National Distillers and Chemical Corporation

Quantum Chemical Corporation

William D Baugh

Jawad H Murib

Ronnie M Hanes

David Horvitz

Orville D Frampton

A process is disclosed for forming alkyl 4-oxobutyrates and its acetals which comprises reacting under anhydrous conditions acrolein or its acetals with carbon monoxide and an alcohol of the formula R OH wherein R is lower alkyl in the presence of a catalytically effective amount of a catalyst comprising palladium metal which is either unsupported or supported on an inert carrier and a promoting effective amount of hydrogen halide. An intermediate in the process, i.e., .beta.-halopropionaldehyde or acetal thereof can also be used in forming alkyl 4-oxobutyrates and acetals thereof by reacting under anhydrous conditions said .beta.-halopropionaldehyde or its acetals with carbon monoxide and an alcohol of the formula ROH wherein R is lower alkyl in the presence of a catalytically effective amount of a catalyst comprising palladium metal which is either unsupported or supported on an inert carrier.

Process for the preparation of alkyl 4-oxobutyrate and its acetals

Methyl 4-oxobutyrate and its methanol addition products, methyl 4,4-dimethoxybutyrate and gamma-methoxy-gamma-butyrolactone, which are useful as intermediates in the preparation of such industrially important compounds as gamma-butyrolactone, 1,4-butanediol and glutamic acid, are produced from the reaction of acrolein, carbon monoxide and methanol in the presence of a catalyst system which consists of (a) a Group VIII metal component selected from palladium metal or a palladium-containing composition which generates palladium metal under reaction conditions, (b) a hydrogen halide and (c) an arylarsine catalyst copromoter.

Process for the preparation of methyl 4-oxobutyrate and its methanol

Allyl alcohol is reacted with carbon monoxide in the presence of a catalytically effective amount of a heterogeneous catalyst composition comprising zero valent palladium and a catalyst promoting amount of hydrogen halide to provide a mixture of products predominantly made up of carboxylic acids containing four and five carbon atoms, e.g., 3-butenoic acid, crotonic acid, butyric acid, isobutyric acid, glutaric acid and methyl succinic acid and possibly minor amounts of other oxygenated compounds such as allyl ether and allyl 3-butenoate.

Process for preparing carboxylic acids

A method is disclosed for the production of esters by reaction of an alkyl acyclic allylic ether such as 8-methoxy-1,6-octadiene with carbon monoxide in the presence of a halide of nickel, cobalt or iron as a catalyst and especially nickel iodide for the production of esters. Carbonylation of 8-methoxy-1,6-octadiene results in the production of methyl-3,8-nonadienoate; 2-(carbomethoxymethyl)-vinylcyclopentane; 2-(carbomethoxymethyl)-6-vinylcyclohexanone and 2-carbomethoxymethylbicyclo(3.3.0)-octan-3-one.

Cyclic esters

9-methoxy-7-nonenal may be isomerized in the presence of methanol and ruthenium chloride to provide 1,1,9,9-tetramethoxynonane. The rates of reaction are increased by pre-formation of 1,1,9-trimethoxy-7-nonene and removal of the water generated prior to conducting the isomerization reaction.

Conversion of allyl ethers to acetals

Carbonylation of allylic ethers to esters

Alkanoic acids containing largely the alpha-methyl isomers thereof, and/or the corresponding esters, are prepared by reacting an alpha-olefin, carbon monoxide and water and/or a monoalkanol in the presence of a catalytically effective amount of a catalyst composition comprising (i) a zero-valent Group VIII metal or metal alloy in which the Group VIII metal is the major component by weight thereof, (ii) an aryl ligand selected from the group consisting of arylarsine, arylstibine and arylbismuthine and (iii) a Lewis acid and/or hydrochloric acid.

Process for preparing alpha-methyl monobasic acid and esters thereof

An improvement in the reaction of olefin with aldehyde, and optionally, carboxylic acid, in the liquid phase in the presence of a catalytically effective amount of strong acid to provide a 1,3-difunctional compound or a mixture of 1,3-difunctional compounds is provided by carrying out the aforesaid reaction in the further presence of a co-catalyst selected from the group consisting of antimony oxide, bismuth oxide, antimony salt, bismuth salt and mixtures thereof.

Production of 1,3-difunctional compounds

Gamma-butyrolactones are manufactured from olefins by reacting an olefin with an aldehyde to produce a 1,3-difunctional compound, reacting the 1,3-difunctional compound with carbon monoxide, and thereafter recovering the lactone thus produced.

Growing community of inventors

Wilmington, OH, United States of America

William D Baugh