH3 OCH2-SCH3 Br H 1.194 C2H5 0 CH3 CH20CH3 S02CH3 H 1.195 C2H5 0 CH3 C02CH3 SCH3 H 0ClClSO2CH3H1.196C2H5 0ClOCH3SO2CH3H1.197C2H5 0ClOC2H5SO2C2H5H1.198C2H5 0ClOC2H5SO2CH3H1.199C2H5 0ClCH2OPhClH1.200C2H5 0ClCOPhClH1.201C2H5 0ClCO2CH3SO2CH3H1.202C2H5 0ClClClH1.203C2H5 0ClClOCH3H1.204C2H5 0ClClOSO2CH3H1.205C2H5 0ClHOSO2C2H5H1.206C2H5 0ClHOCH3H1.207C2H5 0ClHClH1.208C2H5 No. R92R93R94R95M.p.(°C)z /nD35 0ClHSO2CH3H1.209C2H5 1.210 C2H5 0 Cl H SO2CH3 H 0ClHSO2CH3H1.211C2H5 0SCH3ClClH1.212C2H5 1.213 C2H5 0 SCH3 COCH3 SCH3 H 1.214 C2H5 0 SCH3 CH20Ph SCH3 H 1.215 C2H5 0 SCH3 COCH3 S2CH5 H 1.216 CH3 1 CH3 H Br H 1.217 CH3 1 CH3 H SCH3 H 1.218 CH3 1 CH3 H S02CH3 H 1CH3HClH1.219CH3 1.220 CH3 1 CH3 H CH3 H 1CH2SO2CH3HBrH1.221CH3 1.222 CH3 0 CH3 H Br H 1.223 CH3 0 CH3 H SCH3 H 1.224 CH3 0 CH3 H S02CH3 H 1.225 CH3 0 CH3 H Cl H 1.226 CH3 0 CH3 H CH3 H 0CH2SO2CH3HBrH1.227CH3 1.228 C2H5 0 CH3 H Br H 1.229 C2H5 0 CH3 H SCH3 H 1.230 C2H5 0 CH3 H S02CH3 H 0CH3HClH1.231C2H5 1.232 C2H5 0 CH3 H CH3 H 0CH2SO2CH3HBrH1.233C2H5 1.234 C2H5 1 CH3 H Br H 1.235 C2H5 1 CH3 H SCH3 H 1CH3HSO2CH3H1.236C2H5 1CH3HClH1.237C2H5 1.238 C2H5 1 CH3 H CH3 H 1.239 C2H5 1 CH2SO2CH3 H Br H No. R92R93R94R95M.p.(°C)z /nD35 1.240 C2H5 0 N02 H S02CF3 H 0NO2HSOWCHF2H1.241C2H5 0NO2HFH1.242C2H5 0NO2HBrH1.243C2H5 0NO2ClHH1.244C2H5 1.245 C2H5 0 N02 CH3 H H 1.246 C2H5 0 N02 H SC2H5 H 0NO2HCH3H1.247C2H5 0NO2HSO2C2H5H1.248C2H5 1.249 C2H5 0 SO2CH3 H Br H 1.250 C2H5 0 S02CH3 H CF3 H 0SO2CH3ClClH1.251C2H5 0SO2CH3HClH1.252C2H5 0SO2CH3HNO2H1.253C2H5 0CO2CH3HSO2CH3H1.254C2H5 0SO2C2H5HClH1.255C2H5 0SO2-isoC3H7HClH1.256C2H5 0SO2PhHCF3H1.257C2H5 0SO2-isoC3H7HOCF2-CH2FH1.258C2H5 0SO2-isoC3H7HOCF2-CHBr2H1.259C2H5 1.260 CH3 0 OCH3 H S02CH3 H 167-169 1.261 CH3 1 OCH3 H S02CH3 H 176-177 1.262 CH3 2 OCH3 H S02CH3 H resin 2SO2CH3HCF3H178-1801.263CH3 0SO2CH3HCF3H120-1211.264isoC3H7 1.265 CH3 1 CH3 OCH3 S02CH3 H 1.266 CH3 1 CH3 CH20CH3 S02CH3 H 1ClCO2CH3SO2CH3H1.267CH3 1.268 CH2COzCHs'0 S02CH3 H CF3 H 0SO2CH3HCF3H1.269CH2CO2C2H5 0SO2CH3HCF3H1.270C2H4CO2CH3 Table 2: Compounds of formula Ib: 1-methylcyclopropyl1-CH3-Cp= No. R92R93R94R95Phys.Z data 2.001 ClHSO2CH3H0 2.002 CH3ClSO2CH3H0 2.003 tert-C4H9 0 CH3 H Cl H 2.004 tert-C4H9 0 CH3 OC2H5 S02CH3 H 2.005 tert-C4H9 0 SO2CH3 H Cl H 2.006 tert-C4H9 0 CF3 H S02CH3 H 2.007 CH3ClSCH3H0 2.008 CH3OC2H5BrH0 2.009 tert-C4H9 0 CH3 OCH2CF3 Br H 2.010 tert-C4H9 0 CH3 H S02CH3 H 2.011 ClHSO2CH3H0 2.012 SO2CH3HCF3H0 2.013 tert-C4H9 0 CH3 OCH3 S02CH3 H 2.014 tert-C4H9 0 N02 H CF3 H 2.015 tert-C4H9 0 N02 H S02CH3 H 2.016 tert-C4H9 0 CF3 H F H 2.017 tert-C4H9 0 F H CF3 H 2.018 ClO-C2H4-SCH3BrH0 No. R z R92 R93 R94 R95 Phys. data 2.019 ClHSCH3H0 2.020 NCH3-SO2CH3HClH0 2.021 NCH3-SO2CH3HCF3H0 2.022 ClHNCH3-SO2-CH3H0 2.023 ClOCH3SO2CH3H0 2.024 1-CH3-Cp 0 Cl H SO2CH3 H 2.025 1-CH3-Cp 0 CH3 Cl SO2CH3 H 2.026 1-CH3-Cp 0 CH3 H Cl H 2.027 CH3OC2H5SO2CH3H0 2.028 1-CH3-Cp 0 SO2CH3 H Cl H 2.029 CF3VHSO2CH3H0 2.030 1-CH3-Cp 0 CH3 Cl SCH3 H 2.031 1-CH3-Cp 0 CH3 OC2H5 Br H 2.032 1-CH3-Cp 0 CH3 OCH2CF3 Br H 2.033 CH3HSO2CH3H0 2.034 ClHSO2CH3H0 2.035 SO2CH3HCF3H0 2.036 CH3OCH3SO2CH3H0 2.037 NO2HCF3H0 2.038 NO2HSO2CH3H0 2.039 1-CH3-Cp 0 CF3 H F H 2.040 FHCF3H0 2.041 1-CH3-Cp 0 Cl O-C2H4-SCH3 Br H 2.042 1-CH3-Cp 0 Cl H SCH3 H 2.043 NCH3-SO2CH3HClH0 2.044 1-CH3-Cp 0 NCH3-SO2CH3 H CF3 H 2.045 1-CH3-Cp 0 Cl OCH3 SO2CH3 H Table 3: Compounds of formula la: No. R93R94R95Phys.R92 data 3.001 CH3 0 N02 OCH3 OCH3 H- 0NO2OCH3ClH-3.002CH3 0NO2OC2H4OCH3ClH-3.003CH3 0NO2CH3SO2CH3CH3-3.004CH3 0NO2OCH3OSO2CH3H-3.005CH3 0NO2OCH3OCHF2H-3.006CH3 0NO2OisoC3H7ClH-3.007CH3 0NO2HClCl-3.008CH3 3.009 CH3 0 Br OCH3 S02C2H5 H- 3.010 CH3 0 Br OCH3 CH3 H- BrOC2H4OCH3BrH-3.011CH30 3.012 CH3 0 Br OCH3 Br H- 3.013 CH3 0 Br OCH2SCH3 Br H- 0BrOC2H4OCH3BrH-3.014CH3 3.015 CH3 0 Br OCH2SO2CH3 Br H 3.016 CH3 0 Br OCH2SOCH3 Br H- 0NO2HClOisoC3H7-3.017CH3 0NO2OCH2CCHClH-3.018CH3 0NO2HClOCH3-3.019CH3 0NO2OHClH-3.020CH3 0NO2OC2H5ClH-3.021CH3 No. R92R93R94R95Phys.z data 0NO2OCH2CH=CH2ClH-3.022CH3 0NO2O(CH2)5CH3ClH-3.023CH3 