Insecticidal N-heterocyclylalkyl-or N-[(polycyclyl)alkyl]-N′substituted piperazines

Abstract

Compounds of the following structure are disclosed as effective insecticides:in which: A and B are independently lower alkyl; U is lower alkylidene, lower alkenylidene, or CH-Z, where Z is hydrogen, lower alkyl, lower cycloalkyl, or phenyl; R is phenyl or a dibenzocyclo(C5-8)alkyl, each optionally substituted, orwhere R3 and R4 are independently selected from phenyl, optionally substituted with, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkenyl, or phenyl; R1 is selected from a variety of substituents, including 3-R2, where R2 iswhere D, E, and G are hydrogen, hydroxy, halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, nitro, lower haloalkylsuffonyloxy, lower alkylcarboxylato, lower alkylcarbonylamino, lower alkylcarbonyl, lower alkoxycarbonyl, arylcarbonylamino; D and E taken together may form the group -O(CH2)O-; J is hydrogen or lower alkyl; m is 2 or 3, n is 1, 2, or 3; and halogen is chlorine, bromine, or fluorine.

What is claimed is:  
     
       1. A compound of the formula                    
       in which: 
       A and B are independently selected from lower alkyl;  
       U is selected from lower alkylidene, lower alkenylidene, and CH—Z, where Z is independently selected from hydrogen, lower alkyl, lower cycloalkyl, and phenyl;  
       R is                    
        where R 3  and R 4  are independently selected from phenyl, optionally substituted with, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkenyl, or phenyl;  
       R 1  is phenyl, naphthyl, tetrazolylphenyl, phenylcyclopropyl, phenoxyphenyl, benzyloxyphenyl, pyridylphenyl, pyridyloxyphenyl, or thiadiazolyloxyphenyl, each optionally substituted with halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, amino, lower dialkylamino, nitro, lower haloalkylsulfonyloxy, lower alkylcarbonyloxy, lower alkylcarbonylamino, lower alkoxycarbonyl, lower alkoxyalkoxycarbonyl, lower cycloalkylalkoxycarbonyl, lower alkoxyalkylalkoxycarbonyl, lower alkoxycarbonylamino, alkoxythiocarbonylamino, lower alkyldithiocarbonylamino, lower dialkyldioxolylalkoxycarbonylamino, or halophenylamino; or lower alkyl substituted with any one of the foregoing cyclic R 1  groups;  
       m is 2 or 3 and n is 1, 2, or 3;  
       halogen is chlorine, fluorine, or bromine, lower means having from 1 to 6 carbon atoms, and any aliphatic chain of three or more carbons may be straight or branched.  
     
     
       2. A compound of claim  1  in which 
       U is selected from lower alkylidene, carbonyl, lower alkenylidene, and CH—Z, where Z is independently selected from hydrogen and lower alkyl;  
       R is and                    
        where R 3  and R 4  are independently selected from hydrogen and phenyl, optionally substituted with halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy;  
       R 1  is phenyl, tetrazolylphenyl, pyridylphenyl, pyridyloxyphenyl; each optionally substituted with halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, amino, lower dialkylamino, lower alkylcarbonyloxy, lower alkylcarbonylamino, lower alkoxycarbonyl, lower alkoxyalkoxycarbonyl, lower cycloalkylalkoxycarbonyl, lower alkoxyalkylalkoxycarbonyl, or lower alkoxycarbonylamino; or lower alkyl substituted with any one of the foregoing cyclic R 1  groups;  
       m and n are 2; and  
       halogen is chlorine or fluorine, for aliphatic groups lower means having from 1 to 3 carbon atoms, and for alicyclic groups lower means having 3 to 6 carbons.  
     
     
       3. A compound of claim  2  of the formula                    
       in which 
       R is                    
        where R 3  and R 4  are independently selected from phenyl substituted in the 4-position with halogen, lower alkyl, lower haloalkyl, lower alkoxy, or lower haloalkoxy;  
       R 1  is phenyl substituted in the 4-position with lower dialkylamino, lower alkoxycarbonylamino, tetrazolyl, pyridyl, or pyridyloxy; each tetrazolyl or pyridyl group optionally substituted with halogen, cyano, lower alkyl, lower haloalkyl, or lower alkoxy;  
       m and n are 2; and  
       halogen is chlorine or fluorine, for aliphatic groups lower means having from 1 to 3 carbon atoms, and for alicyclic groups lower means having 3 to 6 carbons.  
     
     
       4. A compound of claim  3  in which U is CH 2 , and R 3  and R 4  are independently selected from chlorophenyl, fluorophenyl, methylphenyl, trifluoromethylphenyl, methoxyphenyl, and trifluoromethoxyphenyl. 
     
