2-(2,3-epoxypropyl)phenol composition and method of making

Abstract

Disclosed herein is a method of making a 2-(2,3-epoxypropyl)phenol by reacting a 2-allylphenol with an oxidant in the presence of a catalyst. A 3-chromanol can be formed as a by-product. The method can be used to make 2-(2,3-epoxypropyl)-6-methylphenol. Transition metal catalysts and peroxide oxidants can be used. Also disclosed is a composition comprising 1 to 90 weight percent of a 2-(2,3-epoxypropylphenol, 5 to 90 weight percent of a 2-allylphenol, and 0 to 40 weight percent of a 3-chroman-ol, and in particular, a composition comprising 1 to 90 weight percent 2-(2,3-epoxypropyl)-6-methylphenol, 5 to 90 weight percent 2-allyl-6-methylphenol, and 0 to 40 weight percent 8-methyl-3-chromanol.

1 . A method of making 2-(2,3-epoxypropyl)-6-methylphenol, comprising reacting 2-allyl-6-methylphenol with an oxidant in the presence of a catalyst. 
     
     
         2 . (canceled) 
     
     
         3 . The method of  claim 1 , wherein the catalyst is a transition metal catalyst comprising molybdenum, vanadium, tungsten, titanium, manganese, niobium, or combination thereof. 
     
     
         4 . The method of  claim 1 , wherein the catalyst comprises bis(acetylacetonato)dioxomolybdenum (VI), molybdenum dichloride dioxide, tungstic acid, tungsten hexacarbonyl, or combination thereof. 
     
     
         5 . The method of  claim 1 , wherein the oxidant comprises hydrogen peroxide, an alkyl peroxide, an alkyl hydroperoxide, a ketone peroxide, a diacyl peroxide, a diperoxy ketal, a peroxyester, a peroxydicarbonate, a peroxy acid, a perbenzoic acid, or combination thereof. 
     
     
         6 . The method of  claim 1 , wherein the oxidant comprises m-chloroperbenzoic acid. 
     
     
         7 . The method of  claim 1 , wherein the oxidant comprises hydrogen peroxide. 
     
     
         8 . The method of  claim 1 , wherein reaction temperature is −10 to 50° C., and reaction time is 10 minutes to 6 hours. 
     
     
         9 . The method of  claim 1 , wherein there is 50 to 100% conversion of the 2-allyl-6-methylphenol in 10 minutes to 6 hours at a reaction temperature of −10 to 50° C. 
     
     
         10 . The method of  claim 1 , wherein there is 50 to 100% selectivity for 2-(2,3-epoxypropyl)-6-methylphenol. 
     
     
         11 . The method of  claim 1 , wherein 8-methyl-3-chromanol is made along with 2-(2,3-epoxypropyl)-6-methylphenol. 
     
     
         12 . The method of  claim 1 , wherein: the oxidant comprises m-chloroperbenzoic acid and the catalyst comprises bis(acetylacetonate)dioxomolybdenum (VI), tungstic acid, tungsten hexacarbonyl, or combination thereof. 
     
     
         13 . A composition comprising:
 1 to 90 weight percent of 2-(2,3-epoxypropyl)-6-methylphenol   5 to 90 weight percent of 2-allyl-6-methylphenol   0 to 40 weight percent of 8-methyl-3-chromanol   wherein all weight percents are based on the total weight of the 2-(2,3-epoxypropyl)-6-methylphenol, 2-allyl-6-methylphenol, and 8-methyl-3-chromanol.   
     
     
         14 - 16 . (canceled) 
     
     
         17 . A thermoset polymer made by reacting a 2-allylphenol of structure 
       
         
           
           
               
               
           
         
         wherein each occurrence of Z is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms, 
         with an oxidant in the presence of a catalyst. 
       
     
     
         18 . The thermoset polymer of  claim 17 , wherein the 2-allylphenol comprises 2-allyl-6-methylphenol, and the thermoset polymer has a glass transition temperature of 235 to 245° C. 
     
     
         19 . A method of making a 2-(2,3-epoxypropyl)phenol, comprising reacting a 2-allylphenol with an oxidant in the presence of a catalyst;
 wherein the 2-allylphenol comprises   
       
         
           
           
               
               
           
         
         and the 2-(2,3-epoxypropyl)phenol comprises 
       
       
         
           
           
               
               
           
         
       
       and
 wherein each occurrence of Z is independently hydrogen, halogen, unsubstituted or substituted C 1 -C 12  hydrocarbyl provided that the hydrocarbyl group is not tertiary hydrocarbyl, C 1 -C 12  hydrocarbylthio, C 1 -C 12  hydrocarbyloxy, or C 2 -C 12  halohydrocarbyloxy wherein at least two carbon atoms separate the halogen and oxygen atoms; and 
 wherein the oxidant comprises m-chloroperbenzoic or hydrogen peroxide, and/or the catalyst comprises bis(acetylacetonato)dioxomolybdenum (VI), molybdenum dichloride dioxide, tungstic acid, tungsten hexacarbonyl, or combination thereof.