3-Alkylated-5,5',6,6',7,7,'8,8'-octahydro-2,2'-binaphthols and 3,3'-dialkylated-5,5',6,6',7,7',8,8'-octahydro-2,2'-binaphthols and processes for making them

Abstract

The compositions 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol are disclosed, as well as various processes for making them, all involving the alkylation of 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol.

What is claimed is:  
     
         1 . A compound of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 R is C 1  to C 20  alkyl, C 3  to C 20  cycloalkyl, or benzyl of the formula  
                     
  wherein each R′ is independently H, alkyl or cycloalkyl of up to 6 carbons; and/or a compound of the formula  
                     
  wherein R is C 1  to C 20  alkyl other than methyl or t-butyl, C 3  to C 20  cycloalkyl, or benzyl of the formula  
                     
  wherein each R′ is independently H, alkyl or cycloalkyl of up to 6 carbons.  
 
     
     
         2 . A process for making 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with at least one alkene or cycloalkene in the presence of an acid catalyst.  
     
     
         3 . The process of  claim 2  wherein the at least one alkene or cycloalkene is monoethylenically unsaturated and contains from 3 to 20 carbon atoms.  
     
     
         4 . The process of  claim 3  wherein at least one alkene or cycloalkene is selected from the group consisting of propylene, butene, pentene, hexene, cyclopentene, and cyclohexene.  
     
     
         5 . The process of  claim 2  wherein the acid catalyst is selected from the group consisting of aluminum chloride, trifluoromethanesulfonic acid, tosylic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, zirconium triflate, aluminum triflate, polymeric perfluorinated sulfonic acid and polymeric sulfonic acid.  
     
     
         6 . The process of  claim 5  wherein the acid catalyst is aluminum chloride, phosphotungstic acid, or phosphomolybdic acid.  
     
     
         7 . The process of  claim 6  wherein the acid catalyst is phosphotungstic acid.  
     
     
         8 . The process of  claim 2  wherein the contacting is done in the presence of at least one solvent selected from the group consisting of nitromethane, methylene chloride, dichloroethane, chlorobenzene, dichlorobenzene, and nitrobenzene.  
     
     
         9 . The process of  claim 2  wherein the contacting is done at a temperature between 20° C. and 220° C.  
     
     
         10 . The process of  claim 9  wherein the temperature is between 90° C. and 180° C. and wherein the 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol is contacted with a mono- or 1,2-disubstituted alkene.  
     
     
         11 . The process of  claim 9  wherein the temperature is between 40° C. and 90° C. and wherein the 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol is contacted with at least one alkene selected from the group consisting of 1,1-disubstituted alkene, tri-substituted alkene, tetra-substituted alkene or aryl-substituted alkene.  
     
     
         12 . A process for making 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with a benzyl halide or tertiary alkyl halide, wherein the halide is bromide or chloride, in the presence of a Lewis acid catalyst.  
     
     
         13 . The process of  claim 12  wherein the Lewis acid catalyst is selected from the group consisting of aluminum chloride, zinc chloride, boron trichloride, SnCl 4 , SbCl 5 , and ZrCl 4 .  
     
     
         14 . The process of  claim 13  wherein the Lewis acid catalyst is zinc chloride.  
     
     
         15 . A process for making 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or 3,3′-dialkylated-5,5′, 6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, comprising contacting 5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol with an alkyl sulfonate, alkyl triflate, alkyl p-toluenesulfonate, or alkyl benzenesulfonate, in the presence of an acid catalyst selected from the group consisting of aluminum chloride, tosylic acid, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, trifluoromethanesulfonic acid and a rare earth metal triflate selected from the group consisting of scandium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, and lanthanum trifluoromethanesulfonate.  
     
     
         16 . The process of  claim 15  in which the alkyl sulfonate is of the formula A-SO 3 —B, wherein A is C 1  to C 8  alkyl, C 1  to C 8  fluorinated alkyl, C 6  to C 10  aryl, or C 6  to C 10  fluorinated aryl; and B is C 1  to C 20  alkyl.  
     
     
         17 . A process for making 3-alkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol and/or 3,3′-dialkylated-5,5′,6,6′,7,7′,8,8′-octahydro-2,2′-binaphthol, comprising contacting 5,5′,6,6′,7,7′,8,81-octahydro-2,2′-binaphthol with a benzyl, secondary or tertiary alcohol containing fro 3 to 20 carbon atoms, in the presence of an acid catalyst selected from the group consisting of trifluoromethanesulfonic acid, sulfuric acid, HF, phosphoric acid, and aluminum chloride.  
     
     
         18 . A compound of the formula  
       
         
           
           
               
               
           
         
       
       wherein: 
 R is H; and  
 R′ is ethyl, C 3  to C 6  secondary, tertiary, or cyclic alkyl;  
 or a compound of the above formula wherein 
 R and R′ are the same and are selected from the group consisting of  
 ethyl, C 3  to C 6  secondary or cyclic alkyl.  
 
 
     
     
         19 . A compound of  claim 18  wherein R and R′ are the same are selected from the group consisting of ethyl, isopropyl, cyclopentyl, and cyclohexyl.