     
       5. A composition of claim  3  in which 
       R is                    
        where R 3  and R 4  are independently selected from 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, and 4-trifluoromethoxyphenyl;  
       R 1  is 3-R 2 , where R 2  is                    
        where D is selected from hydrogen, hydroxy, chloro, fluoro; methyl, phenylcarbonylamino, and methoxy, and E and G are independently selected from hydrogen, chloro, fluoro; methyl, and methoxy.  
     
     
       6. A composition of claim  5  in which 
       R 2  is                    
        in which D is selected from hydrogen, 4-chloro, 4-fluoro, 4-hydroxy, and 4-phenylcarbonylamino; E is selected from hydrogen, 5-chloro, 5-methyl, 6-fluoro; G is selected from hydrogen and 5-methoxy; and R 3  and R 4  are independently selected from 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, and 4-trifluoromethoxyphenyl.  
     
     
       7. A composition of claim  6  in which R 3  and R 4  are each 4-trifluoromethoxyphenyl. 
     
     
       8. A composition of claim  6  in which E and G are hydrogen. 
     
     
       9. A composition of claim  8  in which D is 4-fluoro. 
     
     
       10. The composition of claim  9  in which R 3  and R 4  are each 4-trifluoromethoxyphenyl. 
     
     
       11. The composition of claim  9  in which R 3  and R 4  are each 4-chlorophenyl. 
     
     
       12. The composition of claim  9  in which R 3  and R 4  are each 4-fluorophenyl. 
     
     
       13. The composition of claim  9  in which R 3  and R 4  are each 4-methylphenyl. 
     
     
       14. A composition of claim  6  in which and R 3  and R 4  are each 4-chlorophenyl. 
     
     
       15. A composition of claim  14  in which D is 4-fluoro. 
     
     
       16. The composition of claim  15  in which E is 5-chloro, and G is hydrogen. 
     
     
       17. The composition of claim  15  in which E is 5-methyl, and G is hydrogen. 
     
     
       18. The composition of claim  15  in which E is 6-fluoro, and G is hydrogen. 
     
     
       19. The composition of claim  15  in which E is 6-fluoro, and G is 5-methoxy. 
     
     
       20. A composition of claim  14  in which E and G are hydrogen. 
     
     
       21. The composition of claim  20  in which D is 4-hydroxy. 
     
     
       22. The composition of claim  20  in which D is 4-phenylcarbonylamino. 
     
     
       23. A compound of claim  4  in which 
       R is                    
        where R 3  and R 4  are independently selected from 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, and 4-trifluoromethoxyphenyl;  
       R 1  is phenyl substituted in the 4-position with lower dialkylamino, lower alkoxycarbonylamino, tetrazolyl, pyridyl, or pyridyloxy; each tetrazolyl or pyridyl group optionally substituted with halogen, cyano, lower alkyl, lower haloalkyl, or lower alkoxy, with the proviso that when R 1  is lower dialkylaminophenyl, R 3  and R 4  are each trifluoromethoxyphenyl.  
     
     
       24. A compound of claim  23  in which R 1  is lower dialkylaminophenyl. 
     
     
       25. The compound of claim  24  in which R 1  is dimethylaminophenyl. 
     
     
       26. A compound of claim  23  in which 
       R 1  is phenyl substituted in the 4-position with lower alkoxycarbonylamino, tetrazol-4-yl or pyrid-2-yloxy; each tetrazolyl or pyridyl group optionally substituted with lower alkyl, lower haloalkyl, or lower alkoxy; and  
       R 3  and R 4  are independently selected from 4-trifluoromethylphenyl and 4-trifluoromethoxyphenyl.  
     
