Pesticide substituted diketonitriles

Abstract

The invention relates to diketontrile derivatives which have been discovered useful against arthropods, plant nematodes, helminth protozoan pests or as intermediates for such useful compounds which have a general formula: ##STR1##

What is claimed is: 
     
       1. A method of controlling insects, aphids, mites, or nematodes at a locus which comprises treatment of the locus with an effective amount of a compound of the formula: ##STR26## wherein: R is: a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from four to six carbon atoms, optionally bearing one or more substituents selected from the group consisting of R 6 , halogen, --CO 2  R 7 , --SR 71  and --OR 71  ;   c) cycloalkenyl having five or six carbon atoms, optionally bearing one or more substituents selected from the group consisting of R 6 , halogen and --CO 2  R 7  ; or   d) --(CH 2 ) p  -phenyl-(R 21 ) r  ; R 1  is:     hydrogen, chlorine, bromine, fluorine, methyl, methoxy or trifluoromethyl; R 2 , R 3 , R 4  and R 5 , each being the same or different, are:     a) hydrogen;   b) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   c) straight- or branched-chain alkyl having up to six carbon atoms, substituted by an --OR 6  group;   d) halogen;   e) nitro, cyano, -CO 2  R 6 , --COR 7 , --X--S(O) q  R 8 , --S(O) n  R 9 , --O(CH 2 ) m  OR 6 , --NR 10  R 11 , --CONR 10  R 15  or --OR 61  ;   f) cycloalkyl having from three to six carbon atoms, with the proviso that when R 2  is --S(O) n  R 9  or OR 61 , then R 9  and R 61  cannot be cycloalkyl with three to six carbon atoms;   with the proviso that when R 2  is --S(O)nR 9  or OR 61 , then R 9  and R 61  cannot be cycloalkyl with three to six carbon atoms; R 6  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen; or   b) cycloalkyl having from three to six carbon atoms; R 61  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from three to six carbon atoms; R 7  is:     a) straight- or branched-chain alkyl having up to six carbon atoms, optionally substituted by one or more halogen; or   b) cycloalkyl having from three to six carbon atoms; R 71  is:     straight- or branched-chain alkyl having up to three carbon atoms; R 8  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from three to six carbon atoms;   c) phenyl, optionally substituted by from one to five R 21  groups, which can be the same or different; or   d) --CH 2  CN, --CH 2  CO 2  R 6  or --NR 10  R 11  ; R 9  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from three to six carbon atoms;   c) --CH 2  CN, --CH 2  CO 2  R 6  or NR 10  R 11  ; R 10  is:     a) hydrogen;   b) straight- or branched-chain alkyl having up to six carbon atoms, optionally substituted by one or more halogen; or   c) cycloalkyl having from three to six carbon atoms; provided that when R 7  and R 10  are part of a group --CONR 7  R 10  they can, together with the nitrogen to which they are attached, form a five or six membered ring optionally having one additional hetero ring atom which is oxygen or nitrogen, said ring being optionally substituted by one or more alkyl, each having up to three carbon atoms;   R 11  is:     a) straight- or branched-chain alkyl having up to six carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from three to six carbon atoms; or   c) --COR 7 , --CO 2  R 7  or --CONR 7  R 10  ; provided that when R 10  and R 11  are part of a group --NR 10  R 11  they can, together with the nitrogen to which they are attached, form a five or six membered ring optionally having one additional hetero ring atom which is oxygen or nitrogen, said ring being optionally substituted by one or more alkyl, each having up to three carbon atoms;   X is:     oxygen, --N(R 12 )--, --(CR 13  R 14  --) t  -- or --S(O) u  --; R 12  is:     a) hydrogen;   b) straight- or branched-chain alkyl, alkenyl or alkynyl having up to six carbon atoms, optionally substituted by one or more halogen;   c) cycloalkyl having from three to six carbon atoms;   d) phenyl, optionally substituted by from one to five R 21  groups, which can be the same or different; or   e) --COR 7 , --CO 2  R 7 , --CONR 7  R 10 , --OR 17  or --SO 2  R 7  ; each of R 13  and R 14 , which can be the same or different, is:     a) hydrogen; or   b) straight- or branched-chain alkyl having up to six carbon atoms, optionally substituted by one or more halogen; R 15  is:     R 7  or --OR 17  ; provided that when R 10  and R 15  are part of a group --CONR 10  R 15  they can, together with the nitrogen to which they are attached, form a five or six membered ring optionally having one additional hetero ring atom which is oxygen or nitrogen, said ring being optionally substituted by one or more alkyl, each having up to three carbon atoms;   R 17  is:     straight- or branched-chain alkyl having up to six carbon atoms; R 21  is:     halogen, R 7 , nitro, cyano, --CO 2  R 7 , --S(O) n  R 7 , --NR 10  R 11  or --OR 7  ;   m is one, two, or three;   n is zero, one or two;   p is zero or one;   q is zero, one or two; provided that when X is --N(R 12 )-- or oxygen, then q is two and that when X is --S(O)n--, then q is zero or two;   r is zero or an integer from one to five;   t is an integer from one to four, provided that when t is greater than one, the groups --(CR 13  R 14 )-- can be the same or different; and   u is zero or two; with the proviso that when R 1 , R 3 , and R 5  are hydrogen, R 4  is S(O)nR 9  and n is two, then R 9  is methyl;     i) and R 2  is chlorine, then R is the definition other than t-butyl;   ii) and R 2  is trifluoromethyl, then R is other than methyl. also with the proviso that when R 1 , R 3 , and R 5  are hydrogen, R 2  is S(O)nR 9 , n is 0, R 9  is methyl, R 4  is chlorine, R is not 3,5-bis(trifluoromethyl)phenyl.     
     