0NO2OCH2PhClH-3.024CH3 3.025 C2H5 0 Br OCH3 S02C2H5 H- 0BrOCH3CH3H-3.026C2H5 0BrOC2H4OCH3BrH-3.027C2H5 0BrOCH3BrH-3.028C2H5 3.029 C2H5 0 Br OCH2SCH3 Br H- 3.030 C2H5 0 Br OC2H40CH3 Br H- 3.031 C2H5 0 Br OCH2SO2CH3 Br H 3.032 C2H5 0 Br OCH2SOCH3 Br H- 1BrOCH3SO2C2H5H-3.033CH3 1BrOCH3CH3H-3.034CH3 3.035 CH3 1 Br OC2H40CH3 Br H- 1BrOCH3BrH-3.036CH3 1BrOCH2SCH3BrH-3.037CH3 1BrOC2H4OCH3BrH-3.038CH3 3.039 CH3 1 Br OCH2SO2CH3 Br H 3.040 CH3 1 Br OCH2SOCH3 Br H- 3.041 CH3 2 SCH3 COCH3 SCH3 H- 2SCH3CH2OPHSCH3H-3.042CH3 2SCH3COCH3S2CH5H-3.043CH3 2SCH3ClHH-3.044CH3 Table 4: Compounds of formula Ic: No. Phenyl z R92 R93 R94 R95 Phys. data 0ClHSO2CH3H4.0012-NO2 4.002 2-CI 0 CH3 Cl SO2CH3 H 4.003 2-CH3 0 N02 H S02CH3 H 4.004 2-SCH3 0 N02 H CF3 H 0SO2CH3HCF3H4.0052-SO2CH3 4.006 2-CF3 0 CF3 H S02CH3 H 0CH3ClSCH3H4.0072-NH2 0SO2CH3OC2H5CF3H4.0082-O-isoC3H7 4.009 2-CI-4-0 NO2 H H H S02CH3 0ClHHH4.0102-NO2-4-SO2CH3 0CH3HHH4.0112-NO2-4-CF3 0SCH3HHH4.0122-SO2CH3-4-CF3 0SO2CH3HHH4.0132-CF3-4-SO2CH3 Table 5: Compounds of formula Id: No. Phenyl z R92 R93 R94 R95 M. p. (°C) 0ClHSO2CH3H5.0012-NO2 0CH3ClSO2CH3H5.0022-Cl 5.003 2-CH3 0 N02 H S02CH3 H 5.004 2-SCH3 0 N02 H CF3 H 0SO2CH3HCF3H5.0052-SO2CH3 5.006 2-CF3 0 CF3 H S02CH3 H 0CH3ClSCH3H5.0072-NH2 5.008 2-O-isoC3H7 0 SO2CH3 OC2H5 CF3 H 0NO2HHH5.0092-Cl-4-SO2CH3 0ClHHH5.0102-NO2-4-SO2CH3 0CH3HHH5.0112-NO2-4-CF3 0SCH3HHH5.0122-SO2CH3-4-CF3 0SO2CH3HHH5.0132-CF3-4-SO2CH3 5.014 4-CI 0 S02CH3 H CF3 H 72-75 Table 6: Compounds of formula le: No. R85R86X3Y3Phys.z data 0ClHOO6.001CH3 0NO2HOO6.002CH3 6.003 CH3 0 CH3 H O O 6.004 CH3 0 SCH3 H O O 6.005 CH3 0 SOCH3 H O O 0SO2CH3HOO6.006CH3 6.007 CH3 0 CH3 CH3 O O 0ClCH3OO6.008CH3 0CH3BrOO6.009CH3 0ClHOO6.010C2H5 0NO2HOO6.011C2H5 6.012 C2H5 0 CH3 H O O 0SCH3HOO6.013C2H5 0SOCH3HOO6.014C2H5 0SO2CH3HOO6.015C2H5 0CH3CH3OO6.016C2H5 0ClCH3OO6.017C2H5 6.018 C2H5 0 CH3 Br O O 6.019CHs1C)HSOzCHs0 1NO2HSO2CH3O6.020CH3 1CH3HSO2CH3O6.021CH3 1SCH3HSO2CH3O6.022CH3 1SOCH3HSO2CH3O6.023CH3 No. R, z R85 R86 X3 Y3 Phys. data 1SO2CH3HSO2CH3O6.024CH3 1CH3CH3SO2CH3O6.025CH3 1ClCH3SO2CH3O6.026CH3 1CH3BrSO2CH3O6.027CH3 1ClHOSO2CH36.028C2H5 1NO2HOSO2CH36.029C2H5 1CH3HOSO2CH36.030C2H5 1SCH3HOSO2CH360.31C2H5 1SOCH3HOSO2CH36.032C2H5 1SO2CH3HOSO2CH36.033C2H5 1CH3CH3OSO2CH360.34C2H5 6.035 C2Hs 1 Cl CH3 O SO2CH3 1CH3BrOSO2CH36.036C2H5 Table 7: Compounds of formula If: No. R, z R87 R88 X4 Y4 Phys. data 0ClHOO -7.001CH3 7.002 CH3 0 NO2 H O O 0CH3HOO-7.003CH3 0SCH3HOO-7.004CH3 7.005 CH3 0 SOCH3 H O O 0SO2CH3HOO-7.006CH3 0CH3CH3OO-7.007CH3 No. R87R88X4Y4Phys.z data 7.008 CH3 0 Cl CH3 O O 7.009 CH3 0 CH3 Br O O 7.010 ClHOO-0 7.011 C2H5 0 NO2 H O O 7.012 CH3HOO-0 7.013 SCH3HOO-0 7.014 SOCH3HOO-0 7.015 SO2CH3HOO-0 7.016 CH3CH3OO-0 7.017 ClCH3OO-0 7.018 CH3BrOO-0 7.019 CH3 1 Cl H SO2CH3 O 7.020 CH3 1 N02 H S02CH3 O- 7.021 CH3HSO2CH3O-1 7.022 SCH3HSO2CH3O-1 7.023 SOCH3HCH3O-1 7.024 SO2CH3HSO2CH3O-1 7.025 CH3 1 CH3 CH3 S02CH3 O- 7.026 CH3 1 Cl CH3 SO2CH3 O 7.027 CH3BrSO2CH3O-1 7.028 ClHOSO2CH3-1 7.029 NO2HOSO2CH3-1 7.030 CH3HOSO2CH3-1 7.031 SCH3HOSO2CH3-1 7.032 C2H5 1 SOCH3 H O SO2CH3 7.033 SO2CH3HOSO2CH3-1 7.034 CH3CH3OSO2CH3-1 7.035 ClCH3OSO2CH3-1 7.036 CH3BrOSO2CH3-1 Table 8: Compounds of formula lg : No. R81R82X1Y1Phys.z data 0ClHOSO2CH38.001CH3 0NO2HOO8.002CH3 0CH3HOSO2CH38.003CH3 0CH3HOS8.004C2H5 8.005 CH3 0 CH3 CH3 C=NOCH3 S02CH3 8.006 CH3 0 CH3 CH3 C (CH3) 2 S02CH3 0CH3CH3OO8.007CH3 8.008 CH3 0 CH3 CH3 OCH3 S02CH3 8.009 CH3 0 CH3 CH3 OC2H5 S02CH3 0ClHOSO2CH38.010C2H5 0NO2HOO8.011C2H5 0CH3HOSO2CH38.012C2H5 0CH3HOS8.013C2H5 8.014 C2H5 0 CH3 CH3 C=NOCH3 S02CH3 8.015 C2H5 0 CH3 CH3 C (CH3) 2 S02CH3 0CH3CH3OO8.016C2H5 8.017 C2H5 0 CH3 CH3 OCH3 S02CH3 0CH3CH3OC2H5SO2CH38.018C2H5 1ClHOSO2CH38.019C2H5 1NO2HOO8.020CH3 8.021 CH3 1 CH3 H O S02CH3 1CH3HOS8.022CH3 No. R81R82X1Y1Phys.z data 8.023 CH3 1 CH3 CH3 C=NOCH3 S02CH3 8.024 CH3 1 CH3 CH3 C (CH3) 2 S02CH3 1CH3CH3OO8.025CH3 8.026 CH3 1 CH3 CH3 OCH3 S02CH3 8.027 CH3 1 CH3 CH3 OC2H5 S02CH3 1ClHOSO2CH38.028C2H5 8.029CzHs1NOzH00 1CH3HOSO2CH38.030C2H5 1CH3HOS8.031C2H5 1CH3CH3C=NOCH3SO2CH38.032C2H5 8.033 C2H5 1 CH3 CH3 C (CH3) 2 S02CH3 1CH3CH3OO8.034C2H5 1CH3CH3OCH3SO2CH38.035C2H5 8.036 C2H5 1 CH3 CH3 OC2H5 S02CH3 8.037 CH3 2 CH3 H O S02CH3 2CH3HOS8.038CH3 8.039 CH3 2 CH3 CH3 C=NOCH3 S02CH3 2CH3CH3C(CH3)2SO2CH38.040CH3 2CH3CH3OO8.041CH3 2CH3CH3OCH3SO2CH38.042CH3 2CH3CH3OC2H5SO2CH38.043CH3 Table 9: Compounds of formula Ih: No. R, z R83 R84 X2 Y2 Phys. data 0ClHSO2CH3O-9.001CH3 NOCH3 9.003 CH3 0 CH3 H S02CH3 O- 0CH3HOS-9.004CH3 0CH3HOSO2CH3-9.005CH3 9.006 CH3 0 CH3 H S02CH3 CH2- 0ClHSO-9.007CH3 0HHSO-9.008CH3 0CH3HSO-9.009CH3 9. 