     
       27. A compound of claim  26  in which R 3  and R 4  are each 4-trifluoromethylphenyl. 
     
     
       28. The compound of claim  27  in which R 1  is N-4-(methoxycarbonylamino)phenyl. 
     
     
       29. The compound of claim  27  in which R 1  is N-4-(1-methylethoxycarbonylamino)phenyl. 
     
     
       30. The compound of claim  27  in which R 1  is N-4-(1-methyl-1,2,3,5-(1-H)-tetrazol4-yl)phenyl. 
     
     
       31. The compound of claim  27  in which R 1  is N-4-[1-(2-fluorooethyl)-1,2,3,5-(1-H)-tetrazol-4-yl]phenyl. 
     
     
       32. The compound of claim  27  in which R 1  is N-4-(pyrid-2-yloxy)phenyl. 
     
     
       33. The compound N-[bis(4-trifluoromethoxyphenyl)methyl]piperazine. 
     
     
       34. An insecticidal composition comprising an insecticidally effective amount of an adjuvant or carrier and at least one compound of the formula                    
       in which: 
       A and B are independently selected from lower alkyl;  
       U is selected from lower alkylidine, lower alkenylidene, and CH—Z, where Z is independently selected from hydrogen, lower alkyl, lower cycloalkyl, and phenyl;  
       R is selected from phenyl, optionally substituted with halogen, lower alkyl, lower alkoxy, phenyl, or phenoxy, and from a dibenzocyclo(C 5-8 )alkyl, optionally substituted with halogen, lower alkyl, or lower alkoxy; and                    
        where R 3  and R 4  are independently selected from phenyl, optionally substituted with, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkenyl, or phenyl;  
       R 1  is phenyl, naphthyl, tetrazolylphenyl, phenylcyclopropyl, phenoxyphenyl, benzyloxyphenyl, pyridylphenyl, pyridyloxyphenyl, thiadiazolyloxyphenyl, benzothienyl, benzimidazolyl, indolyl, pyrrolyl, or quinolyl, each optionally substituted with halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, amino, lower dialkylamino, nitro, lower haloalkylsulfonyloxy, lower alkoxycarbonyl, lower alkoxyalkoxycarbonyl, lower cycloalkylalkoxycarbonyl, lower alkoxyalkylalkoxycarbonyl, lower alkoxycarbonylamino, alkoxythiocarbonylamino, lower alkyldithiocarbonylamino, lower dialkyldioxolylalkoxycarbonylamino, or halophenylamino; or lower alkyl substituted with any one of the foregoing cyclic R 1  groups; or 3-R 2 , where R 2  is                    
        where D, E, and G are independently selected from hydrogen, hydroxy, halogen, cyano, lower alkyl, lower haloalkyl, lower alkoxy, nitro, lower haloalkylsulfonyloxy, lower alkylcarboxylato, lower alkylcarbonylamino, arylcarbonylamino, lower alkylcarbonyl. lower alkoxycarbonyl, or D and E taken together form the group —O(CH2)O—, and J is hydrogen or lower alkyl;  
       m is 2or 3 and n is 1, 2, or 3;  
       halogen is chlorine, fluorine, or bromine, lower means having from 1 to 6 carbon atoms, and any aliphatic chain of three or more carbons may be straight or branched.  
     
     
       35. A composition of claim  34  in which 
       U is selected from lower alkylidene, carbonyl, lower alkenylidene, and CH—Z, where Z is independently selected from hydrogen and lower alkyl;  
       R is selected from phenyl, optionally substituted with halogen, lower alkyl, lower alkoxy, phenyl, or phenoxy; and                    
        where R 3  and R 4  are independently selected from hydrogen and phenyl, optionally substituted with halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy;  
       R 1  is phenyl, tetrazolylphenyl, pyridylphenyl, pyridyloxyphenyl; each optionally substituted with halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, amino, lower dialkylamino, lower alkylcarbonyloxy, lower alkylcarbonylamino, lower alkoxycarbonyl, lower alkoxyalkoxycarbonyl, lower cycloalkylalkoxycarbonyl, lower alkoxyalkylalkoxycarbonyl, or lower alkoxycarbonylamino; or lower alkyl substituted with any one of the foregoing cyclic R 1 groups; or 3-R 2 , where R 2  is                    
        where D is hydrogen, hydroxy, chloro, fluoro; methyl, methoxy, or phenylcarbonylamino; E and G are independently selected from hydrogen, chloro, fluoro; methyl, and methoxy, with the proviso that when R 1  is lower dialkylaminophenyl, R 3  and R 4  are each trifluoromethoxyphenyl;  
       m and n are 2; and  
       halogen is chlorine or fluorine, for aliphatic groups lower means having from 1 to 3 carbon atoms, and for alicyclic groups lower means having 3 to 6 carbons.  
     
     
       36. A composition of claim  35  wherein said compound is of the formula                    
       in which 
       R is                    
        where R 3  and R 4  are independently selected from phenyl substituted in the 4-position with halogen, lower alkyl, lower haloalkyl, lower alkoxy, or lower haloalkoxy;  
       R 1  is phenyl substituted in the 4-position with lower dialkylamino, lower alkoxycarbonylamino, tetrazolyl, pyridyl, or pyridyloxy; each tetrazolyl or pyridyl group optionally substituted with halogen, cyano, lower alkyl, lower haloalkyl, or lower alkoxy; or 3-R 2 , where R 2  is                    
        where D is hydrogen, 4-chloro, 4-fluoro, 4-hydroxy, or 4-phenylcarbonylamino; E is hydrogen, 5-chloro, 5-methyl, or 6-fluoro; G is hydrogen or 5-methoxy;  
       m and n are 2; and  
       halogen is chlorine or fluorine, for aliphatic groups lower means having from 1 to 3 carbon atoms, and for alicyclic groups lower means having 3 to 6 carbons.  
     
     
       37. A composition of claim  36  in which U is CH 2 , and R 3  and R 4  are independently selected from chlorophenyl, fluorophenyl, methylphenyl, trifluoromethylphenyl, methoxyphenyl, and trifluoromethoxyphenyl. 
     
