Pesticidal heterocyclic dihaloallyl compounds

Abstract

The invention relates to compounds of formula wherein Het, A 1 , A 2 , A 3 , A 4 , D, W, T, Q, Y, X 1 , X 2 , R 1 , R 2 , R 3 , R 4 , k and m are as defined hereinabove, and, where applicable, to possible E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form, to a process for the preparation of and to the use of those compounds, E/Z isomers, mixtures of E/Z isomers and/or tautomers, to pesticidal compositions in which the active ingredient has been selected from those compounds, E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in agrochemically usable salt form, to a process for the preparation of and to the use of those compositions, to plant propagation material treated with those compositions, to a method of controlling pests, to intermediates and, where applicable, to possible E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form, for the preparation of those compounds, E/Z isomers, mixtures of E/Z isomers and/or tautomers, and to a process for the preparation of and to the use of those intermediates and, where applicable, possible E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof.

1 . A compound of formula 
     
       
         
         
             
             
         
       
       wherein 
       Het is non-aromatic heterocyclyl that does not contain cumulative double bonds and that has 5 or 6 ring members of which the linking ring member, by way of which Het is linked, by means of a first single bond, to the remainder of the compound of formula I, is either a nitrogen atom that carries two further single bonds which lead to the two ring members of Het directly adjacent to that nitrogen atom, or a carbon atom that carries a further single bond and a double bond which lead to the two ring members of Het directly adjacent to that carbon atom, and the remaining 4 or 5 ring members of Het are, independently of one another, selected from the group consisting of the ring members —C(R i )(R ii )—, —C(═O)—, —C(═S)—, —O—, —S—, —C(R iv )═ and —N═, wherein (A) of the 5 or 6 ring members of Het, from 1 up to and including 4 ring members, independently of one another, each contributes a hetero atom to the basic ring structure of Het consisting of 5 or 6 ring atoms, (B) two directly adjacent ring members of Het are not both —O—, and (C), when the mentioned linking ring member of Het is a nitrogen atom, either (i) at least one ring member of the mentioned remaining 4 or 5 ring members of Het is —N═ or (ii) at least one of the 2 or 3 ring members of Het that are neither the mentioned linking ring member of Het nor its two directly adjacent ring members is —C(═O)— or —C(═S)— or (iii) at least three ring members of the mentioned remaining 4 or 5 ring members of Het are each independently of the others —C(R iv )═ or (iv) at least two ring members of the mentioned remaining 4 or 5 ring members of Het are each independently of the other(s) —O—, —S— or —N(R iii )— and, when the mentioned linking ring member of Het is a carbon atom, either (v) the mentioned double bond starting from that carbon atom leads to a nitrogen atom or (vi) the ring member of Het bonded to the mentioned further single bond starting from that carbon atom is —C(═O)— or —C(═S)—; 
       R i  and R ii  are each independently of the other hydrogen, halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 1 -C 6 alkoxy-C 1 -C 6 alkyl; 
       R iii  is C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 1 -C 6 alkoxy-C 1 -C 6 alkyl; 
       R iv  is hydrogen, halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 1 -C 6 alkoxy-C 1 -C 6 alkyl; 
       A i , A 2  and A 3  are each independently of the others a bond or a C 1 -C 6 alkylene bridge which is unsubstituted or substituted from one to six times by, each independently of the other(s), C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C 1 -C 6 alkyl or halo-C 1 -C 3 alkyl; 
       A 4  is a C 1 -C 6 alkylene bridge which is unsubstituted or substituted from one to six times by, each independently of the other(s), C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C 1 -C 6 alkyl or halo-C 1 -C 3 alkyl; 
       D is CH or N; 
       W is O, NR 5 , S, S(═O), S(═O) 2 , —C(═O)—O—, —O—C(═O)—, —C(═O)—NR 6 — or —NR 6 —C(═O)—; 
       T is a bond, O, NH, NR 5 , S, S(═O), S(═O) 2 , —C(═O)—O—, —O—C(═O)—, —C(═O)—NR 6 — or —NR 6 —C(═O)—; 
       Q is O, NR 5 , S, S(═O) or S(═O) 2 ; 
       Y is O, NR 5 , S, S(═O) or S(═O) 2 ; 
       X i  and X 2  are each independently of the other fluorine, chlorine or bromine; 
       R 1  and R 2  are each independently of the other H, halogen, CN, nitro, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 2 -C 6 alkenyl, halo-C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, halo-C 2 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 alkoxycarbonyl or halo-C 3 -C 6 alkynyloxy; 
       R 3  is halogen, CN, nitro, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 2 -C 6 alkenyl, halo-C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, halo-C 2 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 alkoxycarbonyl or halo-C 3 -C 6 alkynyloxy, the two R 3  substituents being identical or different when m is 2; 
       R 4  is halogen, CN, nitro, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 2 -C 6 alkenyl, halo-C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy, halo-C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, halo-C 2 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 1 -C 6 alkoxycarbonyl or halo-C 3 -C 6 alkynyloxy, the R 4  substituents being identical or different when k is greater than 1; 
       R 5  is H, C 1 -C 6 alkyl, halo-C 1 -C 3 alkyl, halo-C 1 -C 3 alkylcarbonyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkylcarbonyl or C 3 -C 8 cycloalkyl; 
       R 6  is H, C 1 -C 6 alkyl, halo-C 1 -C 3 alkyl, halo-C 1 -C 3 alkylcarbonyl, C 1 -C 6 alkoxyalkyl, C 1 -C 6 alkylcarbonyl or C 3 -C 8 cycloalkyl; 
       k is 0, 1, 2 or 3 when D is N or is 0, 1, 2, 3 or 4 when D is CH; and 
       m is 0, 1 or 2, 
       and, where applicable, possible E/Z isomers, mixtures of E/Z isomers and/or tautomers thereof, in each case in free form or in salt form 
       wherein HET is not. 
     
