Methods and compositions for controlling pests

Abstract

The present invention is directed to pest-controlling compositions comprising as active ingredients one or more β-diones, particularly β-diketones and β-triketones, and to the use of these compositions inter alia for preventing, eradicating, destroying, repelling or mitigating harmful, annoying or undesired pests including insects, arachnids, helminths, molluscs, protozoa and viruses. The present invention is further directed to processes of preparing β-diones by de novo synthesis or from natural sources such as volatile oil-bearing plants from families including Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae.

1 . A method for controlling insects, arachnids, molluscs, protozoa and helminths, said method comprising exposing the insects, arachnids, molluscs, protozoa and helminths to a pest-controlling effective amount of a compound being represented by the general formula (I) 
       
         
           
           
               
               
           
         
       
       wherein
 A is (C═O)R 1 , (C═S)R 1 , OR 2 , SR 2 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2  or SO 4 R 2 ; 
 R 1  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 1 -C 10  haloalkyl, C 1 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, C 1 -C 10  hydroxyalkyl, C 1 -C 10  thioalkyl and C 1 -C 10  nitroalkyl, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, NR 4 OR 7  or SO 4 R 7 ; 
 R 2  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2  or NR 4 OR 7 ; 
 R 3  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 7 , SR 7 , CR S NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 ; 
 R 4  and R 5  are independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, OR 7  or SR 7 ; 
 R 6  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 7 , SR 7 , CR 8 NR 9 R 10 , NR 9 R 10  or NR 9 OR 7 ; 
 R 7  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl; 
 R 8  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, OR 11 , SR 11  or NR 9 R 10 ; 
 R 9  and R 10  are independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, OR 12  or SR 12 ; 
 R 11  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl; 
 R 12  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl; 
 B is H, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, aryl or heteroaryl; 
 X and Y are independently selected from oxygen, sulfur, —N—R 4 ; and 
 Q completes a 5-8-member saturated or unsaturated carbocyclic ring in which optionally one or more members comprise —C(═X)—; and wherein Q is optionally substituted with one or more substituents selected from C 1 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, C 2 -C 10  haloalkyl, dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2 , SO 4 R 2 , 1-arylC 2 -C 10  alkyl, 2-arylC 2 -C 10  alkyl or (C═X)R 1 . 
 
     
     
         2 . The method of  claim 1 , wherein the compound is represented by the general formula (III) 
       
         
           
           
               
               
           
         
       
       wherein
 X, Y and Z are each independently selected from oxygen, sulfur, —N—R 4  or one of C═X, C═Y or C═Z is CH 2 ; 
 A is (C═O)R 1 , (C═S)R 1 , OR 2 , SR 2 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2  or SO 4 R 2 ; 
 B is H, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, aryl or heteroaryl; 
 C, D, E and F are each independently selected from H, C 1 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, OR 2 , SR 2 , CR 3 NR 4 R 3 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2 , SO 4 R 2 , 1-arylC 2 -C 10  alkyl, 2-arylC 2 -C 10  alkyl or (C═X)R 1 ; 
 R 1  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 1 -C 10  haloalkyl, C 1 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, C 1 -C 10  hydroxyalkyl, C 1 -C 10  thioalkyl and C 1 -C 10  nitroalkyl, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 ; 
 R 2  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2  or NR 4 OR 7 ; 
 R 3  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 7 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 7 , SR 7 , CR 8 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 ; and 
 R 4  and R 5  are independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 13  trihaloalkyl, OR 7  or SR 7 . 
 
     
     
         3 . The method of  claim 2 , wherein the compound is selected from flavesone (1-isobutyroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), isoleptospermone (1-isovaleroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), leptospermone (1-valeroyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), papuanone (1-pentoyl-3,3,5,5-tetramethylcyclohexan-2,4,6-trione), grandiflorone (1-(2-phenylethyl)-3,3,5,5-tetramethylcyclohexan-2,4,6-trione) and jensenone (1-valeroyl-3,5-dicarbonylcyclohexan-2,4,6-trione). 
     
