Patent DE-10311300-A1 (DE)
Title: New 2-alkoxy-4-halo-6-alkylphenyl-substituted (hetero)cyclic ketoenols, useful as total or selective herbicides and pesticides, e.g. insecticides, acaricides and nematocides for plant protection
Inventor: FISCHER REINER
IPC: C07D491/10
Filed: 2003-03-14
Abstract: 2-Alkoxy-4-halo-6-alkylphenyl-substituted cyclic keto-enol compounds (I), derived from pyrrole, furan, thiophene, pyran, 1,3-thiazine, cyclopentane, cyclohexane or pyrazole, are new. Also new are 19 classes of intermediates, e.g. 2-alkoxy-4-halo-6-alkylphenylacetic acids (XXVII) and various ester or amide derivatives. Cyclic keto-enol derivatives of formula R-Ar (I) are new. Ar : 2-alkoxy-4-halo-6-alkylphenyl; R : cyclic keto-enol residue of formula (a) - (c); T 1N(D), O or S; T 2-C(A)=C(D)-O-, -C(A)(B)-C(Q 1>)(Q 2>)-, -C(A)(B)-C(Q 3>)(Q 4>)-C(Q 5>)(Q 6>)- or -N(A)-N(D)-; A : H; alkyl, alkenyl, alkoxyalkyl or alkylthioalkyl (all optionally substituted (os) by halo); os, optionally unsaturated cycloalkyl (optionally having at least one ring atom replaced by a heteroatom); or aryl, aralkyl or heteroaryl (all os by halo, alkyl, haloalkyl, alkoxy, haloalkoxy, CN or NO 2); B : H, alkyl or alkoxyalkyl; or C(A)(B) : os, (un)saturated ring (optionally containing heteroatom(s)); D : H; or alkyl, alkenyl, alkynyl, alkoxyalkyl, optionally unsaturated cycloalkyl (optionally having at least one ring atom replaced by a heteroatom), aryl, aralkyl, heteroarakyl or heteroaryl (all os); or A + D : group completing an (un)saturated ring (optionally containing heteroatom(s) (or additional heteroatom(s) in the case of (R 2>; T 2 = N(A)-N(D))); or A + Q 1>alkanediyl or alkenediyl (both os by OH or (all os) alkyl, alkoxy, alkylthio, cycloalkyl, benzyloxy or aryl); Q 1>, Q 2>, Q 4> - Q 6>H or alkyl; Q 3>H, os alkyl, alkoxyalkyl, alkylthioalkyl, os cycloalkyl (optionally having one CH 2 replaced by O or S) or os phenyl; or C(Q 3>)(Q 4>) : os, (un)saturated ring (optionally containing a heteroatom); G : H, -COR 1>, -C(L)MR 2>, -SO 2R 3>, -P(L)R 4>R 5>, E or -C(L)-NR 6>R 7>; E : 1 equivalent of metal or ammonium ion; L, M : O or S; R 1>alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl (all os by halo); cycloalkyl (os by halo, alkyl or haloalkyl and optionally interrupted by heteroatom(s)); or phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryloxy (all os); R 2>alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl (all os by halo); or cycloalkyl, phenyl or benzyl (all os); R 3> - R 5>alkyl, alkoxy, mono- or dialkylamino, alkylthio, alkenylthio or cycloalkylthio (all os by halo); or phenyl, benzyl, phenoxy or phenylthio (all os); R 6>, R 7>H; alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl (all os by halo); or phenyl or benzyl (both os); or NR 6>R 7>heterocycle (optionally interrupted by O or S). [Image] Independent claims are included for: (a) the preparation of (I); and (b) new intermediates of formulae R 8>OOC-C(A)(B)-N(D)-COCH 2Ar (II), R 8>OOC-C(A)(B)-OCOCH 2Ar (III), V-C 6H 4-CH 2S-C(A)(B)-CO-CH(Ar)COOR 8> (IV), O=C=C(CO-Hal)-CH 2Ar (VI), R 8>OOC-C(A)(B)-C(Q 1>)(Q 2>)-COCH 2Ar (VIII), R 8>OOC-C(A)(B)-C(Q 3>)(Q 4>)-C(Q 5>)(Q 6>)-COCH 2Ar (IX), ArCH(COU) 2 (XI), ArCH 2CO-N(D)-N(A)-COOR 8> (XII), ArCH 2COZ (XXIV), HOOC-C(A)(B)-N(D) -COCH 2Ar (XXV), ArCH 2COOH (XXVII), ArCH 2CO-N(D)-C(A)(B)-CN (XXIX), ArCH 2COOR 8> 1> (XXXI), ArCH(COOH) 2 (XXXIII), ArCH 2CO-C(Q 1>)(Q 2>)-C(A)(B)-COOH (XXXIV), ArCH(COOR 8> 1>)-CO-C(Q 1>)(Q 2>)-C(A)(B)-COOR 8> 1> (XXXV), ArCH 2CO-C(Q 5>)(Q 6>)-C(Q 3>)(Q 4>)-C(A)(B)-COOH (XXXVIII), ArCH(COOR 8> 1>)-CO-C(Q 5>)(Q 6>)-C(Q 3>) (Q 4>)-C(A)(B)-COOR 8> 1> (XXXIX) and D-NH-N(A)-COOR 8> (XLII). R 8>, R 8> 1>alkyl; V : H, halo, alkyl or alkoxy; Hal : halogen; U : NH 2 or OR 8>; Z : leaving group derived from a carboxylic acid activating reagent. ACTIVITY : Herbicide; Insecticide, Acaricide; Nematocide; Parasiticide; Antifouling; Fungicide; Antimicrobial. 3-(4-Chloro-2-methoxy-6-methylphenyl)-4-hydroxy-5,5-(3-methylpentamethylene)-2-oxo-2,5-dihydropyrrole (Ia). at a concentration of 1000 ppm gave 100% mortality of Spodoptera frugiperda caterpillars on cabbage leaves within 7 days. MECHANISM OF ACTION : None given in the source material.