Aryl ether derivatives and processes for their preparation and herbicidal and desiccant compositions containing them

Abstract

Substituted aryl ether derived compounds represented by general structure (I) are described. X and Y are independent of each other and are represented by hydrogen, halogen, cyano, nitro, (C 1-4 )alkyl, (C 1-4 )haloalkyl, or (C 1-4 )haloalkoxy; Z is oxygen or sulfur, Q is selected form Q1 to Q6; A is oxygen, sulfur, or imino; R 1 is hydrogen, (C 1-4 )alkyl, (C 1-4 )haloalkyl, or amino and can be independent of each other in a single molecule; R 2 and R 3 are independent of each other and may be selected from the group consisting of hydrogen, halogen, cyano nitro, (C 1-4 )alkyl, (C 1-4 )haloalkyl, (C 2-4 )alkenyl, (C 2-6 )haloalkenyl and amino which may be optionally substituted with (C 1-4 )alkyl or (C 1-4 )haloalkyl; Ar is substituted or unsubstituted carbocyclic or heterocyclic aromatic ring being at least a five or six membered ring. This ring can be fused with another substituted or unsubstituted five or six membered carbocyclic or heterocyclic ring. When Q is Q5, unsubstituted or substituted phenyl is excluded. Also described are the processes for the manufacture of these compounds and argiculturally suitable compositions containing these as active ingredients which are useful as herbicides for general or selective pre-emergent or post-emergent control of undesired plant species and defoliants.

What is claimed is:  
     
         1 . A compound represented by the formula (I) or its salts:  
       
         
           
           
               
               
           
         
       
       wherein X and Y are independent of each other and represent hydrogen, halogen, cyano, nitro, (C 1-4 )alkyl, (C 1-4 )haloalkyl, or (C 1-4 )haloalkoxy; 
 Z is oxygen or sulfur;  
 Q is  
                     
 A is oxygen, sulfur, or imino;  
 R 1  is hydrogen, (C 1-4 )alkyl, or (C 1-4 )haloalkyl, and can be independent of each other;  
 R 2  and R 3  are independent of each other and may be selected from the group consisting of hydrogen, halogen, cyano, nitro, (C 1-4 )alkyl, (C 1-4 )haloalkyl, (C 2-6 )alkenyl, (C 2-6 )haloalkenyl and amino which may be optionally substituted with (C 1-4 )alkyl or (C 1-4 )haloalkyl;  
 Ar is a substituted or unsubstituted carbocyclic or heterocyclic aromatic ring being at least a five or six membered ring. When Q is Q5, unsubstituted or substituted phenyl is excluded.  
 
     
     
         2 . The compound or its salt according to  claim 1  wherein 
 Ar is a substituted or unsubstituted carbocyclic or heterocyclic aromatic ring being at least a five or six membered ring, which can be fused with another substituted or unsubstituted five or six membered carbocyclic or heterocyclic aromatic ring, in which the carbocyclic or heterocyclic aromatic ring may be substituted with upto seven substituents independently selected from the group consisting of halogen, (C 1-4 )alkyl, halo(C 1-4 )alkyl, (C 1-6 )alkoxy, halo(C,)alkoxy, (C 1-6 )alkylthio, (C 1-6 )alkylsulfonyl, (C 1-6 ,)alkylsulfinyl, (C 1-6 )dialkylaminocarbonyl, cyano, nitro, amino, hydroxy, (C 1-6 )alkylsulfonylamino, (C 1-4 )alkoxycarbonyl(C 1-6 )alkoxy, (C 1-6 )alkoxycarbonyl-halo(C 1-6 )alkyl, (C 2-6 )alkenyloxycarbonyl(C 1-6 )alkoxy(C 1-6 )alkyl, (C 1-6 )alkylcarbonylamino, bisbenzoylamino, aminoacetyl, aminotrifluoroacetyl, and amino(C 1-6 )allylsulfonate. When Q is Q5, unsubstituted or substituted phenyl is excluded.  
 
