1,1-disubstituted ethylene process

Abstract

New and improved processes for the production of 1,1-disubstituted ethylenes.

We claim: 
     
         1 . A method of producing 1,1-disubstituted ethylenes which method comprises reacting compounds containing a methylene linkage having attached thereto at least one electron withdrawing group with an iminium salt in the presence of an acid chloride and/or acid anhydride under appropriate conditions and for an appropriate time period to yield the corresponding 1,1-disubstituted ethylene. 
     
     
         2 . The method of  claim 1  wherein iminium salt corresponds to the formula 
       
         
           
           
               
               
           
         
         wherein R 4 , R 5 , R 6  and R 7  are each independently H or a hydrocarbon or substituted hydrocarbon moiety or a hydrocarbon, substituted hydrocarbon or heterohydrocarbon bridge whereby the nitrogen atom, the carbon, or both of formula II are in a ring structure and X is an anion. 
       
     
     
         3 . The method of  claim 2  herein R 4 , R 5 , R 6  and R 7  are each independently H or an alkyl, alkenyl or alkynyl and X is a halogen, a non-nucleophilic anion, and/or an acidic anion. 
     
     
         4 . The method of  claim 2  wherein R 4  and R 5  are hydrogen (H) and R 6  and R 7  are each independently an alkyl, alkenyl or alkynyl moiety and X is a halogen, a carboxylate or a sulfonate. 
     
     
         5 . The method of  claim 1  wherein the electron withdrawing groups are selected from selected from nitriles, carboxylic acids, carboxylic esters, sulphonic acids, ketones or nitro. 
     
     
         6 . The method of  claim 1  wherein the compounds to be reacted upon are the esters, especially the diesters, of malonic acid. 
     
     
         7 . The method of  claim 1  wherein the acid chlorides and acid anhydrides are selected from the group consisting of acetyl chloride, propionyl chloride, isobutyryl chloride, trimethylacetyl chloride, trifluroacetate, acetic anhydride, isobutyric anhydride, trimethylacetic anhydride, trifluoroacetic anhydride, sulfonic acid anhydride, benzoyl chloride, chloroacetylchloride. 
     
     
         8 . A method of producing 1,1-disubstituted ethylenes which method comprises reacting an amine with an acid chloride and/or an acid anhydride and then reacting the reaction product thereof with a compound containing a methylene linkage having attached thereto at least one electron withdrawing group under appropriate conditions and for an appropriate time period to yield the corresponding 1,1-disubstituted ethylene. 
     
     
         9 . The method of  claim 8  wherein the acid chloride and/or acid anhydride is present in an equivalent excess relative to the compound containing the methylene linkage. 
     
     
         10 . The method of  claim 1  wherein reaction product of the amine and the acid chloride and/or anhydride comprises a iminium salt according to the formula 
       
         
           
           
               
               
           
         
         wherein R 4 , R 5 , R 6  and R 7  are each independently H or a hydrocarbon or substituted hydrocarbon moiety or a hydrocarbon, substituted hydrocarbon or heterohydrocarbon bridge whereby the nitrogen atom, the carbon, or both of formula II are in a ring structure and X is chloride anion or a carboxylate anion. 
       
     
     
         11 . The method of  claim 10  wherein R 4 , R 5 , R 6  and R 7  are each independently H or an alkyl, alkenyl or alkynyl. 
     
     
         12 . The method of  claim 10  wherein R 4  and R 5  are hydrogen (H) and R 6  and R 7  are each independently an alkyl, alkenyl or alkynyl. 
     
     
         13 . The method of  claim 8  wherein the electron withdrawing groups are selected from selected from nitriles, carboxylic acids, carboxylic esters, sulphonic acids, ketones or nitro. 
     
     
         14 . The method of  claim 8  wherein the compounds to be reacted upon are the esters, especially the diesters, of malonic acid. 
     
     
         15 . The method of  claim 8  wherein the acid chlorides and acid anhydrides are selected from the group consisting of acetyl chloride, propionyl chloride, isobutyryl chloride, trimethylacetyl chloride, trifluroacetate, acetic anhydride, isobutyric anhydride, trimethylacetic anhydride, trifluoroacetic anhydride, sulfonic acid anhydride, benzoyl chloride, chloroacetylchloride. 
     
     
         16 . A method of producing 1,1-disubstituted ethylenes which method comprises reacting compounds containing a methylene linkage having attached thereto at least one electron withdrawing group with an iminium salt in the presence of a non-polar solvent for a sufficient time to yield the corresponding 1,1-disubstituted ethylene wherein the anionic portion of the iminium salt is a carboxylate anion. 
     
     
         17 . The method of  claim 16  wherein the iminium salt is preformed or is formed in-situ and corresponds to the formula: 
       
         
           
           
               
               
           
         
         wherein R 4 , R 5 , R 6  and R 7  are each independently H or a hydrocarbon or substituted hydrocarbon moiety or a hydrocarbon, substituted hydrocarbon or heterohydrocarbon bridge whereby the nitrogen atom, the carbon, or both of formula II are in a ring structure and X is a carboxylate anion. 
       
     
     
         18 . The method of  claim 17  wherein R 4 , R 5 , R 6  and R 7  are each independently H or an alkyl, alkenyl or alkynyl. 
     
     
         19 . The method of  claim 17  wherein R 4  and R 5  are hydrogen (H) and R 6  and R 7  are each independently an alkyl, alkenyl or alkynyl. 
     
     
         20 . The method of  claim 16  wherein the non-polar solvent is selected from toluene, benzene, diethylether, chloroform, hexane, cyclohexane and carbontetrachioride. 
     
     
         21 . An improved method of producing 1,1-disubstituted ethylenes involving the reaction of compounds containing a methylene linkage having attached thereto at least one electron withdrawing group with an iminium salt wherein the improvement comprises treating a non-polar solvent solution of the 1,1-disubstituted ethylenic reaction product with a solid phase material having an acidic to neutral pH an known to adsorb or absorb polar materials. 
     
     
         22 . The improved process of  claim 21  wherein the solid phase material has an acidic pH and is selected from ion-exchange resins, molecular sieves, zeolites and alumina. 
     
     
         23 . The improved process of  claim 21  wherein the treatment is conducted until free amine compounds have been removed or substantially removed. 
     
     
         24 . The improved process of  claim 21  wherein the 1,1-disubstituted ethylene is produced in a non-polar solvent. 
     
     
         25 . The improved process of  claim 21  wherein the 1,1-disubstituted ethylene is produced in a polar solvent and the polar solvent is replaced with a non-polar solvent prior to the addition of the solid phase material. 
     
     
         26 . The improved process of  claim 21  wherein the solid phase material is an acidic, activated alumina and the non-polar solvent is toluene.