1,1-disubstituted ethylene process

Abstract

Improved iminium based processes for the production of cyanoacrylates and methylidene malonates wherein the improvement pertains to the presence of acid chlorides and/or acid anhydrides in the reaction mix.

We claim: 
     
         1 - 20 . (canceled) 
     
     
         21 . 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. 
     
     
         22 . 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. 
     
     
         23 . The method of  claim 22  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. 
     
     
         24 . The method of  claim 22  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. 
     
     
         25 . The method of  claim 21  wherein the electron withdrawing groups are selected from selected from nitriles, carboxylic acids, carboxylic esters, sulphonic acids, ketones or nitro. 
     
     
         26 . The method of  claim 21  wherein the compounds to be reacted upon are the esters, especially the diesters, of malonic acid. 
     
     
         27 . The method of  claim 21  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. 
     
     
         28 . 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. 
     
     
         29 . The method of  claim 28  wherein the acid chloride and/or acid anhydride is present in an equivalent excess relative to the compound containing the methylene linkage. 
     
     
         30 . The method of  claim 21  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. 
     
     
         31 . The method of  claim 30  wherein R 4 , R 5 , R 6  and R 7  are each independently H or an alkyl, alkenyl or alkynyl. 
     
     
         32 . The method of  claim 30  wherein R 4  and R 5  are hydrogen (H) and R 6  and R 7  are each independently an alkyl, alkenyl or alkynyl. 
     
     
         33 . The method of  claim 28  wherein the electron withdrawing groups are selected from selected from nitriles, carboxylic acids, carboxylic esters, sulphonic acids, ketones or nitro. 
     
     
         34 . The method of  claim 28  wherein the compounds to be reacted upon are the esters, especially the diesters, of malonic acid. 
     
     
         35 . The method of  claim 28  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. 
     
     
         36 . 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. 
     
     
         37 . The method of  claim 36  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. 
     
     
         38 . The method of  claim 37  wherein R 4 , R 5 , R 6  and R 7  are each independently H or an alkyl, alkenyl or alkynyl. 
     
     
         39 . The method of  claim 37  wherein R 4  and R 5  are hydrogen (H) and R 6  and R 7  are each independently an alkyl, alkenyl or alkynyl. 
     
     
         40 . The method of  claim 36  wherein the non-polar solvent is selected from toluene, benzene, diethylether, chloroform, hexane, cyclohexane and carbontetrachioride.