Salts of avermectins substituted in the 4"-position and having pesticidal properties

Abstract

A compound of formula wherein X − is an anion; n is 1,2,3 or 4; R 1 is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl; or C 2 -C 12 alkenyl; R 2 is hydrogen, unsubstituted or substituted C 1 -C 12 alkyl or C 2 -C 12 alkenyl; R 3 is hydrogen, unsubstituted or substituted C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 2 -C 12 alkenyl; or C 2 -C 12 alkynyl; or R 2 and R 3 together are an alkylene or alkenylene bridge; and, where applicable, E/Z isomers, E/Z isomeric mixtures and/or tautomers; with the proviso that RI is not sec-butyl or isopropyl when R 2 is H and R 3 is methyl; and, where applicable, their possible tautomers; a process for the preparation of those compounds and their tautomers and the use thereof; pesticidal compositions in which the active ingredient has been selected from those compounds and their tautomers; and a process for the preparation of those compositions and the use thereof; intermediates, in free form or in salt form, for the preparation of those compounds and, where applicable, their tautomers, in free form or in salt form, are described.

1 . a compoun of formula  
       
         
           
           
               
               
           
         
         wherein  
         X −  is an anion;  
         n is 1, 2, 3 or 4;  
         R 1  is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl; or C 2 -C 12 alkenyl;  
         R 2  is hydrogen, unsubstituted or mono- to penta-substituted C 1 -C 12 alkyl, unsubstituted or mono- to penta-substituted C 2 -C 12 alkenyl;  
         R 3  is hydrogen, unsubstituted or mono- to penta-substituted C 1 -C 12 alkyl, unsubstituted or mono- to penta-substituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to penta-substituted C 2 -C 12 alkenyl; unsubstituted or mono- to penta-substituted C 2 -C 12 alkynyl; or  
         R 2  and R 3  together are a three- to seven-membered alkylene bridge, or a four- to seven-membered alkenylene bridge wherein a —CH 2 — group may have been replaced by O, S or NR 4 ;  
         and wherein the substituents of the mentioned alkyl, alkenyl, alkynyl, alkylene, alkenylene and cycloalkyl radicals are selected from the group consisting of OH, halogen, halo-C 1 -C 2 alkyl, CN, NO 2 , C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, norbomylenyl, C 3 -C 8 cycloalkenyl; C 3 -C 8 cycloalkenyl unsubstituted or substituted by from one to three methyl groups; C 3 -C 8 halocycloalkyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 8 cycloalkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio, C 3 -C 8 cycloalkylthio, C 1 -C 12 haloalkylthio, C 1 -C 12 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 12 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 12 alkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 12 haloalkylsulfonyl, C 3 -C 8 halocycloalkylsulfonyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, NH(C 1 -C 6 alkyl), N(C 1 -C 6 alkyl) 2 , —C(═O)R 5 , —NHC(═O)R 6 , —P(═O)(OC 1 -C 6 alkyl) 2 ;  
         aryl, heterocyclyl, aryloxy, heterocyclyloxy; and also aryl, heterocyclyl, aryloxy and heterocyclyloxy that, depending upon the possibilities of substitution at the ring, are mono- to penta-substituted by substituents selected from the group consisting of OH, halogen, CN, NO 2 , C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, dimethylamino-C 1 -C 6 alkoxy, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenoxy, phenyl-C 1 -C 6 alkyl; phenoxy unsubstituted or substituted by from one to three substituents selected independently of one another from halogen, methoxy, trifluoromethyl and trifluoromethoxy; phenyl-C 1 -C 6 alkoxy unsubstituted or substituted in the aromatic ring by from one to three substituents selected independently of one another from halogen, methoxy, trifluoromethyl and trifluoromethoxy; phenyl-C 2 -C 6 alkenyl, phenyl-C 2 -C 6 alkynyl, methylenedioxy, —C(═O)R 5 , —O—C(═O)R 6 , —NH—C(═O)R 6 , NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , C 1 -C 6 alkylsulfinyl, C 3 -C 8 cycloalkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 3 -C 8 halocycloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 1 -C 6 haloalkylsulfonyl and C 3 -C 8 halocycloalkylsulfonyl;  
         R 4  is C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, benzyl or —C(═O)-R 5 ;  
         R 5  is H, OH, SH, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 1 -C 12 alkylthio, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy; phenyl, phenoxy, benzyloxy, —NH-phenyl, —N(C 1 -C 6 alkyl)-phenyl, NH—C 1 -C 6 alkyl-C(═O)-R 7 , —N(C 1 -C 6 alkyl)-C 1 -C 6 alkyl-C(═O)-R 7 ; or phenyl, phenoxy, benzyloxy, NH-phenyl or —N(C 1 -C 6 alkyl)-phenyl substituted in the aromatic ring by from one to three substituents selected independently of one another from halogen, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl and C 1 -C 6 haloalkoxy;  
         R 6  is H, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, benzyl, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , —NH-phenyl or —N(C 1 -C 12 alkyl)-phenyl; and  
         R 7  is H, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 2 -C 8 alkenyloxy, phenyl, phenoxy, benzyloxy, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , —NH-phenyl or —N(C 1 -C 12 alkyl)-phenyl;  
         and, where applicable, to E/Z isomers, E/Z isomeric mixtures and/or tautomers;  
         with the proviso that RI is not sec-butyl or isopropyl when R 2  is H and R 3  is methyl.  
       
     
     
         2 . A compoun according to  claim 1  of formula (I) wherein R 1  is Isopropyl r sec-butyl.  
     
     
         3 . A pesticidal composition comprising as active ingredient at least one c rnpound according to  claim 1  of formula (1), in free form or in agrochemically acceptable salt f )rn, and at least one adjuvant.  
     
     
         4 . A method of controlling pests, which comprises applying a composition according to  claim 3  to the pests or to the locus thereof.  
     
     
         5 . A process for the preparation of a composition according to  claim 3  con iprising at least one adjuvant, which cormprises Intimately mixing and/or grinding the active ingredier with the adjuvant(s).  
     
     
         6 . (canceled)  
     
     
         7 . (canceled)  
     
     
         8 . A method according to  claim 4  for the protection of plant propagation m aterial, which comprises treating the propagation material or the planting site of the propagation m Mterial.  
     
     
         9 . Plant propagation material treated in accordance with the method dc scribed in  claim 8.