Monsanto Company

Donald E Morris

William Vanderlinde

Arnold Hershman

Denis Forster

Albert S Chan

Harold Burnham Tinker

Frank P Jakse

The invention relates to a process of producing carbonate esters wherein an alkyl chloroformate is reacted with a phenolsulfonate in an alkaline medium and discloses the improvement of conducting the reaction in the presence of an organic solvent.

Process for the production of carbonate esters

The invention relates to a process of producing carbonate esters wherein an alkyl chloroformate is reacted with a phenolsulfonate in an alkaline medium and discloses the improvement whereby dialkylcarbonate formation is reduced by adding an acidifying agent to the reaction mixture after the reaction and before precipitation of the alkylsulfophenyl carbonate.

The dicarbonylation product of 1,4-disubstituted-2-butene is useful as intermediate in the production of adipic acid, hexamethylenediamine and 1,6-hexanediol. It is produced by carbonylating a solution of the disubstituted butene in a polar, aprotic non-basic solvent at 80.degree.-140.degree. C. in the presence of a catalyst comprised of a halide of the transition metal. The dicarbonylation product is converted to adipic acid by hydrogenation followed by hydrolysis.

Production of adipic acid from 1,4-disubstituted-2-butene

The dicarbonylation product of 1,4-dialkoxy substituted-2-butene is useful as intermediate in the production of adipic acid, hexamethylenediamine and 1,6-hexanediol. It is produced by carbonylating a solution of the dialkoxy substituted butene in a polar, aprotic non-basic solvent at 80.degree.-140.degree. C. in the presence of a catalyst comprising a halide of the transition metal.

Production of hex-3-enedioate esters from 1,4 dialkoxy butenes

Vinyl esters such as vinyl acetate are hydrocarboxylated with tertiary organo-phosphine stabilized palladium catalysts utilizing low water concentration; the ready hydrolysis of the .alpha.-acetoxypropionic acid affords a convenient route to lactic acid.

Hydrocarboxylation of vinyl alkanoates

The present process is suitable for preparing carboxylic acids wherein greater than 50 mole percent of the carboxylate groups are at the terminal position which comprises bringing together in a reaction zone an olefin or mixture of olefins wherein greater than 50 mole percent of the olefin has unsaturation at other than the terminal position, water and carbon monoxide in the presence of a cobalt catalyst and a pyridine-type promoter, preferably pyridine, in a mole ratio of promoter to catalyst between about 5:1 and 15:1, at pressures from about 70 kilograms per square centimeter to about 300 kilograms per square centimeter, at temperatures between about 180.degree. C. and about 220.degree. C.

Preparation of carboxylic acids from internal olefins

The invention relates to a process for the preparation of aldehydes by the hydroformylation of olefinically unsaturated compounds using a rhodium catalyst which catalyst is provided by (1) introducing rhodium into the reaction solution in the form of an ionic rhodium compound, the said ionic compound consisting of (a) a rhodium-containing cation having rhodium complexed with ligands other than halide, and (b) a non-coordinating anion; and (2) furnishing to the reaction solution at least two moles of a modifying ligand per mole of ionic rhodium compound where the modifying ligand is furnished either pre-coordinated in the said ionic rhodium compound or as a free compound, and where the modifying ligand is a tertiary organo phosphorous compound having from 3 to 90 carbon atoms, or a tertiary organo arsenic compound having from 3 to 90 carbon atoms, or a tertiary organo antimony compound having from 3 to 90 carbon atoms. The process is especially useful for the production of aldehydes from olefinically unsaturated compounds having from 2 to 30 carbon atoms, carbon monoxide, and hydrogen at a total pressure of from 4.6 to 142 kg/cm.sup.2 (50 to 2,000 psig), and at a temperature of from about 60.degree. C to about 180.degree. C. A preferred embodiment of the invention utilizes the modifying ligand at a molar concentration in excess of that required stoichiometrically by the ionic rhodium compound. Another preferred embodiment of this invention employs the modifying ligand as the solvent for the reaction system.

Hydroformylation process

The complexes [Ir(CO).sub.3 I], [HIr(CO).sub.3 I.sub.2 ], [HIr(CO).sub.2 I.sub.2 (H.sub.2 O)], [RIr(CO).sub.2 I.sub.2 ], [(RCO)Ir(CO).sub.2 I.sub.2 ] where R is an alkyl radical, are described. Processes for preparing the aforesaid complexes are described and in addition a new process for preparation of [Ir(CO).sub.3 I.sub.3 ] is described.

Iridium carbonyl complexes

The present invention relates to an improved process for the preparation of carboxylic acids, specifically by the reaction of ethylenically unsaturated compounds with carbon monoxide and water, in the presence of catalyst compositions essentially comprising iridium compounds and complexes, together with an iodide promoter, the improvement being the provision of at least 50 percent by weight of the iridium in the reaction solution in a highly catalytically active form as a species having infrared absorption bands at 2098 cm.sup.-.sup.1 (vs), 2155 cm.sup.-.sup.1 (w), 2180 cm.sup.-.sup.1 (vw, br). By monitoring the infrared absorption spectra of reacting solutions and following the magnitude of the 2098 cm.sup.-.sup.1 band the operating conditions are adjusted so that this band is present in 50 percent or more concentration relative to the infrared absorption spectral bands of the other iridium species in solution. Through this monitoring and control process significantly increased reactor productivity to carboxylic acids is achieved.

Production of carboxylic acids by controlling the active form of iridium

The invention concerns novel compositions of matter having the formula

Production of propionic acid and propionic anhydride with the repression of polyketone formation by carboxylating ethylene utilizing a catalyst system essentially composed of an iridium compound in the substantial absence of added halide components.

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Kirkwood, MO, United States of America

Donald E Morris