Feeding deterrence in agricultural pests such as hemiptera, lepidoptera and coleoptera

Abstract

Compounds are used as agents that deter feeding on crops by agricultural pests, such as hemiptera, lepidoptera and coleoptera, including, but not limited to, stink bugs, codling moth larvae and granary weevils. Feeding deterrence is obtained by contact of the insects with at least one of the compounds of the structure (I) wherein R is —OH, ═O, —OC(O)R 4 , —OR 6 or —(OR 6 ) 2 , wherein each R 6 is independently an alkyl group containing from 1 to 4 carbon atoms and R 4 is a branched or straight chain, saturated or unsaturated, hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; X is O or CH 2 with the proviso that when X is O, R can only be ═O; each Z is independently (CH) or (CH 2 ); y is a numeral selected from 1 and 2; R 1 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; R 2 is H or a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; R 3 is selected from H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, —(CH 2 ) n OH, —C(O)OR 5 , —CH 2 C(O)OR 7 , —CH 2 C(O)R 8 , —C(O)NR 9 R 10 , and —CH 2 C(O)NR 11 R 12 where each of R 5 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 is independently selected from H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms and n is an integer of from 1 to 12; the bond between the 2 and 3 positions in the ring structure may be a single or a double bond; and wherein the compounds of structure (I) contain from 9 to 20 total carbon atoms in the compounds.

I claim: 
     
         1 . A method for deterring the feeding of one or more agricultural pests selected from the group consisting of hemiptera, lepidoptera and coleoptera on food or crops is obtained by:
 contacting of the pests with an effective amount of a formulation comprising at least one of the compounds of the structure (I)   
       
         
           
           
               
               
           
         
       
       wherein
 R is selected from the group consisting of —OH, ═O, —OC(O)R 4 , —OR 6 , and —(OR 6 ) 2 , wherein each R 6  is independently selected from an alkyl group containing from 1 to 4 carbon atoms and R 4  is a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; 
 X is O or CH 2  with the proviso that when X is O, R can only be ═O; 
 each Z is independently selected from the group consisting of (CH) and (CH 2 ) 
 y is a numeral selected from 1 and 2; 
 R 1  is selected from the group consisting of H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to two double bonds and from 1 to 15 carbon atoms; 
 R 2  is selected from the group consisting of H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms; 
 R 3  is selected from H, a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, —(CH 2 ) n OH, —C(O)OR 5 , —CH 2 C(O)OR 7 , —CH 2 C(O)R 8 , —C(O)NR 9 R 10 , and —CH 2 C(O)NR 11 R 12  where each of R 5 , R 7 , R 8 , R 9 , R 10 , R 11  and R 12  is independently selected from H and a branched or straight chain, saturated or unsaturated hydrocarbyl group with zero to three double bonds and from 1 to 15 carbon atoms, and n is n integer of from 1 to 12; 
 the bond between the 2 and 3 positions in the ring structure may be a single or a double bond, and wherein the compounds of structure (I) contain from 9 to 20 total carbon atoms in the compounds. 
 
     
     
         2 . The method according to  claim 1  wherein the agricultural pest is selected from the group consisting of: cicadas, aphids, stink bugs, butterflies, moths and beetles. 
     
     
         3 . The method according to  claim 1  wherein the compounds of structure (I) have from 10 to 16 carbon atoms in the compound. 
     
     
         4 . The method according to  claim 1  wherein the at least one compound of structure (I) is a compound wherein:
 R is selected from the group consisting of —OH and ═O, X is CH 2 , y is 1 or 2, each Z is selected from the group consisting of (CH) and (CH 2 ), the bond between positions 2 and 3 in the ring is a single bond, one of R 1  and R 2  is H or —CH 3  and the other of R 1  and R 2  is a hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R 3  is H. 
 
     
     
         5 . The method of  claim 1  wherein the at least one compound of structure (I) is a compound wherein:
 R is selected from the group consisting of —OH and ═O, X is CH 2 , y is 1 or 2, each Z is selected from (CH) and (CH 2 ), the bond between positions 2 and 3 in the ring is a single or double bond, one of R 1  and R 2  is H and the other of R 1  and R 2  is a hydrocarbyl group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R 3  is selected from the group consisting of —C(O)OR 5  and —CH 2 C(O)R 8  where R 5  and R 8  are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms. 
 
