Spiroindolinepiperidine derivatives

Abstract

Insecticidal, acaricidal, nematicidal or molluscicidal compounds of formula (I) wherein Y is a single bond, C═O, C═S or C═(O) q where q is 0, 1 or 2; and R 1 , R 2 , R 3 , R 4 , R 8 , R 9 and R 10 are as defined in the claims or salts or N-oxides thereof, processes for preparing them and compositions containing them.

1 . A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I):  
     
       
         
         
             
             
         
       
     
     wherein Y is a single bond, C═O, C═S or S(O) q  where q is 0, 1 or 2; R 1  is hydrogen, optionally substituted alkyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted heterocyclyloxy, cyano, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, formyl, optionally substituted heterocyclyl, optionally substituted alkylthio, NO or NR 13 R 14  where R 13  and R 14  are independently hydrogen, COR 40 , optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl or R 13  and R 14  together with the N atom to which they are attached form a group —N═C(R 41 )—NR 42 R 43 ; R 2 and R 3  are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl or C(O)NR 15 R 16  where R 15  and R 16  are independently hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heterocyclyl, or R 2  and R 3  together are ═O, or R 2  and R 3  together with the atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring; each R 4  is independently halogen, nitro, cyano, optionally substituted C 1-8  alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl, optionally substituted alkylaminocarbonyl, optionally substituted dialkylaminocarbonyl, optionally substituted C 3-7  cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroaryloxy, optionally substituted alkylthio or R 19 R 20 N where R 19  and R 20  are, independently, hydrogen, C 1-8  alkyl, C 3-7  cycloalkyl, C 3-6  alkenyl, C 3-6  alkynyl, C 3-7  cycloalkyl(C 1-4 )alkyl, C 2-6  haloalkyl, C 1-6  alkoxy(C 1-6 )alkyl, C 1-6  alkoxycarbonyl or R 19  and R 20  together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C 1-6  alkyl groups, or 2 adjacent groups R 4  together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocyclic or heterocyclic ring which may be optionally substituted by halogen; n is 0, 1, 2, 3 or 4; R 8  is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted alkoxycarbonyl, optionally substituted alkylcarbonyl or optionally substituted alkenylcarbonyl; R 9  and R 10  are independently hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl or R 9  and R 10  together form a group —CH 2 —, —CH═CH— or —CH 2 CH 2 —; R 40  is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxy or NR 44 R 45 ; R 41 , R 42  and R 43  are each independently H or lower alkyl; R 44  and R 45  are independently optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl or salts or N-oxides thereof.  
   
   
       2 . A method according to  claim 1  wherein Y is a bond or is C═O.  
   
   
       3 . A method according to  claim 1  wherein R 1  is hydrogen, C 1-6  alkyl, C 1-6  cyanoalkyl, C 1-6  haloalkyl, C 3-7  cycloalkyl(C 1-4 )alkyl, C 1-6  alkoxy(C 1-6 )alkyl, heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy, C 1-6  haloalkoxy, C 1-6  alkylsulfonyl, C 1-6  alkylsulfinyl, C 1-6  alkylthio, C 1-6  alkoxycarbonyl, C 1-6  alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), aryl(C 1-6 )alkyl (wherein the aryl group may be optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy, C 1-6  haloalkoxy, C 1-6  alkylsulfonyl, C 1-6  alkylsulfinyl, C 1-6  alkylthio, C 1-6  alkoxycarbonyl, C 1-6  alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C 1-6  alkylcarbonylamino(C 1-6 )alkyl, aryl (which may be optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy, C 1-6  haloalkoxy, C 1-6  alkylsulfonyl, C 1-6  alkylsulfinyl, C 1-6  alkylthio, C 1-6  alkoxycarbonyl, C 1-6  alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the aryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), heteroaryl (which may be optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy, C 1-6  haloalkoxy, C 1-6  alkylsulfonyl, C 1-6  alkylsulfinyl, C 1-6  alkylthio, C 1-6  alkoxycarbonyl, C 1-6  alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the heteroaryl system may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen), C 1-6  alkoxy, C 1-6  haloalkoxy, phenoxy (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryloxy (optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heterocycyloxy (optionally substituted by halo, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), cyano, C 2-6  alkenyl, C 2-6  alkynyl, C 3-6  cycloalkyl, C 5-7  cycloalkenyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), C 1-6  alkylthio, C 1-6  haloalkylthio or NR 13 R 14  where R 13  and R 14  are independently hydrogen, C 2-6  alkyl, C 2-6  haloalkyl, phenyl (which may be optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino, dialkylamino or C 1-4  alkoxycarbonyl) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy, C 1-4  alkoxycarbonyl C 1-6  alkylcarbonylamino, phenyloxycarbonylamino (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), amino, C 1-6  alkylamino or phenylamino (wherein the phenyl group is optionally substituted halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino).  
   