     
     
         3 . The compound or its salt according to  claim 1  wherein 
 X and Y are independently hydrogen or halogen;  
 Z is oxygen or sulfur;  
 R 1  is (C 1-4 )alkyl;  
 R 2  is (C 1-4 )haloalkyl;  
 R 3  is hydrogen;  
 Ar is phenyl, pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl or isothiazolyl, or phenyl, pyridyl, pyrimidyl, pyridazinyl, triazolyl, thiazolyl or isothiazolyl substituted with upto five substituents independently selected from the group consisting of halogen, (C 1-6 )alkyl, (C 1-6 )haloalkyl, (C 1-6 )alkoxy, (C 1-6 )haloalkoxy, (C 1-6 )alkylthio, (C 1-6 )alkylsulfonyl, (C 1-6 )alkylsulfinyl, di(C 1-6 )alkylaminocarbonyl, cyano, nitro, amino, hydroxy, (C 1-6 )alkylsulfonylamino, (C 1-6 )alkoxycarbonyl(C 1-6 )alkoxy, (C 1-6 )alkoxycarbonyl-halo(C 1-6 )alkyl, (C 2-6 )alkenyloxycarbonyl(C 1-6 )alkoxy(C 1-6 )alkyl, (C 1-6 )alkoxycarbonylamino, bisbenzoylamino, aminoacetyl, aminotrifluoroacetyl, and amino(C 1-6 )alkylsulfonate.  
 
     
     
         4 . The compound or its salt according to  claim 1  wherein 
 X is fluorine;  
 Y is chlorine;  
 R 1  is methyl;  
 R 2  is trifluoromethyl;  
 Ar is 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-bromo-2-pyridyl, 5-bromo-2-pyridyl, 6-bromo-2-pyridyl, 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 6-chloro-2-pyridyl, 3-fluoro-2-pyridyl, 5-fluoro-2-pyridyl, 6-fluoro-2-pyridyl, 3-cyano-2-pyridyl, 5-cyano-2-pyridyl, 6-cyano-2-pyridyl, 3-nitro-2-pyridyl, 5-nitro-2-pyridyl, 6-nitro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 5-amino-2-pyridyl, 3-dimethyl-aminocarbonyl-2-pyridyl, 3-methylsulfonyl-2-pyridyl, 3-isopropylsulfonyl-2-pyridyl, 6-chloro-3-tri fluoromethyl-2-pyridyl, 3,5,6-trifluoropyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-bromo-2-pyrimidyl, 4-chloro-2-pyrimidyl, 4-trifluoromethyl-2-pyrimidyl, 4,6-dimethoxy-2-pyrimidyl, 2,6-dimethoxy-4-pyrimidyl, 4,6-dimethoxy-2-triazinyl, phenyl, 2-iodo-phenyl, 2-trifluoromethoxyphenyl, 2-nitrophenyl, 4-nitrophenyl, 4-aminophenyl, 4-hydroxyphenyl, 4-methylsulfonylaminophenyl, 4-(1-ethoxycarbonylethoxy)phenyl, 2-cyanophenyl, 2-cyano-3-fluorophenyl, 2-cyano-4-fluorophenyl, 2-amino-4-(1 ethoxy-carbonylethoxy)phenyl, 2-cyano-4-nitrophenyl, 4-amino-2-cyanophenyl, 4-nitro-2-trifluoromethylphenyl, 4-amino-2-trifluoro'methylphenyl, 4-acetylamino-2-trifluoro-methylphenyl, 4-(1-ethoxycarbonylethoxy)-2-nitrophenyl, 5-chloro-4-(1-ethoxycarbonyl-ethoxy)-2-nitrophenyl, 3-methyl-4-nitro-5-isothiazolyl, or 5-nitro-2-thiazolyl.  
 
     
     
         5 . A process for producing a compound represented by the formula (1) in said  claim 1  or its salt, wherein X, Y, Z, and Q are as defined therein which comprises reacting a compound represented by the formula (II):  
       
         
           
           
               
               
           
         
       
       with a compound of the formula: Ar-Hal wherein Hal is a halogen atom, in the presence of a base.  
     
     
         6 . A process for producing a compound or its salt represented by the formula (I) in said  claim 1  wherein X, Y, Z, R 1 , R 2 , R 3 , A, and Ar are as defined and Q is Q1 therein which comprises reacting a compound represented by formula (III):  
       
         
           
           
               
               
           
         
         with a compound of the formula (IV):  
         
           
             
             
                 
                 
             
           
         
         wherein R 1  and R 2  are as defined in  claim 1  and R 4  represents a C 1-4  alkyl group, in the presence of a base.  
       
     
     
         7 . A process for producing a compound or its salt represented by the formula (I) in said  claim 1  wherein X, Y, Z, R 1 , R 2 , R 3 , A, and Ar are as defined therein which comprises reacting a compound represented by formula (V):  
       
         
           
           
               
               
           
         
       
       wherin R 5  represents a C 1-4  alkyl or phenyl group;  
       with a compound of the formula (IV):  
       
         
           
           
               
               
           
         
       
       wherein R 1  and R 2  are as defined in  claim 1  and R 4  represents a C 1-4  alkyl group, in the presence of a base.  
     
