Patent Publication Number: US-4257973-A

Title: Process of making acids or esters from unsaturated compounds

Description:
FIELD OF THE INVENTION 
     This invention relates to a method of making acids and esters from organic compounds containing aliphatic unsaturation. More particularly, this invention relates to a method of making acids and esters by the catalytic addition of hydroxy compounds and carbon monoxide across olefinic or acetylenic unsaturation. 
     SUMMARY OF THE INVENTION 
     The process of the present invention is a process for making carboxylic compounds (acids or esters) from aliphatically unsaturated organic compounds by catalytic carboxylation or alkoxycarbonylation by the addition of carbon monoxide and a hydroxy compound, preferably having 1 to 4 primary or secondary hydroxy groups, or water. 
     The reaction is conducted at a temperature of 35° to 200° C. at a pressure of 1 to 1000 atmospheres in the presence of a catalyst composed of an organophosphorus palladium halide compound and 0.5 to 5 moles per mole of palladium compound of a metallic halide promoter. 
     The aliphatically unsaturated compounds which are employed as reactants in the practice of this invention are organic compounds having one or more ethylenic or acetylenic groups with the following provisos: 
     (i) ethylenic groups must have two hydrogen substituents. 
     (ii) the unsaturated groups are not conjugated with other aliphatic unsaturation 
     (iii) halogen or hydroxyl, if present, must be removed by at least 2 carbon atoms from the unsaturation 
     (iv) the compounds are free of amine groups. 
     The organophosphorus palladium halide can be represented by the formula 
     
         (PR.sub.3).sub.2 PdXY 
    
     wherein 
     X is chlorine or bromine 
     Y is hydrogen, chlorine, bromine, alkyl of 1 to 5 carbon atoms, aralkyl, acyl of 2 to 4 carbon atoms, or aryl of up to 12 carbon atoms, 
     each R is selected from lower alkyl, cycloalkyl of 3 to 8 carbon atoms, lower alkoxy, aryl of up to 12 carbon atoms, substituted with up to 3 halogen atoms or lower alkoxy groups, aryloxy groups of up to 12 carbon atoms, arylthio of up to 12 carbon atoms, aralkyl of up to 12 carbon atoms, lower alkylthio, di(lower alkyl) amino, pyrrolidino, piperidino and vinyl groups, 
     with the proviso that not more than one aryl group attached to phosphorus contains a substituent in a sterically hindered position. 
     The promoter is a chloride of Ti, Tl, Ni, Fe, Cr, Mn, Cu, Pd, Zn or Co or a halide compound of Sn. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The process of the present invention is a catalyzed addition reaction, carboxylation or alkoxycarbonylation, of water or alcohols and carbon monoxide to aliphatically unsaturated compounds. The reaction is applicable to a wide variety of unsaturated compounds, including compounds with more than one ethylenic and/or acetylenic groups. Difficulty has been experienced where the ethylenic unsaturation is highly branched. Accordingly, two substituents of the olefinic groups should be hydrogen. Hydroxyl or halogen substituents must be removed from the double bond by at least two carbon atoms. Difficulty has also been had with compounds in which two or more aliphatically unsaturated groups are conjugated, or where amine substituents (primary, secondary or tertiary) are present. 
     Substituents which do not interfere with the reaction of the invention include aryl, lower alkoxy, lower alkoxycarbonyl, carboxyl, lower acyloxy, cyano, carbamoyl, lower acyl and aroyl substituents. Halo and hydroxy substituents can also be present subject to the above noted proviso. 
     The preferred unsaturated compounds are hydrocarbons or hydrocarbon substituted with the above substituents which hydrocarbon contains at least one group of ##STR1## wherein at least two of R 3 , R 4 , R 5  and R 6  are hydrogen, 
     R 3  to R 8  are hydrogen or aliphatically saturated hydrocarbyl radicals, and 
     any two of R 3 , R 4 , R 5  and R 6  can be joined to form a ring of 3 to 12 carbon atoms. 
     When more than one unsaturated group is present in the molecule, then at least one of R 3  to R 8  will be a common, linking radical. Preferably the unsaturated compounds contain up to 30 carbon atoms. 
     Preferred olefins for the practice of this invention include: 
     
         ______________________________________                                    
Ethylene         Nonadecene-1                                             
Propylene        Docosene-1                                               
Butene-1         1,5-Hexadiene                                            
Pentene-1        1,6-Heptadiene                                           
Hexene-1         1,7-Octadiene                                            
Heptene-1        1,8-Nonadiene                                            
Octene-1         1,9-Decadiene                                            
Nonene-1         1,10-Undecadiene                                         
Decene-1         1,11-Dodecadiene                                         
Undecene-1       4-Vinylcyclohexene                                       
Dodecene-1       Methyl 10-undecenoate                                    
Tridecene-1      Ethyl 10-undecenoate                                     
Tetradecene-1    10-Undecenoic acid                                       
Pentadecene-1    10-Undecen-1-ol                                          
Hexadecene-1     5-Hexen-2-one                                            
Heptadecene-1    5-Hexenenitrile                                          
Octadecene-1     trans-1,4,9-Decatriene                                   
______________________________________                                    
 
    
     Other olefins that can be used in this invention include: 
     
         ______________________________________                                    
Isobutylene      2,3-Dimethylbutene-1                                     
2-Methylbutene-1 3,3-Dimethylbutene-1                                     
3-Methylbutene-1 2-Methylhexene-1                                         
2-Methylpentene-1                                                         
                 3-Methylhexene-1                                         
3-Methylpentene-1                                                         
                 4-Methylhexene-1                                         
4-Methylpentene-1                                                         
                 5-Methylhexene-1                                         
3-Ethylpentene-1 2,3,3-Trimethylpentene-1                                 
2,3-Dimethylpentene-1                                                     
                 2,3,4-Trimethylpentene-1                                 
2,4-Dimethylpentene-1                                                     
                 2,4,4-Trimethylpentene-1                                 
3,3-Dimethylpentene-1                                                     
                 3,3,4-Trimethylpentene-1                                 
4,4-Dimethylpentene-1                                                     
                 3,4,4-Trimethylpentene-1                                 
2,3,3-Trimethylbutene-1                                                   
                 2-Methyloctene-1                                         
2-Methylheptene-1                                                         
                 3-Methyloctene-1                                         
3-Methylheptene-1                                                         
                 7-Methyloctene-1                                         
4-Methylheptene-1                                                         
                 2,6-Dimethylheptene-1                                    
5-Methylheptene-1                                                         
                 3,3-Dimethylheptene-1                                    
6-Methylheptene-1                                                         
                 4,4-Dimethylheptene-1                                    
3-Ethylhexene-1  4-Methyl-4-ethylhexene-1                                 
4-Ethylhexene-1  3,3,5-Trimethylhexene-1                                  
2,3-Dimethylhexene-1                                                      
                 4,4,5-Trimethylhexene-1                                  
2,4-Dimethylhexene-1                                                      
                 2,6-Dimethyloctene-1                                     
2,5-Dimethylhexene-1                                                      
                 3,7-Dimethyloctene-1                                     
3,3-Dimethylhexene-1                                                      
                 2,5,6-Trimethylheptene-1                                 
3,4-Dimethylhexene-1                                                      
                 3,3,6-Trimethylheptene-1                                 
3,5-Dimethylhexene-1                                                      
                 2,3-Dimethyloctene-1                                     
4,4-Dimethylhexene-1                                                      
                 3-Butyloctene-1                                          
4,5-Dimethylhexene-1                                                      
                 3-Propylnonene-1                                         
5,5-Dimethylhexene-1                                                      
                 3,7,11-Trimethyldodecene-1                               
2-Methyl-3-ethylpentene-1                                                 
                 2-Methylnonadecene-1                                     
3-Methyl-3-ethylpentene-1                                                 
                 Eicosene-1                                               
Cyclopentene     Cyclodecene                                              
Cyclohexene      Cycloundecene                                            
Cycloheptene     Cyclododecene                                            
Cyclooctene      Cycloocta-1,5-diene                                      
Cyclononene      Butene-2                                                 
Pentene-2        Hexene-2                                                 
Hexene-3         Heptene-2                                                
Octene-2         Octene-3                                                 
Octene-4         Nonene-2                                                 
4-Methyloctene-2 5-Methyloctene-2                                         
4,6-Dimethyloctene-2                                                      
4-Methylheptene-2                                                         
                 2-Methylhexene-3                                         
2-Ethylhexene-3                                                           
 ##STR2##                                                                 
                       ##STR3##                                           
                       ##STR4##                                           
 ##STR5##                                                                 
             ##STR6##                                                     
                       ##STR7##                                           
 ##STR8##                                                                 
             ##STR9##                                                     
                       ##STR10##                                          
 ##STR11##                                                                
                       ##STR12##                                          
______________________________________                                    
 