010 C2H5 0 Cl H SO2CH3 O 9.011 C2H5 0 H H SO2CH3 ::: NOCH3 0CH3HSO2CH3O-9.012C2H5 9.013 C2Hs 0 CH3 H O S 0CH3HOSO2CH3-9.014C2H5 9.015 C2H5 0 CH3 H S02CH3 CH2- 0ClHSO-9.016C2H5 0HHSO-9.017C2H5 0CH3HSO-9.018C2H5 9.019 CH3 1 Cl H SO2CH3 O 9. 020 CH3 1 H H SO2CH3 ::: NOCH3 1CH3HSO2CH3O-9.021CH3 1CH3HOS-9.022CH3 No. R, z R83 R84 X2 Y2 Phys. data 1CH3HOSO2CH3-9.023CH3 9.024 CH3 1 CH3 H S02CH3 CH2- 1ClHSO-9.025CH3 1HHSO-9.026CH3 1CH3HSO-9.027CH3 1ClHSO2CH3O-9.028C2H5 9. 029 CH3 1 H H SO2CH3 ::: NOCH3 9.030 C2H5 1 CH3 H S02CH3 O- 1CH3HOS-9.031C2H5 9.032 C2H5 1 CH3 H O S02CH3- 9.033 C2H5 1 CH3 H S02CH3 CH2- 9.034 C2H5 1 Cl H S O 1HHSO-9.035C2H5 1CH3HSO-9.036C2H5 9.037 CH3 0 H CH3 O S02CH3- 0HClOSO2CH3-9.038CH3 2ClHSO2CH3O-9.039CH3 9. 040 CH3 2 H H SO2CH3 ::: NOCH3 2CH3HSO2CH3O-9.041CH3 Table 10: Compounds of formula Ila: No. R92R93R94R95M.p.(°C)/z nD35 0ClHClH79-8110.001CH3 0NO2HSOCH3H10.002CH3 10.003 CH3 0 N02 H OCHF2 H 10.004 CH3 0 N02 H OS02CH3 H 0NO2HClH10.005CH3 0NO2HSCH3H10.006CH3 0NO2HSO2CH3H10.007CH3 10.008 CH3 0 N02 H OCF2-CHCIF H 10.009 CH3 0 N02 H OCF2-CH2F-CF3 H 0NO2HOCF3H10.010CH3 0NO2HHH10.011CH3 1NO2HCF3H10.012CH3 1NO2HSOCHEH10.013CH3 1NO2HOCHF2H10.014CH3 1NO2HOSO2CH3H10.015CH3 1NO2HClH10.016CH3 10.017 CH3 1 N02 H SCH3 H 1NO2HSO2CH3H10.018CH3 1NO2HOCF2-CHClFH10.019CH3 10.020 CH3 1 N02 H OCF2-CH2F-CF3 H 1NO2HOCF3H10.021CH3 0SO2CH3HBrH10.022CH3 0SO2CH3HCF3H190-19110.023CH3 No. R92R93R94R95M.p.(°C)/z nD35 10.024 CH3 0 S02CH3 CI Cl H 0SO2CH3HClH10.025CH3 10.026 CH3 0 S02CH3 H N02 H 10.027 CH3 0 S02CH3 H S02CH3 H 0SO2C2H5HClH10.028CH3 0SO2-isoC3H7HClH10.029CH3 10.030 CH3 0 S02Ph H CF3 H 0SO2-isoC3H7HOCF2-CH2FH10.031CH3 10.032CH30S02-isoC3H7HOCF2-CHBr2H 10.033 CH3 2 N02 H CF3 H 10.034 CH3 2 N02 H SOCH3 H 10.035 CH3 2 N02 H OCHF2 H 10.036 CH3 2 N02 H OS02CH3 H 2NO2HClH10.037CH3 2NO2HSCH3H10.038CH3 2NO2HSO2CH3H10.039CH3 0NO2HCF3H10.040CH3 0ClHFH10.041CH3 0ClHSO2CH3H10.042CH3 0ClHOCHF2H10.043CH3 0ClHSCH3H10.044CH3 0ClHBrH10.045CH3 0ClHNO2H10.046CH3 0ClHSC2H5H10.047CH3 0ClHOSO2CH3H10.048CH3 0ClHSOCH3H10.049CH3 0ClHS-nC3H7H10.050CH3 0ClHSO2nC3H7H10.051CH3 0CF3HSCH3H10.052C2H5 0CF3HClH10.053C2H5 10.054 C2H5 0 CF3 H F H No. R9, z R92 R93 R94 R95 M.p.(°C)/ nD35 0CF3HBrH10.055C2H5 10.056 C2H5 0 CF3 H S02CH3 H 10.057 C2H5 0 CF3 H CF3 H 10.058 CH3 0 N02 H S02CF3 H 0NO2HSO2CHF2H10.059CH3 0NO2HFH10.060CH3 10.061 CH3 0 N02 H Br H 0NO2ClHH10.062CH3 10.063 CH3 0 N02 CH3 H H 0NO2HSC2H5H10.064CH3 10.065 CH3 0 N02 H CH3 H 10.066 CH3 0 N02 H S02C2H5 H 10.067 CH3 1 S02CH3 H Br H 1SO2CH3HCF3H10.068CH3 1SO2CH3ClH10.069CH3 1SO2CH3HClH10.070CH3 1SO2CH3HNO2H10.071CH3 10.072 CH3 1 S02CH3 H S02CH3 H 1SO2C2H5HClH10.073CH3 1SO2-isoC3H7HClH10.074CH3 10.075 CH3 1 S02Ph H CF3 H 1SO2-isoC3H7HOCF2-CH2FH10.076CH3 1SO2-isoC3H7HOCF2-CHBr2H10.077CH3 10.078 CH3 0 CF3 H SCH3 H 0CF3HClH10.079CH3 10.080 CH3 0 CF3 H F H 10.081 CH3 0 CF3 H Br H 0CF3HSO2CH3H10.082CH3 10.083 CH3 0 CF3 H CF3 H 0NO2HNO2H10.084CH3 0NO2HOHH10.085CH3 No. R92R93R94R95M.p.(°C)/z nD35 0NO2HOCH3H10.086CH3 10.087 CH3 0 N02 H OS02Ph H 0NO2HOSO2C2H5H10.088CH3 0NO2HOSO2-isoC3H7H10.089CH3 0NO2CH3HH10.090CH3 0NO2HOSO2CF3H10.091CH3 10.092 CH3 0 N02 H S02CH2-CF3 H 10.093 CH3 0 N02 H S02CF2-CF3 H 10.094 CH3 0 N02 H S-nC4H9 H 0NO2HS-nC3H7H10.095CH3 10.096 C2H5 0 N02 H OS02CF3 H 10.097 C2H5 0 N02 H S02CH2-CF3 H 0NO2HSO2CF2-CF3H10.098C2H5 0NO2HS-nC4H9H10.099C2H5 10.100 C2H5 0 N02 H S-nC3H7 H 10.101 CH3 1 CF3 H SCH3 H 1CF3HClH10.102CH3 10.103 CH3 1 CF3 H F H 10.104 CH3 1 CF3 H Br H 10.105 CH3 1 CF3 H S02CH3 H 10.106 CH3 1 CF3 H CF3 H 10.107 CH3 2 CF3 CH3 H H 10.108 CH3 2 CF3 H SC2H5 H 10.109 CH3 2 CF3 H CH3 H 10.110 CH3 2 CF3 H S02C2H5 H 10.111 CH3 2 CF3 H Br H 10.112 CH3 2 CF3 H CF3 H 1ClHClH10.113CH3 1ClHFH10.114CH3 1ClHSO2CH3H10.115CH3 1ClHOCHF2H10.116CH3 No. R92R93R94R95M.p.