Mono- and dialkyl ethers of furan-2,5-dimethanol and (tetra-hydrofuran-2,5-diyl)dimethanol and amphiphilic derivatives thereof

Abstract

Linear mono- and dialkyl ethers of furan-2,5-dimethanol (FDM) and/or (tetrahydrofuran-2,5-diyl)dimethanol (bHMTHF), methods for their preparation, and derivative chemical compounds thereof are described. In general, the synthesis process entails a reaction of FDM or bHMTHFs in a polar aprotic organic solvent with a permittivity (∈) >8, at a temperature ranging from about −25° C. to about 100° C., with either a) an unhindered Brønsted base with a ΔpKa≧15 relative to the hydroxyl groups of the FDM or bHMTHF, or b) a hindered Brønsted base having minimum pKa of about 16 and a nucleophile.

We claim: 
     
         1 . A process for preparing a derivative compound from a mono-ether, the process comprising contacting a mono-ether of 2,5-bis(hydroxymethyl)tetrahydrofuran (bHMTHF) with a) chlorosulfonic acid to generate a sulfate, or b) trifluoromethanesulfonic anhydride to generate a trifluoromethanesulfonate. 
     
     
         2 . A sulfate prepared according to  claim 1 , wherein said sulfate is at least one of the following compounds:
 a. ((2S,5R)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methyl hydrogen sulfate   
       
         
           
           
               
               
           
         
         b. ((2S,5S)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methyl hydrogen sulfate 
       
       
         
           
           
               
               
           
         
         c. ((2S,5S)-5-((hexyloxy)methyl)tetrahydrofuran-2-yl)methyl hydrogen sulfate 
       
       
         
           
           
               
               
           
         
       
     
     
         3 . A trifluoromethanesulfonated monoether generated according to  claim 1 , wherein said trifluoromethanesulfonated monoether is at least one of the following compounds:
 a. ((2S,5R)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate   
       
         
           
           
               
               
           
         
         b. ((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate 
       
       
         
           
           
               
               
           
         
         c. ((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate 
       
       
         
           
           
               
               
           
         
         d. ((2S,5R)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate 
       
       
         
           
           
               
               
           
         
         e. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate 
       
       
         
           
           
               
               
           
         
         f. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methyl trifluoromethanesulfonate 
       
       
         
           
           
               
               
           
         
       
     
     
         4 . The process according to  claim 1 , further comprising generating an ethoxyethanolamine derivative of a bHMTHF mono-ether sulfonate compound by substitutions of a sulfonate group with an ethnaolamine. 
     
     
         5 . A ethoxyethanolamine prepared according to  claim 4 , wherein said ethoxyethanolamine is at least one of the following compounds:
 a. 2-(2-((((2S,5R)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl)amino)ethoxy)-ethanol   
       
         
           
           
               
               
           
         
         b. 2-(2-((((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl)amino)ethoxy)-ethanol 
       
       
         
           
           
               
               
           
         
         c. 2-(2-((((2S,5S)-5-((dodecyloxy)methyl)tetrahydrofuran-2-yl)methyl)amino)ethoxy)-ethanol 
       
       
         
           
           
               
               
           
         
       
     
     
         6 . The process according to  claim 1 , further comprising generating a primary amine of a bHMTHF monoether by substitution of a trifluoromethanesulfonate group followed by catalytic debenzylation. 
     
     
         7 . A primary amine prepared according to  claim 6 , wherein said primary amine is at least one of the following compounds:
 a. ((2S,5R)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanamine   
       
         
           
           
               
               
           
         
         b. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanamine 
       
       
         
           
           
               
               
           
         
         c. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanamine 
       
       
         
           
           
               
               
           
         
       
     
     
         8 . The process according to  claim 1 , further comprising preparing a primary ammonium salt of said bHMTHF monoether by substitution of a trifluoromethanesulfonate group followed by catalytic debenzylation and protonation by a Brønsted acid having a pKa ≦0. 
     
     
         9 . An primary ammonium salt according to  claim 8 , wherein said primary ammonium salt is at least one of the following compounds:
 a. ((2S,5R)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium chloride   
       
         
           
           
               
               
           
         
         b. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium chloride 
       
       
         
           
           
               
               
           
         
         c. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium chloride 
       
       
         
           
           
               
               
           
         
         d. ((2S,5R)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium bromide 
       
       
         
           
           
               
               
           
         
         e. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium bromide 
       
       
         
           
           
               
               
           
         
         f. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium bromide 
       
       
         
           
           
               
               
           
         
         g. ((2S,5R)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium iodide 
       
       
         
           
           
               
               
           
         
         h. ((2S,5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanammium iodide 
       
       
         
           
           
               
               
           
         
         i. ((2S 5S)-5-((octadecyloxy)methyl)tetrahydrofuran-2-yl)methanaminium iodide 
       
       
         
           
           
               
               
           
         
       
     
     
         10 . A process for preparing a derivative compound from a mono-ether, the process comprising contacting a mono-ether of FDM with a) chlorosulfonic acid to generate a sulfate or b) trifluoromethanesulfonic anhydride to generate a trifluoromethanesulfonate. 
     
     
         11 . A sulfate made according to  claim 10 , wherein said sulfate is the following compound:
 (5-((dodecyloxy)methyl)furan-2-yl)methyl hydrogen sulfate   
       
         
           
           
               
               
           
         
       
     
     
         12 . A trifluoromethanesulfonate made according to  claim 10 , wherein said the trifluoromethanesulfonate is at least one of the following structures:
 a. (5-((hexyloxy)methyl)furan-2-yl)methyl trifluoromethanesulfonate   
       
         
           
           
               
               
           
         
       
       and
 b. (5-((octadecyloxy)methyl)furan-2-yl)methyl trifluoromethanesulfonate 
 
       
         
           
           
               
               
           
         
       
     
     
         13 . The process according to  claim 10 , further comprising preparing a primary ammonium derivative of said FDM monoether by substitution of a trifluoromethanesulfonate group followed by catalytic debenzylation and protonation by a Brønsted acid having a pKa ≦0. 
     
     
         14 . A aminoethylethanolamine, wherein said the aminoethylethanolamine is the following:
 2-((2-(((5-((octadecyloxy)methyl)furan-2-yl)methyl)amino)ethyl)amino)-ethanol   
       
         
           
           
               
               
           
         
       
     
     
         15 . A primary amine, wherein said primary amine is the following:
 (5-((hexyloxy)methyl)furan-2-yl)methanamine   
       
         
           
           
               
               
           
         
       
     
     
         16 . A quaternary trimethylammonium salt, wherein said quarternary trimethyl-ammonium salt is the following:
 1-(5-((hexyloxy)methyl)furan-2-yl)-N,N,N-trimethylmethanaminium iodide