   
       4 . A method according to  claim 1 , wherin R 2  and R 3  are are independently hydrogen or C 1-4  alkyl.  
   
   
       5 . A method according to  claim 1 , wherein each R 4  is independently halogen, cyano, C 1-8  alkyl, C 1-8  haloalkyl, C 1-6  cyanoalkyl, C 1-6  alkoxy(C 1-6 )alkyl, C 3-7  cycloalkyl(C 1-6 )alkyl, C 5-6  cycloalkenyl(C 1-6 )alkyl, C 3-6  alkenyloxy(C 1-6 )alkyl, C 3-6  alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6  carboxyalkyl, C 1-6  alkylcarbonyl(C 1-6 )alkyl, C 2-6  alkenylcarbonyl(C 1-6 )alkyl, C 2-6  alkynylcarbonyl(C 1-6 )alkyl, C 1-6  alkoxycarbonyl(C 1-6 )alkyl, C 3-6  alkenyloxycarbonyl(C 1-6 )alkyl, C 3-6  alkynyloxycarbonyl(C 1-6 )alkyl, aryloxycarbonyl(C 1-6 )alkyl, C 1-6  alkylthio(C 1-6 )alkyl, C 1-6  alkylsulfinyl(C 1-6 )alkyl, C 1-6  alkylsulfonyl(C 1-6 )alkyl, aminocarbonyl(C 1-6 )alkyl, C 1-6  alkylaminocarbonyl(C 1-6 )alkyl, di(C 1-6 )alkylaminocarbonyl(C 1-6 )alkyl, phenyl(C 1-4 )alkyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl(C 1-4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heterocyclyl(C 1-4 )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), C 2-6  alkenyl, aminocarbonyl(C 2-6 )alkenyl, C 1-6  alkylaminocarbonyl(C 2-6 )-alkenyl, di(C 1-6 )alkylaminocarbonyl(C 2-6 )alkenyl, phenyl(C 2-4 )alkenyl, (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), C 2-6  alkynyl, trimethylsilyl(C 2-6 )alkynyl, aminocarbonyl(C 2-6 )alkynyl, C 1-6  alkylaminocarbonyl(C 2-6 )alkynyl, di(C 1-6 )alkylaminocarbonyl(C 2-6 )alkynyl, C 1-6  alkoxycarbonyl, C 3-7  cycloalkyl, C 3-7  halocycloalkyl, C 3-7  cyanocycloalkyl, C 1-3  alkyl(C 3-7 )-cycloalkyl, C 1-3  alkyl(C 3-7 )halocycloalkyl,phenyl (optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl (optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), or 2 adjacent groups R 4  together with the carbon atoms to which they are attached form a 4, 5, 6,or 7 membered carbocylic or heterocyclic ring which may be optionally substituted by halogen, C 1-8  alkoxy, C 1-6  haloalkoxy, phenoxy (optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heteroaryloxy (optionally substituted by halo, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), C 1-8  alkylthio or R 19 R 20 N where R 19  and R 20  are, independently, hydrogen, C 1-8  alkyl, C 3-7  cycloalkyl, C 3-6  alkenyl, C 3-6  alkynyl, C 2-6  haloalkyl, alkoxycarbonyl or R 19  and R 20  together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C 1-6  alkyl groups; n is 0, 1, 2, 3 or 4.  
   
   
       6 . A method according to  claim 1 , wherin R 8  is C 1-10  alkyl, C 1-10  haloalkyl, aryl(C 1-6 )alkyl (wherein the aryl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), heteroaryl(C 1-6 )alkyl (wherein the heteroaryl group is optionally substituted halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), arylcarbonyl-(C 1-6 )alkyl (wherein the aryl group may be optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino and the alkyl group may be optionally substituted by aryl), C 2-8  alkenyl, C 2-8  haloalkenyl, aryl(C 2-6 )alkenyl (wherein the aryl group is optionally substituted halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino, C 1-6  alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring), C 2-6  alkynyl, phenyl(C 2-6 )alkynyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), C 3-7  cycloalkyl, C 1-6  alkoxycarbonyl, C 1-6  alkylcarbonyl, C 1-6  haloalkylcarbonyl or aryl(C 2-6 )alkenylcarbonyl (wherein the aryl group may be optionally substituted halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino), or —C(R 51 )(R 52 )—[CR 53 ═CR 54 ]z-R 55  where z is 1 or 2, R 51  and R 52  are each independently H, halo or C 1-2  alkyl, R 53  and R 54  are each independently H, halogen, C 1-4  alkyl or C 1-4  haloalkyl and R 55  is optionally substituted aryl or optionally substituted heteroaryl.  
   