     
       2. A method according to claim 1 wherein: R is:   a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to four carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from four to six carbon atoms, optionally bearing one or more substituents selected from the group consisting of R 6 , halogen, --CO 2  R 7 , --SR 71  and --OR 71  ;   c) cycloalkenyl having five or six carbon atoms, optionally bearing one or more substituents selected from the group consisting of R 6  and halogen;   R 1  and R 5  are hydrogen; R 2 , R 3  and R 4  each being the same or different, are:     a) hydrogen;   b) straight- or branched-chain alkyl, alkenyl or alkynyl having up to four carbon atoms, optionally substituted by one or more halogen;   c) straight- or branched-chain alkyl having up to four carbon atoms, substituted by an --OR 6  group;   d) halogen;   e) nitro, cyano, --X--S(O) q  R 8 , --S(O) n  R 9 , --NR 10  R 11  or --OR 61  ;   f) cycloalkyl having from three to four carbonatoms;   with the proviso that when R 2  is OR 61 , R 61  cannot be cycloalkyl with three to six carbon atoms; R 6  is:     a) straight- or branched-chain alkyl having up to six carbon atoms, optionally substituted by one or more halogen; or R 61  is:     a) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen;   b) cycloalkyl having from three to six carbon atoms; R 7  is:     a) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen; or R 71  is:     straight- or branched-chain alkyl having up to four carbon atoms; R 8  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to four carbon atoms, optionally substituted by one or more halogen;   b) phenyl, optionally substituted by from one to five R 21  groups, which can be the same or different; or R 9  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to four carbon atoms, optionally substituted by one or more halogen; R 10  is:     a) hydrogen;   b) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen; or   c) cycloalkyl having from three to six carbon atoms; provided that when R 7  and R 10  are part of a group --CONR 7  R 10  they can, together with the nitrogen to which they are attached, form a five or six membered ring optionally having one additional hetero ring atom which is oxygen or nitrogen, said ring being optionally substituted by one or more alkyl, each having up to three carbon atoms;   R 11  is:     a) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen;   b) --CONR 7  R 10  ; provided that when R 10  and R 11  are part of a group --NR 10  R 11  they can, together with the nitrogen to which they are attached, form a five or six membered ring optionally having one additional hetero ring atom which is oxygen or nitrogen, said ring being optionally substituted by one or more alkyl, each having up to three carbon atoms;   X is:     --N(R 12 )-- or --(CR 13  R 14  --) t  --; R 12  is:     a) hydrogen;   b) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen;   c) cycloalkyl having from three to six carbon atoms;   d) phenyl, optionally substituted by from one to five R 21  groups, which can be the same or different; each of R 13  and R 14 , which can be the same or different, is:     a) hydrogen; or   b) straight- or branched-chain alkyl having up to four carbon atoms, optionally substituted by one or more halogen; R 21  is:     halogen, R 7 , nitro, cyano,--S(O) n  R 7 , or--OR 7  ;   n is zero, one or two;   q is zero, one or two; provided that when X is --N(R 12 )--, then q is two;   t is an integer from one to four, provided that when t is greater than one, the groups --(CR 13  R 14 )-- can be the same or different; and with the proviso that when R 3  is hydrogen, R 4  is S(O)nR 9 , n is two, R 9  is methyl   i) and R 2  is chlorine, then R is the definition other than t-butyl;   ii) and R 2  is trifluoromethyl, then R is other than methyl.     
     
     
       3. A method according to claim 2 wherein: R is:   a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to four carbon atoms, optionally substituted by one or more halogen; R 2 , R 3  and R 4 , each being the same or different, are:     a) hydrogen;   b) straight- or branched-chain alkyl having up to three carbon atoms, optionally substituted by one or more halogen;   c) halogen;   d) nitro, cyano, --S(O)nR 9 , or --OR 61  ; R 9  is:     a) straight- or branched-chain alkyl, alkenyl or alkynyl having up to three carbon atoms, optionally substituted by one or more halogen;   R 61  is straight- or branched alkyl having up to three carbon atoms, optionally substituted by one or more halogen;   n is zero, one or two; with the proviso that when R 3  is hydrogen, R 4  is S(O)nR 9 , n is two, R 9  is methyl   i) R 2  is chlorine, R is the definition other than t-butyl;   ii) R 2  is trifluoromethyl, R is other than methyl.     
     
     
       4. A method according to claim 1 wherein the compound is: a) 1-(4-chloro-2-methylsulfonylphenyl)-2-cyano-4-methylpentan-1,3-dione; or   b) 1-(4-chloro-2-nitrophenyl)-2-cyano-4-methylpentan-1,3-dione.   
     
     
       5. A composition for controlling insects, aphids, mites or nematode pests at a locus formulated for application to the locus of said pest and comprising an effective amount of the compound of anyone of claims 1 to 4.