     
         8 . A process for producing a compound or its salt represented by the formula (I) in said  claim 1  wherein X, Y, Z, R 1 , R 2 , R 3 , A, and Ar are as defined and Q is Q1 therein which comprises reacting a compound represented by formula (VI):  
       
         
           
           
               
               
           
         
       
       with a compound of the formula (VI):  
       
         
           
           
               
               
           
         
         wherein X, Y, Z, and Ar are as defined in  claim 1  and L represents a leaving group, in the presence of a base.  
       
     
     
         9 . A process for producing a compound or its salt represented by the formula (IX) in said  claim 1 ,  
       
         
           
           
               
               
           
         
       
       wherein X, Y, Z, R 1 , R 2 , R 3  and Ar are as defined therein,  
       which comprises reacting a compound represented by formula (VIII):  
       
         
           
           
               
               
           
         
         with a thionating agent in the presence of a base.  
       
     
     
         10 . A process for producing a compound or its salt represented by the formula (I) in said  claim 1  wherein X, Y, Z, R 2 , R 3 , A, and Ar are as defined, R 1  is alkyl, haloalkyl, or amino, and Q is Q1 therein which comprises reacting a compound represented by formula (VIII) wherein R 1  is hydrogen with an alkylating agent or an aminating reagent.  
       
         
           
           
               
               
           
         
       
     
     
         11 . A process for producing a compound or its salt represented by the formula (I) in said  claim 1  wherein X, Y, Z, R 1 , R 2 , R 3 , A, and Ar are as defined and Q is Q2 therein which comprises reacting a compound represented by formula (X):  
       
         
           
           
               
               
           
         
       
       with a compound of the formula (XI):  
       
         
           
           
               
               
           
         
       
       wherein R 1  is as defined in  claim 1  in the presence of a base and a carbonylation reagent.  
     
     
         12 . A process for producing a compound or its salt represented by the formula I wherein X, Y, Z, R 1 , R 2 , R 3 , A, Ar and Q are as defined in  claim 1 , which comprises reacting a haloaryl compound of formula (XII):  
       
         
           
           
               
               
           
         
       
       wherein hal represents a halogen atom;  
       with an aryl or heteroaryl hydroxyl compound or thiohydroxy compound, or its salt.  
     
     
         13 . A process for producing a compound or its salt represented by the formula (II)  
       
         
           
           
               
               
           
         
       
       wherein X, Y, Z, R 1 , R 2 , R 3 , A, and Q are as defined in  claim 1 ,  
       which comprises reacting a compound of formula (XIII):  
       
         
           
           
               
               
           
         
       
       wherein R 6  represents a C 1-4 alkyl or a heteroaryl group;  
       with a hydrolytic reagent.  
     
     
         14 . A herbicidal compositions, characterized in that it contains at least one compound according to  claim 1 .  
     
     
         15 . A herbicidal composition which comprises an effective amount of a compound of  claim 1  and an agricultural adjuvant.  
     
     
         16 . A method for controlling weeds, which comprises applying to the locus to be protected a herbicidally effective amount of a compound of  claim 1 .  
     
     
         17 . A method for controlling weeds in a corn field which comprises applying a herbicidally effective amount of a compound of  claim 1  to the corn field.  
     
     
         18 . A method for controlling weeds in a soybean field which comprises applying a herbicidally effective amount of a compound of  claim 1  to the soybean field.  
     
     
         19 . A method for controlling weeds, which comprises applying to the locus to be protected a herbicidally effective amount of a compound of  claim 1  in combination with another herbicide.  
     
     
         20 . A method for controlling weeds of  claim 16  wherein the compound of  claim 1  is applied to soil as a preemergent herbicide.  
     
     
         21 . A method for controlling weeds of  claim 16  wherein the compound of  claim 1  is applied to plant foliage.  
     
     
         22 . A method for controlling weeds of  claim 16  wherein the another herbicide is an acetanilide, sulfonylurea, or any referenced in the text.  
     
     
         23 . A method to desiccate a plant which comprises applying to the plant a compound of  claim 1 .  
     
     
         24 . A method to desiccate a plant of  claim 23  wherein the plant to which the compound is applied is a potato plant or a cotton plant.