   
       7 . A method according to  claim 1 , wherein R 9  and R 10  are both hydrogen.  
   
   
       8 . A compound of formula IK  
     
       
         
         
             
             
         
       
     
     wherein Y is a single bond, C═O or S(O) q  where is 0, 1 or 2; R 1  is C 1-8  alkyl, C 1-6  haloalkyl, C 1-6  cyanoalkyl, C 3-7  cycloalkyl(C 1-6 )alkyl, C 1-6  alkoxy(C 1-6 )alkyl, C 3-6  alkenyloxy-(C 1-6 )alkyl, C 3-6  alkynyloxy(C 1-6 )alkyl, aryloxy(C 1-6 )alkyl, C 1-6  carboxyalkyl, C 1-6  alkylcarbonyl(C 1-6 )alkyl, C 2-6  alkenylcarbonyl(C 1-6 )alkyl, C 2-6  alkynylcarbonyl(C 1-6 )alkyl, C 1-6  alkoxycarbonyl(C 1-6 )alkyl, C 3-6  alkenyloxycarbonyl(C 1-6 )-alkyl, C 3-6  alkynyloxycarbonyl(C 1-6 )alkyl, aryloxycarbonyl(C 1-6 )alkyl, C 1-6  alkylthio(C 1-6 )-alkyl, C 1-6  alkylsulfinyl(C 1-6 )alkyl, C 1-6  alkylsulfonyl(C 1-6 )alkyl, aminocarbonyl(C 1-6 )alkyl, C 1-6  alkylaminocarbonyl(C 1-6 )alkyl, di(C 1-6 )alkylaminocarbonyl(C 1-6 )alkyl, phenyl(C 1-4 )alkyl (wherein the phenyl group is optionally substituted by halogen, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heteroaryl(C 1-4 )alkyl (wherein the heteroaryl group may be substituted by halogen, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heterocyclyl(C 1-4 )alkyl (wherein the heterocyclyl group may be substituted by halogen, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), phenyl (optionally substituted by halogen, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), heteroaryl (optionally substituted by halogen, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy), C 1-6  alkoxy, C 1-6  haloalkoxy, C 2-6  alkenyl, C 2-6  haloalkenyl, C 2-6  cyanoalkenyl, C 2-6  alkynyl, C 3-7  cycloalkyl, formyl, heterocyclyl (optionally substituted by halogen, nitro, cyano, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or C 1-6  haloalkoxy) or C 1-6  alkylthio; R 2  and R 3  are independently hydrogen or C 1-4  alkyl; each R 4  is independently halogen, cyano, C 1-10  alkyl optionally substituted by C 1-6  alkoxy, halogen, phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy), C 2-6 alkenyl optionally substituted by C 1-6 alkoxy, halogen, phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy) or C 2-6  alkynyl optionally substituted by C 1-6  alkoxy, halogen, phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy); n is 0, 1, 2, 3 or 4; R 8  is C 1-10  alkyl optionally substituted by C 1-6  alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy), C 2-6  alkenyl optionally substituted by C 1-6 alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy) or C 2-6  alkynyl optionally substituted by C 1-6  alkoxy, halogen or phenyl (itself optionally substituted by halogen, C 1-4  alkyl or C 1-4  alkoxy); R 9  and R 10  are both hydrogen; and salts or N-oxides thereof provided that R 8  is not methyl and YR 1  is not SO 2 CH 3 , methyl, ethyl, phenyl or fluoro-substituted phenyl.  
   
   
       9 . A compound of formula (11)  
     
       
         
         
             
             
         
       
     
     where R 8  is phenyl(C 2-4 )alkenyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino, provided the substituent is not para-fluoro); or a compound of formula (10)  
     
       
         
         
             
             
         
       
     
     where R 8  is phenyl(C 2-4 )alkenyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino, provided the substituent is not a para-fluoro); or a compound of formula (9)  
     
       
         
         
             
             
         
       
     
     where R 2  is as defined for formula (I) in  claim 1  and R 8  is phenyl(C 2-4 )alkenyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino); or a compound of formula (9A)  
     
       
         
         
             
             
         
       
     
     where R 2  and where (R 4 )n are as defined for formula (I) in  claim 1  and R 8  is phenyl(C 2-4 )alkenyl (wherein the phenyl group is optionally substituted by halogen, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  haloalkyl, C 1-4  haloalkoxy, CN, NO 2 , aryl, heteroaryl, amino or dialkylamino).  
   
   
       10 . An insecticidal acaricidal and nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula I as defined in  claim 1.