Novel esters as useful broad spectrum herbicidal compounds

Abstract

The instant invention relates to the discovery of certain novel herbicidal esters of agriculturally active acids. These esters present agronomical advantages over traditional herbicidal products by presenting multiple herbicidal mechanisms that ensure activity over a broad weed spectrum while limiting the appearance of plant resistance.

1 . A compound of the formula:  
         R—CO—O—R′ wherein RCOO is an acetate of an acid selected from the group consisting of    N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine(benzoylprop),    N-benzoyl-N-(3-chloro-4-fluorophenyl)-D-alanine (flamprop-M),    (RS)-2-[4-(3,5-dichloro-2-pyridyloxy)phenoxy]propionic acid (Chlorazifop),    (R)-2-[4-(5-chloro-3-fluoro-2-pyridyloxy)phenoxy]propionic acid (Clodinafop),    (RS)-2-[4-(4-chlorophenoxy)phenoxy]propionic acid (Clofop),    (R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionic acid (Cyhalofop),    (RS)-2-[4-(2,4-dichlorophenoxy)phenoxy]propionic acid (Diclofop),    (RS)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid (Fenoxaprop),    (R)-2-[4-(6-chloro-1,3-benzoxazol-2-yloxy)phenoxy]propionic acid (Fenoxaprop-P),    (RS)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid (fluazifop),    (R)-2-[4-(5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid (fluazifop-P),    (RS)-2-[4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]propionic acid (haloxyfop),    (RS)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid (quizalofop),    (R)-2-[4-(6-chloroquinoxalin-2-yloxy)phenoxy]propionic acid (quizalofop-P),    (RS)-2-[4-(α,α,α-trifluoro-p-tolyloxy)phenoxy]propionic acid (trifop),    3-amino-2,5-dichlorobenzoic acid (Chloramben),    3,6-dichloro-o-anisic acid (Dicamba),    3,5,6-trichloro-o-anisic acid (Tricamba),    (E)-(RS)-3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylic acid (Alloxydim),    (RS)-2-(5-ethyl-2-{4-[1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]phenoxymethyl}phenoxy)propionic acid (benzfendizone),    (Z)-2-chloro-3-[2-chloro-5-(cyclohex-1-ene-1,2-dicarboximido)phenyl]acrylic acid (Cinidon),    [2-chloro-5-(cyclohex-1-ene-1,2-dicarboximido)-4-fluororophenoxy]acetic acid (flumiclorac),    2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(or 5)-methylbenzoic acid (imazamethabenz),    (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methoxymethylnicotinic acid (imazamox),    (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methyln icotinic acid (imazapic),    2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (Imazapyr),    (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid (Imazaquin),    (RS)-5-ethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid (Imazethapyr),    5-(2-chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitrobenzoic acid (acifluorfen),    5-(2,4-dichlorophenoxy)-2-nitrobenzoic acid (Bifenox),    O-[5-(2-chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitrobenzoyl]glycolic acid (Fluoroglycofen),    0-[5-(2-chloro-α,α,α-trifluoro-p-tolyloxy)-2-nitrobenzoyl]-DL-lactic acid (Lactofen),    (2,4-dichlorophenoxy)acetic acid (2,4-D),    4-chlorophenoxyacetic acid (4-CPA),    (4-chloro-2-methylphenoxy)acetic acid (MCPA),    4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),    4-(4-chloro-o-tolyloxy)butyric acid (MCPB),    (RS)-2-(3-chlorophenoxy)propionic acid (cloprop),    (RS)-2-(2,4-dichlorophenoxy)propionic acid (dichlorprop),    (R)-2-(2,4-dichlorophenoxy)propionic acid (dichlorprop-P),    (RS)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),    (R)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop-P),    4-amino-3,6-dichloropyridine-2-carboxylic acid (aminopyralid),    3,6-dichloropyridine-2-carboxylic acid (clopyralid),    4-amino-3,5-dichloro-6-fluoro-2-pyridyloxyacetic acid (fluoroxypyr),    4-amino-3,5,6-trichloropyridine-2-carboxylic acid (picloram),    5-[4-bromo-1-methyl-5-(trifluoromethyl)pyrazol-3-yl]-2-chloro-4-fluorobenzoic acid (fluazolate),    2-chloro-5-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-4-fluorophenoxyacetic acid (pyraflufen),    2-chloro-5-[1,6-dihydro-5-methyl-6-oxo-4-(trifluoromethyl)pyridazin-1-yl]-4-fluorophenoxyacetic acid (Flufenpyr),    5-bromo-1,6-dihydro-6-oxo-1-phenylpyridazin-4-yloxamic acid (Oxapyrazon),    (RS)-hexahydro-4-hydroxy-3,6-dioxopyridazin-4-ylacetic acid (Pydanon),    2-difluoromethyl-5-(4,5-dihydro-1,3-thiazol-2-yl)-4-isobutyl-6-trifluoromethylnicotinic acid (Thiazopyr),    3,5,6-trichloro-2-pyridyloxyacetic acid (Triclopyr),    2,6-bis(4,6-dimethoxypyrimidin-2-yloxy)benzoic acid (Bispyribac),    2-(4,6-dimethoxypyrimidin-2-yloxy)-6-(1-methoxyiminoethyl)benzoic acid (Pyriminobac),    2-chloro-6-(4,6-dimethoxypyrimidin-2-ylthio)benzoic acid (Pyrithiobac),    3,7-dichloroquinoline-8-carboxylic acid (Quinclorac),    7-chloro-3-methylquinoline-8-carboxylic acid (Quimerac),    3-chloro-2-(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidin-2-ylsulfonamido)benzoic acid (Cloransulam),    (RS)-2-chloro-3-{2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorophenyl}propionic acid (Carfentrazone),    [2-chloro-4-fluoro-5-(5,6,7,8-tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-a]pyridazin-1-ylideneamino)phenylthio]acetic acid (fluthiacet),    1-(allyloxycarbonyl)-1-methylethyl 2-chloro-5-[1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]benzoic acid (Butafenacil),    2-chloro-5-(1,2,3,6-tetrahydro-3-methyl-2,6-dioxo-4-trifluoromethylpyrimidin-1-yl)benzoic acid (Flupropasil), and    2-{1-[4-(3,5-difluorophenyl)semicarbazono]ethyl}nicotinic acid (diflufenzopyr); 
 and where R′ is the corresponding alkyl group of an alcohol selected from the group consisting of:  
   methyl(E)-(RS)-3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate,    (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(3-chloroallyloxy)iminobutyl]-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-en-1-one,    2-{(EZ)-1-[(2RS)-2-(4-chlorophenoxy)propoxyimino]butyl}-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one,    6-chloro-3-phenylpyridazin-4-ol,    (RS)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one,    4-hydroxy-3,5-di-iodobenzonitrile,    3,5-dibromo-4-hydroxybenzonitrile,    3,5-dichloro-4-hydroxybenzonitrile,    3,5-dichloro-2,6-difluoropyridin-4-ol,    2,3,5-trichloropyridin-4-ol, and    6-chloro-3-phenylpyridazin-4-ol.    
     
