Abstract: Propylene is oxidized directly to allyl acetate in the presence of acetic acid air or oxygen in the liquid phase under moderate reaction conditions employing a palladium-on-carbon catalyst which has been pre-treated be activating it with propylene at temperatures of greater than about 50.degree. C., preferably from 60.degree. to 150.degree. C., for a period of time sufficient to form a small but perceptible quantity of said activated catalyst, preferably for at least 10 minutes in the substantial absence of oxygen.

Abstract: Ruthenium-cobalt carbonyl catalysts which have been promoted with an organophosphite effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this phosphite-promoted ruthenium carbonyl cobalt catalyst to form the monomethyl ether of ethylene glycol. In a like manner acetaldehyde may be converted to the corresponding propylene glycol monoether. The process may advantageously be carried out with high yields and selectivities in the presence of a polar or non-polar organic solvent in combination with the catalyst system of this invention.The invention is also directed to certain of the organophosphite-promoted cobalt and ruthenium-cobalt carbonyl catalyst systems per se.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.The novel catalyst combination of R.sup.5 CCo.sub.3 (CO).sub.9 and Ru.sub.3 (CO).sub.12 is likewise claimed herein.

Abstract: The cobalt carbonyl catalyst R.sup.5 CCo.sub.3 (CO).sub.9, desirably with Ru.sub.3 (CO).sub.12, wherein R.sup.5 is hydrogen; alkyl, preferably C.sub.1-5 lower alkyl; cycloalkyl or substituted cycloalkyl; cycloalkenyl, such as cyclohexenyl or cyclooctenyl; C.sub.1-12 alkoxy, such as methoxy or propoxy; aryl or alkyl-, cycloalkyl-, alkoxy-, halo-, or cyano-substituted aryl; cyano; or a silyl carbyne moiety of the formula R.sub.3.sup.6 Si, wherein R.sup.6 is alkyl or aryl, effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas; i.e., CO and H.sub.2, in the presence of this catalyst system to form the corresponding ethylene glycol monomethyl ether.

Abstract: The ruthenium-cobalt carbonyl metal cluster catalyst Co.sub.2 Ru(CO).sub.11 effectively catalyzes the dealkoxyhydroxymethylation of aldehyde acetals to form glycol monoethers. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this ruthenium-cobalt cluster catalyst to form the monomethyl ether of ethylene glycol.

Abstract: Ruthenium carbonyl-cobalt carbonyl catalyst mixtures effectively catalyze the dealkoxyhydroxymethylation of aldehyde acetals, wherein said acetal may be prepared separately or in situ from an aldehyde and an alcohol. Methylal, for example, may be reacted with syngas, i.e., CO and H.sub.2, in the presence of this ruthenium carbonyl-cobalt carbonyl catalyst to form the monomethyl ether of ethylene glycol.The invention also is directed to the ruthenium carbonyl-promoted cobalt carbonyl catalysts per se, including novel precipitated forms of these ruthenium-cobalt carbonyl catalyst mixtures.

Abstract: C.sub.4 olefins comprising cis- and trans-butane-2 and butene-1 may be oxidized to their corresponding mono- and diacetates in the presence of acetic acid and an olefin-activated palladium catalyst under mild conditions. With this catalyst, and depending in part upon the solvent employed, as well as other operating conditions, the formation of linear allylic 1-acetates over the corresponding branched compounds can be favored in order to increase the yield of the corresponding linear 1,4-diacetates. The latter, in turn, may then be converted, for example, to butanediol by known hydrogenation methods.In a similar manner, isobutylene may be converted to a dialcohol.

Abstract: Propylene is oxidized directly to allyl acetate in the presence of acetic acid with air or oxygen in the liquid phase under moderate reaction conditions employing a palladium-on-carbon catalyst which has been pre-treated by activating it with propylene at temperatures of greater than about 50.degree. C., preferably from 60.degree. to 150.degree. C., for a period of time sufficient to form a small but perceptible quantity of said activated catalyst, preferably for at least 10 minutes in the substantial absence of oxygen.

Abstract: Olefins are hydroformylated with syngas in the presence of a novel organometallic complex catalyst to form the corresponding aldehydes at high reaction rates and improved selectively of linear aldehydes over branched aldehydes.The novel catalyst comprises an organometallic complex formed from a mixture of(1) a platinum (O) complex containing two bidentate diphosphine, diarsine or distibine ligands; and(2) A Group IVB metal halide.