    
     Acetylenic compounds include acetylene, methylacetylene, dimethylacetylene, phenylacetylene, penta-1-yne-4-ene and the like. 
     Preferred classes include: 
     (1) 1-alkenes of the formula 
     
         CH.sub.3 (CH.sub.2).sub.n CH═CH.sub.2 
    
      (2) diolefins of the formula 
     
         CH.sub.2 ═CH.(CH.sub.2).sub.n CH═CH.sub.2 
    
      (3) esters of the formula 
     
         lower alkyl O.CO.(CH.sub.2).sub.n CH═CH.sub.2, where n is &lt;25. 
    
     The alcohols which can be employed in the practice of this invention can be formulated 
     
         R.sup.9 (OH).sub.m 
    
     m=1 to 4, preferably 1, and 
     where R 9  is a radical of up to 30 carbon atoms derived from a hydrocarbon having at least one aliphatic or alicyclic group and the hydroxy groups are joined to a saturated carbon atom having at least one hydrogen substituent, and removed from aliphatic unsaturation by at least 2 carbon atoms. R 9  can also be substituted with the same substituents as R 3  to R 8 . 
     Preferably the alcohol is a saturated aliphatic monohydric primary or secondary alcohol and most preferably contains up to 10 carbon atoms. 
     Examples of such alcohols include: 
     
         ______________________________________                                    
Methanol           Hexanol-1                                              
Ethanol            Heptanol-1                                             
Propanol-1         β-Chloroethanol                                   
Propanol-2         β-Methoxyethanol                                  
Pentanol-1         Benzylalcohol                                          
Butanol-1          Neopentyl alcohol                                      
______________________________________                                    
 
    
     Other alcohols that are suitable for this invention include: 
     
         ______________________________________                                    
Isobutyl alcohol   4,4-Dimethyl-1-pentanol                                
sec-Butyl alcohol  4,4-Dimethyl-2-pentanol                                
Isoamyl alcohol    2,2-Dimethyl-3-pentanol                                
3,3-Dimethyl-1-pentanol                                                   
                   2-Methylpentan-1-ol                                    
3,3-Dimethyl-2-pentanol                                                   
                   4-Methylpentan-2-ol                                    
1-Octanol          2-Methylpentan-3-ol                                    
2-Octanol          3,3-Dimethylbutan-1-ol                                 
3-Octanol          3,3-Dimethylbutan-2-ol                                 
4-Octanol          6-Methyl-1-heptanol                                    
5-Methyl-1-hexanol 6-Methyl-2-heptanol                                    
5-Methyl-2-hexanol 6-Methyl-3-heptanol                                    
5-Methyl-3-hexanol 4-Methyl-3-heptanol                                    
4-Methyl-1-hexanol 6-Methyl-4-heptanol                                    
4-Methyl-2-hexanol 5-Methyl-1-heptanol                                    
4-Methyl-3-hexanol 5-Methyl-2-heptanol                                    
5-Methyl-4-heptanol                                                       
                   5-Methyl-3-heptanol                                    
2-Methyl-4-heptanol                                                       
                   5,5-Dimethyl-1-hexanol                                 
4-Methyl-1-heptanol                                                       
                   5,5-Dimethyl-2-hexanol                                 
4-Methyl-2-heptanol                                                       
                   5,5-Dimethyl-4-hexanol                                 
3-Methyl-1-heptanol                                                       
                   1-Nonanol                                              
3-Methyl-2-heptanol                                                       
                   2-Nonanol                                              
2,2-Dimethyl-1-hexanol                                                    
                   3-Nonanol                                              
2,2-Dimethyl-3-hexanol                                                    
                   4-Nonanol                                              
3,3-Dimethyl-1-hexanol                                                    
                   5-Nonanol                                              
3,3-Dimethyl-2-hexanol                                                    
                   8-Methyl-1-octanol                                     
4,4-Dimethyl-3-hexanol                                                    
                   8-Methyl-2-octanol                                     
2,3-Dimethyl-1-hexanol                                                    
                   7-Methyl-1-octanol                                     
4,5-Dimethyl-1-hexanol                                                    
                   6-Methyl-1-octanol                                     
4,5-Dimethyl-1-hexanol                                                    
                   5-Methyl-1-octanol                                     
4,5-Dimethyl-3-hexanol                                                    
                   2-Methyl-1-octanol                                     
3,5-Dimethyl-1-hexanol                                                    
                   3-Methyl-1-octanol                                     
3,5-Dimethyl-2-hexanol                                                    
                   3-Methyl-2-octanol                                     
3,5-Dimethyl-4-hexanol                                                    
                   1,3-propanediol                                        
______________________________________                                    
 
    
     Lauryl alcohols and other dodecanols 
     
         ______________________________________                                    
Tridecanol             1,4-butanediol                                     
Tetradecanol           1,5-pentanediol                                    
Pentadecanol           1,6-hexanediol                                     
Cetyl and other hexadecanols                                              
Oleyl alcohol          Pentaerythritol                                    
Heptadecanol           Trimethylolpropane                                 
Octadecanol                                                               
Nonadecanol                                                               
Arachic alcohol or 1-eicosanol                                            
α-Phenethyl alcohol                                                 
β-Phenethyl alcohol                                                  
3-Phenylpropanol                                                          
1-Methyl-2-phenylethanol                                                  
4-Phenylbutanol                                                           
Cyclopentyl alcohol                                                       
Cyclohexyl alcohol                                                        
Methylcyclohexyl alcohols                                                 
Decanols                                                                  
Hendecanols                                                               
2-Hydroxymethyl-2-methyl-1,3-propanediol                                  
______________________________________                                    
 
    
     As noted above, the unsaturated reactant can contain hydroxy groups, and in suitable combination the hydroxy reactant and the unsaturated reactant can be the same. In this case, polyesters are produced by the reaction. The preferred reactants can be represented by the formula 
     
         HO--CH.sub.2.R.sup.10.CH═CH.sub.2 
    
     wherein R 10  is an aliphatically saturated biradical and preferably a polymethylene chain of 2 to 15 carbon atoms. 
     The catalyst system employed in the practise of the present invention requires a palladium halide compound complexed with two organophosphorus ligands and a promoter. 
     The phosphorus ligands have the formula 
     
         PR.sub.3 
    
     wherein, in general, the R 3  groups can be selected from lower alkyl, cycloalkyl of 3 to 8 carbon atoms, lower alkoxy or aryl groups substituted with up to 3 halogen or lower alkoxy groups, aryloxy groups of up to 12 carbon atoms, arylthio of up to 12 carbon atoms, aralkyl, lower alkylthio, di(lower alkyl) amino, pyrrolidino, piperidino or vinyl groups, and can be alike or different, provided that not more than one of the aryl groups has a substituent in a sterically hindered position, i.e., in an adjacent position on the ring system or in the peri position in the naphthalene series. 
     In the context of this invention, an aryl group is defined as a radical derived from a hydrocarbon containing at least one six-membered aromatic ring by removal of a hydrogen directly attached to a carbon atom of such ring. As thus defined aryl radicals include such species as phenyl groups substituted with lower alkyl groups. 
     The term &#34;aralkyl&#34; refers to a radical derived from aromatic hydrocarbon having at least one alkyl substituent by removal of an aliphatic hydrogen atom. 
     The term &#34;lower alkyl&#34; refers to radicals derived from an aliphatic hydrocarbon having from 1 to 6 carbon atoms, by removal of a hydrogen atom. 
     The term &#34;cycloalkyl&#34; refers to a radical derived from a saturated alicyclic compound by removal of a hydrogen atom. 
     Examples of suitable ligands include: 
     
