Abstract: This invention is intended to provide a method for producing pinacoline by means of pinacol rearrangement in supercritical water, which affords an extremely high reaction rate without the addition of high concentrations of acid, and this invention is directed to a method for increasing the reaction rate during organic synthesis by utilizing the supply of protons from water under noncatalytic conditions in supercritical water, a method of pinacol rearrangement comprising the production of pinacoline by pinacol rearrangement under noncatalytic conditions without the addition of an acid catalyst in supercritical water, and a method of synthesis comprising the production of cyclic compounds from pinacol under noncatalytic conditions without the addition of an acid catalyst around the critical point (375 to 380° C., 22.5 to 25 MPa) in supercritical water.

Abstract: A new family of crystalline manganese phosphate compositions has been prepared. These compositions have an extended network which network can be a one-, two-, or three-dimensional network. The composition has an empirical formula of:(A.sup.3+).sub.v (Mn.sup.b+)(M.sup.c+).sub.x P.sub.y O.sub.zwhere A is a structure directing agent such as an alkali metal, M is a metal such as Al, Fe.sup.3+ and "b" is the average manganese oxidation state and varies from greater than 2.0 to a maximum of 3.0. These compositions can be used as adsorbents and as catalysts in the oxidation of hydrocarbons.

Abstract: The use of polar organic solvent as the solvent in the direct fluorination, to make an .alpha.-fluoroketone, of an enol ester or enol trialkylsilyl ether of a compound containing a tautomerisable ketone group, the solvent being relatively inert to fluorine and one in which the enol ester or enol trialkylsilyl ether is relatively stable to hydrolysis. Preferably the solvent is anhydrous, e.g. anhydrous acetonitrile. Alternatively commercial formic acid containing 3% water may be used with a said enol ester.

Abstract: A method for the preparation of a fluorinated ketone of the formula: ##STR1## where R.sub.1 and R.sub.2 are independently fluorine, alkyl of from about 1 to about 8 carbon atoms, fluoroalkyl of from about 1 to about 8 carbon atoms, or ##STR2## where R.sub.3 and R.sub.4 are independently fluorine, alkyl of from about 1 to about 8 carbon atoms, or fluoroalkyl of from about 1 to about 8 carbon atoms and n is 0 or 1. The method includes heating an anhydride of the formula: ##STR3## with a catalyst including a cationic salt of a fluorocarboxylic acid or an alkali metal fluoride to obtain the fluorinated ketone.

Abstract: This invention relates to a process for the selective monochlorination or dichlorination of certain substituted alkenes using trichloroisocyanuric acid. The chlorinated alkenes can be easily hydrolyzed to provide .alpha.-monochloroketones or .alpha.,.alpha.-dichloroketones with a high degree of selectivity. The resulting .alpha.-monochloroketones or .alpha.,.alpha.-dichloroketones have utility as fungicides or function as useful intermediates for fungicides.

Abstract: A process for the production of methyl ethyl ketone by means of oxidative dehydrogenation of secondary butyl alcohol using an amorphous copper-silica catalyst prepared by a sol-gel route, in which an alkoxide or other suitable salt or complex of copper is reacted with an alkoxide of silicon in the absence of base, but in the presence of water or an alcohol; the resultant product is dried and calcined.

Abstract: Selective oxidation employs ferromagnetic chromium dioxide followed by magnetic separation.

Abstract: The present invention relates to sustaining high reaction rates at lower reaction temperatures than conventionally utilized with the particular catalyst. The improved reaction rates are obtained using various techniques and combinations thereof including simulated boiling, utilizing the reactant in the form of a thin film, employing microwaves, and the use of micromachines.

Abstract: A process is provided for the production of branched C.sub.4+ oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

Abstract: The present invention relates to a new method of condensing polyenic compounds wherein a compound having the formula III ##STR1## is condensed with a compound having the formula IV ##STR2## under the influence of a Lewis acid or a protic acid. R.sub.1 through R.sub.7 represent alkyl or alkenyl groups, A' is preferably chlorine, B is preferably a hydroxyl group, and n' is 0 to 10. The invention also relates to novel intermediates for use in the preparation of Vitamins A and E produced by means of the new method.