(°C)/z nD35 1ClHSCH3H10.117CH3 1ClHBrH10.118CH3 1ClHNO2H10.119CH3 10.120 CH3 1 Cl H SC2H5 H 1ClHOSO2CH3H10.121CH3 1ClHSOCH3H10.122CH3 1ClHS-nC3H7H10.123CH3 1ClHSO2nC3H7H10.124CH3 10.125 CH3 0 F H Br H 0FHClH10.126CH3 10.127 CH3 0 F H CF3 H 0CH3ClSO2CH3H10.128CH3 09CH3OCH3SO2CH3H1360138°C10.129CH3 10.130 CH3 0 CH3 OC2H5 S02CH3 H 10.131 CH3 0 CH3 H S02CH3 CH3 10.132 CH3 0 CH3 CH3 OS02CH3 CH3 10.133 CH3 0 CH3 OC2H5 Br H 10.134 CH3 0 CH3 OC2H5 S02CH2CI H 0CH3ClSCH3H10.135CH3 10.136 CH3 0 CH3 OCH2CF3 Br H 10.137 CH3 0 CH3 OCH3 Br H 10.138 CH3 0 CH3 OC2H40CH3 Br H 10.139 CH3 0 CH3 C02CH3 S02CH3 H 0CH3OCH3ClH10.140CH3 10.141 CH3 0 CH3 OCH3 Br CH3 10.142 CH3 0 CH3 OCH3 S02CH3 CH3 10.143 CH3 0 CH3 OCH2CCH Br H 10.144 CH3 0 CH3 OCH2Ph Br H 10.145 CH3 0 CH3 OCH2CH=CH2 Br H 10.146 CH3 0 CH3 C (CH3) =NOCH3 S02CH3 H 10.147 CH3 0 CH3 O-C2H4-SCH3 Br H No. R92R93R94R95M.p.(°C)/z nD35 0CH3O-isoC3H7BrH10.148CH3 10.149 CH3 0 CH3 OCH2-SCH3 Br H 10.150 CH3 0 CH3 CH20CH3 S02CH3 H 10.151 CH3 0 CH3 C02CH3 SCH3 H 0ClClSO2CH3H10.152CH3 0ClOCH3SO2CH3H10.153CH3 0ClOC2H5SO2C2H5H10.154CH3 10.155 CH3 0 Cl OC2H5 SO2CH3 H 0ClCH2OPhClH10.156CH3 0ClCOPhClH10.157CH3 0ClCO2CH3SO2CH3H10.158CH3 0ClClClH10.159CH3 0ClClOCH3H10.160CH3 0ClClOSO2CH3H10.161CH3 0ClHOSO2C2H5H10.162CH3 0ClHOCH3H10.163CH3 0ClHClH10.164CH3 10.165 CH3 0 Cl H SO2CH3 H 0ClHSO2CH3H10.166CH3 0ClHSO2CH3H10.167CH3 0SCH3ClClH10.168CH3 10. 169 CH3 0 SCH3 COCH3 SCH3 H 10.170 CH3 0 SCH3 CH20Ph SCH3 H 10.171 CH3 0 SCH3 COCH3 S2CH5 H 0CH3ClSO2CH3H10.172C2H5 10.173 C2H5 0 CH3 OCH3 S02CH3 H 10.174 C2H5 0 CH3 OC2H5 S02CH3 H 0CH3HSO2CH3CH310.175C2H5 10.176 C2H5 0 CH3 CH3 OS02CH3 CH3 10.177 C2H5 0 CH3 OC2H5 Br H 10.178 C2H5 0 CH3 OC2H5 S02CH2CI H No. R92R93R94R95M.p.(°C)/z nD35 0CH3ClSCH3H10.179C2H5 10.180 C2H5 0 CH3 OCH2CF3 Br H 10.181 C2H5 0 CH3 OCH3 Br H 10.182 C2H5 0 CH3 OC2H40CH3 Br H 10.183 C2H5 0 CH3 C02CH3 S02CH3 H 0CH3OCH3ClH10.184C2H5 10.185 C2H5 0 CH3 OCH3 Br CH3 10.186 C2H5 0 CH3 OCH3 S02CH3 CH3 10.187 C2H5 0 CH3 OCH2CCH Br H 10.188 C2H5 0 CH3 OCH2Ph Br H 10.189 C2H5 0 CH3 OCH2CH=CH2 Br H 10.190 C2H5 0 CH3 C (CH3) =NOCH3 S02CH3 H 10.191 C2H5 0 CH3 O-C2H4-SCH3 Br H 0CH3O-isoC3H7BrH10.192C2H5 10.193 C2H5 0 CH3 OCH2-SCH3 Br H 10.194 C2H5 0 CH3 CH20CH3 S02CH3 H 10.195 C2H5 0 CH3 C02CH3 SCH3 H 0ClClSO2CH3H10.196C2H5 0ClOCH3SO2CH3H10.197C2H5 0ClOC2H5SO2C2H5H10.198C2H5 0ClOC2H5SO2CH3H10.199C2H5 0ClCH3OPhClH10.200C2H5 10.201 C2H5 0 Cl COPh Cl H 0ClCO2CH3SO2CH3H10.202C2H5 0ClClClH10.203C2H5 0ClClOCH3H10.204C2H5 0ClClOSO2CH3H10.205C2H5 0ClHOSO2C2H5H10.206C2H5 0ClHOCH3H10.207C2H5 0ClHClH10.208C2H5 0ClHSO2CH3H10.209C2H5 No. R92R93R94R95M.p.(°C)/z nD35 0ClHSO2CH3H10.210C2H5 0ClHSO2CH3H10.211C2H5 0SCH3ClClH10.212C2H5 10.213 C2H5 0 SCH3 COCH3 SCH3 H 10.214 C2H5 0 SCH3 CH20Ph SCH3 H 10.215 C2H5 0 SCH3 COCH3 S2CH5 H 10.216 CH3 1 CH3 H Br H 10.217 CH3 1 CH3 H SCH3 H 10.218 CH3 1 CH3 H S02CH3 H 1CH3HClH10.219CH3 10.220 CH3 1 CH3 H CH3 H 1CH2SO2CH3HBrH10.221CH3 10.222 CH3 0 CH3 H Br H 10.223 CH3 0 CH3 H SCH3 H 10.224 CH3 0 CH3 H S02CH3 H 10.225 CH3 0 CH3 H Cl H 10.226 CH3 0 CH3 H CH3 H 0CH2SO2CH3HBrH10.227CH3 10.228 C2H5 0 CH3 H Br H 10.229 C2H5 0 CH3 H SCH3 H 10.230 C2H5 0 CH3 H S02CH3 H 10.231 C2H5 0 CH3 H Cl H 10.232 C2H5 0 CH3 H CH3 H 0CH2SO2CH3HBrH10.233C2H5 10.234 C2H5 1 CH3 H Br H 10.235 C2H5 1 CH3 H SCH3 H 10.236 C2H5 1 CH3 H S02CH3 H 1CH3HClH10.237C2H5 10.238 C2H5 1 CH3 H CH3 H 1CH2SO2CH3HBrH10.239C2H5 10.240 C2H5 0 N02 H S02CF3 H No. Rg, z 92R939495M.P.