Method for the production of bisepoxides and dithiols

Abstract

Process for the preparation of bisepoxides, wherein a conjugated diene of the formula I where R 1 is selected from hydrogen and C 1 -C 12 -alkyl, unsubstituted or substituted by one or more S—H or O—H groups, is reacted in the presence of a catalyst which is obtainable by bringing at least one manganese compound selected from A 2 MnX 4 , AMnX 3 , MnY, MnX 2 and MnX 3 into contact with at least one ligand L of the formula II where X are identical or different and are selected from monovalent anions, Y is a divalent anion, A is selected from alkali metal and ammonium, which may be alkylated, R 2 are identical or different and are selected from C 1 -C 20 -alkyl, and at least one coligand which is derived from monocarboxylic acids, dibasic or polybasic carboxylic acids or diamines, with at least one peroxide, up to 4 equivalents of peroxide being used per equivalent of C—C double bond.

1 . A process for the preparation of a bisepoxide, comprising:
 reacting at least one conjugated diene of formula I   
     
       
         
         
             
             
         
       
       where 
       R 1  is selected from the group consisting of hydrogen, an unsubstituted C 1 -C 12 -alkyl, and a C 1 -C 12 -alkyl substituted by one or more S—H or O—H groups, 
     
     with at least one peroxide in the presence of a catalyst, said catalyst obtained by a process comprising contacting
 at least one manganese compound selected from the group consisting of A 2 MnX 4 , AMnX 3 , MnY, MnX 2  and MnX 3  with 
 at least one ligand L of formula II 
 
     
       
         
         
             
             
         
       
       
         where 
         X 2 , X 3 , and X 4  are each a monovalent anion, 
         Y is a divalent anion, 
         A is selected from the group consisting of an alkali metal ammonium, and an alkylated ammonium, 
       
       R 2  are each different or identical and are C 1 -C 20 -alkyl, 
     
     and
 at least one coligand of a monocarboxylic acid, a dibasic carboxylic acid, a polybasic carboxylic acid, or a diamine, 
 
     wherein up to 4 equivalents of peroxide are present per equivalent of C—C double bond. 
   
   
       2 . The process according to  claim 1 , which is carried out in the presence of at least one solvent. 
   
   
       3 . The process according to  claim 1 , wherein said at least one coligand is oxalate. 
   
   
       4 . A process for the preparation of dithiol mixtures, comprising:
 reacting a bisepoxide obtained by the process according to  claim 1  with H 2 S in the presence of at least one basic catalyst.   
   
   
       5 . The process according to  claim 4 , wherein said at least one basic catalyst is at least one member selected from the group consisting of alkali metal hydrogen sulfide, alkali metal hydroxide and benzyltri(C 1 -C 10 -alkyl)ammonium hydroxide. 
   
   
       6 - 10 . (canceled) 
   
   
       11 . The process according to  claim 1 , wherein R 1  is hydrogen. 
   
   
       12 . The process according to  claim 1 , wherein said at least one coligand is at least one isomer of 1,2-diaminocyclohexane. 
   
   
       13 . The process according to  claim 1 , wherein said at least one manganese compound is at least one selected member from the group consisting of manganese(II) sulfate, MnSO 4 .H 2 O, manganese(II) acetate, Mn(OAc) 2 .4H 2 O, manganese(II) chloride, MnCl 2 .4H 2 O, manganese(II) perchlorate, Mn(ClO 4 ) 2 .6H 2 O and potassium hexachloromanganate(IV). 
   
   
       14 . The process according to  claim 1 , wherein said at least one manganese compound is present in an amount of from 0.001 to 0.1 equivalents, based on the amount of said at least one conjugated diene of formula I. 
   
   
       15 . The process according to  claim 1 , wherein said at least one manganese compound is present in an amount of from 0.005 to 0.1 equivalents, based on the amount of said at least one conjugated diene of formula I. 
   
   
       16 . The process according to  claim 1 , wherein said at least one manganese compound is present in an amount of from 0.00001 to 0.001 equivalents, based on the amount of said at least one conjugated diene of formula I. 
   
   
       17 . The process according to  claim 1 , wherein said at least one manganese compound is present in an amount of from 0.00001 to 0.0005 equivalents, based on the amount of said at least one conjugated diene of formula I. 
   
   
       18 . The process according to  claim 1 , wherein said at least one ligand of formula II is present in an amount of from 1 to 5 equivalents based on the amount of manganese. 
   
   
       19 . The process according to  claim 1 , wherein said at least one ligand of formula II is present in an amount of from 1.1 to 2 equivalents based on the amount of manganese. 
   
   
       20 . The process according to  claim 1 , wherein said at least one peroxide is at least one member selected from the group consisting of tert-butyl hydroperoxide, cumyl hydroperoxide, 1,3-diisopropyl monohydroperoixde, 1-phenylethyl hydroperoxide, and hydrogen peroxide. 
   
   
       21 . The process according to  claim 1 , occurring at a temperature of from −50 to 100° C. 
   
   
       22 . The process according to  claim 1 , occurring at a pressure of from 1 to 200 bar. 
   
   
       23 . The process according to  claim 1 , occurring at a pH of from 1 to 7. 
   
   
       24 . The process according to  claim 1 , wherein said bisepoxide is the bisepoxide of formula VII.1: 
     
       
         
         
             
             
         
       
     
   
   
       25 . The process according to  claim 1 , wherein at least one equivalent of peroxide is present per equivalent of C—C double bond.