Pesticidal n-phenylpyrazole derivatives

Abstract

The invention relates to 5-(substituted dithio- or dioxy-alkylamino)pyrazole derivatives of formula (I) or salts thereof: wherein the various symbols are as defined in the description, to processes for their preparation, to compositions thereof, and to their use for the control of pests (including arthropods and helminths).

1 . A compound of formula (I):  
     
       
         
         
             
             
         
       
     
     wherein: 
 Q is CN or CSNH 2 ;  
 R 1  is CN, CF 3  or CSNH 2 ;  
 R 2  is (C 1 -C 3 )-alkyl or (C 1 -C 3 )-haloalkyl;  
 R 3  is (C 3 -C 6 )-alkenyl, (C 3 -C 6 )-alkynyl, R 6 , (C 3 -C 6 )-cycloalkyl or (C 1 -C 4 )-alkyl which last mentioned group is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )-alkoxy, S(O) m R 7 , R 6 , (C 3 -C 6 )-cycloalkyl, CO 2 (CD 2 ) q R 6 , CO 2 (C 2 ) q R 6a  and CO 2 R 7 ;  
 R 4  is (C 2 -C 4 )-alkyl or (C 2 -C 4 )-haloalkyl which groups are unsubstituted or substituted by a radical selected from the group consisting of NHCOR 8 , NHR 8 , NR 8 COR 8 , OCOR 8 , OR 6 , OR 6a , S(O) p (CH 2 ) q R 6 , S(O) p (CH 2 ) q R 6a , αN—R 8 , —NNHR 8 , ═NOR 8 , ═NOH, ═NNHC(═X)R 8 , ═NNHC(═X)NNH 2 , ═NNR 8 C(═X)NH 2 , ═NNHC(═O)O(CH 2 ) q R 9 , (C 1 -C 4 )-alkoxy and S(O) m R 7  (wherein two (C 1 -C 4 )-alkoxy or S(O) m R 7  radicals may be attached to the same carbon atom to form an acetal, thioacetal or hemithioacetal group or a cyclic acetal, thioacetal or hemithioacetal which contains 5 or 6 ring atoms); or is CO 2 R 9 , COCOR 10 , SO 2 R 8 , COR 8 , COCH 2 OR 8  or P(═X)(—YR 8 )(-ZR 8a );  
 R 5  is CF 3 , OCF 3 , SF 5  or halogen;  
 W is C-halogen, C—NR 11 R 12  or N;  
 X is O or S;  
 Y and Z are each independently O, S or a covalent, bond;  
 R 36  is phenyl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkoxy, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalkoxy, CN, NO 2 , S(O) p R 7  and NR 11 R 12 ;  
 R 6a  is heteroaryl unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalkoxy, CN, NO 2 , S(O) p R 7 , NR 11 R 12 , OH and oxo;  
 R 7  and R 8a  are independently (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 3 -C 6 )-cycloalkyl-(C 1 -C 3 )-alkyl or (CH 2 ) q R 6 ;  
 R 9  is R 6 , (C 3 -C 4 )-alkenyl, (C 3 -C 4 )-alkynyl or (C 1 -C 4 )-alkyl which last mentioned group is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-haloalkoxy, R 6 , S(O) m R 6  and (C 3 -C 6 )-cycloalkyl;  
 R 10  is OR 9  or NR 13 R 14 ;  
 R 11  and R 12  are each independently H, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 3 -C 4 )-alkenyl, (C 3 -C 4 )-haloalkenyl, (C 3 -C 4 )-alkynyl, (C 3 -C 6 )-cycloalkyl or (C 3 -C 6 )-cycloalkyl-(C 1 -C 4 )-alkyl; or  
 R 11  and R 12  together with the attached N atom form a five- or six-membered saturated or unsaturated ring which optionally contains an additional hetero atom in the ring which is selected from O, S and N, the ring being unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C 1 -C 4 ) alkyl and (C 1 -C 4 )-haloalkyl;  
 R 13  is H, (C 1 -C 4 )-alkyl or R 6 ;  
 R 14  is H or R 9 ;  
 m, n and p are each independently 0, 1, or 2;  
 q is 0 or 1; and  
 each heteroaryl in the above-mentioned radicals is independently a heteroaromatic radical having 3 to 7 ring atoms and 1, 2 or 3 hetero atoms in the ring selected from the group consisting of N, O and S;  
 or a pesticidally acceptble salt thereof.  
 
   
   
       2 . A compound or a salt thereof as claimed in  claim 1  wherein Q and R 1  are each CN.  
   
   
       3 . A compound or a salt thereof as claimed in  claim 1  wherein R 2  and R 5  are each CF 3 .  
   
   
       4 . A compound or a salt thereof as claimed in  claim 1  wherein Q and R 1  are each CN; 
 R 2  and R 5  are each CF 3 ;    W is C—Cl; and    the other radicals are as defined in  claim 1 .    
   