         ______________________________________                                    
Triethylphosphine                                                         
                Diphenyl-N-piperidinylphosphine                           
Tri-n-butylphosphine                                                      
                Diphenyl-N-pyrrolidinylphosphine                          
Dimethylphenylphosphine                                                   
                Diphenylbenzylphosphine                                   
Diethylphenylphosphine                                                    
                Methyldiphenylphosphinite                                 
Methyldiphenylphosphine                                                   
                Ethyldiphenylphosphinite                                  
Ethyldiphenylphosphine                                                    
                Phenyldiphenylphosphinite                                 
Hexyldiphenylphosphine                                                    
                Dimethylphenylphosphonite                                 
Triphenylphosphine                                                        
                Diethylphenylphosphonite                                  
Tri-p-tolylphosphine                                                      
                Methyldiphenylthiophosphinite                             
Tri-m-tolylphosphine                                                      
                Ethyldiphenylthiophosphinite                              
                Phenyldiphenylthiophosphinite                             
______________________________________                                    
 
    
     Other suitable ligands include: 
     Trimethylphosphine 
     Triisopropylphosphine 
     Tri-sec-butylphosphine 
     Tri-2-methylbutylphosphine 
     Tripentylphosphine 
     Triisopentylphosphine 
     Triheptylphosphine 
     Dimethylethylphosphine 
     Methyldiethylphosphine 
     Diethylisopropylphosphine 
     Ethyl-t-butylisopropylphosphine 
     Dipropylbutylphosphine 
     Tricyclopropylphosphine 
     Tris(methylcyclopropyl)phosphine 
     Tricyclohexylphosphine 
     Dimethyl-p-methoxyphenylphosphine 
     Dimethyl-p-butylphenylphosphine 
     Dimethyl-3,4-dimethylphenylphosphine 
     Dimethyl-2,5-dimethylphenylphosphine 
     Diethyl-p-methoxyphenylphosphine 
     Diethyl-p-ethoxyphenylphosphine 
     Diethyl-p-chlorophenylphosphine 
     Diethyl-p-bromophenylphosphine 
     Diethyl-o-tolylphosphine 
     Diethyl-m-tolylphosphine 
     Diethyl-p-ethylphenylphosphine 
     Diethyl-2-methyl-5-isopropylphenylphosphine 
     Diethyl-2,4,5-trimethylphenylphosphine 
     Diethyl-1-naphthylphosphine 
     Dipropylphenylphosphine 
     Diisopropylphenylphosphine 
     Diisopropyl-p-methoxyphenylphosphine 
     Diisopropyl-o-methoxyphenylphosphine 
     Tri(m-methoxyphenyl)phosphine 
     Tri(α-naphthyl)phosphine 
     Tris(4-biphenylyl)phosphine 
     Diphenyl-p-chlorophenylphosphine 
     Diphenyl-p-bromophenylphosphine 
     Diphenyl-p-tolylphosphine 
     Diphenyl-p-methoxyphenylphosphine 
     Di-p-tolyl-p-methoxyphenylphosphine 
     Di-p-tolyl-p-chlorophenylphosphine 
     Di(p-tolyl)phenylphosphine 
     Phenyldi(p-bromophenyl)phosphine 
     Phenyldi(p-chlorophenyl)phosphine 
     Phenyldi(4-methyl-1-naphthyl)phosphine 
     Phenyl-p-bromophenyl-p-methoxyphenylphosphine 
     Phenyl-p-tolyl-p-methoxyphenylphosphine 
     Diphenyl-2-naphthylphosphine 
     Phenyldi(1-naphthyl)phosphine 
     Phenyldi(m-tolyl)phosphine 
     Phenyldi(3,5-dimethylphenyl)phosphine 
     Di-p-tolylbenzylphosphine 
     Isopropyl diphenyl phosphinite 
     Isobutyl diphenyl phosphinite 
     Hexyl diphenyl phosphinite 
     Ethylphenyl p-tolyl phosphinite 
     Ethyl di(p-tolyl)phosphinite 
     Ethyl di(p-chlorophenyl)phosphinite 
     Diisopropyl benzene phosphonite 
     Diisobutyl benzene phosphonite 
     Dihexyl benzene phosphonite 
     Diisopropyl-p-tolylphosphine 
     Diisopropyl-p-ethylphenylphosphine 
     Diisopropyl-3,5-dimethylphenylphosphine 
     Dibutylphenylphosphine 
     Dibutyl-p-methoxyphenylphosphine 
     Dibutyl-p-tolylphosphine 
     Dibutyl-p-ethylphenylphosphine 
     Dibutyl-2,5-dimethylphenylphosphine 
     Diisobutylphenylphosphine 
     Diisobutyl-p-tolylphosphine 
     Diisobutyl-2,5-dimethylphenylphosphine 
     Dipentylphenylphosphine 
     Dipentyl-p-methoxyphenylphosphine 
     Dipentyl-p-tolylphosphine 
     Dipentyl-p-ethylphenylphosphine 
     Dipentyl-2,5-dimethylphenylphosphine 
     Dihexyl-p-chlorophenylphosphine 
     Di(3-methylbutyl)phenylphosphine 
     Methyldi-p-tolylphosphine 
     Methylphenyl-p-tolylphosphine 
     Ethylphenyl-p-bromophenylphosphine 
     Ethylphenyl-p-methoxyphenylphosphine 
     Propylphenyl-p-methoxyphenylphosphine 
     Butylphenyl-p-methoxyphenylphosphine 
     Ethylphenyl-p-tolylphosphine 
     Ethylphenyl-2,4,5-trimethylphenylphosphine 
     Isopentylphenyl-p-tolylphosphine 
     Isohexylphenyl-p-tolylphosphine 
     Heptylphenyl-p-tolylphosphine 
     Tri(m-chlorophenyl)phosphine 
     Tri(p-chlorophenyl)phosphine 
     Diheptyl benzene phosphonite 
     Diethyl p-toluene phosphonite 
     Diethyl 2,4,5-trimethylbenzene phosphonite 
     Of the remaining ligands attached to the palladium atom, at least one should be chlorine or bromine. The other ligand can be, in addition to chlorine or bromine, hydrogen, lower alkyl, aralkyl, acyl of 2 to 4 carbon atoms or aryl of up to 12 carbon atoms. 
     Examples of suitable palladium compounds include: ##STR13## 
     Suitable methods of making palladium complexes for use in the present invention are given by G. Calvin and G. E. Coates, J. Chem. Soc. 1960, 2008, H. Munakata and M. L. H. Green, Chem. Comm. 1970 881, J. M. Jenkins and B. L. Shaw, J. Chem. Soc. (A) 1966, 770, G. Booth and J. Chatt, J. Chem. Soc. (A) 1966, 634, J. M. Jenkins and J. G. Verkode, Inorg. Syn. XI, 108 (1968), K. Kudo, M. Hidai, T. Murayama and Y. Uchida, Chem. Comm. 1970, 1701, G. Booth, Adv. Inorg. Chem. Radiochem., 6, 1 (1964), and in my copending application Ser. No. 189,834, filed Oct. 18, 1971, now U.S. Pat. No. 3,776,929. 
     The promoter employed with the above palladium compounds are the chlorides of certain metals, namely TiCl 4 , TiCl 3 , NiCl 2 , CrCl 3 , MnCl 2 , FeCl 3 , FeCl 2 , PdCl 2 , CuCl, CoCl 2 , ZnCl 2  and TlCl, or halogen compounds of tin. 
     The halogen compounds of tin can be 
     
         R.sup.11.sub.p SnX.sub.4-p, SnXZ, or MSnZ.sub.3 
    
     wherein R 11  is an aromatic radical of up to 12 carbon atoms consisting of one aryl radical or haloaryl radical, 
     X is chlorine or bromine as defined hereinabove, 
     Z is fluorine, chlorine or bromine, 
     M is a monovalent cation which can be an alkali metal cation or ammonium, 
     p is 0 to 3 inclusive. 
     Of the halotin compounds, stannous chloride is particularly preferred since it is readily available. 
     Other preferred tin halide promoters include 
     
