Patent EA-000278-B1 (EA)
Title: Hydroximic acid derivatives and administration thereof
Inventor: KIRIO YOSHIE
IPC: C07C/
Filed: 1996-03-29
Abstract: 1. Hydroximic acid derivatives of general formula (I):   wherein: G is either G1 or G2 or G3 or G4 of formula:   X1, X2, X3 are independently a hydrogen or halogen atom; a hydroxy, mercapto, nitro, thiocyanato, azido group, cyano group; -a alkyl or haloalkyl group, cyanoalkyl, alkoxy, haloalkoxy, cyanoalkoxy, alkylthio, haloalkylthio, cyanoalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, these alkyl or alkoxy being lower radicals, -a cycloalkyl or halocycloalkyl group, alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, alkynylthio, these alkyl or alkenyl or alkynyl being lower radicals, -amino, lower alkylamino, lower dialkylamino, acylamino, -a lower alkoxycarbonyl group, -N,N-dialkylcarbamoyl, -N-alkylsulfamoyl, -N,N-dialkylsulfamoyl, R1, R2 are independently a hydrogen atom, or a alkyl or haloalkyl, a cycloalkyl or halocycloalkyll cyano, alkoxyalkyl, alkoxycarbonyl; or R1 and R2 can form together a divalent radical such as an alkylene group, these alkyl or alkoxy or alkylene being lower radicals, R3 is a hydrogen atom, or a alkyl or haloalkyl, a cycloalkyl or halocycloalkyl, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl, cyanoalkyl, haloalkoxyalkyl, dialkylaminoalkyl, an optionnally substituted phenyl or an optionnally substituted benzyl group, these alkyl or alkoxy or alkenyl or alkynyl being lower radicals, W is an oxygen or a sulfur atom, SO or SO2 R4, R5 are a lower alkyl group, R6, R7 are independently a hydrogen atom or a lower alkyl group, the adjective "lower" qualifying an organic group meaning that this group has up to 6 carbons. 2. Hydroximic acid derivatives according to Claim 1 wherein when G is either G1 or G2, R4 is methyl; R5 is methyl; or when G is either G3 or G4, R5 is methyl; R6 is methyl and R7 is hydrogen. 3. Hydroximic acid derivatives according to any of the foregoing Claims wherein: R3 is a hydrogen atom, a lower alkyl or cycloalkyl group, and/or R1 is a hydrogen atom or a lower alkyl or cycloalkyl, cyano, alkoxycarbonyl, haloalkylgroup and/or R2 is hydrogen or methyl and/or X3 is H and/or X1 or X2 are alkyl, cyano, halogen, haloalkyl, alkoxy, haloalkoxy, the adjective "lower" qualifying an organic group meaning that this group has up to 6 carbons. 4. Hydroximic acid derivatives according to any of the foregoing Claims wherein both double bonds in the formula (I) as shown in Claim 1 are of E configuration. 5. Hydroximic acid derivatives according to any of the foregoing Claims wherein X1 is methyl or hydrogen, X2 and X3 are hydrogen; R.1 is hydrogen or methyl; R2 is hydrogen; R3 is hydrogen or lower alkyl group; W is an oxygen atom. 6. Intermediate compounds which may be used in the preparation of compounds according to any of the foregoing Claims which have the general formula (II) wherein W is S, that is to say,   wherein R.1, R2, R3,.X1, X2, X3, are the same as defined in any of the foregoing Claims. 7. A process for the preparation of a compound according to any of the foregoing Claims which comprises the reaction of a compound of general formula (II)   with a compound of general formula (III)   wherein, R.1, R2, R3, W.X1, X2, X3, G, are the same as defined in the general formula (I) above; V is a halogen atom. 8. A process for the preparation of a compound according to Claim 7 in the presence of an acid binding agent, optionally in the presence of a solvent and/or at a temperature from -80 degree C to 150 degree C or to the boiling point of the solvent, and/or with a relative amount of compound of formula (III) versus compound of formula (II) within the range from 0.5 to 2, preferably 0.9 to 1.1. 9. A process for the preparation of a compound according to any of the Claims 1 to 5 which comprises the reaction of a compound of general formula (1-1) with methylamine according to the reaction scheme   wherein, R.1, R2, R3, R4, R5, W.X1, X2, X3 are the same as defined in any of 1-5 Claims 1-5, and Z is N or CH. 10. A process for the preparation of a compound according to Claim 9 wherein the reaction temperatures are from -50 degree C to 100 degree C or the boiling point of the solvent and/or a molar ratio of methylamine to the compound of formula (I-1) is within the range from 1 to 5, preferably 1.1 to 2. 11. A process for the preparation of a compound according to any of the Claims 1 to 5 and having a Z stereochemistry on the hydroximic moiety of the molecule wherein a compound of same chemical formula and having a Z stereochemistry on the hydroximic moiety of the molecule is heated in a solvent preferably under UV irradiation and/or in the presence of an acid catalyst until the proper and desired transformation rate of the Z isomer into an E is obtained. 12. A process for the preparation of a compound according to any of the Claims 1 to 6 wherein W is SO or S02 in-the formula (I) thereof, whereby a corresponding compound wherein W is S is treated by mean of an oxidising agent in an inert solvent. 13. A pesticidal composition which comprises, as active material(s), compound according to any one of Claim 1 to 5 in association with liquid carrier which is acceptable in agriculture, and/or a surface active agent which is also acceptable in agriculture. 14. A pesticidal composition according to Claim 13 which is fungicidal and which comprises 0.1 to 99 % w/w of active ingredient. 15. A pesticidal composition according to Claim 14 which is fungicidal and which comprises 1 to 60 %w/w of active ingredient. 16. A process for the treatment of cultivated plants affected or capable of being affected by fungal diseases, characterized in that an effective dose of a compound according to any one of Claims 1 to 5 is applied to the plants. 17. A process according to Claim 16 characterized in that, in the case of foliar application, the effective dose lies in the range of from 1 to 10000 ppm, and the application rate is from 5 g/ha to 10 kg/ha. 18. A process according to Claim 17 charcaterized in that the effective dose lies in the range from 1 to 500 ppm. 19. A process according to any of Claims 17 and 18 charcaterized in that the application rate is from 10 g/ha to 1 kg/ha. 20. A process according to any of Claims 18 to 20 charcaterized in that the application rate is from 50 g/ha to 500 g/ha. 21. A process according to Claim 16 characterized in that, in the case of soil application, the effective dose lies in the range from 0.01 to 100 kg/ha. 22. A process according to Claim 21 characterized in that the effective dose lies in the range from 0.01 to 2 kg/ha. 23. A process according to any of Claims 16 to 22 wherein the dose is applied to cereals.