   
       5 . A compound or a salt thereof as claimed in  claim 1  wherein 
 Q and R 1  are each CN;    R 2  is CF 3 ;    R 4  is (C 2 -C 4 )-alkyl or (C 2 -C 4 )-haloalkyl which groups are substituted by a radical selected from the group consisting of NHCOCR 8 , NHR 8 , NR 8 COR 8 , OCOR 8 , OR 6 , OR 6a , S(O) p (CH 2 ) q R 6 , S(O) p (CH 2 ) q R 6a , ═N—R 8 , ═NNHR 8 , ═NOR 8 , ═NOH, ═NNHC(═X)R 8 , ═NNHC(═X)NH 2 , ═NNR 8 C(═X)NH 2 , ═NNR 8 C(═X)NH 2 , ═NNHC(═O)O(CH 2 ) q R 9 , (C 1 -C 4 )-alkoxy and S(O) m R 7  (wherein two (C 1 -C 4 )-alkoxy or S(O) m R 7  radicals may be attached to the same carbon atom to form an acetal, thioacetal or hemithioacetal group or a cyclic acetal, thioacetal or hemithioacetal which contains 5 or 6 ring atoms); or is CO 2 R 9 , COCOR 10 , SO 2 R 8 , COR 8 , COCH 2 OR 8  or P(═X)(—YR 8 )(-ZR 8a );    R 5  is CF 3 ;    W is C—Cl, and    the other radicals are as defined in  claim 1 .    
   
   
       6 . A process for the preparation of a compound of formula (I) or a salt thereof as defined in  claim 1 , which process comprises: 
 a) where Q is CN, R 1  is CN or CF 3 , and R 2 , R 3 , R 4 , R 5 , W and n are as defined in  claim 1 , reacting a corresponding compound of formula (II):                          wherein the various values are as defined in  claim 1 , with a compound of formula (III):      R 1 -L  (III)    wherein R 4  is as defined in  claim 1  and L is a leaving group; or    b) where Q is CN, R 1  is CN or CF 3 , and R 2 , R 3 , R 4 , R 5 , W and n are as defined in  claim 1 , reacting a compound of formula (IV):                          wherein L 1  is a leaving group, and the other values are as defined in  claim 1 , with a compound of formula (V):      R 3 R 4 N—H  (V)    wherein R 3  and R 4  are as defined in  claim 1 , in the presence of a base; or    c) where R 4  is (C 2 -C 4 )-alkyl or (C 2 -C 4 )-haloalkyl which groups are substituted by a radical selected from the group consisting of ═N—R 8 , ═NNHR 8 , ═NOR 8 , ═NOH, ═NNHC(═X)R 8 , ═NNHC(═X)NH 2 , NNR 8 C(═X)NH 2  and ═NNHC(═O)O(CH 2 ) q R 9 , Q is CN, R 1  is CN or CF 3 , and R 2 , R 3 , R 5 , W and n are as defined in  claim 1 , recting a corresponding compound of formula (I) in which the (C 2 -C 4 )-alkyl carbon atom bearing the relevant radical is replaced by a carbon atom substituted by a carbonyl group or an acetal derivative thereof, with a compound of formula (VI), (VII), (VIII), (IX), (X), (XI), (XII) or (XIII):      NH 2 —R 8   (VI)  NH 2 NHR 8   (VII)  NH 2 OR 8   (VIII)  NH 2 OH  (IX)  NH 2 NHC(═X)R 8   (X)  NH 2 NHC(═X)NH 2   (XI)  NH 2 NR 8 C(═X)NH 2   (XII)  NH 2 NHC(═O)O(CH 2 ) q R 9   (XIII)    wherein the various values are as defined in  claim 1 , or an acid salt thereof, in the presence of a strong acid; or    d) where Q and/or R 1  is CSNH 2 , and the other values are as defined in  claim 1 , reacting the corresponding compound of formula (I) wherein Q and/or R 1  is CN, with an alkali or alkaline earth metal hydrosulfide, or with H 2 S in the presence of an organic base, or with the reagent Ph 2 PS 2 ; or    e) where Q and/or R 1  is CSNH 2 , and the other values are as defined in  claim 1 , reacting the corresponding compound of formula (I) wherein Q and/or R 1  is CN, with a bis(trialkylsilyl)sulfide, in the presence of a base; or    f) where n is 1 or 2 and R 1 , R 2 , R 3 , R 4 , R 5  and W are as defined in  claim 1 , oxidising the corresponding compound in which n is 0 or 1; and    g) if desired, converting a resulting compound of formula (I) into a pesticidally acceptable salt thereof.    
   
   
       7 . A pesticidal composition comprising a compound of formula (1) or a pesticidally acceptable salt thereof as defined in  claim 1 , in association with a pesticidally acceptable diluent or carrier and/or surface active agent.  
   
   
       8 . The use of a compound of formula (1) or a salt thereof according to  claim 1 , for the preparation of a veterinary medicament.  
   
   
       9 . The use of a compound of formula (1) or a salt thereof according to  claim 1 , for the control of pests.  
   
   
       10 . A method for controlling pests at a locus which comprises applying thereto an effective amount of a compound of formula (1) or a salt thereof as claimed in  claim 1 .  
   
   
       11 . A compound of formula (XVIII):  
     
       
         
         
             
             
         
       
     
     wherein n is 0, 1 or 2.