Heterogeneous catalyst and process for producing oxirane compound with the catalyst

Abstract

There is provided a process for producing oxirane compound comprising treating with hydrogen peroxide in the presence of either an olefin oxidation catalyst prepared from an organic compound or a polymer compound of formula (1) a tungstic acid compound, a phosphoric acid, hydrogen peroxide and a quaternary ammonium salt of formula (2) or (3) or an olefin oxidation catalyst prepared from an organic compound or a polymer compound of formula (1), a tungsten compound and a quaternary ammonium salt of formula (2) or (3). The process is useful especially industrially.

1 . An olefin oxidation catalyst, prepared from 
 an organic compound or a polymer compound of formula (1)                          wherein R 11 , R 12  and R 13  are independently of one another hydrogen atom, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group), C 3-10 cycloalkyl group, C 6-10 aryl group, C 1-6 alkylcarbonyl group (the C 1-6 alkylcarbonyl group may be substituted by C 6-10 aryl group) or C 6-10 arylcarbonyl group;    a tungstic acid compound;    a phosphoric acid;    hydrogen peroxide; and    a quaternary ammonium salt of formula (2) or (3)                          wherein R 5 , R 6 , R 7 , R 8  and R 9  are independently of one another hydrogen atom, a halogen atom, cyano group, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group, C 1-10 alkoxy group or benzyloxy group), C 1-10 alkoxy group, benzyloxy group or phenyl group, or    any two of R 5 , R 6 , R 7 , R 8  and R 9  together may form 1 or 2 fused benzene rings,    R 10 , R 14 , R 15 , R 16  and R 17  are independently of one another C 1-20 alkyl group, and    X is a halogen atom.    
   
   
       2 . An olefin oxidation catalyst, prepared from 
 an organic compound or a polymer compound of formula (1)                          wherein R 11 , R 12  and R 13  are independently of one another hydrogen atom, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group), C 3-10 cycloalkyl group, C 6-10 aryl group, C 1-6 alkylcarbonyl group (the C 1-6 alkylcarbonyl group may be substituted by C 6-10 aryl group) or C 6-10 arylcarbonyl group;    a tungsten compound; and    a quaternary ammonium salt of formula (2) or (3)                          wherein R 5 , R 6 , R 7 , R 8  and R 9  are independently of one another hydrogen atom, a halogen atom, cyano group, C 1-10 alkyl group (the C 1-10 alkyl group may be arbitrarily substituted by C 6-10 aryl group, C 1-10 alkoxy group or benzyloxy group), C 1-10 alkoxy group, benzyloxy group or phenyl group, or    any two of R 5 , R 6 , R 7 , R 8  and R 9  together may form 1 or 2 fused benzene rings,    R 10 , R 14 , R 15 , R 16  and R 17  are independently of one another C 1-20 alkyl group, and    X is a halogen atom.    
   
   
       3 . The olefin oxidation catalyst according to  claim 1 , wherein the polymer compound is composed of a repeating unit of formula (8)  
     
       
         
         
             
             
         
       
       wherein R 18  is a tetravalent organic group derived from tetracarboxylic acid, and  
       R 19  is a divalent organic group derived from diamine, and is a polyimide having a number average molecular weight of 5×10 3  or more.  
     
   
   
       4 . The olefin oxidation catalyst according to  claim 1 , wherein the quaternary ammonium salt is a compound of formula (2)  
     
       
         
         
             
             
         
       
       wherein R 5 , R 6 , R 7 , R 8  and R 9  are independently of one another hydrogen atom, a halogen atom, cyano group, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group, C 1-10 alkoxy group or benzyloxy group), C 1-10 alkoxy group, benzyloxy group or phenyl group, or  
       any two of R 5 , R 6 , R 7 , R 8  and R 9  together may form 1 or 2 fused benzene rings,  
       R 10  is C 1-20 alkyl group, and  
       X is a halogen atom.  
     
   
   
       5 . The olefin oxidation catalyst according to  claim 4 , wherein the quaternary ammonium salt of formula (2) in which R 5 , R 6 , R 7 , R 8  and R 9  are hydrogen atom is used.  
   
