Process for making 5-cyanovaleric acid, adipic acid or dimethyl adipate

Abstract

Disclosed in a process for making (1) a compound of the formula NC—CH 2 —CH 2 —CH 2 —CH 2 —CO 2 R′, wherein R′ is H or C 1 to C 12 alkyl, or (2) adipic acid or (3) dimethyl adipate, using as the substrate, 3-pentenenitrile, (2) 3-pentenoic acid or methyl 3-pentenoate, respectively, by contacting the substrate with carbon monoxide and a nucleophile in the presence of a Group VIII metal, a selected ligand, and an acid promoter. The nucleophile, which (a) an alcohol or water, or (b) water or (c) methanol, respectively, in the presence of a Group VIII metal, preferably palladium, a selected phosphine ligand, and an acid promoter.

What is claimed is:  
     
         1 . The present invention is a process for producing (1) a compound of the formula NC—CH 2 —CH 2 —CH 2 —CH 2 —CO 2 R′, wherein R′ is H or C 1  to C 12  alkyl, or 
 (2) adipic acid, or  
 (3) dimethyl adipate,  
 comprising: contacting a substrate selected from the group consisting of (A) (B) and (C) 
 wherein substrate (A) is 3-pentenenitrile,  
 wherein substrate (B) is 3-pentenoic acid, and  
 wherein substrate (C) is methyl 3-pentenoate,  
 with a nucleophile (a), (b), or (c), respectively, 
 wherein nucleophile (a) is alcohol or water,  
 wherein nucleophile (b) is water and  
 wherein nucleophile (c) is methanol,  
 and carbon monoxide, in the presence of a Group VIII metal;  
 a ligand having the formula  
                     
 wherein  
 
 
 X is a substituted or unsubstituted bridging group selected from the group consisting of a divalent aryl, a divalent alkylene group, and a divalent combination of alkylene and aromatic groups; and  
 wherein R 1 , R 4 , R 7 , and R 10 , independently are H, or C 1  to C 12  alkyl;  
 provided that R 2 , R 3 , R 5 , R 6 , R 8 , R 9 , R 11 , and R 12 , independently are C 1  to C 12  alkyl or cycloalkyl,  
 wherein R 2  and R 3 ; R 5  and R 6 ; R 8  and R 9 ; and R 11  and R 12  may be taken together to form a cycloalkyl group; and  
 a promoter, said promoter comprising a strong acid having a pKa in water of less than 1 and, when the nucleophile is water, at least one carboxylic acid.  
 
     
     
         2 . The process of  claim 1  wherein the ligand is selected from the group consisting of the  
       
         
           
           
               
               
           
         
       
     
     
         3 . The process of  claim 1  wherein said Group VIII metal is palladium.  
     
     
         4 . The process of  claim 1  wherein said promoter is methanesulphonic acid.  
     
     
         5 . The process of  claim 1  wherein at least one of R 1 , R 4 , R 7 , and R 10  is H, C 1 , C 2 , or C 6  to C 12  alkyl.  
     
     
         6 . The process of  claim 1  wherein the substrate is (a) or (c).  
     
     
         7 . The process of  claim 6  wherein the nucleophile is water and the substrate is 3-pentenenitrile, said process further comprising adding a carboxylic acid.  
     
     
         8 . The process of  claim 7  wherein the carboxylic acid is acetic acid.