Bicyclic amine derivatives

Abstract

The present invention provides compounds of formula (I): wherein R, A, Ar and R 1 are as defined in the specification. The invention also provides insecticidal, acaricidal and nematicidal compositions comprising the compound of formula (I), and methods for combating and controlling insect, acarine and nematdoe pests at a locus by treating the pests or the locus with an effective amount of the compound of formula (I) or compositions thereof.

1 . A compound of formula (I):  
       
         
           
           
               
               
           
         
         wherein A represents a bidentate group of formula —CH 2 —X—CH 2 — (wherein X is methylene, sulfur or oxygen), X′C═CY or X′WC—CYZ (wherein X′, W, Y and Z are independently hydrogen, hydroxy, acyloxy, alkoxy, alkylsilyloxy, cyano or halogen, or X′ and W or Y and Z together with the carbon to which they are attached form a carbonyl group), provided that A is not CH 2 —CH 2 ; Ar is an optionally substituted phenyl or 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, said heterocyclic ring being optionally fused to a benzene ring, wherein the substutuents, if present, are selected from halogen atoms, cyano, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and alkyl amino groups, any of which groups contain up to six carbon atoms; R is hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl, dithiocarboxyl or X″R 3  (where X″ represents oxygen or a group NR 4 ), provided that when R is alkenyl, aralkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I); R 1  is hydrogen, cyano, hydroxy, alkyl, alkoxy, amino, nitro, isocyanato, acylamino, hydroxyalkyl, optionally substituted heteroaryl, alkoxyalkyl, haloalkyl, halohydroxyalkyl, aralkyloxyalkyl, acyloxyalkyl, amidoximido, sulfonyloxyalkyl, aminoalkyl, alkoxycarbonylamino, acylaminoalkyl, cyanoalkyl, imino, formyl, acyl or carboxylic acid or an ester or amide thereof, or alkenyl or alkynyl either of which is optionally substituted by halogen, alkoxy, cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl or cyano; R 3  and R 4  are, independently, hydrogen, alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, heterocyclylalkyl, alkoxycarbonyl or carboxylic acyl; alkyl moieties of R, R 3  and R 4  comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from, halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, amino, acylamino, imidate and phosphonato groups; aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkanyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl, dithiocarboxyl moieties of R, R 3  and R 4  comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from, halogen, cyano, carboxyl, carboxylic acyl, carbamyl, alkoxycarbonyl, alkoxy, alkylenedioxy, hydroxy, nitro, haloalkyl, alkyl, amino, acylamino, imidate and phosphonato groups; or an acid addition salt, quaternary ammonium salt or N-oxide derived therefrom.  
       
     
     
         2 . A compound of formula (I) as claimed in  claim 1  wherein A is CH═CH.  
     
     
         3 . A compound of formula (I) as claimed in  claim 1  wherein R 1  is cyano.  
     
     
         4 . A compound of formula (I) as claimed in  claim 1  wherein R is C 1-4  alkyl (optionally substituted with cyano, CO 2 (C 1-4  alkyl) or phenyl (itself optionally substituted with halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl or C 1-4  haloalkoxy)), C 2-4  haloalkyl (the α-carbon being unsubstituted), C 3-4  alkenyl or C 3-4  alkynyl; provided that when R is alkenyl or alkynyl said goup does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I).  
     
     
         5 . A compound of formula (I) as claimed in  claim 1  wherein Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen, C 1-4  alkyl, C 1-4  alkoxy, C 2-4  alkenyl, C 2-4  alkynyl or cyano.  
     
     
         6 . A compound of formula (I) as claimed in  claim 1  wherein Ar is pyridinyl optionally substituted with halogen.  
     
     
         7 . An insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.  
     
     
         8 . A method of combating and controlling insect, acarine or nematode pests at a locus which comprises treating the pests or the locus of the pests with an effective amount of a compound according to  claim 1  or a composition according to  claim 7 .  
     
     
         9 . A method according to  claim 8  wherein the pests are insect pests of growing plants.  
     
     
         10 . A method of preparing a compound of formula (I), wherein A is CH═CH, which comprises dehydrating a compound of formula (I) wherein A is CH 2 —CH(OH).