   
       6 . A process for producing oxirane compound of formula (5)  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3  and R 4  are independently of one another hydrogen atom, phenyl group, C 1-10 alkyl group, C 3-10 cycloalkyl group (the C 1-10 alkyl group and C 3-10 cycloalkyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group), carboxyl group, C 1-6 alkylcarbonyl group, C 1-6 alkoxycarbonyl group (the C 1-6 alkylcarbonyl group and C 1-6 alkoxycarbonyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group) or phenoxycarbonyl group (the phenoxycarbonyl group may be substituted by a halogen atom, phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group), or  
       any two of R 1 , R 2 , R 3  and R 4  together are —(CH 2 ) m — wherein m is 3, 4 or 5, —CO 2 (CH 2 ) n — wherein n is 1, 2 or 3, —CO(CH 2 ) o — wherein o is 2, 3 or 4, —(CH 2 ) p —O—(CH 2 ) q — wherein p and q are independently of each other 0, 1, 2, 3 or 4, and a sum of p and q is 2, 3 or 4,  
       
         
           
           
               
               
           
         
       
       wherein R 20  and R 21  are independently of one another hydrogen atom or C 1-6 alkoxy group (the C 1-6 alkoxy group may be substituted by C 2-4 alkenyl group or phenyl group (the phenyl group may be substituted by a halogen atom, C 1-6 alkyl group or C 1-10 alkoxy group)), characterized by treating an olefin of formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  have the same meaning as the above, with hydrogen peroxide in the presence of the olefin oxidation catalyst according to  claim 1 .  
     
   
   
       7 . The olefin oxidation catalyst according to  claim 2 , wherein the polymer compound is composed of a repeating unit of formula (8)  
     
       
         
         
             
             
         
       
       wherein R 18  is a tetravalent organic group derived from tetracarboxylic acid, and  
       R 19  is a divalent organic group derived from diamine, and is a polyimide having a number average molecular weight of 5×10 3  or more.  
     
   
   
       8 . The olefin oxidation catalyst according to  claim 2 , wherein the quaternary ammonium salt is a compound of formula (2)  
     
       
         
         
             
             
         
       
       wherein R 5 , R 6 , R 7 , R 8  and R 9  are independently of one another hydrogen atom, a halogen atom, cyano group, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group, C 1-10 alkoxy group or benzyloxy group), C 1-10 alkoxy group, benzyloxy group or phenyl group, or  
       any two of R 5 , R 6 , R 7 , R 8  and R 9  together may form 1 or 2 fused benzene rings,  
       R 10  is C 1-20 alkyl group, and  
       X is a halogen atom.  
     
   
   
       9 . The olefin oxidation catalyst according to  claim 3 , wherein the quaternary ammonium salt is a compound of formula (2)  
     
       
         
         
             
             
         
       
       wherein R 5 , R 6 , R 7 , R 8  and R 9  are independently of one another hydrogen atom, a halogen atom, cyano group, C 1-10 alkyl group (the C 1-10 alkyl group may be substituted by C 6-10 aryl group, C 1-10 alkoxy group or benzyloxy group), C 1-10 alkoxy group, benzyloxy group or phenyl group, or  
       any two of R 5 , R 6 , R 7 , R 8  and R 9  together may form 1 or 2 fused benzene rings,  
       R 10  is C 1-20 alkyl group, and  
       X is a halogen atom.  
     
   
   
       10 . A process for producing oxirane compound of formula (5)  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3  and R 4  are independently of one another hydrogen atom, phenyl group, C -10 alkyl group, C 3-10 cycloalkyl group (the C 1-10 alkyl group and C 3-10 cycloalkyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group), carboxyl group, C 1-6 alkylcarbonyl group, C 1-6 alkoxycarbonyl group (the C 1-6 alkylcarbonyl group and C 1-6 alkoxycarbonyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group) or phenoxycarbonyl group (the phenoxycarbonyl group may be substituted by a halogen atom, phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group), or  
       any two of R 1 , R 2 , R 3  and R 4  together are —(CH 2 ) m — wherein m is 3, 4 or 5, —CO 2 (CH 2 ) n — wherein n is 1, 2 or 3, —CO(CH 2 ) o — wherein o is 2, 3 or 4, —(CH 2 ) p —O—(CH 2 ) q — wherein p and q are independently of each other 0, 1, 2, 3 or 4, and a sum of p and q is 2, 3 or 4,  
       
         
           
           
               
               
           
         
       
       wherein R 20  and R 21  are independently of one another hydrogen atom or C 1-6 alkoxy group (the C 1-6 alkoxy group may be substituted by C 2-4 alkenyl group or phenyl group (the phenyl group may be substituted by a halogen atom, C 1-6 alkyl group or C 1-10 alkoxy group)), characterized by treating an olefin of formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  have the same meaning as the above, with hydrogen peroxide in the presence of the olefin oxidation catalyst according to  claim 2 .  
     