     
         2 . A compound of the formula:  
         M + − O 3 P—CH 2 —NH—CH 2 —CO—O—R′ wherein M +  is an agronomically acceptable cation, and    where R′ represents the alkyl of an alcohol selected from the group consisting of:    methyl(E)-(RS)-3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate,    (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(3-chloroallyloxy)iminobutyl]-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-en-1-one,    2-{(EZ)-1-[(2RS)-2-(4-chlorophenoxy)propoxyimino]butyl}-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one,    6-chloro-3-phenylpyridazin-4-ol,    (RS)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one,    4-hydroxy-3,5-di-iodobenzonitrile,    3,5-dibromo-4-hydroxybenzonitrile,    3,5-dichloro-4-hydroxybenzonitrile,    3,5-dichloro-2,6-difluoropyridin-4-ol,    2,3,5-trichloropyridin-4-ol, and    6-chloro-3-phenylpyridazin-4-ol.    
     
     
         3 . A compound of the formula:  
       
         
           
           
               
               
           
         
         wherein M +  is an agronomically acceptable cation, and R′ is the corresponding alkyl group of an alcohol selected from the group consisting of:  
         methyl(E)-(RS)-3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate,  
         (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-en-1-one,  
         (RS)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,  
         (RS)-(EZ)-2-[1-(3-chloroallyloxy)iminobutyl]-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-en-1-one,  
         (RS)-(EZ)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-en-1-one,  
         2-{(EZ)-1-[(2RS)-2-(4-chlorophenoxy)propoxyimino]butyl}-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one,  
         6-chloro-3-phenylpyridazin-4-ol,  
         (RS)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,  
         (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,  
         (RS)-(EZ)-2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one,  
         4-hydroxy-3,5-di-iodobenzonitrile,  
         3,5-dibromo-4-hydroxybenzonitrile,  
         3,5-dichloro-4-hydroxybenzonitrile,  
         3,5-dichloro-2,6-difluoropyridin-4-ol,  
         2,3,5-trichloropyridin-4-ol, and  
         6-chloro-3-phenylpyridazin-4-ol.  
       