(°C)/ nD35 10.241 C2H5 0 N02 H S02CHF2 H 0NO2HFH10.242C2H5 0NO2HBrH10.243C2H5 0NO2ClHH10.244C2H5 10.245 C2H5 0 N02 CH3 H H 10.246 C2H5 0 N02 H SC2H5 H 10.247 C2H5 0 N02 H CH3 H 0NO2HSO2C2H5H10.248C2H5 0SO2CH3HBrH10.249C2H5 10.250 C2H5 0 S02CH3 H CF3 H 0SO2CH3ClClH10.251C2H5 0SO2CH3HClH10.252C2H5 0SO2CH3HNO2H10.253C2H5 0SO2CH3HSO2CH3H10.254C2H5 0SO2CH3HClH10.255C2H5 0SO2-isoC3H7HClH10.256C2H5 0SO2PhHCF3H10.257C2H5 0SO2-isoC3H6HOCF2-CH2FH10.258C2H5 0SO2-sioC3H6HOCF2-CHBr2H10.259C2H5 10.260 CH3 0 OCH3 H S02CH3 H 126-128 10.261 CH3 1 OCH3 H S02CH3 H 10.262 CH3 2 OCH3 H S02CH3 H 2SO2CH3HCF3H10.263CH3 0SO2CH3HCF3H10.264isoC3H7 10.265 CH3 1 CH3 OCH3 S02CH3 H 10.266 CH3 1 CH3 CH20CH3 S02CH3 H 1ClCO2CH3SO2CH3H10.267CH3 10.268 CH2CO2CH3 0 SO2CH3 H CF3 H 0SO2CH3HCF3H10.269CH2CO2C2H5 0SO4CH3HCF3H10.270C2H4CO2CH3 Table 11: Compounds of formula Ilb : 1-methylcyclopropyl1-CH3-Cp= <BR> <BR> <BR> <BR> <BR> <BR> No. R z R92 R93 R94 R95 Phys. data 0ClHSO2CH3H11.001tert-C4H9 0CH3ClSO2CH3H11.002tert-C4H9 0CH3HClH11.003tert-C4H9 11.004 tert-C4H9 0 CH3 OC2H5 S02CH3 H 0SO2CH3HClH11.005tert-C4H9 11.006 tert-C4H9 0 CF3 H S02CH3 H 0CH3ClSCH3H11.007tert-C4H9 11.008 tert-C4H9 0 CH3 OC2H5 Br H 11.009 tert-C4H9 0 CH3 OCH2CF3 Br H 0CH3HSO2CH3H11.010tert-C4H9 0ClHSO2CH3H11.011tert-C4H9 11.012 tert-C4H9 0 S02CH3 H CF3 H 11.013 tert-C4H9 0 CH3 OCH3 S02CH3 H 0NO2HCF3H11.014tert-C4H9 11.015 tert-C4H9 0 N02 H S02CH3 H 0CF3HFH11.016tert-C4H9 0FHCF3H11.017tert-C4H9 0ClO-C2H4-SCH3BrH11.18tert-C4H9 0ClHSCH3H11.019tert-C4H9 0NCH3-SO2CH3HClH11.020tert-C4H9 No. R z R92 R93 R94 R95 Phys. data 11.021 tert-C4H9 0 NCH3-SO2CH3 H CF3 H 11.022 ClHNCH3-SO2CH3H0 11.023 ClOCH3SO2CH3H0 11.024 ClHSO2CH3H0 11.025 1-CH3-Cp 0 CH3 Cl SO2CH3 H 11.026 1-CH3-Cp 0 CH3 H Cl H 11.027 1-CH3-Cp 0 CH3 OC2H5 SO2CH3 H 11.028 SO2CH3HClH0 11.029 1-CH3-Cp 0 CF3 H S02CH3 H 11.030 1-CH3-Cp 0 CH3 Cl SCH3 H 11.031 1-CH3-Cp 0 CH3 OC2H5 Br H 11.032 1-CH3-Cp 0 CH3 OCH2CF3 Br H 11.033 1-CH3-Cp 0 CH3 H S02CH3 H 11.034 1-CH3-Cp 0 Cl H SO2CH3 H 11.035 SO2CH3HCF3H0 11.036 CH3OCH3SO2CH3H0 11.037 1-CH3-Cp 0 N02 H CF3 H 11.038 1-CH3-Cp 0 N02 H S02CH3 H 11.039 1-CH3-Cp 0 CF3 H F H 11.040 1-CH3-Cp 0 F H CF3 H 11.041 1-CH3-Cp 0 Cl O-C2H4-SCH3 Br H 11.042 ClHSCH3H0 11.043 1-CH3-Cp 0 NCH3-SO2CH3 H Cl H 11.044 1-CH3-Cp 0 NCH3-SO2CH3 H CF3 H 11.045 ClOCH3SO2CH3H0 Table 12: Compounds of formula Ila : No. R91 z R92 R93 R94 R95 Phys. data 12.001 CH3 0 NO2 OCH3 OCH3 H - 12.002 CH3 0 NO2. OCH3 Cl H - 0NO2OC2H4OCH3ClH-12.003CH3 12. 004 CH3 0 NO2 CH3 SO2CH3 CH3 0NO2OCH3OSO2CH3H-12.005CH3 12.006 CH3 0 N02 OCH3 OCHF2 H- 0NO2OisoC3H7ClH-12.007CH3 12.008 CH3 0 NO2 H Cl Cl - 12.009 CH3 0 Br OCH3 SO2C2H5 H 12.010 CH3 0 Br OCH3 CH3 H - 12.011 CH3 0 Br OC2H40CH3 Br H- 12.012 CH3 0 Br OCH3 Br H - 12.013 CH3 0 Br OCH2SCH3 Br H- 12.014 CH3 0 Br OC2H40CH3 Br H- 12.015 CH3 0 Br OCH2SO2CH3 Br H 0BrOCH2SOCH3BrH-12.016CH3 12.017 CH3 0 NO2 H Cl OisoC3H7 - 12.018 CH3 0 NO2 OCH2CCH Cl H - 12.019 CH3 0 NO2 H Cl OCH3 - 12.020 CH3 0 NO2 OH Cl H - 12.021 CH3 0 NO2 OC2H5 Cl H - No. Rgt z R92 R93 R94 R95 Phys. data 12.022 CH3 0 NO2 OCH2CH=CH2 Cl H - 12.023 CH3 0 NO2 O(CH2)5CH3 Cl H - 12.024 CH3 0 NO2 OCH2Ph Cl H - 12.025 C2H5 0 Br OCH3 S02C2H5 H- 12.026 C2H5 0 Br OCH3 CH3 H - 0BrOC2H4OCH3BrH-12.027C2H5 0BrOCH3BrH-12.028C2H5 0BrOCH2SCH3BrH-12.029C2H5 12.030 C2H5 0 Br OC2H40CH3 Br H- 12.031 C2H5 0 Br OCH2SO2CH3 Br H 0BrOCH2SOCH3BrH-12.032C2H5 12.033 CH3 1 Br OCH3 S02C2H5 H- 1BrOCH3CH3H-12.034CH3 12.035 CH3 1 Br OC2H40CH3 Br H- 1BrOCH3BrH-12.036CH3 1BrOCH2SCH3BrH-12.037CH3 1BrOC2H4OCH3BrH-12.038CH3 1BrOCH2SO2CH3BrH-12.039CH3 12.040 CH3 1 Br OCH2SOCH3 Br H- 2SCH3COCH3SCH3H-12.041CH3 12.042 CH3 2 SCH3 CH20Ph SCH3 H- 12.043 CH3 2 SCH3 COCH3 S2CH5 H - 12.044 CH3 2 SCH3 Cl H H - Table 13: Compounds of formula llc: No. Phenyl z R92 R93 R94 R95 Phys. data 13.001 2-NO2 0 Cl H SO2CH3 H 0CH3ClSO2CH3H13.0022-Cl 13.003 2-CH3 0 N02 H S02CH3 H 13.004 2-SCH3 0 NO2 H CF3 H 13.005 2-SO2CH3 0 S02CH3 H CF3 H 0CFHSO2CH3H13.0062-CF3 0CH3ClSCH3H13.0072-NH2 0SO2CH3OC2H5CF3H13.0082-O-isoC3H7 0NO2HHH13.0092-Cl-4- S02CH3 0ClHHH3.0102-NO2-4-SO2CH3 0CH3HHH13.0112-NO2-4-CF3 0SCH3HHH13.0122-SO2CH3-4-CF3 0SO2CH3HHH13.0132-CF3-4-SO2CH3 Table 14: Compounds of formula lid: No. Phenyl z R92 R93 R94 R95 M.p.