   
   
       2 . A compound according to  claim 1  in free form. 
   
   
       3 . A compound according to  claim 1 , wherein X 1  and X 2  are chlorine or bromine. 
   
   
       4 . A compound according to  claim 1 , wherein A 1  is a bond. 
   
   
       5 . A compound according to  claim 1 , wherein the group A 2 -T-A 3  is a bond. 
   
   
       6 . A compound according to  claim 1 , wherein W is O, —C(═O)O— or —C(═O)NH—. 
   
   
       7 . A compound according to  claim 1 , wherein A 4  is a straight-chain alkylene bridge. 
   
   
       8 . A compound according to  claim 1 , wherein Q is oxygen. 
   
   
       9 . A compound according to  claim 1 , wherein Y is oxygen. 
   
   
       10 . A compound according to  claim 1 , wherein R 1  and R 2  are bromine or chlorine. 
   
   
       11 . A compound according to  claim 1 , wherein m is 0. 
   
   
       12 . A compound according to  claim 1 , wherein R 4  is halogen and k is 2 or 0. 
   
   
       13 . A compound according to  claim 1 , wherein D is CH. 
   
   
       14 . A pesticidal composition comprising as active ingredient at least one compound according to  claim 1 , in free form or in agrochemically usable salt form, and at least one adjuvant. 
   
   
       15 . A process for the preparation of a composition as described in  claim 14 , which comprises intimately mixing the active ingredient with the adjuvants. 
   
   
       16 . A method of controlling pests, which comprises applying a composition as described in  claim 14  to the pests or to the locus thereof. 
   
   
       17 . A compound according to  claim 1 , wherein X 1  and X 2  are chlorine or bromine; A 1  is a bond; the group A 2 -T-A 3  is a bond; W is —O—, —C(═O)O—, or —C(═O)NH—; A4 is a straight-chain alkylene bridge; Q is oxygen; Y is oxygen; R 1  and R 2  are bromine or chlorine; m is 0; R 4  is halogen; k is 2 or 0; and D is CH.