Synthesis of non-ionic amphiphiles from 1,4-anhydroxylitol

Abstract

Amphipathic amine-esters derived from anhydropentitols are prepared through a short sequence of synthetic steps. The process is initiated by the esterification of an anhydropentitol with a fatty acid chloride or a lipase enzyme to form anhydropentitol fatty acid esters, preferably leaving at least one free hydroxyl. The free hydroxyl group(s) are then sulfonated, forming sulfonated anhydropentitol fatty acid esters. The sulfonyl moiety on the sulfonated anhydropentitol fatty acid esters are then subject to nucleophilic displacement by a hydrophilic moiety, illustrated by a primary amine such as AEE or AEEA. The synthetic pathway is efficient and affords modest to high yields of target amphiphilic compounds, which are useful at least as surfactants and plasticizer substitutes for petroleum derived compounds.

1 ) An esterified anhydropentitol compound selected from the group consisting of: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein R is a carbon side chain of a fatty acid. 
     
     
         2 ) The compound of  claim 1  where said carbon side chain is between 8 and 30 carbons. 
     
     
         3 ) The compound of  claim 1  wherein the esterified anhydropentitol compound is selected from the group consisting of anhydroxylitol, anhydroarabitol and anhydroribitol. 
     
     
         4 ) A method of making a monoester, diester, or triester fatty acid of an anhydropentitol according to  claim 1  comprising, contacting an anhydropentitol compound with a fatty acid in the presence of a lipase enzyme. 
     
     
         5 ) The method of  claim 4  wherein the lipase enzyme is selected from the group consisting of Novozyme 435 (an immobilized  Candida antarctica  lipase B with a permanently open active site), Lipozyme RM IM (a  Muchor miehei  lipase immobilized with an active site covered by a moveable lid), Lipozyme TM IM (a  Thermomyces lanuginosis  lipase on porous silica with an active site covered by moveable lid), Lipex 100L (a  Thermomyces lanuginosis  mutant lipase with enhanced lipid surface absorption with an a active site covered by moveable lid and detergent stable), Palatase 20000 L (a  Mucor miehei  lipase with an active site covered by a moveable lid), Novozym CALB L (a  Candida Articans  lipase B with a permanently open active site), Lipozyme TL100 L (a  Thermomyces lanuginosis  lipase with an active site covered by moveable lid). 
     
     
         6 ) The method of  claim 4  wherein the lipase enzyme is  Candida Antarctica  B lipase. 
     
     
         7 ) The method of  claim 4  wherein the contacting with the lipase enzyme is done undervacuum pressure of from about 0.1 torr to about 100 torr. 
     
     
         8 ) The method of  claim 4  wherein the vacuum pressure is about 5 torr. 
     
     
         9 ) The method of  claim 4  wherein the temperature is from about 40° C. to about 100° C. 
     
     
         10 ) The method of  claim 4  wherein the temperature is about 70° C. 
     
     
         11 ) A method of making a monoester, diester, or triester fatty acid of an anhydropentitol according to  claim 1  comprising, contacting an anhydropentitol compound with a fatty acid chloride in the presence of a nucleophilic base. 
     
     
         12 ) The method of  claim 11  wherein the nucleophilic base is selected from the group consisting of pyridine, dimethylaminopyridine, imidazole and pyrazole. 13) The method of  claim 11  wherein the contacting of the anhydropentitol compound with a fatty acid chloride is done at a temperature of from about 0° C. to about 50° C. 
     
     
         14 ) The method of  claim 11  wherein the contacting of the anhydropentitol compound with a fatty acid chloride is done at a temperature of about 25° C.