   
   
       11 . A process for producing oxirane compound of formula (5)  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3  and R 4  are independently of one another hydrogen atom, phenyl group, C 1-10 alkyl group, C 3-10 cycloalkyl group (the C 1-10 alkyl group and C 3-10 cycloalkyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group), carboxyl group, C 1-6 alkylcarbonyl group, C 1-6 alkoxycarbonyl group (the C 1-6 alkylcarbonyl group and C 1-6 alkoxycarbonyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group) or phenoxycarbonyl group (the phenoxycarbonyl group may be substituted by a halogen atom, phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group), or  
       any two of R 1 , R 2 , R 3  and R 4  together are —(CH 2 ) n — wherein m is 3, 4 or 5, —CO 2 (CH 2 ) n — wherein n is 1, 2 or 3, —CO(CH 2 ) o — wherein o is 2, 3 or 4, —(CH 2 ) p —O—(CH 2 ) q — wherein p and q are independently of each other 0, 1, 2, 3 or 4, and a sum of p and q is 2, 3 or 4,  
       
         
           
           
               
               
           
         
       
       wherein R 20  and R 21  are independently of one another hydrogen atom or C 1-6 alkoxy group (the C 1-6 alkoxy group may be substituted by C 2-4 alkenyl group or phenyl group (the phenyl group may be substituted by a halogen atom, C 1-6 alkyl group or C 1-10 alkoxy group)), characterized by treating an olefin of formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  have the same meaning as the above, with hydrogen peroxide in the presence of the olefin oxidation catalyst according to  claim 3 .  
     
   
   
       12 . A process for producing oxirane compound of formula (5)  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3  and R 4  are independently of one another hydrogen atom, phenyl group, C 1-10 alkyl group, C 3-10 cycloalkyl group (the C 1-10 alkyl group and C 3-10 cycloalkyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group), carboxyl group, C 1-6 alkylcarbonyl group, C 1-6 alkoxycarbonyl group (the C 1-6 alkylcarbonyl group and C 1-6 alkoxycarbonyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group) or phenoxycarbonyl group (the phenoxycarbonyl group may be substituted by a halogen atom, phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group), or  
       any two of R 1 , R 2 , R 3  and R 4  together are —(CH 2 ) m — wherein m is 3, 4 or 5, —CO 2 (CH 2 ) n — wherein n is 1, 2 or 3, —CO(CH 2 ) o — wherein o is 2, 3 or 4, —(CH 2 ) p —O—(CH 2 ) q — wherein p and q are independently of each other 0, 1, 2, 3 or 4, and a sum of p and q is 2, 3 or 4,  
       
         
           
           
               
               
           
         
       
       wherein R 20  and R 21  are independently of one another hydrogen atom or C 1-6 alkoxy group (the C 1-6 alkoxy group may be substituted by C 2-4 alkenyl group or phenyl group (the phenyl group may be substituted by a halogen atom, C 1-6 alkyl group or C 1-10 alkoxy group)), characterized by treating an olefin of formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  have the same meaning as the above, with hydrogen peroxide in the presence of the olefin oxidation catalyst according to  claim 4 .  
     
   
   
       13 . A process for producing oxirane compound of formula (5)  
     
       
         
         
             
             
         
       
       wherein R 1 , R 2 , R 3  and R 4  are independently of one another hydrogen atom, phenyl group, C 1-10 alkyl group, C 3-10 cycloalkyl group (the C 1-10 alkyl group and C 3-10 cycloalkyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group), carboxyl group, C 1-6 alkylcarbonyl group, C 1-6 alkoxycarbonyl group (the C 1-6 alkylcarbonyl group and C 1-6 alkoxycarbonyl group may be substituted by a halogen atom, phenyl group, hydroxy group or C 1-6 alkoxy group) or phenoxycarbonyl group (the phenoxycarbonyl group may be substituted by a halogen atom, phenyl group, C 1-6 alkyl group or C 1-6 alkoxy group), or  
       any two of R 1 , R 2 , R 3  and R 4  together are —(CH 2 ) m — wherein m is 3, 4 or 5, —CO 2 (CH 2 ) n — wherein n is 1, 2 or 3, —CO(CH 2 ) o — wherein o is 2, 3 or 4, —(CH 2 ) p —O—(CH 2 ) q — wherein p and q are independently of each other 0, 1, 2, 3 or 4, and a sum of p and q is 2, 3 or 4,  
       
         
           
           
               
               
           
         
       
       wherein R 20  and R 21  are independently of one another hydrogen atom or C 1-6 alkoxy group (the C 1-6 alkoxy group may be substituted by C 2-4 alkenyl group or phenyl group (the phenyl group may be substituted by a halogen atom, C 1-6 alkyl group or C 1-10 alkoxy group)), characterized by treating an olefin of formula (4)  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2 , R 3  and R 4  have the same meaning as the above, with hydrogen peroxide in the presence of the olefin oxidation catalyst according to  claim 5.