         ______________________________________                                    
SnF.sub.2       SnBr.sub.4    SnBr.sub.2                                  
NH.sub.4 SnCl.sub.3                                                       
                SnCl.sub.4                                                
(C.sub.6 H.sub.5).sub.3 SnCl                                              
                C.sub.6 H.sub.5 SnCl.sub.3                                
KSnF.sub.3      KSnCl.sub.3                                               
SnClF           (C.sub.6 H.sub.5).sub.2 SnCl.sub.2                        
______________________________________                                    
 
    
     The promoters can be employed as the anhydrous compounds, or in the form of hydrates. In this specification and the the appended claims it is to be understood that the formulae for the promoter compounds includes such modifications as the hydrates. 
     In general, the promoters are employed in a ratio of 0.5 to 5 moles of promoter per mole of the complex palladium compounds and preferably in about equimolar proportion to the palladium complex compounds. 
     The promoters increase the conversion of the olefin to acids or esters when reacted with carbon monoxide and water or alcohols respectively in the presence of the aforesaid palladium compounds. The tin halogen compounds have the additional desirable effect of promoting the formation of the linear acid, or ester when the olefin reactant is a terminal olefin. 
     Temperature 
     The alkoxycarbonylation and carboxylation of this invention can be effected by heating the olefin, alcohol, or water, organophosphorus palladium catalyst and metal halide promoter in an atmosphere of carbon monoxide at temperatures from 35°-200° C., generally at 50°-150° C., and preferably at 60°-120° C. 
     Pressure 
     While carbon monoxide pressures of 1-1000 atmospheres or more can be used in practising this invention, it is preferred to employ pressures in the range of 10-700 atmospheres. 
     Time 
     These reactions may be run for as long as 24 hours but 5-10 hour reaction periods generally suffice and are therefore preferred. 
     Reactors 
     The process of this invention can be readily carried out using well-known chemical engineering practice which includes continuous, semi-continuous and batch operation. 
     Reactors used in this invention are not critical as long as they are able to withstand the temperatures and pressures involved. Pressure vessels of high tensile steel are generally used and they may be either lined or unlined. Suitable reactor liners include Hastelloy® metals, stainless steel, silver, aluminum, copper, glass and glazed ceramics. 
     The reactions are carried out by charging the olefin, if liquid or solid, the alcohol or water, the palladium complex and the metal halide into a suitable pressure-resistant vessel. In cases using water as a reactant, it is sometimes useful to employ a solvent such as acetone, tetrahydrofuran, dioxane, or acetonitrile. For laboratory work, a shaker or rocker system is convenient for agitating the reactants and effecting intimate contact of the reactants. The charged reactor is closed, chilled in Dry Ice, evacuated to remove air, and placed in a shaker or rocker. Olefin, if gaseous, is then added and the system connected to a supply of carbon monoxide and sufficient carbon monoxide added to give the desired pressure at the chosen reaction temperature. 
     The system is then heated under agitation until reaction is complete. As the reaction proceeds, more carbon monoxide is added periodically to maintain the pressure in the desired range. The course of the reaction is readily followed by observation of the drop in pressure. The product or products can be removed from the reaction mixture by conventional methods of isolation such as distillation. 
     EMBODIMENTS OF THE INVENTION 
     The following examples illustrate specific embodiments of the invention. The conversions reported are calculated by the formula: ##EQU1## 
     The amounts of total ester and linear ester were determined by gas-liquid partition chromatography, abbreviated to chromatography in the examples. 
    
    
     EXAMPLE 1 
     An 80-cc Hastelloy C lined shaker tube was charged with 20 g (0.238 mol) of 1-hexane, 20 g (0.43 mol) of ethanol, 0.7 g (1 mmol) of dichlorobis(triphenylphosphine)palladium, and 0.23 g (1 mmol) of stannous chloride dihydrate. The mixture was heated at 90° C. under 700 atmospheres of carbon monoxide for 10 hours. A chromatographic analysis of the crude reaction mixture showed that the resulting mixture of esters contained 86.0% of the linear product, ethyl heptanoate. The mixture was evaporated under vacuum, and the residue was distilled to give 20.12 g (0.127 mol, 53.5% yield based on charged 1-hexene) of a mixture of esters which was shown to be mainly ethyl heptanoate by a comparison of its proton nmr spectrum with that of an authentic sample. 
     EXAMPLE 2 
     An 80-cc Hastelloy C lined shaker tube was charged with 20 g (0.238 mol) of 1-hexene, 20 g (0.435 mol) of ethanol, 0.56 g (0.8 mmol) of dichlorobis(triphenylphosphine)palladium, and 0.18 g (0.8 mmol) of stannous chloride dihydrate. The mixture was heated at 90° C. under 700 atmospheres of carbon monoxide for 10 hours. A chromatographic analysis of the crude mixture showed an 86% conversion of 1-hexane to a mixture of esters containing 83% of the linear product, ethyl heptanoate. The mixture was evaporated to dryness under vacuum, and the residue was distilled to give 25 g (0.158 mol, 77% yield based on reacted 1-hexene) of esters. 
     EXAMPLES 3-25 
     These examples, designed to illustrate the varied complex palladium halides that can be used in catalyzing the alkoxycarbonylation of olefins, follow. The reactor charges had the compositions: 
     
         ______________________________________                                    
20 g (0.238 mol) of 1-hexene                                              
20 g (0.435 mol) of ethanol                                               
(0.8 mmol) L.sub.2 PdCl.sub.2 (where L is abbreviation for                
the organophosphorus ligand)                                              
0.18 g (0.8 mmol) SnCl.sub.2  . 2H.sub.2 O                                
______________________________________                                    
 
    
     The reaction mixtures were heated at 90° C. under 700 atmospheres of carbon monoxide for 10 hours. The crude reaction mixtures were analyzed as in Examples 1 and 2. The data are summarized in Table I. 
     
