Immobilized metal complex catalysts, process for preparation thereof and use thereof

Abstract

The present invention provides a novel immobilized metal complex catalyst of Formula I wherein M is a Group VIII metal, L x is a phosphine ligand, n is an integer with a value between 2 and 6, ML x is an organometallic complex.

1 - 11 . (canceled)  
   
   
       12 . A process for the carbonylation of an aryl olefin or an alcohol of Formulae III and IV respectively,  
     
       
         
         
             
             
         
       
     
     wherein R1, R2, R3, R4 and R are independently selected from the group consisting of hydrogen, alkyl, aryl, arylalkyl and arylalkyl cycloaromatic group with or without substituents; which comprises reacting the aryl olefin or alcohol with carbon monoxide (CO) and water (H 2 O) as reagents, in the presence of an immobilized metal complex catalyst of Formula I,  
     
       
         
         
             
             
         
       
     
     wherein M is a Group VIII metal, L x  is a phosphine ligand, n is an integer with a value between 2 and 6, ML x  is an organometallic complex, and in the presence of a promoter selected from an alkali metal halide, and a proton source, in an organic solvent, heating the reaction mixture to a temperature between 30 to 120° C., for a period of 8 hours to 24 hours at a pressure ranging from 1 to 60 atm, cooling the reaction mixture thereafter to ambient temperature, flushing the mixture with inert gas, removing the catalyst by filtration, removing the solvent and isolating a product comprising an isomeric saturated carboxylic acid of Formula V,  
     
       
         
         
             
             
         
       
     
     wherein R1, R2, R3, R4 are independently selected from the group consisting of hydrogen, alkyl, aryl, arylalkyl and arylalkyl cycloaromatic group with or without substituents; R is H or a carboxylic acid group —COOH and R5 is H or a carboxylic acid group —COOH, provided that when R is H, R5 is —COOH and when R is —COOH, R5 is H; in a chemo-selective and regioselective manner.  
   
   
       13 . A process as claimed in  claim 12  wherein the proton source is selected from the group consisting of water, a Bronsted acid selected from the group consisting of formic acid, acetic acid, and oxalic acid, a hydrohalic acid selected from the group consisting of hydrochloric acid, hydrobromic acid and hydroiodic acid, and a protonic acid selected from the group consisting of para-toluenesulphonic acid, methane sulphonic acid, trifluoromethanesulphonic acid, and trifluoroacetic acid.  
   
   
       14 . A process as claimed in  claim 12  wherein the organic solvent used in the carbonylation reaction is an aprotic solvent selected from an aromatic hydrocarbons selected from the group consisting of benzene, toluene and xylene; a ketone selected from the group consisting of methyl ethyl ketone and acetone; an amide comprising N-methylpyrrolidone; a cycle ether selected from the group consisting of tetrahydrofuran and dioxin; and a nitrile comprising acetonitrile.  
   
   
       15 . A process as claimed in  claim 12  wherein the promoter used is an alkali metal promoter selected from the group consisting of an alkali metal halide of the formula M′X, wherein M′ is a metal selected from the group consisting of Lithium, Sodium and Potassium and X is a halide selected from the group consisting of chloride, bromide and iodide.  
   
   
       16 . A process as claimed in  claim 12  wherein the reaction is carried out in the presence of a phosphorous ligand.  
   
   
       17 . A process as claimed in  claim 16  wherein the phosphorous ligand used in the preparation of complex of Formula II as well as in the carbonylation is a mono-phosphine selected from the group consisting of triphenyl phosphine, tris-paratolyl phosphine, trisparachlorophenyl phosphine, tris-paramethoxy phenyl phosphine, tricyclohexyl phosphine, tributyl phosphine and methyldiphenyl phosphine.  
   
   
       18 . A process as claimed in  claim 12  wherein the concentration of the Group VIII, metal in the immobilized metal complex catalyst is one mole for 1000 to 8000 moles of the substrate, preferably 5600.  
   
   
       19 . A process as claimed in  claim 12  wherein the number of moles of the acid promoter per gram atom of Group VIII metal in the catalyst system is in the range of 10 to 1000, preferably 580.  
   
   
       20 . A process as claimed in  claim 12  wherein the number of moles of the alkali metal promoter per gram atom of palladium in the catalyst system is in the range of 10 to 1000, preferably 580.  
   
   
       21 . A process as claimed in  claim 12  wherein the number of moles of the blocking agent for blocking the exterior surface of the porous matrix for one gram of the support is in the range of 0.1 to 1 mmoles, preferable 0.142 mmols.  
   
   
       22 . A process as claimed in  claim 12  wherein the amount of the anchoring agent used to anchor the metal complexes to the pretreated support materials is in the range of 1 to 10 mmoles preferentially 5.73 mmols.  
   
   
       23 . A process as claimed in  claim 12  wherein the carbonization reaction is carried out in a stirred reactor with catalyst employed being employed as a heterogeneous phase with a suitable solvent in presence of halide and acid promoters, and carbon monoxide.