Formate production method, formic acid production method, catalyst for producing formate, and ruthenium complex

Abstract

The invention relates to a method for producing a formate, the method including reacting hydrogen with carbon dioxide, a hydrogen carbonate or a carbonate using a catalyst in the presence of a solvent, wherein the reaction is a two-phase system in which an organic solvent and an aqueous solvent are present in a separated state in the solvent, and the catalyst is at least one selected from a ruthenium complex represented by the formula (1) in the specification, a tautomer or stereoisomer thereof, and a salt compound of the complex, tautomer or stereoisomer.

1 . A method for producing a formate, the method comprising reacting hydrogen with carbon dioxide, a hydrogen carbonate or a carbonate using a catalyst in the presence of a solvent,
 wherein the reaction is a two-phase system in which an organic solvent and an aqueous solvent are present in a separated state in the solvent, and   the catalyst is at least one selected from a ruthenium complex represented by the following formula (1), a tautomer or stereoisomer thereof, or a salt compound of the complex, tautomer or stereoisomer:   
       
         
           
           
               
               
           
         
       
       wherein R 0  represents a hydrogen atom or an alkyl group,
 Q 1  each independently represents CH 2 , NH or O, 
 R 1  each independently represents an alkyl group or an aryl group (provided that when Q 1  represents NH or O, at least one of R 1  represents an aryl group), 
 A each independently represents CH, CR 5  or N, R 5  represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group or an alkoxy group, 
 X represents a halogen atom, 
 n represents 0 to 3, and 
 when more than one L are present, L each independently represents a neutral or anionic ligand. 
 
     
     
         2 . The method for producing a formate according to  claim 1 , wherein the ruthenium complex represented by the formula (1) is a ruthenium complex represented by the following formula (3): 
       
         
           
           
               
               
           
         
       
       wherein R 0  represents a hydrogen atom or an alkyl group,
 Q 2  each independently represents NH or O, 
 R 3  each independently represents an aryl group, 
 A each independently represents CH, CR 5  or N, R 5  represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group or an alkoxy group, 
 X represents a halogen atom, 
 n represents 0 to 3, and 
 when more than one L are present, L each independently represents a neutral or anionic ligand. 
 
     
     
         3 . The method for producing a formate according to  claim 1 , wherein the R 1  represents a phenyl group. 
     
     
         4 . The method for producing a formate according to  claim 2 , wherein the R 3  represents a phenyl group. 
     
     
         5 . The method for producing a formate according to  claim 4 , wherein the A represents CH, and the Q 2  represents NH. 
     
     
         6 . The method for producing a formate according to  claim 1 , wherein the R 0  represents a hydrogen atom or a methyl group. 
     
     
         7 . The method for producing a formate according to  claim 1 , wherein the X represents a chlorine atom. 
     
     
         8 . The method for producing a formate according to  claim 1 , wherein the n represents 1 to 3, and the L each independently represents a hydrogen atom, carbon monoxide or triphenylphosphine. 
     
     
         9 . The method for producing a formate according to  claim 1 , wherein the organic solvent contains toluene or dioxane. 
     
     
         10 . The method for producing a formate according to  claim 1 , wherein an ammonium salt is further used as a phase transfer catalyst. 
     
     
         11 . The method for producing a formate according to  claim 1 , wherein a ligand represented by the following formula (4) is further added: 
       
         
           
           
               
               
           
         
       
       wherein R 0  represents a hydrogen atom or an alkyl group,
 Q 2  each independently represents NH or O, 
 R 3  each independently represents an aryl group, 
 A each independently represents CH, CR 5  or N, and R 5  represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group or an alkoxy group. 
 
     
     
         12 . A method for producing formic acid, the method comprising:
 a step of producing a formate by the method for producing a formate according to  claim 1 ; and   a second step of protonating at least a part of the formate to form formic acid.   
     
     
         13 . A catalyst for the production of a formate, for use in the production of a formate by a reaction of hydrogen with carbon dioxide, a hydrogen carbonate or a carbonate, the catalyst comprising a ruthenium complex represented by the following formula (2): 
       
         
           
           
               
               
           
         
       
       wherein R 0  represents a hydrogen atom or an alkyl group,
 Q 1  each independently represents CH 2 , NH or O, 
 R 2  each independently represents an alkyl group or an aryl group (provided that at least one of R 2  represent an aryl group), 
 A each independently represents CH, CR 5  or N, R 5  represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group or an alkoxy group, 
 X represents a halogen atom, 
 n represents 0 to 3, and 
 when more than one L are present, L each independently represents a neutral or anionic ligand. 
 
     
     
         14 . A ruthenium complex represented by the following formula (3): 
       
         
           
           
               
               
           
         
       
       wherein R 0  represents a hydrogen atom or an alkyl group,
 Q 2  each independently represents NH or O, 
 R 3  each independently represents an aryl group, 
 A each independently represents CH, CR 5  or N, R 5  represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group or an alkoxy group, 
 X represents a halogen atom, 
 n represents 0 to 3, and 
 when more than one L are present, L each independently represents a neutral or anionic ligand. 
 
     
     
         15 . The ruthenium complex according to  claim 14 , wherein the R 3  represents a phenyl group. 
     
     
         16 . The ruthenium complex according to  claim 14 , wherein the A represents CH and the Q 2  represents NH. 
     
     
         17 . The ruthenium complex according to  claim 14 , wherein the R 0  represents a hydrogen atom or a methyl group. 
     
     
         18 . The ruthenium complex according to  claim 14 , wherein the X represents a chlorine atom. 
     
     
         19 . The ruthenium complex according to  claim 14 , wherein the n represents 1 to 3, and the L each independently represents a hydrogen atom, carbon monoxide or triphenylphosphine.