Synthesis of derivatives of dicarbamates from reduction products of 2-hydroxymethyl-5-furufural (hmf)

Abstract

Dicarbamates of the reduction products of 2-hydroxymethyl-5-furfural (HMF) and a method of preparing the same are described. The method involves reacting a mixture of an isohexide and a cynate salt in a non-aqueous solvent, with a miscible acid having a pKa of about 3.7 or less. The dicarbamates of HMF-reduction products can serve as precursor materials from which various derivative compounds can be synthesized.

We claim: 
     
         1 . A precursor chemical compound comprising at least one of the following: 
       
         
           
           
               
               
           
         
       
     
     
         2 . A chemical compound derived from at least one of the precursor chemical compounds according to  claim 1 , said derived chemical compound is a polymer containing said precursor chemical compound as a substituent. 
     
     
         3 . The derived chemical compound according to  claim 2 , wherein said polymer is a homopolymer with a structure: 
       
         
           
           
               
               
           
         
       
     
     
         4 . A method of preparing a derivative chemical compound from at least one of the precursor chemical compounds according to claim  13 , comprising performing a Lewis-acid-(LA)-triflate-mediated N-acylation of reduction products of HMF, according to: 
       
         
           
           
               
               
           
         
       
     
     
         5 . The method according to  claim 4 , wherein said Lewis acid triflate is water-tolerant. 
     
     
         6 . The method according to  claim 4 , wherein said derivative chemical compound is at least one of the following for bHMTHF: 
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((113-dichloranylidene)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((113-dichloranylidene)carbamate 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(methacryloylcarbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(methacryloylcarbamate) 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((4-formylphenyl)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((4-formylphenyl)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((2,2,2-trifluoroacetyl)carbamate 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((2,2,2-trifluoroacetyl)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(tert-butylcarbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis(tert-butylcarbamate) 
       
       
         
           
           
               
               
           
         
         diethyl N′,N″-(((((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene))bis(oxy))bis(carbonyl))(1E,1′E)-diformimidate 
       
       
         
           
           
               
               
           
         
         diethyl N′,N″-(((((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene))bis(oxy))bis(carbonyl))(1E,1′E)-diformimidate 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((oxo-λ 4 -sulfanylidene)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((oxo-λ 4 -sulfanylidene)carbamate) 
       
       
         
           
           
               
               
           
         
         dimethyl (((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene)) bis(carbonate) 
       
       
         
           
           
               
               
           
         
         dimethyl (((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene)) bis(carbonate) 
       
       
         
           
           
               
               
           
         
         ((2R,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((diaminophosphoryl)carbamate) 
       
       
         
           
           
               
               
           
         
         ((2S,5S)-tetrahydrofuran-2,5-diyl)bis(methylene) bis((diaminophosphoryl)carbamate) 
       
     
     
         7 . The method according to  claim 4 , wherein said derivative chemical compound is at least one of the following for FDM: 
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis((chloroimino)-13-chloranecarboxylate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis(methacryloylcarbamate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis((4-formylphenyl)carbamate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis((2,2,2-trifluoroacetyl)carbamate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis(tert-butylcarbamate) 
       
       
         
           
           
               
               
           
         
         diethyl N′,N″-(((furan-2,5-diylbis(methylene))bis(oxy))bis(carbonyl))(1E,1′E)-diformimidate 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis((oxo-λ 4 -sulfanylidene)carbamate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) dimethyl bis(carbonate) 
       
       
         
           
           
               
               
           
         
         furan-2,5-diylbis(methylene) bis((diaminophosphoryl)carbamate)