Methods of Making Functionalized Internal Olefins and Uses Thereof

Abstract

A method of isomerizing a substance includes combining a substance including a terminal alkenyl group and a substance including a fluorosulfonic acid group in a reaction mixture, and forming a substance including a 2-alkenyl group from the substance including a terminal alkenyl group in the reaction mixture. The method may be used to functionalize a substance, as the substance including a 2-alkenyl group can be reacted with a functionalizing agent to form a substance including a first functional group. The methods may be used to form a dicarboxylic acid, such as suberic acid, from a renewable feedstock.

1 . A method of isomerizing a substance, comprising:
 combining a substance comprising a terminal alkenyl group and a substance comprising a fluorosulfonic acid group in a reaction mixture; and   forming a substance comprising a 2-alkenyl group from the substance comprising the terminal alkenyl group in the reaction mixture.   
     
     
         2 . The method of  claim 1 , where the substance comprising the terminal alkenyl group further comprises a substituent selected from the group consisting of a halide group, a heteroalkyl group, an aryl group, a heteroaryl group, a nitrile group, an amide group, an imide group, a nitro group, a ketone group, an ether group, a sulfide group, a sulfoxide group, a sulfone group, and combinations thereof. 
     
     
         3 . The method of  claim 2 , where the substance comprising the terminal alkenyl group is an α-ester-alk-ω-ene molecule. 
     
     
         4 . The method of  claim 3 , where the substance comprising the terminal alkenyl group is 9-decenoic acid methyl ester. 
     
     
         5 . The method of  claim 1 , where the substance comprising the fluorosulfonic acid group is trifluoromethanesulfonic acid. 
     
     
         6 - 8 . (canceled) 
     
     
         9 . The method of  claim 1 , where
 the substance comprising the terminal alkenyl group is 9-decenoic acid methyl ester;   the substance comprising the fluorosulfonic acid group is trifluoromethanesulfonic acid or comprises a copolymer comprising perfluorosulfonic acid monomeric units and monomer units derived from tetrafluoroethylene; and   the substance comprising the 2-alkenyl group is 8-decenoic acid methyl ester.   
     
     
         10 - 11 . (canceled) 
     
     
         12 . A method of functionalizing a substance, comprising:
 combining a substance comprising a terminal alkenyl group and a substance comprising a fluorosulfonic acid group in a first reaction mixture;   forming a substance comprising a 2-alkenyl group from the substance comprising the terminal alkenyl group in the first reaction mixture;   combining the substance comprising the 2-alkenyl group and a functionalizing agent in a second reaction mixture; and   forming a substance comprising a first functional group from the substance comprising the 2-alkenyl group in the second reaction mixture.   
     
     
         13 - 14 . (canceled) 
     
     
         15 . The method of  claim 12 , where
 the functionalizing agent comprises an oxidizing agent selected from the group consisting of KMnO 4 , ozone, periodic acid, lead tetraacetate, and combinations thereof; and   the first functional group is a carboxylic acid group.   
     
     
         16 . The method of  claim 15 , where
 the substance comprising the terminal alkenyl group is an α-ester-alk-ω-ene molecule; and   the substance comprising the first functional group is a dicarboxylic acid molecule.   
     
     
         17 - 18 . (canceled) 
     
     
         19 . The method of  claim 12 , where
 the substance comprising the terminal alkenyl group is 9-decenoic acid methyl ester;   the substance comprising the 2-alkenyl group is 8-decenoic acid methyl ester; and   the substance comprising the first functional group comprises a 7-heptanoic acid group or a salt thereof, or a methyl 7-heptanoate group.   
     
     
         20 - 25 . (canceled) 
     
     
         26 . A method of making a dicarboxylic acid, comprising:
 forming a first reaction mixture from ingredients comprising a first olefin ester, a second olefin ester, and a metathesis catalyst;   forming an unsaturated dicarboxylic ester from the first reaction mixture;   forming a second reaction mixture from ingredients comprising the unsaturated dicarboxylic ester and a hydrogenating agent;   forming a second dicarboxylic ester;   forming a third reaction mixture from ingredients comprising the second dicarboxylic ester and a hydrolyzing agent; and   hydrolyzing the second dicarboxylic ester, to form a dicarboxylic acid.   
     
     
         27 - 31 . (canceled) 
     
     
         32 . The method of  claim 26 , where the first olefin ester is a terminal olefin ester and the second olefin ester is an internal olefin ester. 
     
     
         33 . The method of  claim 32 , where the terminal olefin ester is a compound of formula (V): 
       
         
           
           
               
               
           
         
       
       where:
 X 1  is C 3-18  alkylene, C 3-18  alkenylene, C 2-18  heteroalkylene, or C 2-18  heteroalkenylene, each of which is optionally substituted one or more times by substituents selected independently from R 12 ; 
 V is C 1-12  alkyl, C 1-12  heteroalkyl, C 2-12  alkenyl, or C 2-12  heteroalkenyl, each of which is optionally substituted one or more times by substituents selected independently from R 12 ; and 
 R 12  is a halogen atom, —OH, —NH 2 , C 1-6  alkyl, C 1-6  heteroalkyl, C 2-6  alkenyl, C 2-6  heteroalkenyl, C 3-10  cyclokalkyl, or C 2-10  heterocycloalkyl. 
 
     
     
         34 - 40 . (canceled) 
     
     
         41 . The method of  claim 32 , where the terminal olefin ester is 9-decenoic acid alkyl ester. 
     
     
         42 . (canceled) 
     
     
         43 . The method of  claim 26 , where the first olefin ester is an internal olefin ester, and the second olefin ester is an internal olefin ester. 
     
     
         44 . The method of  claim 43 , where the first olefin ester and the second olefin ester are independently compounds of Formula (VI): 
       
         
           
           
               
               
           
         
       
       where:
 X 2  is C 3-18  alkylene, C 3-18  alkenylene, C 2-18  heteroalkylene, or C 2-18  heteroalkenylene, each of which is optionally substituted one or more times by substituents selected independently from R 15 ; 
 R 13  is C 1-12  alkyl, C 1-12  heteroalkyl, C 2-12  alkenyl, or C 2-12  heteroalkenyl, each of which is optionally substituted one or more times by substituents selected independently from R 15 ; 
 R 14  is a halogen atom, —OH, —NH 2 , C 1-6  alkyl, C 1-6  heteroalkyl, C 2-6  alkenyl, C 2-6  heteroalkenyl, C 3-10  cyclokalkyl, or C 2-10  heterocycloalkyl; 
 R 15  is a halogen atom, —OH, —NH 2 , C 1-6  alkyl, C 1-6  heteroalkyl, C 2-6  alkenyl, C 2-6  heteroalkenyl, C 3-10  cyclokalkyl, or C 2-10  heterocycloalkyl. 
 
     
     
         45 - 55 . (canceled) 
     
     
         56 . The method of  claim 43 , where the first olefin ester is an 9-decenoic acid alkyl ester, and the second olefin ester is an 8-decenoic acid alkyl ester. 
     
     
         57 . The method of  claim 56 , where the 8-decenoic acid alkyl ester is formed by isomerizing an ester of 9-decenoic acid. 
     
     
         58 . The method of  claim 26 , where the hydrogenating agent comprises hydrogen gas and a hydrogenation catalyst. 
     
     
         59 - 60 . (canceled)