                       TABLE I                                                     
______________________________________                                    
                        % Conver-  % Ethyl                                
                        sion of    Heptanoate                             
Example                                                                   
         L              1-Hexene   in Esters                              
______________________________________                                    
 3     (C.sub.6 H.sub.5).sub.2 POC.sub.2 H.sub.5                          
                        36.0       80.6                                   
 4.sup.(1)                                                                
       (C.sub.6 H.sub.5).sub.2 PC.sub.2 H.sub.5                           
                        100.0      85.5                                   
 5.sup.(2)                                                                
       (p-CH.sub.3 OC.sub.6 H.sub.4).sub.3 P                              
                        100.0      82.5                                   
 6     C.sub.6 H.sub.5 P(C.sub.2 H.sub.5).sub.2                           
                        48.5       80.1                                   
 7     (m-FC.sub.6 .sub.4).sub.3 P                                        
                        15.0       70.0                                   
 8                                                                        
        ##STR14##       19.0       84.0                                   
 9     (p-FC.sub.6 H.sub.4).sub.3 P                                       
                        84.0       68.9                                   
10     (C.sub.6 H.sub.5).sub.2 PCH.sub.2 C.sub.6 H.sub.5                  
                        43.0       87.0                                   
11     (CH.sub.3).sub.2 PC.sub.6 H.sub.5                                  
                        26.0       88.6                                   
12     (C.sub.6 H.sub.5).sub.2 PSC.sub.6 H.sub.5                          
                        30.0       82.4                                   
13.sup.(3)                                                                
       (C.sub.6 H.sub.5).sub.2 PCH.sub.3                                  
                        57.0       83.1                                   
14     o-CH.sub.3 C.sub.6 H.sub.4 P(C.sub.6 H.sub.5).sub.2                
                        2.0        69.0                                   
15     (C.sub.2 H.sub.5).sub.3 P                                          
                        9.0        73.3                                   
16     o-CH.sub.3 C.sub.6 H.sub.4 P(C.sub.6 H.sub.5).sub.2.sup.(4)        
                        5.0        75.4                                   
17     (C.sub.2 H.sub.5).sub.3 P                                          
                        5.0        70.4                                   
18     (p-CH.sub.3 C.sub.6 H.sub.4).sub.3 P                               
                        39.0       86.4                                   
19     C.sub.6 H.sub.5 (C.sub.6 H.sub.5 CH.sub.2).sub.2 P                 
                        2.0        63.0                                   
20                                                                        
        ##STR15##       99.0       71.1                                   
21     (C.sub.2 H.sub.5 O).sub.3 P                                        
                        9.0        73.0                                   
22.sup.(6,7)                                                              
       C.sub.6 H.sub.5 PdCl[P(C.sub.6 H.sub.5).sub.3 ].sub.2.sup.(5)      
                        12.0       90.2                                   
23.sup.(6,8)                                                              
       C.sub.6 HD.sub.5 PdCl[P(C.sub.6 H.sub.5).sub.3 ].sub.2.sup.(5)     
                        92.0       84.3                                   
24.sup.(6,8)                                                              
       CH.sub.3 COPdCl[P(C.sub.6 H.sub.5).sub.3 ].sub.2                   
                        98.0       82.2                                   
25     CH.sub.2 CHP (C.sub.6 H.sub.5).sub.2                               
                        100.0      76.1                                   
______________________________________                                    
 .sup.(1) A parallel experiment run at 80° C. and 50 atmospheres; C
 pressure for 10 hours gave 7% conversion to esters of which 84% was ethyl
 heptanoate.                                                              
 .sup.(2) A parallel experiment run at 70° C. and 50 atmospheres; C
 pressure for 10 hours gave 29% conversion to esters of which 87.4% was   
 ethyl heptanoate.                                                        
 .sup. (3) A parallel experiment run at 80° C. and 100 atmospheres;
 CO pressure for 10 hours gave 19% conversion to esters of which 64.2% was
 ethyl heptanoate.                                                        
 .sup.(4) mmol + 1.27 mmol SnCl.sub.2 . 2H.sub.2 O.                       
 .sup.(5) Complete formula of Pd complex.                                 
 .sup.(6) 1 mmol Pd complex and 1 mmol SnCl.sub.2 . 2H.sub.2 O.           
 .sup.(7) Run at 80° C./100 atmospheres CO.                        
 .sup.(8) Run at 90° C./100 atmospheres CO.                        
 
    
     EXAMPLES 26-58 
     The set of Examples in Table II is designed to illustrate the operability of specific metal halide promoters with dichlorobis(triphenylphosphine)palladium. All reactions were run at 90° C. for 10 hours. 
     
                                           TABLE II                                
__________________________________________________________________________
                                       % Ethyl                            
     [(C.sub.6 H.sub.5).sub.3 P].sub.2 PdCl.sub.2                         
              Metal Halide                                                
                          Pressure                                        
                               % Conversion                               
                                       Heptanoate                         
Example                                                                   
     g (mmol) g/(mmol)    Atm. of Hexene                                  
                                       in Ester                           
__________________________________________________________________________
26   0.7 (1)  SnBr.sub.2                                                  
                      0.28 (1)                                            
                          700  49      78.0                               
27   0.7 (1)  NH.sub.4 SnCl.sub.3                                         
                      0.24 (1)                                            
                          700  61      86.5                               
28   0.7 (1)  SnBr.sub.2 + H.sub.2 O                                      
                      0.28 (1)                                            
                          700  75      81.6                               
                      3 drops                                             
29   0.7 (1)  NH.sub.4 SnCl.sub.3                                         
                      0.24 (1)                                            
                          100  97      83.5                               
                      3 drops                                             
30   0.7 (1)  Ph.sub.3 SnCl                                               
                      0.39 (1)                                            
                          100  81      87.1                               
31   0.7 (1)  Ph.sub.3 SnCl                                               
                      0.39 (1)                                            
                          100  99      86.5                               
32   0.7 (1)  KSnF.sub.3                                                  
                      0.22 (1)                                            
                          700  11      84.0                               
33   0.7 (1)  SnClF + 0.18 (1)                                            
                          700  99      88.0                               
              H.sub.2 O                                                   
                      0.1 g                                               
34   0.7 (1)  SnClF   0.18 (1)                                            
                          700  99      86.4                               
35   0.7 (1)  PhSnCl.sub.3                                                
                      0.31 (1)                                            
                          700  100     77.4                               
36   0.7 (1)  SnCl.sub.4 . 5H.sub.2 O                                     
                      0.35 (1)                                            
                          100  95      83.1                               
37   0.7 (1)  SnF.sub. 2                                                  
                      0.32 (2)                                            
                          100  31      82.1                               
38   0.7 (1)  SnF.sub.2                                                   
                      0.16 (1)                                            
                          700  75      88.5                               
39   0.7 (1)  KSnCl.sub.3 +                                               
                      0.27 (1)                                            
                          100  97      81.4                               
              H.sub.2 O                                                   
                      3 drops                                             
40   0.7 (1)  KSnCl.sub.3                                                 
                      0.27 (1)                                            
                          100  88      79.7                               
41   0.7 (1)  SnF.sub.2                                                   
                      0.16 (1)                                            
                          700  19      90.5                               
42   0.7 (1)  Ph.sub.2 SnCl.sub.2                                         
                      0.35 (1)                                            
                          700  99      81.7                               
43   0.7 (1)  Ph.sub.2 SnCl.sub.2                                         
                      0.35 (1)                                            
                          100  90      84.7                               
44   0.7 (1)  (none)  --  700  47      52.5                               
45   0.7 (1)  TlCl*   --(1)                                               
                          700  97      60.0                               
46   0.7 (1)  CuCl    --(1)                                               
                          700  74      42.2                               
47   0.7 (1)  PdCl.sub.2                                                  
                      --(1)                                               
                          700  83      44.0                               
48   0.7 (1)  ZnCl.sub.2                                                  
                      --(1)                                               
                          700  99      52.0                               
49   0.7 (1)  CoCl.sub.2                                                  
                      --(1)                                               
                          700  70      51.2                               
50   0.7 (1)  FeCl.sub.2                                                  
                      --(1)                                               
                          700  78      56.1                               
51   0.7 (1)  TlCl.sub.3 . 4H.sub.2 O                                     
                      --(1)                                               
                          700  89      48.0                               
52   0.7 (1)  TiCl.sub.3                                                  
                      --(1)                                               
                          700  82.2    50.4                               
53   0.7 (1)  NiCl.sub.2                                                  
                      --(1)                                               
                          700  58      43.0                               
54   0.7 (1)  NiCl.sub.2 . 6H.sub.2 O                                     
                      --(1)                                               
                          700  80      44.5                               
55   0.7 (1)  FeCl.sub.3                                                  
                      --(1)                                               
                          700  80      50.0                               
56   0.7 (1)  CrCl.sub.3                                                  
                      --(1)                                               
                          700  49      52.0                               
57   0.7 (1)  CrCl.sub.3 . 6H.sub.2 O                                     
                      --(1)                                               
                          700  59      50.0                               
58   0.7 (1)  MnCl.sub.2 . 4H.sub.2 O                                     
                      --(1)                                               
                          700  63      53.0                               
__________________________________________________________________________
 *Plus 0.2 g of H.sub.2 O                                                 
 
    
     EXAMPLES 59-75 
     These examples were carried out as Example 2 with the exceptions noted in Table III. The reactor was charged with 20 g of 1-hexene, 20 g of ethanol and catalyst as shown in the Table. 
     These examples form the basis for preferred operating ranges of temperature and pressure. 
     