     
         4 . The method of  claim 2 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         5 . The method of  claim 2 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         6 . The method of  claim 2 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         7 . The method of  claim 2 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         8 . The method of  claim 1 , wherein the compound is represented by the general formula (IV) 
       
         
           
           
               
               
           
         
       
       wherein
 X and Y are each independently selected from oxygen, sulfur —N—R 4  or one of C═X or C═Y is CH 2 ; 
 A is (C═O)R 1 , (C═S)R 1 , OR 2 , SR 2 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2  or SO 4 R 2 , 
 B is H, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, aryl or heteroaryl; 
 C, D, E and F are each independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2 , SO 4 R 2 ; 
 R 1  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 1 -C 1  haloalkyl, dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, C 1 -C 10  hydroxyalkyl, C 1 -C 10  thioalkyl and C 1 -C 10  nitroalkyl, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 ; 
 R 2  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2  or NR 4 OR 7 ; 
 R 3  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 7 , SR 7 , CR 8 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, NR 4 OR 7  or SO 4 R 7 , and 
 R 4  and R 5  are independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, trihaloalkyl, OR 7  or SR 7 . 
 
     
     
         9 . The method of  claim 8 , wherein the compound is selected from the group consisting of agglomerone (1-isobutroyl-4-methoxy-5,5-dimethylcyclohex-3-en-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione) and platyphyllol (6,6-dimethyl-2-acetyl-5-methoxycyclohex-4-ene-1,3-dione). 
     
     
         10 . The method of  claim 8 , wherein the compound is a tasmanone derivative having a structural formula selected from the group consisting of: 
       
         
           
           
               
               
           
         
       
     
     
         11 . The method of  claim 1 , wherein the compound is represented by the general formula (V) 
       
         
           
           
               
               
           
         
       
       wherein
 X and Y are independently selected from oxygen, sulfur or —N—R 4 ; and 
 A is (C═O)R 1 , (C═S)R 1 , OR 2 , SR 2 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2  or SO 4 R 2 ; 
 B is H, C 1 -C 10  alkyl, C 2 -C 10  alkenyl, aryl or heteroaryl; 
 C, D, E, F, G and H are each independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 1 , N═O, N(═O) 2 , NR 4 OR 2  or SO 4 R 2 , R 1  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 1 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, C 1 -C 10  hydroxyalkyl, C 1 -C 10  thioalkyl and C 1 -C 10  nitroalkyl, OR 2 , SR 2 , CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 ; 
 R 2  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, CR 3 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2  or NR 4 OR 7 ; 
 R 3  is selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, C 2 -C 10  haloalkoxy, OR 7 , SR 7 , CR 8 NR 4 R 5 , NR 4 R 5 , (C═N—R 4 )R 6 , N═O, N(═O) 2 , NR 4 OR 7  or SO 4 R 7 , and 
 R 4  and R 5  are independently selected from H, C 1 -C 10  alkyl, arylC 2 -C 10  alkyl, C 3 -C 6  cycloalkyl, C 2 -C 10  alkenyl, heteroarylC 2 -C 10  alkyl, C 2 -C 10  haloalkyl, C 2 -C 10  dihaloalkyl, C 2 -C 10  trihaloalkyl, OR 7  or SR 7 . 
 
     
     
         12 . The method of  claim 11 , wherein the compound is selected from angustione (1-acetyl-3,5,5-trimethylcyclohex-2,6-dione), dehydroangustione (1-acetyl-3,5,5-trimethylcyclohex-3-en-2,6-dione) and xanthostemone (1-isobutroyl-5,5-dimethylcyclohex-3-en-2,6-dione). 
     
     
         13 . The method of  claim 11 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         14 . The method of  claim 11 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         15 . The method of  claim 11 , wherein the compound has a structural formula selected from: 
       
         
           
           
               
               
           
         
       
     
     
         16 . The method of  claim 1 , wherein the compound is obtainable from a volatile oil-bearing organism. 
     
     
         17 . The method of  claim 16 , wherein the volatile oil-bearing organism is selected from volatile oil-bearing plants. 
     
     
         18 . The method of  claim 16 , wherein the volatile oil-bearing organism is selected from plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae. 
     
     
         19 . The method of  claim 16 , wherein the volatile oil-bearing organism is selected from genera of the Myrtaceae family. 
     
     
         20 . The method of  claim 16 , wherein the volatile oil-bearing organism belongs to a genus selected from  Angophora, Austromyrtus, Backhousia, Baeckea, Callistemon, Corymbia, Darwinia, Eucalyptus, Kunzea, Leptospermum, Melaleuca, Syzygium  and  Xanthostemon.    
     
     
         21 . The method of  claim 1 , wherein the pest that is controlled is selected from insects, arachnids and molluscs. 
     
     
         22 . The method of  claim 1 , wherein the helminth is a nematode. 
     
     
         23 . The method of  claim 1 , wherein the compound is used in the form of a pest-controlling composition which comprises from about 0.00005% to about 90% by weight of said compound.