Labile esters of agrochemicals for controlled release and reduction of off-site movement

Abstract

The present invention relates to esters of carboxylic acid agrochemicals comprising a labile protecting group and having formula (I). Certain of the esters of carboxylic acid agrochemicals do not undergo hydrolysis to a significant degree in the dark, but are cleaved to regenerate the parent carboxylic acid agrochemical when exposed to light. Others of the esters of carboxylic acid agrochemicals undergo hydrolysis under both light and dark conditions. The present invention further relates to methods for the controlled release of a carboxylic acid agrochemicals, and to methods of controlling unwanted plants comprising applying to the unwanted plants an ester of a carboxylic acid agrochemical.

1 . An ester of a carboxylic acid agrochemical comprising a labile protecting group and having the formula (I): 
       
         
           
           
               
               
           
         
         wherein LPG is the labile protecting group, and the carboxylic acid agrochemical has the formula (II): 
       
       
         
           
           
               
               
           
         
         wherein A represents the remainder of the carboxylic acid agrochemical bonded to the carboxylic acid moiety. 
       
     
     
         2 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the carboxylic acid agrochemical is a herbicide, a fungicide, an insecticide, a plant health agent, or a plant growth regulator. 
     
     
         3 . The ester of a carboxylic acid agrochemical of  claim 2 , wherein the carboxylic acid agrochemical is a herbicide selected from the group consisting of dicamba, 2,4-dichlorophenoxyacetic acid (2,4-D), fenoxaprop, fenoxaprop-P, desmedipham, cyhalofop, carfentrazone, flufenpyr, fluthiacet, fluroglycofen, pyraflufen, flumiclorac, 4-(4-chloro-2-methylphenoxy)butanoic acid (MCPB), fluroxypyr, picloram, quinclorac, benazolin,
 clodinafop, 4-(2,4-dichlorophenoxy)butanoic acid (2,4-DB), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), dichlorprop, dichlorprop-P, diethatyl, endothall, fluazifop, flufenpyr, flumiclorac, fluoroglycofen, haloxyfop, indole-3-acetic acid, indole-3-butyric acid, mecoprop, mecoprop-P, pyrafluren, fenoprop, triclopyr, aminopyralid, bispyribac, chlorthal, imazamethabenz, pyrothiobac, quinmerac, quizalofop, quizalofop-P, diclofop, and lactofen.   
     
     
         4 . The ester of a carboxylic acid agrochemical of  claim 3 , wherein the carboxylic acid agrochemical is dicamba. 
     
     
         5 . The ester of a carboxylic acid agrochemical of  claim 3 , wherein the carboxylic acid agrochemical is 2,4-dichlorophenoxyacetic acid (2,4-D). 
     
     
         6 . The ester of a carboxylic acid agrochemical of  claim 2 , wherein the carboxylic acid agrochemical is:
 a fungicide selected from the group consisting of benalaxyl and picoxystrobin;   a plant health agent selected from the group consisting of salicylic acid and 3,6-dichlorosalicylic acid; or   a plant growth regulator selected from the group consisting of cloprop and 4-chlorophenoxyacetic acid (4-CPA).   
     
     
         7 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the labile protecting group comprises a nitrophenyl moiety. 
     
     
         8 . The ester of a carboxylic acid agrochemical of  claim 7 , wherein the ester of a carboxylic acid agrochemical has the formula (III): 
       
         
           
           
               
               
           
         
         wherein 
         R is C(R 7 R 8 ), O, or S; 
         R 1  is C(R 9 R 10 ), O, or S; 
         provided that when R is O or S, R 1  must be C(R 9 R 10 ), and when R 1  is O or S, R must be C(R 7 R 8 ); 
         R 7 , R 8 , R 9 , and R 10  are independently H, CH 3 , or CH 2 CH 3 ; 
         at least one of R 2  and R 3  is NO 2  and the other is H, acyclic aliphatic, amine, NO 2  or alkoxy; 
         R 4  is H, alkoxy, acyclic aliphatic, amine, NO 2 , or an ester having the formula (IV): 
       
       
         
           
           
               
               
           
         
         wherein R 11  is C 1 -C 18  acyclic aliphatic; 
         R 5  and R 6  are independently H, alkoxy, acyclic aliphatic, amine, or NO 2 ; 
         provided that if any of R 2 , R 3 , R 4 , R 5  and R 6  is acyclic aliphatic, the acyclic aliphatic does not comprise a double or triple bond between the α and β carbons; 
         n is 0 or 1; and 
         m is 0-3, provided that if R is O and n is 0, m is at least 1. 
       