                                           TABLE III                               
__________________________________________________________________________
                                        % Ethyl                           
     (Ph.sub.3 P).sub.2 PdCl.sub.2                                        
            SnCl.sub.2 . 2H.sub.2 O                                       
                   Temp.                                                  
                       Pressure                                           
                            Time                                          
                                % Conversion                              
                                        Heptanoate                        
Example                                                                   
     g (mmol)                                                             
            g (mmol)                                                      
                   (°C.)                                           
                       Atm. (Hrs.)                                        
                                1-Hexene                                  
                                        in Ester                          
__________________________________________________________________________
59   0.7 (1)                                                              
            0.23 (1)                                                      
                   90  50   10  95      87.0                              
60   0.7 (1)                                                              
            0.23 (1)                                                      
                   90  100  10  100     84.5                              
61   0.7 (1)                                                              
            0.23 (1)                                                      
                   90  25   10  72      85.3                              
62   0.7 (1)                                                              
            0.23 (1)                                                      
                   70  50   10  41      89.6                              
63   0.7 (1)                                                              
            0.23 (1)                                                      
                   80  50   10  84      87.5                              
64   0.7 (1)                                                              
            1.15 (5)                                                      
                   90  700  10  98      80.0                              
65   1.16 (1.6)                                                           
            0.36 (1.5)                                                    
                   70  50   10  54      88.9                              
66   0.7 (1)                                                              
            0.46 (2)                                                      
                   70  50   10  33      90.0                              
67   1.4 (2)                                                              
            0.46 (2)                                                      
                   50  100  10  12      87.8                              
68   0.7 (1)                                                              
            0.23 (1)                                                      
                   80  100   5  62      87.2                              
69   0.7 (1)                                                              
            0.23 (1)                                                      
                   80  100  10  92      88.0                              
70   0.7 (1)                                                              
            0.46 (2)                                                      
                   80  100  10  97      85.2                              
71   0.7 (1)                                                              
            0.23 (1)                                                      
                   90  10   10  27      77.8                              
72   0.7 (1)                                                              
            0.23 (1)                                                      
                   25  100  10  0       --                                
73   0.7 (1)                                                              
            0.23 (1)                                                      
                   80  100  10  99      91.4                              
     + 0.2 g H.sub.2 O                                                    
74   0.7 (1)                                                              
            0.23 (1)                                                      
                   150 100  10  100     65.4                              
75   0.7 (1)                                                              
            0.23 (1)                                                      
                   90  100   1  22      79.6                              
__________________________________________________________________________
 
    
     EXAMPLES 76-110 
     The generality of olefins and alcohols that can be employed in this invention is illustrated by the specific embodiments outlined in Table IV. 
     
                                           TABLE IV                                
__________________________________________________________________________
                                                          %               
                           [(C.sub.6 H.sub.5).sub.3 P].sub.2 PdCl.sub.2   
                                    SnCl.sub.2 . 2H.sub.2 O               
                                           Temp.                          
                                               Pres.                      
                                                  Time                    
                                                     % Con-               
                                                          Linear          
Example                                                                   
     Olefin   mols                                                        
                 Alcohol                                                  
                        mols                                              
                           g (mmol) g (mmol)                              
                                           °C.                     
                                               Atm.                       
                                                  Hrs.                    
                                                     version              
                                                          Ester           
__________________________________________________________________________
76   1-Pentene                                                            
              0.14                                                        
                 Neopentyl                                                
                        0.28                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 89.sup.(1)           
                                                          86.6            
77   2-CH.sub.3 -1-                                                       
              0.24                                                        
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 6    100             
     pentene                                                              
78   5-Hexene-                                                            
              0.11                                                        
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           80  100                        
                                                  10 9.6.sup.(1)          
                                                          74              
     nitrile                                                              
79   Ethyl 10-un-                                                         
              0.094                                                       
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 99.0 88.sup.(2)      
     decenoate                                                            
80   1,9-Decadiene                                                        
              0.12                                                        
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 100.0                
                                                          68.5.sup.(3)    
81   1,9-Decadiene                                                        
              0.12                                                        
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           70  100                        
                                                  10 75.0 73.6.sup.(4)    
82   1,9-Decadiene                                                        
              0.12                                                        
                 Ethyl  0.48                                              
                           1.4 (2)  0.46 (2)                              
                                           70  100                        
                                                  10 100.0                
                                                          79.sup.(5)      
83   1,9-Decadiene                                                        
              0.12                                                        
                 Ethyl  0.48                                              
                           1.4 (2)  0.46 (2)                              
                                           80  100                        
                                                  10 100.0                
                                                          75.sup.(6)      
84   1,9-Decadiene                                                        
              0.12                                                        
                 Ethyl  0.48                                              
                           1.4 (2)  0.46 (2)                              
                                           90  100                        
                                                  10 99   70.6.sup.(7)    
85   1,9-Decadiene                                                        
              0.12                                                        
                 Methyl 0.78                                              
                           0.7 (1)  0.23 (1)                              
                                           90  700                        
                                                  10 18   66.sup.(8)      
86   1,4-Hexadiene                                                        
              0.204                                                       
                 Ethyl  0.78                                              
                           0.7 (1)  0.23 (1)                              
                                           80  100                        
                                                  10 13   100             
87   1-Hexene 0.21                                                        
                 Isopropyl                                                
                        0.38                                              
                           0.61 (0.087)                                   
                                    0.20 (0.087)                          
                                           90  700                        
                                                  10 --   87.8            
88   1-Hexene 0.24                                                        
                 Methyl 0.48                                              
                           0.61 (0.087)                                   
                                    0.20 (0.087)                          
                                           90  700                        
                                                  10 --   85.7            
89   3-Methyl-1-                                                          
              0.25                                                        
                 Ethyl  0.54                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 23   92.6            
     hexene                                                               
90   1-Docosene                                                           
              0.12                                                        
                 Ethyl  0.48                                              
                           0.7 (1)  0.23 (1)                              
                                           90  200                        
                                                  10 --   .sup.(9)        
91   10-Hendecen-                                                         
              0.24                                                        
                  --    -- 0.7 (1)  0.23 (1)                              
                                           80  100                        
                                                  10 --   .sup.(10)       
     1-ol                                                                 
92   10-Hendecen-                                                         
              0.12                                                        
                 Ethyl  0.25                                              
                           0.7 (1)  0.23 (1)                              
                                           80  100                        
                                                  10 --   .sup.(11)       
     1-ol                                                                 
93   4-Vinylcyclo-                                                        
              0.463                                                       
                 Methyl 1.56                                              
                           2.1 (3)  0.68 (1)                              
                                           90  700                        
                                                  15 --   .sup.(12)       
     hexene                                                               
94   5-Hexen-2-one                                                        
              0.51                                                        
                 Ethyl  1.09                                              
                           1.4 (2)  0.46 (2)                              
                                           80  100                        
                                                  10 --   .sup.(13)       
95   1,6-Heptadiene                                                       
              0.52                                                        
                 Ethyl  0.86                                              
                           2.1 (3)  0.7 (1)                               
                                           70  100                        
                                                  10 --   .sup.(14)       
96   1-Allylcyclo-                                                        
              0.41                                                        
                 Ethyl  1.1                                               
                           1.4 (2)  0.46 (2)                              
                                           80  100                        
                                                  10 --   .sup.(15)       
     hexene                                                               
97   1-Pentene                                                            
              0.36                                                        
                 1,4-butane-                                              
                        0.133                                             
                           1.05 (1.5)                                     
                                    0.34 (1.5)                            
                                           90  100                        
                                                  10 --   .sup.(16)       
                 diol                                                     
98   1,8-Nonadiene                                                        
              0.4                                                         
                 Methyl 1.25                                              
                           1.4 (2)  0.46 (2)                              
                                           70  100                        
                                                  10 --   .sup.(17)       
99   1-Hexene 0.18                                                        
                 Benzyl 0.32                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 --   .sup.(18)       
100  1,11-Dodeca-                                                         
              0.3                                                         
                 Methyl 1.25                                              
                           1.0 (1.4)                                      
                                    0.35 (1.5)                            
                                           70  100                        
                                                  10 48   .sup.(19)       
     diene                                                                
101  5-Methyl-1-                                                          
              0.2                                                         
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 89   83.4            
     hexene                                                               
102  4-Methyl-1-                                                          
              0.2                                                         
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 92   84.5            
     hexene                                                               
103  3-Methyl-1-                                                          
              0.2                                                         
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 98   97.3            
     hexene                                                               
104  2-Methyl-1-                                                          
              0.2                                                         
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 6    100             
     hexene                                                               
105  Trans-1,4,9-                                                         
              0.51                                                        
                 Ethyl  1.74                                              
                           0.28 (4) 0.92 (4)                              
                                           90  100                        
                                                  10 79   .sup.(20)       
     decatriene                                                           
106  4-Cyanoyclo-                                                         
              0.187                                                       
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           100 200                        
                                                  10 45   .sup.(21)       
     hexene                                                               
107  Trans-2-hexene                                                       
              0.24                                                        
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           80  100                        
                                                  10 38   9.5.sup.(22)    
108  3-Pentene-                                                           
              0.2                                                         
                 Ethyl  0.43                                              
                           0.7 (1)  0.23 (1)                              
                                           100-                           
                                               100                        
                                                  15 --   .sup.(23)       
     nitrile                               150                            
109  1-Decyne 0.36                                                        
                 Ethyl  0.87                                              
                           1.4 (2)  0.46 (2)                              
                                           90  100                        
                                                  10 90   .sup.(24)       
110  1-Pentene                                                            
              0.36                                                        
                 .sup.(25)                                                
                        0.07                                              
                           0.7 (1)  0.23 (1)                              
                                           90  100                        
                                                  10 --   .sup.(26)       
__________________________________________________________________________
 .sup.(1) By distillation.                                                
 .sup.(2) Dilinear diester; also 12% other diester.                       
 .sup.(3) 88% diesters, 12% monoester; above is dilinear diester.         
 .sup.(4) 38.6% diester; 61.4% monoester; above is dilinear diester.      
 .sup.(5) 81% diester; 19% monoester; above is dilinear diester.          
 .sup.(6) 91% diester; 9% monoester; above is dilinear diester.           
 .sup.(7) 89.9% diester; 10.1% monoester; above is dilinear diester.      
 .sup.(8) % of dilinear diester in diester mixture.                       
 .sup.(9) 0.058 mmols (48% yield based on charged olefin) of recrystallize
 linear ester.                                                            
 ##STR16##                                                                
 .sup.(11) Obtained HO(CH.sub.2).sub.11COOC.sub.2 H.sub.5 in 80% yield    
 (0.096 mol) along with a small amount of the branched ester.             
 ##STR17##                                                                
 .sup.(13) Obtained CH.sub.3 CO(CH.sub.2).sub.4 COOC.sub.2 H.sub.5 in 14% 
 yield based on charged olefin along with a small amount of the branched  
 ester.                                                                   
 .sup.(14) Obtained CH.sub.2CH(CH.sub.2).sub.5 COOEt in 52% yield (0.27   
 mol) containing a small amount of branched ester and (CH.sub.2).sub.7    
 (COOCH.sub.3).sub.3 in 13% yield (0.067 mol) containing branched diesters
 Yields based on charged diolefin.                                        
 ##STR18##                                                                
 .sup.(16) Obtained CH.sub.3 (CH.sub.2).sub.4 COO(CH.sub.2).sub.4         
 OOC(CH.sub.2).sub.4 CH.sub.3 in 65% yield (0.086 mol) based on charged   
 1,4butanediol.                                                           
 .sup.(17) Obtained CH.sub.2CH(CH.sub.2).sub.7 COOCH.sub.3 in 28% yield   
 (0.11 mol) containing a small amount of branched isomer and              
 (CH.sub.2).sub.9 (COOCH.sub.3).sub.2 in 6% yield (0.024 mol) containing  
 branched diesters. Yields based on charged diolefin.                     
 .sup.(18) Obtained CH.sub.3 (CH.sub.2).sub.5 COOCH.sub.2 C.sub.6 H.sub.5 
 in 63% yield (0.114 mol) based on charged 1hexene.                       
 .sup.(19) Obtained CH.sub.2CH(CH.sub.2).sub.10 COOCH.sub.3 in 37% yield  
 (0.053 mol) based on reacted olefin. The diesters were not isolated.     
 .sup.(20) Obtained a 34% yield (0.137 mol) of monoesters based on reacted
 triolefin. The diesters and triesters were not isolated.                 
 .sup.(21) Obtained a 19% yield (0.16 mol) of nitrileesters based on      
 reacted 4cyanocyclohexene.                                               
 .sup.(22) Remainder of esters contained 58.5% CH.sub.3 (CH.sub.2).sub.3  
 CH(CH.sub.3)COOCH.sub.2 CH.sub.3 and 32% CH.sub.3 (CH.sub.2).sub.2       
 CH(CH.sub.2 CH.sub.3)COOCH.sub.2 CH.sub.3.                               
 .sup.(23) Obtained a 5% yield (0.0094 mol) of nitrileesters based on     
 charged olefin.                                                          
 ##STR19##                                                                
 olefin.                                                                  
 .sup.(25) 2Hydroxymethyl-2-methyl-1,3-propanediol.                       
 ##STR20##                                                                
 
