Purified sulfonated organophosphorus compounds and catalysis of organic reactions therewith

Abstract

Water-soluble sulfonated organophosphorus compounds are purified by at least partially removing contaminating sulfite values therefrom, by decreasing the pH of a solution of such sulfonated organophosphorus compounds to a value of less than or equal to 4, and maintaining the pH of the solution at this value of 4 or less for such period of time as to reduce the weight concentration of sulfite in the solution to less than 100 ppm; the organophosphorus compounds thus purified are well suited for the two-phase cocatalysis of a wide variety of organic reactions.

What is claimed is:  
     
         1 . A process for the purification of water-soluble sulfonated organophosphorus compounds by at least partially removing contaminating sulfite values therefrom, comprising decreasing the pH of a solution of said sulfonated organophosphorus compounds to a value of less than or equal to 4, and maintaining the pH of said solution at this value of 4 or less for such period of time as to reduce the weight concentration of sulfite in said solution to less than 100 ppm.  
     
     
         2 . The process as defined by  claim 1 , comprising maintaining the pH of said solution at the value of 4 or less for such period of time as to reduce the weight concentration of sulfite in said solution to less than 50 ppm.  
     
     
         3 . The process as defined by  claim 1 , comprising decreasing the pH of said solution by adding an acidic compound thereto.  
     
     
         4 . The process as defined by  claim 3 , said acidic compound comprising a strong inorganic or organic acid.  
     
     
         5 . The process as defined by  claim 4 , said strong acid having a pKa of 4 or less.  
     
     
         6 . The process as defined by  claim 5 , said strong acid comprising sulfuric acid, hydrochloric acid, trifluoroacetic acid, para-toluenesulfonic acid, perchloric acid, or nitric acid.  
     
     
         7 . The process as defined by  claim 1 , comprising maintaining the temperature of said solution at less than 100° C.  
     
     
         8 . The process as defined by  claim 7 , comprising maintaining the temperature of said solution at a value ranging from 40° C. to 90° C.  
     
     
         9 . The process as defined by  claim 1 , comprising converting contaminating sulfite values into a sulfurous gas and removing said sulfurous gas from said solution.  
     
     
         10 . The process as defined by  claim 9 , comprising removing said sulfurous gas from said solution by entraining same in a carrier fluid.  
     
     
         11 . The process as defined by  claim 10 , said carrier fluid comprising nitrogen, carbon dioxide, water vapor, a rare or inert gas, or an oxygen-depleted air.  
     
     
         12 . The process as defined by  claim 1 , said solution of said sulfonated organophosphorus compound comprising an aqueous or water/alcohol solution.  
     
     
         13 . A water-soluble sulfonated organophosphorus compound containing diminished contaminating amounts of sulfite values, the weight concentration thereof being less than 100 ppm.  
     
     
         14 . A water-soluble sulfonated organophosphorus compound containing diminished contaminating amounts of sulfite values, the weight concentration thereof being less than 50 ppm.  
     
     
         15 . The sulfite-reduced water-soluble sulfonated organophosphorus compound as defined by  claim 13 , having the structural formula (I):  
       
         
           
           
               
               
           
         
       
       in which Ar 1 , Ar 2  and Ar 3 , which may be identical or different, are each an aryl radical; Y 1 , Y 2  and Y 3 , which may be identical or different, are each an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, a halogen atom, a CN group, an N0 2  group, an OH group, an NR 1 R 2  radical, wherein R 1  and R 2 , which may be identical or different, are each an alkyl radical having from 1 to 4 carbon atoms; M is an inorganic or organic cationic residue selected, such that the compound of formula (I) is soluble in water, from the group consisting of H + , cations derived from alkali metals or alkaline earth metals, N(R 3 R 4 R 5 R 6 ) + , wherein R 3 , R 4 , R 5  and R 6 , which may be identical or different, are each an alkyl radical having from 1 to 4 carbon atoms or a hydrogen atom, and other metal cations, the benzenesulfonic acid salts of which are soluble in water; m 1 , m 2  and m 3  which may be identical or different, are each an integer ranging from 0 to 5; and n 1 , n 2  and n 3 , which may be identical or different, are each an integer ranging from 0 to 3, at least one of these being equal to or greater than 1.  
     
