Process for the preparation of glycolaldehyde

Abstract

Disclosed are catalyst solutions for the hydroformylation of formaldehyde comprising one or more fluorophosphite compounds, rhodium and a hydroformylation solvent comprising at least one N,N-disubstituted amide, N-substituted cyclic amide, or a mixture thereof. Also disclosed are hydroformylation processes wherein formaldehyde is contacted with carbon monoxide, hydrogen one or more fluorophosphite compounds, rhodium and a hydroformylation solvent to produce glycolaldehyde. The fluorophosphite-based catalysts provide good reaction rates and high selectivity to glycolaldehyde.

1 . A catalyst solution, comprising:
 (i) at least one fluorophosphite compound having the general formula (I):   
       
         
           
           
               
               
           
         
          wherein R 1  and R 2  are hydrocarbyl radicals which contain a total of up to 40 carbon atoms; 
         (ii) rhodium; and 
         (iii) a hydroformylation solvent comprising at least one N,N-disubstituted amide, N-substituted cyclic amide, or a mixture thereof; 
       
       wherein the ratio of gram moles fluorophosphite compound to gram atoms rhodium is about 1:1 to about 100:1. 
     
     
         2 . The catalyst solution according to  claim 1  wherein R 1  and R 2  individually are independently selected from alkyl radicals of up to 8 carbon atoms, benzyl, cyclopentyl, cyclohexyl, cycloheptyl, and aryl groups having formulas (II-IV): 
       
         
           
           
               
               
           
         
       
       wherein R 3  and R 4  are independently selected from alkyl, alkoxy, halogen, cycloalkoxy, formyl, alkanoyl, cycloalkyl, aryl, aryloxy, aroyl, carboxyl, carboxylate salts, alkoxycarbonyl, alkanoyloxy, cyano, sulfonic acid and sulfonate salts in which the alkyl moiety of such alkyl, alkoxy, alkanoyl, alkoxycarbonyl and alkanoyloxy groups contains up to 8 carbon atoms; m and n each is 0, 1 or 2; and the total carbon atom content of the hydrocarbyl radicals represented by R 1  and R 2  is 2 to 35 and wherein the ratio of gram moles fluorophosphite compound to gram atoms rhodium is about 1:1 to about 70:1. 
     
     
         3 . The catalyst solution according to  claim 1  wherein in R 1  and R 2  collectively represent an arylene group having formulas (V-VII): 
       
         
           
           
               
               
           
         
       
       or a radical having the formula 
       
         
           
           
               
               
           
         
       
       wherein
 each of A 1  and A 2  is an arylene radical having formula (V), (VI) or (VII) above wherein each ester oxygen atom of fluorophosphite (I) is bonded to a ring carbon atom of A 1  and A 2 ; 
 X is (i) a chemical bond directly between ring carbon atoms of A 1  and A 2 ; or (ii) an oxygen atom, a group having the formula —(CH 2 ) y — wherein y is 2 to 4, or a group having the formula 
 
       
         
           
           
               
               
           
         
         wherein
 R 5  is hydrogen, alkyl, or aryl; R 6  is hydrogen or alkyl; and the group —C(R 5 )(R 6 )— contains up to 8 carbon atoms; and 
 
       
       wherein
 R 3  and R 4  are independently selected from alkyl, alkoxy, halogen, cycloalkoxy, formyl, alkanoyl, cycloalkyl, aryl, aryloxy, aroyl, carboxyl, carboxylate salts, alkoxycarbonyl, alkanoyloxy, cyano, sulfonic acid and sulfonate salts in which the alkyl moiety of said alkyl, alkoxy, alkanoyl, alkoxycarbonyl and alkanoyloxy groups contains up to 8 carbon atoms; p and q each are 0, 1 or 2; and the total carbon atom content of the radical collectively represented by R 1  and R 2  is 12 to 35; 
 
     
     
         4 . The catalyst solution according to  claim 3  wherein said fluorophosphite compound has formula (VIII): 
       
         
           
           
               
               
           
         
       
       wherein R 7  represents halogen or C 3  to C 8  alkyl; R 8  represents hydrogen, halogen, C 1  to C 8  alkyl, or C 1  to C 8  alkoxy; r is 0, 1 or 2; and X is a group having the formula 
       
         
           
           
               
               
           
         
       
       wherein R 5  and R 6  each are hydrogen or alkyl. 
     
     
         5 . The catalyst solution according to  claim 4  wherein said fluorophosphite compound has the formula (IX): 
       
         
           
           
               
               
           
         
       
       wherein t-Bu is tertiary butyl and Me is methyl. 
     
     
         6 . The catalyst solution according to  claim 1  wherein said at least one N,N-disubstituted amide has the following formula (X): 
       
         
           
           
               
               
           
         
         wherein R 9  and R 10  are independently selected from alkyl radicals containing 1 to 20 carbon atoms, cycloalkyl radicals containing 5 to 20 carbon atoms, aralkyl radicals containing 7 to 12 carbon atoms, and aryl radicals containing 6 to 12 carbon atoms; and R 11  is independently selected from hydrogen, alkyl radicals containing 1 to 20 carbon atoms, cycloalkyl radicals containing 5 to 20 carbon atoms, aralkyl radicals containing 7 to 12 carbon atoms, and aryl radicals containing 6 to 12 carbon atoms. 
       
     
     
         7 . The catalyst solution according to  claim 6  wherein R 9  and R 10  are independently selected from methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, and heptyl and R 11  is independently selected from hydrogen, methyl, ethyl, propyl, pentyl, and hexyl. 
     
     
         8 . The catalyst solution according to any one of  claims 4 ,  5 , or  6  wherein said hydroformylation solvent comprises N-methyl-2-pyrrolidinone; at least one N,N-disubstituted amide selected from N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, N,N-diethyldodecanamide, N,N-dibutyldodecanamide, N-methyl-N-butyldodecanamide, N,N-diethyltetradecanamide, N,N-dicyclohexyldecanamide, N,N-dibutylbenzamide, and N,N-dibenzyloctanamide; or a mixture thereof. 
     
     
         9 . The catalyst solution according to any one of  claims 4 ,  5 , or  6  wherein said hydroformylation solvent comprises N,N-dimethylacetamide.