    
     EXAMPLE 111 
     A mixture of 20 g of 1-hexene, 10 g of water, 10 g of acetone, 0.7 g of dichlorobis(triphenylphosphine)-palladium(II), and 0.23 g of SnCl 2 .2H 2  O was heated in a shaker tube at 90° C. and 100 atmospheres of carbon monoxide for 10 hours. Volatiles were removed from the reaction mixture under aspirator vacuum, and the residue was mixed with 100 ml of water and extracted twice with ether. The ether extracts were dried over MgSO 4  and evaporated to give the crude acid. The acid was analyzed by dissolving a small portion in methanol, adding excess tetramethylammonium hydroxide, and pyrolyzing (300° C.) in a gas chromatograph to give the methyl esters. The gas chromatographic analysis showed that the acid contained 90% of the linear acid, n-heptanoic acid, and 10% of branched isomers. The residue was distilled to give 9 g of product, bp 63°-65° C. at 0.2 mm. The infrared and nmr spectra of the product were identical to those of n-heptanoic acid. 
     When the procedures detailed in the foregoing examples are applied to the unsaturated compounds of col. 1 and the alcohols of col. 2 in the following table, one obtains the products shown in cols. 3 and 4. In any of the specific alkoxycarbonylations shown, it should be understood that replacement of the alcohol by water and following the procedure of Example 102 leads to the formation of the carboxylic acid corresponding to the ester shown. 
     