     
     
         9 .- 16 . (canceled) 
     
     
         17 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the photolabile protecting group comprises a phenacylmethyl ester moiety. 
     
     
         18 . The ester of a carboxylic acid agrochemical of  claim 17 , wherein the ester of a carboxylic acid agrochemical has the formula (V): 
       
         
           
           
               
               
           
         
         wherein R 2  is hydroxy, alkoxy, or substituted alkoxy; and 
         R 1  and R 3  are independently H, hydroxy, alkoxy, substituted alkoxy, or C 1 -C 18  unsubstituted or substituted acyclic aliphatic, provided that if either of R 1  and R 3  is C 1 -C 18  unsubstituted or substituted acyclic aliphatic, the acyclic aliphatic does not comprise a double or triple bond between the α and β carbons. 
       
     
     
         19 .- 22 . (canceled) 
     
     
         23 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (VI): 
       
         
           
           
               
               
           
         
         wherein at least one of R and R 1  is N, and the other of R and R 1  is N or C—R 5 ; 
         R 2  is N or CH; 
         R 3  and R 4  are H, acyclic alkyl, substituted acyclic alkyl, or together form a phenyl ring; 
         and R 5  is H, acyclic alkyl, or substituted acyclic alkyl. 
       
     
     
         24 .- 31 . (canceled) 
     
     
         32 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (VII): 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are independently H or C 1 -C 8  alkyl, or together form a phenyl ring. 
       
     
     
         33 .- 35 . (canceled) 
     
     
         36 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (VIII): 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , and R 3  are alkyl. 
       
     
     
         37 .- 40 . (canceled) 
     
     
         41 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (IX): 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are halogen. 
       
     
     
         42 .- 43 . (canceled) 
     
     
         44 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (X): 
       
         
           
           
               
               
           
         
       
     
     
         45 . (canceled) 
     
     
         46 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula (XI): 
       
         
           
           
               
               
           
         
       
     
     
         47 . (canceled) 
     
     
         48 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester is a substituted or unsubstituted aromatic ester of dicamba or 2,4-dichlorophenoxyacetic acid (2,4-D). 
     
     
         49 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein at least one of R 1 , R 2 , and R 3  is an electron-donating group; 
         and the others of R 1 , R 2 , and R 3  are independently H or an electron-donating group; 
         provided that none of R 1 , R 2 , and R 3  is an electron-withdrawing group. 
       
     
     
         50 .- 53 . (canceled) 
     
     
         54 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein at least one of R 1 , R 2 , and R 3  is an electron-donating group; 
         and the others of R 1 , R 2 , and R 3  are independently H or an electron-donating group; 
         provided that none of R 1 , R 2 , and R 3  is an electron-withdrawing group. 
       
     
     
         55 .- 58 . (canceled) 
     
     
         59 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein R is alkyl, aryl, or alkoxy; 
         at least one of R 1 , R 2 , R 3 , R 4 , and R 5  is an electron-withdrawing group; 
         and the others of R 1 , R 2 , R 3 , R 4 , and R 5  are independently H, alkyl, alkoxy, dialkylamino or halogen. 
       
     
     
         60 .- 65 . (canceled) 
     
     
         66 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein R 1  is an electron-withdrawing group; 
         and wherein R 2  and R 3  are independently H or alkyl. 
       
     
     
         67 .- 71 . (canceled) 
     
     
         72 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein R 1  is alkyl and R 2  is H, alkyl, or aryl. 
       
     
     
         73 .- 75 . (canceled) 
     
     
         76 . The ester of a carboxylic acid agrochemical of  claim 1 , wherein the ester of a carboxylic acid agrochemical has the formula: 
       
         
           
           
               
               
           
         
         wherein R 1  is an electron-withdrawing group; 
         and R 2  is H, a hydrocarbon, or an aromatic group. 
       
     
     
         77 .- 83 . (canceled) 
     
     
         84 . A composition comprising an ester of a carboxylic acid agrochemical of  claim 1 . 
     
     
         85 .- 91 . (canceled) 
     
     
         92 . A method for the controlled release of a carboxylic acid agrochemical comprising exposing an ester of a carboxylic acid agrochemical of  claim 1  to artificial or natural light, wherein the natural light is optionally sunlight and the artificial light is optionally incandescent light or fluorescent light. 
     
     
         93 . (canceled) 
     
     
         94 . A method of controlling unwanted plants comprising applying to the unwanted plants an ester of a carboxylic acid agrochemical of  claim 1 . 
     
     
         95 . The method of  claim 94 , wherein the carboxylic acid agrochemical is dicamba or 2,4-dichlorophenoxyacetic acid (2,4-D). 
     
     
         96 .- 101 . (canceled)