Abstract: A process for the production of 4-hydroxybutyraldehyde is described. The process comprises reacting allyl alcohol with a mixture of carbon monoxide and hydrogen in the presence of a solvent and a catalyst system comprising a rhodium complex and a substituted or unsubstituted 4,5-bis(di-n-alkylphosphino)xanthene. The process gives high yield of 4-hydroxybutyraldehyde compared to 3-hydroxy-2-methylpropionaldehyde.

Abstract: A process for the production of 1,4-butanediol is described. The process comprises hydroformylating allyl alcohol in the presence of a solvent and a catalyst system comprising a rhodium complex, a ruthenium complex and a diphosphine ligand and hydrogenating the resulting 4-hydroxybutyraldehyde using the same catalyst system. The process gives high yield of 1,4-butanediol compared to 2-methyl-1,3-propanediol.

Abstract: A process for the production of 1,4-butanediol is described. The process comprises hydroformylating allyl alcohol in the presence of a solvent and a catalyst system comprising a rhodium complex, a ruthenium complex and a diphosphine ligand and hydrogenating the resulting 4-hydroxybutyraldehyde using the same catalyst system. The process gives high yield of 1,4-butanediol compared to 2-methyl-1,3-propanediol.

Abstract: Allyl alcohol is hydroformated to 1,4-butanediol using a rhodium and trialkyl phosphine catalyst having at least 2 methyl groups, the reaction first being carried out at milder conditions and subsequently at more, severe conditions.

Abstract: A tertiary amine is used to catalize the stereospecific ring-opening of chiral glycidol with o-methoxyphenol to afford high yields of enantiomerically enriched guaifenesin. The optical purity of the product may be even further enhanced by recrystallization.

Abstract: A process for enriching or improving the optical purity of an asymmetric epoxidation reaction mixture is provided wherein the chiral epoxy alcohol enantiomer present in minor amounts is effectively separated from the predominant chiral epoxy alcohol enantiomer. The minor enantiomer is converted to an epoxy ester by stereoselective transesterification using a carboxylic acid derivative such as an enol ester and a lipase enzyme. The desired major chiral epoxy alcohol enantiomer is then recovered or reacted in situ to form a chiral epoxy alcohol derivative.

Abstract: Organic sulfonate derivatives of optically active epoxy alcohols such as (R)- or (S)- glycidol are conveniently prepared from aqueous solutions of the epoxy alcohols.

Abstract: A process for preparing trisubstituted ureas is disclosed. A nitroarene is reacted with carbon monoxide and a secondary amine in the presence of a Group VIII transition metal catalyst and optionally one or more promoters selected from primary amines, halide ion-containing compounds, and chelating phosphorus and nitrogen compounds.

Abstract: Prochiral ethylenically unsaturated substrates are converted to chiral epoxides by reaction with optically active hydroperoxides in the presence of transition metal catalysts. For example, chiral glycidol is obtained by asymmetric epoxidation of allyl alcohol using optically active ethyl benzene hydroperoxide and a titaniuym alkoxide/tartrate catalyst. The chiral epoxide products are versatile synthetic intermediates.

Abstract: Olefins are oxidized to epoxide compounds by contacting the olefins with organic hydroperoxides in the presence of rhenium catalysts comprised of perrhenate anions and organopnicogen-containing cations. High yields of epoxides are attained, particularly when the olefin substrate bears an aromatic substituent.

Abstract: Olefins are oxidized to epoxide compounds by contacting the olefins with organic hydroperoxides in the presence of oxorhenium porphyrin complex catalysts. High yields of epoxides are attained, particularly when the olefin substrate bears an aromatic substituent.

Abstract: Water-insoluble crystallizable epoxy alcohols such as phenyl glycidol are recovered from epoxidation reaction mixtures by washing the mixture with water, concentrating the mixture by distillation under vacuum to remove unreacted hydroperoxide and alcohol co-product, and crystallizing the epoxy alcohol from solution. Minimal decomposition of the epoxy alcohol is observed.

Abstract: Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefinic compounds with an organic hydroperoxide, by reaction of molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water.

Abstract: Asymmetric epoxidation of allylic alcohols using carboxylic acid treated phenethyl hydroperoxide oxidate and titanium tartrate catalyst gave optically active glycidols following an enantioselection rule opposite to that observed from the Sharpless epoxidation (U.S. Pat. No. 4,471,130). Overall yield and enantiomeric excess of the glycidol made are dependent on the amount of carboxylic acid present in the oxidate feed. This novel finding provides a direct epoxidation route to (R)-glycidol using the less expensive natural L-(+)-dialkyl tartrate ligand.

Abstract: Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefinic compounds with an organic hydroperoxide, by reaction of molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water.

Abstract: A novel method for producing branched carboxylic acids or esters from alpha-unsaturated olefins is disclosed. Such olefins are reacted with a novel, sterically hindered, ortho substituted phenylphosphine palladium halide catalysts in the presence of water or primary or secondary alcohols to produce high branched end product yields. Such catalysts have phosphine ligand cone angles of between about 170.degree. and 180.degree.. Tris(o-methoxyphenyl)phosphine palladium halide and o-trifluoromethylphenyldiphenylphosphine palladium halide catalysts are preferred.

Abstract: A novel method of converting alkanoic acids, such as isobutyric acid, to alpha-beta unsaturated acids, such as methacrylic acid, is disclosed which exhibits a higher degree of selectivity than those vapor phase oxydehydration methods heretofore known to the art. The preferred method comprises contacting a Dawson structure phosphomolybdic acid catalyst with isobutyric acid under specified reaction conditions to achieve a high selectivity for methacrylic acid.

Abstract: Production of novel molybdenum dioxo dialkyleneglycolate compositions, especially adapted for use as catalysts in the epoxidation of olefinic compounds with an organic hydroperoxide, by reaction of molybdenum trioxide with particular dialkylene glycol compounds at specified elevated temperatures while removing water.

Abstract: A novel synthesis of methacrylic acid and methacrolein from isobutylene oxide is provided. This method includes contacting isobutylene oxide with a catalyst, preferably a heteropolyacid catalyst, in the presence of oxygen. Using this method, isobutylene oxide conversion is nearly 100% complete. Depending upon the reaction temperature selected, yields of up to about 60% methacrolein and up to about 12% methacrylic acid may be obtained. A simple, inexpensive high yield process is thus provided for producing reaction mixtures containing methacrylic acid and methacrolein.

Abstract: A novel synthesis of methacrylic acid and methacrolein from isobutylene oxide is provided. This method includes contacting isobutylene oxide with a catalyst, preferably a heteropolyacid catalyst, in the presence of oxygen. Using this method, isobutylene oxide conversion is nearly 100% complete. Depending upon the reaction temperature selected, yields of up to about 60% methacrolein and up to about 12% methacrylic acid may be obtained. A simple, inexpensive high yield process is thus provided for producing reaction mixtures containing methacrylic acid and methacrolein.