           CH.sub.2CH.sub.2 CH.sub.3 CHOHCH.sub.2 CH.sub.3 CH.sub.3 CH.sub.2
 COOCH(CH.sub.3) (C.sub.2 H.sub.5) -- CH.sub.3 CHCH.sub.2 CH.sub.3
 (CH.sub.2).sub.3 CH.sub.2 OH CH.sub.3 CH.sub.2 CH.sub.2
  COO(CH.sub.2).sub.4 CH.sub.3 (CH.sub.3).sub.2 CHCOO(CH.sub.2).sub.4
 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.3 (CH.sub.2).sub.5 OH
 (CH.sub.3).sub.2 CHCH.sub.2 COO(CH.sub.2).sub.5
  CH.sub.3 (CH.sub.3).sub.3 CCOO(CH.sub.2).sub.5 CH.sub.3 CH.sub.3
 (CH.sub.2).sub.5 CHCH.sub.2 (CH.sub.3).sub.3 CCH.sub.2 CH.sub.2 OH
 CH.sub.3 (CH.sub.2).sub.7 COOCH.sub.2 CH.sub.2 C(CH.sub.3).sub.3
  ##STR21##
  ##STR22##
  (CH.sub.3).sub.2 CH(CH.sub.2).sub.3
  OH
 ##STR23##
  CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2 COO(CH.sub.2).sub.3
  CH(CH.sub.3).sub.2 CH.sub.3 (CH.sub.2).sub.7 CHCH.sub.2 CH.sub.3
 (CH.sub.2).sub.7 OH CH.sub.3 (CH.sub.2).sub.9 COO(CH.sub.2).sub.7
 CH.sub.3
  ##STR24##
  CH.sub.3 CHCHCH.sub.3 (CH.sub.3).sub.3 C(CH.sub.2).sub.3
  OH
 ##STR25##
  -- CH.sub.3 CH.sub.2 CHCHCH.sub.3 CH.sub.3 (CH.sub.2).sub.2
  OH
 ##STR26##
  ##STR27##
  CH.sub.3 O(CH.sub.2).sub.3 CHCH.sub.2 NCC.sub.6 H.sub.4 CH.sub.2 OH
 CH.sub.3 O(CH.sub.2).sub.5 COOCH.sub.2 C.sub.6 H.sub.4
  CN
 ##STR28##
  ##STR29##
  CH.sub.3 (CH.sub.2).sub.2 CHOH(CH.sub.2).sub.2
  CH.sub.3
 ##STR30##
  ##STR31##
  CH.sub.2CHCH.sub.2 C.sub.6 H.sub.5 CH.sub.3 (CH.sub.2).sub.15 OH
 C.sub.6 H.sub.5 (CH.sub.2).sub.3 COO(CH.sub.2).sub.15
  CH.sub.3
 ##STR32##
  CH.sub.3 COOCH.sub.2 CHCH.sub.2 (CH.sub.3).sub.2 CHCH.sub.2 OH CH.sub.3
 COO(CH.sub.2).sub.3 COOCH.sub.2
  CH(CH.sub.3).sub.2
 ##STR33##
  C.sub.2 H.sub.5 OCOCH.sub.2 CHCHCH.sub.3 C.sub.4 H.sub.9
  OH
 ##STR34##
  ##STR35##
  CH.sub.3 COCH.sub.2 CHCH.sub.2 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2
 CH.sub.2 OH CH.sub.3 CO(CH.sub.2).sub.3 COOCH.sub.2 C(CH.sub.3).sub. 2
 CH.sub.2
  CH.sub.3
 ##STR36##
  NH.sub.2 CO(CH.sub.2).sub.8 CHCH.sub.2 (CH.sub.3).sub.3
  C(CH.sub.2).sub.2 OH H.sub.2 NCO(CH.sub.2).sub.10 COO(CH.sub.2).sub.2
 C(CH.sub.3).sub.3
  ##STR37##
  CH.sub.3 CCH CH.sub.3 (CH.sub.2).sub.7 (CHCl).sub.2 (CH.sub.2).sub.8 OH
 CH.sub.3 CHCHCOO(CH).sub.8 (CHCl).sub.2(CH.sub.2).sub.7 CH.sub.3
  ##STR38##
  C.sub.6 H.sub.5 COCH.sub.2 CHCH.sub.2 C.sub.10 H.sub.21 OH C.sub.6
 H.sub.5 CO(CH.sub.2).sub.3 COOC.sub.10
  H.sub.21
 ##STR39##
  ClC.sub.6 H.sub.4 CH.sub.2 CHCH.sub.2 (CH.sub.3).sub.2 CHOH ClC.sub.6
 H.sub.4 (CH.sub.2).sub.3
  COOCH(CH.sub.3).sub.2
 ##STR40##
  CH.sub.3 CH.sub.2 CCCH.sub.2 CH.sub.3 C.sub.6 H.sub.5 (CH.sub.2).sub.3
 OH
  ##STR41##
  -- C.sub.6 H.sub.5 CCH C.sub.4 H.sub.9
  OH
 ##STR42##
  ##STR43##
  ##STR44##
  CH(CH.sub.3).sub.2 (CH.sub.2).sub.3
  OH
 ##STR45##
  ##STR46##
  ##STR47##
  C.sub.3 H.sub.7
  OH
 ##STR48##
  ##STR49##
  ##STR50##
  C.sub.2 H.sub.5
  OH
 ##STR51##
  --
  ##STR52##
  CH.sub.3
  OH
 ##STR53##
  --
  ##STR54##
  ##STR55##
  ##STR56##
  ##STR57##
  ##STR58##
  ##STR59##
  ##STR60##
  ##STR61##
  ##STR62##
  C.sub.6 H.sub.13
  OH
 ##STR63##
  --
  ##STR64##
  C.sub.2 H.sub.5
  OH
 ##STR65##
  ##STR66##
  ##STR67##
  CH.sub.3
  OH
 ##STR68##
  ##STR69##
  ##STR70##
  CH.sub.3 CHOH(CH.sub.2).sub.4
  CH.sub.3
 ##STR71##
  --
  ##STR72##
  ##STR73##
  ##STR74##
  ##STR75##
  CH.sub.3 OC.sub.6 H.sub.4 CHCH.sub.2 C.sub.2 H.sub.5 CHOHC.sub.2
 H.sub.5 CH.sub.3 OC.sub.6 H.sub.4 CH.sub.2 CH.sub.2 COOCH(C.sub.2
 H.sub.5).sub.2
  ##STR76##
  ##STR77##
  ##STR78##
  ##STR79##
  ##STR80##
  (CH.sub.3).sub.2 NCO(CH.sub.2).sub.8 CHCH.sub.2 C.sub.2 H.sub.5 OH
 (CH.sub.3).sub.2 NCO(CH.sub.2).sub.10 COOC.sub.2
  H.sub.5
 ##STR81##
  ##STR82##
  C.sub.3 H.sub.7
  OH
 ##STR83##
  ##STR84##
  C.sub.6 H.sub.5 (CH.sub.2).sub.2 CHCH C.sub.5 H.sub.11
  OH
 ##STR85##
  ##STR86##
  CH.sub.3 (CH.sub.2).sub.12 CHCHCH.sub.3 (CH.sub.2).sub.3 CHOHCH.sub.3
 CH.sub.3 (CH.sub.2).sub.14 COOCH(CH.sub.3) (CH.sub.2).sub.3 CH.sub.3
  ##STR87##
  C.sub.6 H.sub.5 CH.sub.2 CHCHCH.sub.2 C.sub.6 H.sub.5 [CH.sub.3
 (CH.sub.2).sub.2 ].sub.2
  CHOH
 ##STR88##
  --
  ##STR89##
  HO(CH.sub.2).sub.2 O(CH.sub.2).sub.2
  OH
 ##STR90##
  ##STR91##
  ##STR92##
  ##STR93##
  C.sub.3 H.sub.7
  OH
 ##STR94##
  ##STR95##
  ##STR96##
  C.sub.2 H.sub.5
  OH
 ##STR97##
  ##STR98##
  ##STR99##
  CH.sub.3
  OH
 ##STR100##
  ##STR101##
  ##STR102##
  CH.sub.3
  OH
 ##STR103##
  ##STR104##
  ##STR105##
  CH.sub.3
  OH
 ##STR106##
  ##STR107##
  CH.sub.2CH(CH.sub.2).sub.2 CHCH.sub.2 C.sub.2 H.sub.5 OH C.sub.2
 H.sub.5 OCO(CH.sub.2).sub.6 COOC.sub.2
  H.sub.5
 ##STR108##
  ##STR109##
  CH.sub.3 C.sub.6 H.sub.4 CHCH.sub.2 (CH.sub.3).sub.2 CHOH CH.sub.3
 C.sub.6 H.sub.4 (CH.sub.2).sub.2
  COOCH(CH.sub.3).sub.2
 ##STR110##
  CH.sub.3 (CH.sub.2).sub.3 CHCH.sub.2 C(CH.sub.2 OH).sub.4 C[CH.sub.2
 OOC(CH.sub.2).sub.5 CH.sub.3
  ].sub.4
 ##STR111##
  ##STR112##
  ##STR113##
  ##STR114##
  CH.sub.3 CH.sub.2
  OH
 ##STR115##
  ##STR116##
 
    
     Esters are a well-known class of useful organic compounds. Many esters are useful as solvents, and as plasticizers for polymers. Some esters are useful in perfumes, essences, and flavoring agents. Diesters are additionally useful for making polymers, such as polyesters and polyamides. As noted above polyesters can be made directly by the process of the present invention from unsaturated alcohols. 
     Carboxylic acids which can be made by the process of this invention are also well known to have a variety of uses. Higher molecular weight acids can be used in detergent compositions. Many low molecular weight acids, and particularly salts thereof, are useful as preservatives, as buffering agents, and as solvents. Acids are also extremely important intermediates for the manufacture of ketones, amides, esters, nitriles and many other organic compounds. 
     The foregoing detailed description has been given for clarity of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described for obvious modifications will be apparent to those skilled in the art.