     
       38. A composition of claim  37  in which 
       R is                    
        where R 3  and R 4  are independently selected from 4-chlorophenyl, 4-fluorophenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, and 4-trifluoromethoxyphenyl;  
       R 1  is phenyl substituted in the 4-position with lower dialkylamino, lower alkoxycarbonylamino, tetrazolyl, pyridyl, or pyridyloxy; each tetrazolyl or pyridyl group optionally substituted with halogen, cyano, lower alkyl, lower haloalkyl, or lower alkoxy, with the proviso that when R 1  is lower dialkylaminophenyl, R 3  and R 4  are each trifluoromethoxyphenyl.  
     
     
       39. A composition of claim  38  in which R 1  is lower dialkylaminophenyl. 
     
     
       40. The composition of claim  39  in which R 1  is dimethylaminophenyl. 
     
     
       41. A composition of claim  38  in which 
       R 1  is phenyl substituted in the 4-position with lower alkoxycarbonylamino, tetrazol-4-yl or pyrid-2-yloxy; each tetrazolyl or pyridyl group optionally substituted with lower alkyl, lower haloalkyl, or lower alkoxy; and  
       R 3  and R 4  are independently selected from 4-trifluoromethylphenyl and 4-trifluoromethoxyphenyl.  
     
     
       42. A composition of claim  41  in which R 3  and R 4  are each 4-trifluoromethylphenyl. 
     
     
       43. The composition of claim  42  in which R 1  is N-4-(methoxycarbonylamino)phenyl. 
     
     
       44. The composition of claim  42  in which R 1  is N-4-(1-methylethoxycarbonylamino)phenyl. 
     
     
       45. The composition of claim  42  in which R 1  is N-4-(1-methyl-1,2,3,5-(1-H)-tetrazol-4-yl)phenyl. 
     
     
       46. The composition of claim  42  in which R 1  is N-4-[l-(2-fluorooethyl)-1,2,3,5-(1-H)-tetrazol-4-yl]phenyl. 
     
     
       47. The composition of claim  42  in which R 1  is N-4-(pyrid-2-yloxy)phenyl. 
     
     
       48. The composition of claim  34  in which said compound is N-[bis(4-trifluoromethoxyphenyl)methyl]piperazine. 
     
     
       49. A method for controlling insects, comprising the steps of identifying a locus where insect control is needed and applying to said locus at least one compound of the formula                    
       in which: 
       A and B are independently selected from lower alkyl;  
       U is selected from lower alkylidine, lower alkenylidene, and CH—Z, where Z is independently selected from hydrogen, lower alkyl, lower cycloalkyl, and phenyl;  
       R is selected from phenyl, optionally substituted with halogen, lower alkyl, lower alkoxy, phenyl, or phenoxy, and from a dibenzocyclo(C 5-8 )alkyl, optionally substituted with halogen, lower alkyl, or lower alkoxy; and                    
        where R 3  and R 4  are independently selected from phenyl, optionally substituted with, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkenyl, or phenyl;  
       R 1  is phenyl, naphthyl, tetrazolylphenyl, phenylcyclopropyl, phenoxyphenyl, benzyloxyphenyl, pyridylphenyl, pyridyloxyphenyl, thiadiazolyloxyphenyl, benzothienyl, benzimidazolyl, indolyl, pyrrolyl, or quinolyl, each optionally substituted with halogen, cyano, hydroxy, lower alkyl, lower haloalkyl, lower alkoxy, amino, lower dialkylamino, nitro, lower haloalkylsulfonyloxy, lower alkoxycarbonyl, lower alkoxyalkoxycarbonyl, lower cycloalkylalkoxycarbonyl, lower alkoxyalkylalkoxycarbonyl, lower alkoxycarbonylamino, alkoxythiocarbonylamino, lower alkyldithiocarbonylamino, lower dialkyldioxolylalkoxycarbonylamino, or halophenylamino; or lower alkyl substituted with any one of the foregoing cyclic R 1  groups; or 3-R 2 , where R 2  is                    
        where D, E, and G are independently selected from hydrogen, hydroxy, halogen, cyano, lower alkyl, lower haloalkyl, lower alkoxy, nitro, lower haloalkylsulfonyloxy, lower alkylcarboxylato, lower alkylcarbonylamino, arylcarbonylamino, lower alkylcarbonyl. lower alkoxycarbonyl, or D and E taken together form the group —O(CH2)O—, and J is hydrogen or lower alkyl;  
       m is 2 or 3 and n is 1, 2, or 3;  
       halogen is chlorine, fluorine, or bromine, lower means having from 1 to 6 carbon atoms, and any aliphatic chain of three or more carbons may be straight or branched.