T-butyl cascade polymers

Abstract

A method for forming cascade polymers specifically utilizing the amine monomer of the formula The monomer is made by initially reacting nitromethane and CH 2 ═CHCO 2 -TBu by nucleophilic addition to form the triester nitrotrialkanoate of the formula and then reducing the nitrosubstituent to afford the said amine monomer.

What is claimed is:  
     
         1 . A method of forming an amine monomer of the formula  
       
         
           
           
               
               
           
         
         by the steps of reacting nitromethane and CH 2 ═CHCO 2 -TBu by nucleophilic addition to form the triester nitrotrialkanoate of the formula  
         
           
             
             
                 
                 
             
           
         
         and reducing the nitrotrialkanoate to said amine monomer.  
       
     
     
         2 . A method as set forth in  claim 1  wherein said reacting step is further defined as reacting said methyl nitromethane and CH 2 ═CHCO 2 -TBu in the presence of dimethoxyethane and Triton-B at a temperature of about 70° to 80° C. or about one hour.  
     
     
         3 . A method as set forth in  claim 1  wherein said reducing step is further defined as reducing the nitrotrialkanoate to the amine monomer with T-1 Raney nickel at a temperature of about 60° C.  
     
     
         4 . A method of forming a one- directional arborol of the formula  
       
         
           
           
               
               
           
         
         wherein R is t-Bu by the steps of treating adamantanecarbonyl chloride with di-tert-butyl 4-amino-[2-tert-butoxy-carbonyl)ethyl]heptanedioate (amine monomer) to form a triester of the formula  
         
           
             
             
                 
                 
             
           
         
         wherein R is TBu and hydrolyzing said triester to a triacid, and peptide coupling amine monomers to each of the acid moieties of said triacid to form said arborol.  
       
     
     
         5 . A method as set forth in  claim 4  wherein said treating step is conducted in the presence of NEt 3  and C 6 H 6  at about 25° C. for about 20 hours.  
     
     
         6 . A method as set forth in  claim 4  wherein said hydrolysis step is conducted in the presence of 96% HCO 2 H at about 25° C. for about 20 hours.  
     
     
         7 . A method as set forth in  claim 4  wherein said peptide coupling step is conducted in the presence of DCC, 1-hydroxybenzotriazole, and dimethylformamide at about 25° C. for about 24 hours.  
     
     
         8 . A method of forming a four- directional spherical dendritic macromolecule by the steps of treating an acid chloride of the formula  
       
         
           
           
               
               
           
         
         with an amine monomer, di-tert-butyl 4-amino-[2-(tert-butoxycarbonyl)ethyl]heptanedioate, to form a dodecaester of the formula  
         
           
             
             
                 
                 
             
           
         
         wherein R is t-Bu and adding additional layers of amine monomer by repeatedly hydrolyzing the ester, coupling the amine monomer to the acid moieties to form an additional tier of ester moieties and hydrolyzing to a corresponding acid.  
       
     
     
         9 . A compound of the formula  
       
         
           
           
               
               
           
         
         wherein R 1 ,R 2 ,R 3 , and R 4 , are selected from the group consisting of hydrogen and cascade arborol branches, at least one of said R 1 , R 2 ,R 3  and R 4  being a cascade arborol branch.  
       
     
     
         10 . A compound of  claim 9  of the formula  
       
         
           
           
               
               
           
         
       
     
     
         11 . A compound as set forth in  claim 9  of the formula  
       
         
           
           
               
               
           
         
       
     
     
         12 . A compound of the formula  
       
         
           
           
               
               
           
         
         wherein R is selected from the group consisting essentially of NH 2  and NO 2 .  
       
     
     
         13 . A compound of the formula  
       
         
           
           
               
               
           
         
       
     
     
         14 . A compound of the formula  
       
         
           
           
               
               
           
         
       
     
     
         15 . A method of forming an amine monomer of the formula  
       
         
           
           
               
               
           
         
         by the steps of  
         (a) treating nitromethane with tert-butyl acrylate to form a nitrotriester of the formula  
         
           
             
             
                 
                 
             
           
         
         (b) recrystallizing the nitrotriester to remove impurities; and  
         (c) hydrogenating the nitrotriester (II) to the aminotriester (I).  
       
     
     
         16 . A method as set forth in  claim 15  wherein said treating step is further defined as treating the nitromethane with greater than three equivalents of the tert-butyl acrylate in dimethoxyethane.  
     
     
         17 . A method as set forth in  claim 15  wherein said hydrogenating step is conducted using T-1 Raney Nickel at 45 to 55° C.  
     
     
         18 . A method as set forth in  claim 15  wherein the hydrogenating step is followed by removing solvent in vacuo below 50° C.