Abstract: Olefins are hydroformylated with syngas in the presence of a novel organometallic complex catalyst to form the corresponding aldehydes at high reaction rates and improved selectively of linear aldehydes over branched aldehydes.The novel catalyst comprises an organometallic complex formed from a mixture of(1) a platinum (O) complex containing two bidentate diphosphine, diarsine or distibine ligands; and(2) A Group IVB metal halide.

Abstract: Phenol or a substituted phenol is oxidized to the corresponding benzoquinone or substituted benzoquinone in the presence of a copper halide or copper nitrate catalyst promoted with an oxide or hydroxide of a Group II metal.

Abstract: Phenol or a substituted phenol is oxidized to the corresponding benzoquinone or substituted benzoquinone in a nitroalkane solvent in the presence of a copper ion catalyst promoted with a base selected from alkali metal phenoxides, and secondary or tertiary lower alkyl amines.

Abstract: Equimolar amounts of phenol and formaldehyde may be prepared from oxygen and toluene. The catalytic oxidation of toluene, when carried out in the presence of acetic anhydride, forms phenyl acetate and methylene diacetate. Pyrolysis of these two intermediates yields phenol and formaldehyde.Significant improvements in this process are achieved when the first stage of the reaction is carried out in the presence of MoO.sub.3.In a further embodiment of this invention it has been found that Group VIII dithiosemibenzil compounds, particularly nickel dithiosemibenzil, serves as a superior promoter for the toluene oxidation reaction.In still a further embodiment of this invention it has been found that persulfate promoters such as potassium persulfate, persulfuric acid, or Caro's dry acid are particularly effective promoters for the toluene oxidation reaction.In a like manner, hydroquinone or resorcinol may be obtained from cresyl acetates.

Abstract: The rate of selective hydrogenation of carboxylic acid anhydrides to esters or lactones in the presence of a ruthenium organophosphorous catalyst which contains or liberates a hydrogen halide during the hydrogenation, is improved by providing in the reaction medium prior to or during the hydrogenation a basic amino compound to remove the hydrogen halide.

Abstract: Process for selective homogeneous catalytic hydrogenation of carboxylic acid anhydrides to ester or lactones at an improved rate and to obtain improved yields wherein the catalyst is a ruthenium trichlorostannate complex of the formula: ##STR1## wherein X is hydrogen, chlorine, bromine, iodine or lower alkyl; m is the integer 1 or 2; n is an integer of from 0 to 3 but when n is 2 or 3, X may be the same or different; M is P, As or Sb; R.sup.6, R.sup.7 and R.sup.8 independently are lower alkyl, cycloalkyl, aryl, benzyl or a bidentate legand; x is an integer of from 1 to 4 but when x is 2 or more, M may be the same or different; L is a neutral ligand, olefin, CO or (R.sup.9).sub.2 CO wherein R.sup.9 is lower alkyl; y is an integer of from 0 to 3 but when y is 2 or 3, L may be the same or different; and the sum of x and y is at least 2.

Abstract: A process for making a hydroquinone from phenol or substituted phenol wherein the phenol is oxidized in the presence of a copper catalyst to a p-benzoquinone compound and the p-benzoquinone compound is directly hydrogenated without additional catalyst to the corresponding hydroquinone.

Abstract: In the process of oxidizing phenol to p-benzoquinone with a bivalent copper ion catalyst, the improvement of promoting the catalyst with a base to obtain improved conversion and/or selectivity. The preferred bases used are alkali metal hydroxides and phenates and secondary and tertiary lower alkyl amines.

Abstract: Acetoxyacetophenone is the predominant product when phenyl acetate, acetic acid and acetic anhydride are reacted in the presence of palladium and a gas mixture containing an inert gas and more than 13 vol. % oxygen. Secondary products are hydroxyacetophenone and phenylene diacetates. The meta isomers predominate when a metal acetate is present in the reaction mixture. Mineral acids cause shift to ortho isomers.

Abstract: Phenol is oxidized to benzoquinone with a bivalent copper catalyst using a vicinal dialkoxy alkane or cycloalkane as promoter, whereby improved conversion and/or selectivity is obtained.

Abstract: A process for converting Udex raffinate to a high octane fuel component by mild, liquid phase oxidation to a product of moderate to low acidity, distilling off a neutral oxidate, esterifying the acidic residue to a neutral product and combining the neutral oxidate and the esterified portion.