(°C) 0ClHSO2CH3H14.0012-NO2 14.002 2-CI 0 CH3 Cl SO2CH3 H 14.003 2-CH3 0 N02 H S02CH3 H 14.004 2-SCH3 0 N02 H CF3 H 0SO2CH3HCF3H14.0052-SO2CH3 14.006 2-CF3 0 CF3 H S02CH3 H 0CH3ClSCH3H14.0072-NH2 0SO2CH3OC2H5CF3H14.0082-O-isoC3H7 0NO2HHH14.0092-Cl-4-SO2CH3 0ClHHH14.0102-NO2-4-SO2CH3 0CH3HHH14.0112-NO2-4-CF3 0SCH3HHH14.0122-SO2CH3-4-CF3 0SO2CH3HHH14.0132-CF3-4-SO2CH3 0SO2CH3HCF3H209-14.0144-Cl 210 Table 15: Compounds of formula lie: No. R85R86X3Y3Phys.z data 0ClHOO15.001CH3 NO2HOO15.002CH3 15.003 CH3 0 CH3 H O O 15.004 CH3 0 SCH3 H O O 15.005 CH3 0 SOCH3 H O O SO2CH3HOO15.006CH3 15.007 CH3 0 CH3 CH3 O O 0ClCH3OO15.008CH3 15.009 CH3 0 CH3 Br O O 0ClHOO15.010C2H5 0NO2HOO15.011C2H5 15.012 C2H5 0 CH3 H O O 0SCH3HOO15.013C2H5 0SOCH3HOO15.014C2H5 0SO2CH3HOO15.015C2H5 0CH3CH3OO15.016C2H5 0ClCH3OO15.017C2H5 0CH3BrOO15.018C2H5 1ClHSO2CH3O15.019CH3 1NO2HSO2CH3O15.020CH3 1CH3HSO2CH3O15.021CH3 1SCH3HSO2CH3O15.022CH3 1SOCH3HSO2CH3O15.023CH3 No. R85R86X3Y3Phys.z data 15.024 CH3 1 S02CH3 H S02CH3 O 1CH3CH3SO2CH3O15.025CH3 1ClCH3SO2CH3O15.026CH3 1CH3BrSO2CH3O15.027CH3 1ClHOSO2CH315.028C2H5 1NO2HOSO2CH315.029C2H5 1CH3HOSO2CH315.030C2H5 1SCH3HOSO2CH315.031C2H5 1SOCH3HOSO2CH315.032C2H5 15.033 C2H5 1 S02CH3 H O S02CH3 1CH3CH3OSO2CH315.034C2H5 1ClCH3OSO2CH315.035C2H5 1CH3BrOSO2CH315.036C2H5 Table 16: Compounds of formula Ilf: No. R87R88X4Y4Phys.z data 0ClHOO-16.001CH3 0NO2HOO-16.002CH3 16.003 CH3 0 CH3 H O O 16.004 CH3 0 SCH3 H O O 16.005 CH3 0 SOCH3 H O O 0SO2CH3HOO-16.006CH3 0CH3CH3OO-16.007CH3 No. R, z ResX4Y4 Phys. data 16.008 CH3 0 Cl CH3 O O 16.009 CH3 0 CH3 Br O O 16.010 C2H5 0 Cl H O O - 16.011 C2H5 0N02H00 16.012 C2H5 0 CH3 H O O 16.013 C2H5 0 SCH3 H O O - 16.014 C2H5 0 SOCH3 H O O - 16.015 C2H5 0 SO2CH3 H O O - 16.016 C2H5 0 CH3 CH3 O O - 16.017 C2H5 0 Cl CH3 O O - 16.018 C2H5 0 CH3 Br O O - 16.019 CH3 1 Cl H SO2 CH3 O - 16.020 CH3 1 N02 H S02CH3 O- 16.021 CH3 1 CH3 H SO2CH3 O - 16.022 CH3 1 SCH3 H SO2CH3 O - 16.023 CH3 1 SOCH3 H SO2CH3 O - 16.024 CH3 1 S02CH3 H S02CH3 O 16.025 CH3 1 CH3 CH3 SO2CH3 O - 16.026 CH3 1 Cl CH3 SO2CH3 O - 16.027 CH3 1 CH3 Br S02CH3 O 16.028 C2H5 1 Cl H O SO2CH3 - 16.029 C2H5 1 NO2 H O SO2 CH3 - 16.030 C2H5 1 CH3 H O SO2CH3 16.031 C2H5 1 SCH3 H O S02CH3- 16.032 C2H5 1 SOCH3 H O SO2CH3 - 16.033 C2H5 1 S02CH3 H O S02CH3- 16.034 C2H5 1 CH3 CH3 O SO2CH3 - 16.035 C2H5 1 Cl CH3 O SO2CH3 - 16.036 C2H5 1 CH3 Br O SO2CH3 - Table 17: Compounds of formula 114 No. R81R82X1Y1Phys.z data 0ClHOSO2CH317.001CH3 17.002CH30N02H00 0CH3HOSO2CH317.003CH3 CH3HOS17.004CH3 17.005 CH3 0 CH3 CH3 C=NOCH3 S02CH3 17.006 CH3 0 CH3 CH3 C (CH3) 2 SO2CH3 17.007 CH3 0 CH3 CH3 O O 17.008 CH3 0 CH3 CH3 OCH3 S02CH3 17.009 CH3 0 CH3 CH3 OC2H5 S02CH3 0ClHOSO2CH317.010C2H5 0NO2HOO17.011C2H5 0CH3HOSO2CH317.012C2H5 17.013 C2H5 0 CH3 H O S 0CH3CH3C=NOCH3SO2CH317.014C2H5 17.015 C2H5 0 CH3 CH3 C (CH3) 2 S02CH3 0CH3CH3OO17.016C2H5 17.017 C2H5 0 CH3 CH3 OCH3 S02CH3 17. 018 C2H5 0 CH3 CH3 OC2H5 S02CH3 1ClHOSO2CH317.019CH3 1NOWHOO17.020CH3 17.021 CH3 1 CH3 H O S02CH3 1CH3HOS17.022CH3 No. R81R82X1Y1z 17.023 CH3 1 CH3 CH3 C=NOCH3 S02CH3 17.024 CH3 1 CH3 CH3 C (CH3) 2 S02CH3 1CH3CH3OO17.025CH3 17.026 CH3 1 CH3 CH3 OCH3 S02CH3 17.027 CH3 1 CH3 CH3 OC2H5 S02CH3 1ClHOSO2CH317.028C2H5 1NO2HOO17.029C2H5 1CH3HOSO2CH317.030C2H5 1CH3HOS17.031C2H5 1CH3CH3C=NOCH3SO2CH317.032C2H5 1CH3CH3C(CH3)2SO2CH317.033C2H5 1CH3CH3OO17.034C2H5 17.035 C2H5 1 CH3 CH3 OCH3 S02CH3 1CH3CH3OC2H5SO2CH317.036C2H5 17. 037 CH3 2 CH3 H O S02CH3 2CH3HOS17.038CH3 2CH3CH3C=NOCH3SO2CH317.039CH3 17.040 CH3 2 CH3 CH3 C (CH3) 2 SO2CH3 2CH3CH3OO17.041CH3 17.042 CH3 2 CH3 CH3 OCH3 S02CH3 17.043 CH3 2 CH3 CH3 OC2H5 S02CH3 Table 18: Compounds of formula lih: No. R, z R83 R84 X2 Y2 Phys. data 0ClHSO2CH3O-18.001CH3 18. 002 CH3 0 H H SO2CH3 ::: NOCH3 18.003 CH3 0 CH3 H S02CH3 O- 0CH3HOS-18.004CH3 0CH3HOSO2CH3-18.005CH3 18.006 CH3 0 CH3 H S02CH3 CH2- 18.007 CH3 0 Cl H S O 0HHSO-18.008CH3 0CH3HSO-18.009CH3 18. 010 C2H5 0 Cl H SO2CH3 O 18. 011 C2H5 0 H H SO2CH3 ::: NOCH3 18.012 C2H5 0 CH3 H S02CH3 O- 0CH3HOS-18.013C2H5 18.014 C2H5 0 CH3 H O S02CH3- 18.015 C2H5 0 CH3 H S02CH3 CH2- 0ClHSO-18.016C2H5 18.017 0HHS0 0CH3HSO-18.018C2H5 18.019ClHSO2CH3O-1 18. 020 CH3 1 H H SO2CH3 ::: NOCH3 1CH3HSO2CH3O-18.021CH3 1CH3HOS-18.022CH3 No. R, z R83 R84 X2 Y2 1CH3HOSO2CH318.023CH3 18.024 CH3 1 CH3 H S02CH3 CH2 1ClHSO18.025CH3 1HHSO18.026CH3 18.027 CH3 1 CH3 H S O 1ClHSO2CH3O18.028C2H5 18. 029 C2H5 1 H H SO2CH3 :: : NOCH3 1CH3HSO2CH3O18.030C2H5 18.031 C2H5 1 CH3 H O S 1CH3HOSO2CH318.032C2H5 1CH3HSO2CH3CH218.033C2H5 1ClHSO18.034C2H5 1HHSO18.035C2H5 1CH3HSO18.036C2H5 0HCH3OSO2CH318.037CH3 0HClOSO2CH318.038CH3 18.039 CH3 2 Cl H SO2CH3 O 18. 040 CH3 2 H H SO2CH3 ::: NOCH3 2CH3HSO2CH3O18.041CH3 Table No. R94R96R97M.p.(°C)/R93 <BR> <BR> <BR> n 35<BR> no HClClSCH319.001Cl 19. 002 Cl H Cl Br SCH3 1.5904 HSO2CH3ClSCH319.003Cl HSO2CH3BrSCH319.004Cl HSO2CH3ClSOCH319.005Cl 19.006 Cl H SO2CH3 Br SOCH3 HCF3ClSCH319.007SO2CH3 HCF3BrSCH3nD40=19.008SO2CH3 1.5399 19. 009 SO2CH3 H CF3 Cl SOCH3 HCF3BrSOCH319.010SO2CH3 HCF3ClSO2CH319.011SO2CH3 19.012 S02CH3 H CF3 Br S02CH3 OCH3SO2CH3ClSCH319.013CH3 19.014 CH3 OCH3 S02CH3 Br SCH3 OC2H5SO2CH3ClSCH319.015CH3 19.016 CH3 OC2H5 S02CH3 Br SCH3 CH2OCH3SO2CH3ClSCH319.017CH3 19.018 CH3 CH20CH3 S02CH3 Br SCH3 CO2CH3SO2CH3ClSCH319.019Cl CO2CH3SO2CH3BrSCH319.020Cl HClClCl19.021Cl HClBrBr88-9019.022Cl No. R94R96R97M.p.(°C)/R93 nD35 HCF3ClCl19.023SO2CH3 19.024 S02CH3 H CF3 Br Br 1.5319 OCH3SO2CH3ClCl19.025CH3 19.026 CH3 OCH3 S02CH3 Br Br CO2CH3SO2CH3ClCl19.027Cl CO2CH3SO2CH3BrBr19.028Cl HClHBr60-6219.029Cl HClHCl19.030Cl HCF3HCl19.031SO2CH3 19.032 S02CH3 H CF3 H Br OCH3SO2CH3HCl19.033CH3 19.034 CH3 OCH3 S02CH3 H Br HSO2CH3ClCl19.035OCH3 19.036 OCH3 H S02CH3 Br Br OC2H5SO2CH3ClCl19.037Cl OC2H5SO2CH3BrBr19.038Cl OC2H5SO2CH3ClSCH319.039Cl 19.040 CI OC2H5 SO2CH3 Br SCH3 CH2OCH3SO2CH3ClCl19.041CH3 19.042 CH3 CH20CH3 S02CH3 Br Br HSO2CH3ClCl19.043Cl HSO2CH3BrBr19.044Cl CO2CH3SO2CH3ClCl19.045CH3 19.046 CH3 C02CH3 S02CH3 Br Br CO2CH3SO2CH3ClSCH319.047CH3 19.048 CH3 C02CH3 S02CH3 Br SCH3 19.049 CF3 H CF3 Br Br Table 20: Compounds of formula Illa No. R92 R93 R94 M. p. (°C) /nD35 HCl80-8220.001Cl HCl20.002Cl HSO2CH320.003Cl HSO2CH320.004Cl HSO2CH320.005Cl HSO2CH320.006Cl 20.007 S02CH3 H CF3 114-116 20.008 S02CH3 H CF3 20.009 S02CH3 H CF3 HCF320.010SO2CH3 HCF320.011SO2CH3 20.012 S02CH3 H CF3 OCH3SO2CH320.013CH3 OCH3SO2CH320.014CH3 OC2H5SO2CH320.015CH3 OC2H5SO2CH320.016CH3 CO2OCH3SO2CH320.017CH3 20.018 CH3 CH20CH3 S02CH3 CO2CH3SO2CH320.019Cl CO2CH3SO2CH320.020Cl HCl20.021Cl HCl20.022Cl HCF320.023SO2CH3 HCF320.024SO2CH3 No. R92 R93 R94 M. p. (°C) /nD35 OCH3SO2CH320.025CH3 20.026 CH3 OCH3 S02CH3 CO2CH3SO2CH320.027Cl CO2CH3SO2CH320.028Cl HCl20.029Cl HCl20.030Cl HCF320.031SO2CH3 20.032 S02CH3 H CF3 20.033 CH3 OCH3 S02CH3 1.5809 20.034 CH3 OCH3 S02CH3 HSO2CH320.035OCH3 HSO2CH320.036OCH3 OC2H5SO2CH320.037Cl OC2H5SO2CH320.038Cl OC2H5SO2CH320.039Cl OC2H5SO2CH320.040Cl CH2OCH3SO2CH320.041CH3 CH2OCH3SO2CH320.042CH3 HSO2CH320.043Cl HSO2CH320.044Cl CO2CH3SO2CH320.045CH3 CO2CH3SO2CH320.046CH3 CO2CH3SO2CH320.047CH3 CO2CH3SO2CH320.048CH3 20.049 CF3 H CF3 66-67 Table 21: Compounds of formula: No. R92 R93 R94 M. p. (°C) /nD35 HCl21.001Cl HCl21.002Cl HSO2CH321.003Cl HSO2CH321.004Cl HSO2CH321.005Cl HSO2CH321.006Cl 21.007 S02CH3 H CF3 21.008 S02CH3 H CF3 HCF321.009SO2CH3 21.010 S02CH3 H CF3 HCF321.011SO2CH3 HCF321.012SO2CH3 OCH3SO2CH321.013CH3 21.014 CH3 OCH3 S02CH3 21.015 CH3 OC2H5 S02CH3 21.016 CH3 OC2H5 S02CH3 CH2OCH3SO2CH321.017CH3 CH2OCH3SO2CH321.018CH3 21.019 SO2CH3CO2CH3 CO2CH3SO2CH321.020Cl HCl21.021Cl HCl21.022Cl HCF321.023SO2CH3 HCF321.024SO2CH3 OCH3SO2CH321.025CH3 OCH3SO2CH321.026CH3 No. R92 R93 R94 M. p. (°C) /nD35 CO2CH3SO2CH321.027Cl CO2CH3SO2CH321.028Cl HCl21.029Cl HCl21.030Cl HCF321.031SO2CH3 HCF321.032SO2CH3 21.033 CH3 OCH3 S02CH3 21.034 CH3 OCH3 S02CH3 21.035 OCH3 H S02CH3 HSO2CH321.036OCH3 OC2H5SO2CH321.037Cl OC2H5SO2CH321.038Cl OC2H5SO2CH321.039Cl OC2H5SO2CH321.040Cl 21.041 CH3 CH20CH3 S02CH3 CH2OCH3SO2CH321.042CH3 HSO2CH321.043Cl HSO2CH321.044Cl 21.045 CH3 C02CH3 S02CH3 CO2CH3SO2CH321.046CH3 CO2CH3SO2CH321.047CH3 CO2CH3SO2CH321.048CH3 21.049 CF3 H CF3 Formulation Examples for active inaredients of formula I (throughout, percentages are bv weight F1. Emulsifiable concentrates a) b) c) d) a compound of Tables 1-19 5% 10% 25% 50% calcium 8%6%8%6% sulfonate castor oil polyglycol ether 4 %-4 % 4 % (36 moles of ethylene oxide) <BR> <BR> <BR> octylphenol polyglycol ether-4 %-2 % (7-8 moles of ethylene oxide) <BR> <BR> <BR> cyclohexanone--10 % 20 % aromatic hydrocarbon 85 % 78 % 55 % 16 % mixture Cg-C12 Emulsions of any desired concentration can be produced from such concentrates by dilution with water.

