Insecticidal spironindane derivatives

Abstract

An insecticidal compound of formula I wherein X is O or NR 11 where R 11 is hydrogen, optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl; Y is a single bond, C═O, C═S or S(O) m where m is 0, 1 or 2; R 1 , R 2 , R 3 , R 4 , R 8 and Ra are specified organic groups and p is 0, 1, 2, 3, 4, 5 or 6; q is 0, 1, 2, 3, 4, 5 or 6 provided that p+q is 1, 2, 3, 4, 5 or 6; or salts or N-oxides thereof; compositions containing them and their using in controlling insects, acarines, nematodes or molluscs.

1 . A compound of formula I: 
       
         
           
           
               
               
           
         
       
       wherein
 X is O or NR 11 ; 
 R 11  is hydrogen, optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl; 
 Y is a single bond, C═O, C═S or S(O) m ; 
 m 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 ; 
 R 13  and R 14  are each independently hydrogen, COR 15 , optionally substituted alkyl, optionally substituted aryl, optionally substituted heteroaryl, or 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 16 )—NR 17 R 18 ; 
 R 15  is H, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted aryloxy optionally substituted heteroaryl, optionally substituted heteroaryloxy or NR 19 R 20 ; 
 R 16 , R 17  and R 18  are each independently H or lower alkyl; 
 R 19  and R 20  are independently optionally substituted alkyl, optionally substituted aryl or optionally substituted heteroaryl; 
 R 2  and R 3  are independently hydrogen, halogen, cyano, optionally substituted alkyl, optionally substituted alkoxy or optionally substituted aryl; 
 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 21 R 22 N; 
 R 21  and R 22  are each 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, or C 1-6  alkoxycarbonyl or R 21  and R 22  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; 
 each Ra is independently hydrogen, halogen, hydroxy, 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, optionally substituted arylthio or R 23 R 24 N; 
 R 23  and R 24  are each 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, or C 1-6  alkoxycarbonyl or R 23  and R 24  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 two Ra groups attached to the same carbon atom are ═O or two Ra groups attached to adjacent carbon atoms form a bond, or two Ra groups together with the carbon atom to which they are attached form a three- to seven-membered ring, that may be saturated or unsaturated, and that may contain one or two hetero atoms selected from the group consisting of N, O and S, and which may be optionally substituted by one or two C 1-6  alkyl groups; 
 or two Ra groups together form a group —CH 2 —, —CH═CH— or —CH 2 CH 2 ; 
 p is 0, 1, 2, 3, 4, 5 or 6; 
 q is 0, 1, 2, 3, 4, 5 or 6 provided that p+q is 1, 2, 3, 4, 5 or 6; and 
 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; 
 
       or salts or N-oxides thereof. 
     
     
         2 . A compound according to  claim 1 , wherein X is NH and Y is a single bond or C═O. 
     
     
         3 . A compound according to  claim 1 , wherein each Ra is hydrogen and R 2  and R 3  are each independently hydrogen, C 1-6  alkyl, C 1-6  haloalkyl, C 1-6  alkoxy or cyano. 
     
     
         4 . A compound 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, or arylcarbonyl, or two adjacent positions on the heteroaryl ring 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, or arylcarbonyl, or two adjacent positions on the aryl ring 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, or arylcarbonyl, or two adjacent positions on the aryl ring 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, or arylcarbonyl, or two adjacent positions on the heteroaryl ring 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; heterocyclyloxy 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 ; and   R 13  and R 14  are each independently hydrogen; C 1-6  alkyl; C 1-6  haloalkyl; C 1-6  alkoxy(C 1-6 )alkyl; 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; phenyl(C 1-6 )alkyl wherein the phenyl 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, dialkylamino, C 1-6  alkylsulfonyl, C 1-6  or alkoxycarbonyl, or two adjacent positions on the phenyl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen; 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, or arylcarbonyl, or two adjacent positions on the heteroaryl ring may be cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itself optionally substituted with halogen; or heteroaryl which may be optionally substituted by (i) halo, (ii) nitro, (iii) cyano, (iv) C 1-6  alkyl, (v) C 1-6  haloalkyl, (vi) C 1-6  alkoxy, (vii) C 1-6  haloalkoxy, (viii) C 1-4  alkoxycarbonyl, (ix) C 1-6  alkylcarbonylamino, (x) 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, (xi) amino, (xii) C 1-6  alkylamino, or (xiii) phenylamino 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.   
     
     
         5 . A compound 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; amino carbonyl(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; amino carbonyl(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; or 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;   R 19  and R 20  are each independently hydrogen, C 1-8  alkyl, C 3-7  cycloalkyl, C 3-6  alkenyl, C 3-6  alkynyl, C 2-6  haloalkyl, or 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; and   n is 0, 1, 2 or 3.   
     
     
         6 . A compound according to  claim 1 , wherein
 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 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; 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 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 1-6  alkoxycarbonyl, or two adjacent substituents on the aryl group cyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring; heteroaryl(C 2-6 )-alkenyl 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, dialkylamino, or C 1-6  alkoxycarbonyl, or two adjacent substituents on the heteroaryl group 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  cyclo alkyl; C 1-6  alkoxycarbonyl; C 1-6  alkylcarbonyl; C 1-6  haloalkylcarbonyl; 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 ;
 
   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 compound according to  claim 1 , wherein p is 1 or 2 and q is 2. 
     
     
         8 . A compound of formula II 
       
         
           
           
               
               
           
         
         wherein R 2 , R 3 , R 4 , R 8 , Ra, n, p and q are as defined in  claim 1  and R 8  may also be hydrogen or tert-butoxycarbonyl; or 
         a compound of formula III 
       
       
         
           
           
               
               
           
         
         wherein X, Y, R 1 , R 2 , R 3 , R 4 , Ra, n, p and q are as defined in claim  11  and R 8  is hydrogen or tert-butoxycarbonyl. 
       
     
     
         9 . An insecticidal acaricidal and nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of  claim 1 . 
     
     
         10 . 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  claim 1 .