     
         16 . The sulfite-reduced water-soluble sulfonated organophosphorus compound as defined by  claim 13 , having the structural formula (II):  
       
         
           
           
               
               
           
         
       
       in which Ar1 and Ar2, which may be identical or different, are each aryl radicals or substituted such aryl radicals bearing one or more substituents: alkyl or alkoxy radicals having from 1 to 4 carbon atoms, halogen atoms, the hydrophilic groups —COOM, —SO 3 M or —PO 3 M, wherein M is an inorganic or organic cationic residue selected from among hydrogen, cations derived from alkali metals or alkaline earth metals, ammonium cations —N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, and other cations derived from metals, the arylcarboxylic acid, arylsulfonic acid or arylphosphonic acid salts of which are soluble in water, —N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, or —OH; Ar 3  is a substituted aryl radical bearing one or more of the following substituents: alkyl or alkoxy radicals having from 1 to 4 carbon atoms, halogen atoms, the hydrophilic groups —COOM or —PO 3 M, wherein M is an inorganic or organic cationic residue selected from among hydrogen, cations derived from alkali metals or alkaline earth metals, ammonium cations —N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, and other metal cations, the arylcarboxylic acid or arylphosphonic acid salts of which are soluble in water, N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, or —OH, with the proviso that at least one of the substituents of Ar 3  is a hydrophilic group as defined above; a is 0 or 1; b is 0 or 1; c is an integer ranging from 0 to 3; D is an alkyl radical, a cycloalkyl radical or an alkyl or cycloalkyl radical substituted by one or more of the following substituents: an alkoxy radical having from 1 to 4 carbon atoms, a halogen atom, a hydrophilic group —COOM, —SO 3 M or —PO 3 M, wherein M is an inorganic or organic cationic residue selected from among hydrogen, cations derived from alkali metals or alkaline earth metals, ammonium cations —N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, and other metal cations, the arylcarboxylic acid, arylsulfonic acid or arylphosphonic acid salts of which are soluble in water, —N(R) 4 , wherein the radicals R, which may be identical or different, are each a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, —OH; d is an integer ranging from 0 to 3; and the sum (a+b+c+d) is equal to 3 or having the structural formula (III);  
       
         
           
           
               
               
           
         
       
       in which Ar1, Ar2 and D are as defined above for the formula (II); a, b, e, and f are each 0 or 1; d and g are each an integer ranging from 0 to 2; the sum (a+b+d) is equal to 2; the sum (e+f+g) is equal to 2; and L is a single valency bond or a divalent hydrocarbonaceous radical, or a radical deriving from a heterocycle comprising one or two oxygen, nitrogen or sulfur atoms in the ring, these various cyclic radicals being bonded directly to one of the phosphorus atoms or both phosphorus atoms or being bonded to one of the phosphorus atoms or to both via a linear or branched alkylene radical having from 1 to 4 carbon atoms, with the proviso that the ring or rings which are optionally moieties of the divalent radical L optionally bear one or more substituents.  
     
     
         17 . In a process for the two-phase catalysis of an organic reaction, wherein the medium of reaction comprises an organic phase containing the reagents and the products of reaction and an aqueous phase containing a catalyst and a water-soluble sulfonated organophosphorus compound cocatalyst, the improvement which comprises, as the cocatalyst therefor, a water-soluble sulfonated organophosphorus compound containing diminished contaminating amounts of sulfite values.  
     
     
         18 . In a process for the two-phase catalysis of an organic reaction, wherein the medium of reaction comprises an organic phase containing the reagents and the products of reaction and an aqueous phase containing a catalyst and a water-soluble sulfonated organophosphorus compound cocatalyst, the improvement which comprises, as the cocatalyst therefor, a water-soluble sulfonated organophosphorus compound containing diminished contaminating amounts of sulfite values as defined by  claim 13 .  
     
     
         19 . In a process for the two-phase catalysis of an organic reaction, wherein the medium of reaction comprises an organic phase containing the reagents and the products of reaction and an aqueous phase containing a catalyst and a water-soluble sulfonated organophosphorus compound cocatalyst, the improvement which comprises, as the cocatalyst therefor, a water-soluble sulfonated organophosphorus compound containing diminished contaminating amounts of sulfite values as defined by  claim 14 .  
     
     
         20 . The process as defined by  claim 17 , said organic reaction comprising a hydroformylation, carbonylation, oxidation, isomerization, or hydrocyanation reaction.  
     
     
         21 . The process as defined by  claim 20 , said organic reaction comprising the hydrocyanation of an organic compound containing at least one site of ethylenic unsaturation.  
     
     
         22 . The process as defined by  claim 21 , said organic compound comprising a diolefin or unsaturated nitrile.  
     
     
         23 . The process as defined by  claim 17 , said catalyst comprising at least one transition metal.  
     
     
         24 . The process as defined by  claim 23 , said at least one transition metal comprising nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, zinc, cadmium, or mercury.  
     
     
         25 . The process as defined by  claim 23 , said catalyst further comprising a promoter or dopant metal element.  
     
     
         26 . The purified, sulfite-reduced, water-soluble sulfonated organophosphorus compound product of the process as defined by  claim 1.