F2. Solutions a) b) c) d) a compound of Tables 1-19 5% 10% 50% 90% 1-methoxy-3- (3-methoxy- 20%20%propoxy)-propane- polyethylene glycol 10% (mol. wt. 400) <BR> <BR> <BR> N-methyl-2-pyrrolidone--30 % 10 % aromatic hydrocarbon 75 % 60 % mixture C9-C12 These solutions are suitable for application in the form of micro-drops.

F3. Wettable powders a) b) c) d) a compound of Tables 1-19 5% 25% 50% 80% sodium lignosulfonate 4 %-3 % sodium laurylsulfate 2 % 3 %-4 % sodium diisobutylnaphthalene--6 % 5 % 6 % sulfonate octylphenol polyglycol ether-1 % 2 % (7-8 moles of ethylene oxide) highly dispersed silicic acid 1% 3% 5% 10% kaolin 88% 62% 35% The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c) a compound of Tables 1-19 0. 1% 5% 15% highly dispersed silicic acid 0.9 % 2 % 2 % inorganic carrier 99.0 % 93 % 83 % (E 0.1-1 mm) e. g. CaCO3 or Si02 The active ingredient is dissolve in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

F5. Coated granule a) b) c) ofTables1-19acompound 15%5% polyethylenepolyethyleneglycol 3%2% (mol. wt. 200) highly dispersed silicic acid 0.9 % 1 % 2 % inorganic carrier 98.0 % 92 % 80 % -1mm)(Æ0.1 e. g. CaCO3 or Si02 The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruder granules a) b) c) d) a compound of Tables 1-19 0. 1% 3% 5% 15% sodium lignosulfonate 1. 5% 2% 3% 4% carboxymethylcellulose 1.4% 2% 2% 2% kaolin 90%79%93% The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c) a compound of Tables 1-19 0. 1% 1% 5% talcum 39.9 % 49 % 35 % kaoiin 60.0% 50% 60% Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.