     
     
         6 . The method according to  claim 5  wherein R is ═O, y is 1, the bond between positions 2 and 3 in the ring is a single bond, and R 2  and R 5  are each —CH 3 . 
     
     
         7 . The method according to  claim 1  wherein the at least one compound of structure (I) is a compounds wherein:
 R is ═O, X is O, y is 1 or 2, each Z is selected from the group consisting of (CH) and (CH 2 ), the bond between positions 2 and 3 of the rings is a single or double bond, one of R 1  and R 2  is H and the other of R 1  and R 2  is a hydrocarbyl group containing group containing from 9 to 15 carbon atoms and 0 to 3 double bonds, and R 3  is selected from the group consisting of —C(O)OR 5  and —CH 2 C(O)R 8  where R 5  and R 8  are each selected from a hydrocarbyl group containing from 1 to 6 carbon atoms and wherein the total number of carbon atoms in the compounds of structure (I) is from 11 to 17. 
 
     
     
         8 . The method according to  claim 7  wherein the bond between positions 2 and 3 of the rings is a single bond and R 5  and R 7  are each selected from a hydrocarbyl group containing from 3 to 5 carbon atoms. 
     
     
         9 . The method according to  claim 7  wherein the bond between positions 2 and 3 of the rings is a single bond and R 5  and R 7  are each —CH 3 . 
     
     
         10 . The method according to  claim 1  wherein the at least one compound of structure (I) is a compound wherein:
 R is ═O, X is O, y is 1 or 2, each Z is selected from (CH) and (CH 2 ), the bond between positions 2 and 3 in the ring is a single bond, R 1  is an alkyl group containing from 5 to 13 carbon atoms, R 2  is selected from the group consisting of H or —CH 3 , and R 3  is H. 
 
     
     
         11 . The method according to  claim 10  wherein:
 R 1  is an alkyl group of from 5 to 10 carbon atoms such that the compound of structure (I) contains from 11 to 14 total carbon atoms. 
 
     
     
         12 . The method according to claim I wherein the at least one compound of structure (I) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         13 . The method according to  claim 1  wherein the at least one compound of structure (I) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         14 . The method according to  claim 1  wherein the at least one compound of structure (I) is selected from the group consisting of 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         15 . The method according to  claim 1  wherein the at east one compound of structure (I) is selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         16 . The method according to  claim 1  wherein the at least one compound of structure (I) is selected from the group consisting of 
       
         
           
           
               
               
           
         
       
     
     
         17 . The method according to claim I wherein the at least one compound of structure (I) is applied to crops, agricultural or ornamental trees, plants, vegetation, produce or packaging materials for plants or crops by way of a formulation selected from the group consisting of direct spray formulations, fogger formulations, microencapsulated formulations, soil treatment formulations, seed treatment formulations, injectable formulations for injection into or onto plants or crops, and formulations for evaporative devices. 
     
     
         18 . The method of  claim 1  wherein the at least one compound of structure (I) is selected from the group consisting of :
 methyl apritone, methyl dihydrojasmonate, propyl dihydrojasmonate, methyl dihydrojasmolate, gamma-dodecalactone, gamma-tridecalactone, gamma methyl dodecalactone, gamma methyl tridecalactone. 3-methyl-5-propyl-2-cyclohexenone, 3-methyl-5-isobutyl-2-cyclohexenone, 3-methyl-5-isobutyl-2-cyclohexenol, 3-methyl-5-pentyl-2-cyclohexenone, 3-methyl-5-hexyl-2-cyclohexenone, and 3-methyl-5-heptyl-2-cyclohexenone. 
 
     
     
         19 . The method according to  claim 1  wherein the at least one compound of the structure (I) is present in the formulation in an amount sufficient to provide increased pest repellency or mortality over control pest repellency or mortality of at least 1%. 
     
     
         20 . The method of  claim 1  wherein the formulation is used to treat food or crops such that the treated food or crops have from about 0.05 to about 250 mg/sq. in. of at least one of the compounds thereon.