     
     
         4 . A compound of the formula:  
         R—CO—O—R′ where R—CO—O represents an acetate of a carboxylic acid selected from the group consisting of:    3-chloro-5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylic acid (Halosulftiron),    33-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-6-(trifluoromethyl)nicotinic acid (Flupyrsulfuron),    2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methanesulfonam-ido-methylbenzoic acid (Mesosulfuron),    2-[4,6-bis(difluoromethoxy)pyrimidin-2-ylcarbamoylsulfamoyl]benzoic acid (Primisulfuron),    5-[(4,6-dimethoxypyrimidin-2-ylcarbamoyl)sulfamoyl]-1-methylpyrazole-4-carboxylic acid (Pyrazosulfuron),    3-chloro-5-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-1-methylpyrazole-4-carboxylate,    5-(4,6-dimethylpyrimidin-2-yl-carbamoylsulfamoyl)-1-(2-pyrid-yl)pyrazole-4-carboxylic acid,    3-chloro-2-(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidin-2-ylsulfonamido)benzoic acid (Cloransulam),    3-chloro-N-(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5-c]pyrimidin-2-ylsulfonyl)anthranilic acid cloransulam,    2-[(4-ethoxy-6-methylamino-1,3,5-triazin-2-yl)carbamoylsulfamoyl]benzoic acid (Ethametsulfuron),    4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoic acid (Iodosulfuron),    3-(4-methoxy-6-methyl-1,3,5-triazin-2-ylcarbamoylsulfamoyl)thiophene-2-carboxylic acid (Thifensulfuron),    2-[4-methoxy-6-methyl-1,3,5-triazin-2-yl(methyl)carbamoylsulfamoyl]benzoic acid (Tribenuron),    2-[4-dimethylamino-6-(2,2,2-trifluoroethoxy)-1,3,5-triazin-2-ylcarbamoylsulfamoyl]-m-toluic acid (Triflusulfuron), and    3-(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methylbenzo[b]thiophen-7-sulfonyl)urea, 
 and R′ represents the corresponding alkyl group of an alcohol selected from the group consisting of:  
   methyl(E)-(RS)-3-[1-(allyloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2-oxocyclohex-3-enecarboxylate,    (RS)-(EZ)-5-(3-butyryl-2,4,6-trimethylphenyl)-2-(1-ethoxyiminopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(3-chloroallyloxy)iminobutyl]-5-(2-ethylthiopropyl)-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-en-1-one,    2-{(EZ)-1-[(2RS)-2-(4-chlorophenoxy)propoxyimino]butyl}-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one,    6-chloro-3-phenylpyridazin-4-ol,    (RS)-(EZ)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-en-1-one,    (RS)-(EZ)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,    (RS)-(EZ)-2-[1-(ethoxyimino)propyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one,    4-hydroxy-3,5-di-iodobenzonitrile,    3,5-dibromo-4-hydroxybenzonitrile,    3,5-dichloro-4-hydroxybenzonitrile,    3,5-dichloro-2,6-difluoropyridin-4-ol,    2,3,5-trichloropyridin-4-ol, and    6-chloro-3-phenylpyridazin-4-ol.    
     
     
         5 . A composition suitable for controlling the growth of unwanted vegetation which comprises an effective amount of a compound of  claim 1  and at least one surfactant, solid diluent, liquid diluent, or a mixture thereof.  
     
     
         6 . A composition suitable for controlling the growth of unwanted vegetation which comprises an effective amount of a compound of  claim 2  and at least one surfactant, solid diluent, liquid diluent, or mixture thereof.  
     
     
         7 . A composition suitable for controlling the growth of unwanted vegetation which comprises an effective amount of a compound of  claim 3  and at least one 
 surfactant, solid diluent, liquid diluent, or mixture thereof.    
     
     
         8 . A composition suitable for controlling the growth of unwanted vegetation which comprises an effective amount of a compound in  claim 4  and at least one surfactant, solid diluent, liquid diluent, or mixture thereof.  
     
     
         9 . A method for controlling the development of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of  claim 1 .  
     
     
         10 . A method for controlling the development of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of  claim 2 .  
     
     
         11 . A method for controlling the development of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of  claim 3 .  
     
     
         12 . A method for controlling the development of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of  claim 4.