F8. Suspension concentrates a) b) c) d) a compound of Tables 1-19 3% 10% 25% 50% <BR> <BR> <BR> ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether-1 % 2% (15 moles of ethylene oxide) sodium lignosulfonate 4%5%3% <BR> <BR> <BR> carboxymethylcellulose 1% 1% 1% 1% 37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil mulsion 0.8 % 0.8 % 0.8 % 0.8 % water 62%38%79% The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

BiologicalExamples Example B1: Pre-emergence herbicidal action Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots.

Immediately after sowing, the test compounds are applied by spraying in the form of an aqueous suspension (prepared from a 25 % wettable powder formulation (Example F3, b)) or in the form of an mulsion (prepared from a 25 % emulsifiable concentrate (Example F1, c)) at the rate of 2 kg a. i./ha (500 litres of water/ha). The test plants are then grown in a greenhouse under optimum conditions. After a 3-week test period, the test is evaluated using a scale of nine ratings (1 = plant completely destroyed, 9 = no action).

Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

In this test, compounds of Tables 1 to 19 exhibit good herbicidal action.

The same results are obtained when the compounds of Tables 1 to 19 are formulated according to Examples F2 and F4 to F8.

Example B2: Post-emergence herbicidal action Monocotyledonous and dicotyledonous test plants are grown in a greenhouse in plastics pots containing standard soil and are sprayed, at the 4-to 6-leaf stage, with an aqueous suspension of the test compounds of formula I prepared from a 25 % wettable powder formulation (Example F3, b)) or with an emulsion of the test compounds of formula I prepared from a 25 % emulsifiable concentrate (Example F1, c)), at the rate of 2 kg a. i./ha (500 litres of water/ha). The test plants are then grown on in the greenhouse under optimum conditions. After a test period of about 18 days, the test is evaluated using a scale of nine ratings (1 = plant completely destroyed, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action. In this test, the compounds of formula I of Tables 1 to 19 exhibit good herbicidal action.

The same results are obtained when the compounds of Tables 1 to 19 are formulated according to Examples F2 and F4 to F8.

Examples of the biological action of the compounds of Tables 1 to 19 are given in Tables B1 and B2 below: Table B1: Pre-emergence action Test plant Sinapsis Solanum Stellaria Rate (g a. i./ha) Compound No.

19.024 2 1 2 2000 10.023 2 3 3 2000 1.023 1 2 2 2000 1.068 2 2 3 2000 1.264 2 2 3 2000 5.014 3 2 3 2000 1.263 2 3 4 2000 1.042 3 2 1 2000 1.115 2 2 1 2000 1.260 3 1 1 2000 10.260 4 2 1 2000 1.261 3 4 1 2000 1.262 4 4 2 2000 Table B2: Post-emerqence action Test plant Sinapsis Solanum Setaria Rate (g a. i./ha) Compound No.

19.024 1 1 2 2000 10.023 3 3 6 2000 14.014 3 4 6 2000 1.023 1 2 5 2000 1.068 3 4 3 2000 1.264 3 3 5 2000 5.014 2 3 4 2000 1.263 3 3 4 2000 1.042 2 2 3 2000 1.115 1 2 4 2000 1.083 2 3 6 2000 1.260 1 2 2 2000 10.260 2 5 2 2000 1.261 1 2 2 2000 1.106 2 2 2 2000