Abstract: Methods are provided for preparing all four diastereomers of 2-alkyl-3-hydroxyalkanals, 2-alkyl-3-silyloxyalkanals, and the like, with high enantiocontrol, using non-aldol chemistry. The synthetic methods also provide novel, stereospecific routes to polypropinates and chiral 2-substituted-1,3 diols.

Abstract: A process is described for the simultaneous production of 1,2- and 1,3-propanediol from glycerol. The process involves the reaction stages (a) dehydration of glycerol by feeding a gaseous glycerol-water mixture with 10 to 40 wt % glycerol at 250.degree. to 340.degree. C. over a solid catalyst with an H.sub.0 value (Hammett acidity function) of less than 2, preferably between -3 and -8.2, (b) hydration of the acrolein contained in the reaction mixture of stage (a), and (c) catalytic hydrogenation of the reaction mixture, containing 3-hydroxypropionaldehyde and hydroxyacetone, of stage (b). Two valuable products, namely 1,2- and 1,3-propanediol, can be obtained simultaneously and in high total yield from glycerol in a simple process.

Abstract: In a tube bundle reactor for carrying out catalytic organic reactions in the gas phase, comprising reaction tubes (A) arranged between tubesheets (B), the reaction tubes have an inside diameter ranging from 0.5 to 3 cm, the ratio of reaction tube length to inside diameter ranges from 2 to 10, and the reaction tubes (A) are surrounded by a fluid heat transport medium flowing in the crosswise direction; said tube bundle reactor is useful in particular in exothermic organic reactions.

Abstract: An improved process for preparing ketones by contacting a secondary aliphatic alcohol in the vapor phase with a trimetallic catalyst containing molybdenum, rhenium and a Group VIII noble metal.

Abstract: Oxidation of alcohols to ketones using bromine suffers from a side reaction of comparable speed in which a bromide substituted product is formed. Additionally, the use of bromine as reagent is relatively unpleasant and it creates a major waste disposal problem.The latter problem can be solved by generating bromine in situ by reaction between hydrogen peroxide and bromide ions or hydrogen bromide, but this inevitably increases the exposure of the alcohol to HBr/Br.sup.-. The selectivity of the process towards non-substituted oxidation depending upon the inherent deactivation or reactivity of the alcohol can be improved by irradiating the reactants with light of suitable frequency to generate bromine radicals in the mixture, and/or by controlling the rate of introduction of the hydrogen peroxide and controlling the extent to which mole ratio of HBr:alcohol is substoichiometric.

Abstract: A process to produce Methyl Amyl Ketone heterogeneously via the cross-aldol condensation reaction between a C.sub.3 (isopropanol or acetone feed) and a C.sub.4 (butanol or butyraldehyde feed). The catalyst, hydrogen reduced copper oxide on gamma alumina, produces both high reactivity and long catalyst lifetimes. The catalyst is successfully regenerated. Efficiencies to MAK range from 50 to 80 wt. % and efficiencies to useful products range from 75 to 95 wt. % depending on the composition of the feed and temperature. Temperatures range from 200.degree. to 262.degree. C.In general, this catalyst readily catalyzes the cross-aldol condensation reaction between aldehydes (or primary alcohols) and ketones (or secondary alcohols) to produce higher molecular weight ketones; likewise, this catalyst catalyzes the aldol condensation reaction between the same or different ketones to again produce higher molecular weight ketones.

Abstract: Higher carbonyl compounds are prepared from C.sub.1 to C.sub.8 cyclic or acyclic alcohols containing at least one active hydrogen atom bonded to the beta carbon atom or readily convertible thereto under the reaction conditions by reacting the alcohol in the presence as catalyst of ruthenium metal or an oxide thereof supported on a solid support.

Abstract: An improved process is provided for forming ketones from the corresponding olefins in the vapor phase in the presence of water vapor employing a heterogeneous catalyst comprising rhenium compounds and complexes, optionally containing at least one metal compound or complex selected from the group consisting of Group VIB metals and Group VIII noble metals, and mixtures thereof. It has been surprisingly found that these catalysts effect the formation of ketones in high selectivities with minimal selectivities to the undesirable carbon dioxide and carbon monoxide by-products.

Abstract: Alkali metal carbonates have been found to be effective catalysts for dehydrogenation of primary and secondary alcohols. The dehydrogenated products may be either predominantly ketones and aldehydes, depending on whether the feed alcohol is secondary or primary, or may be fuel gases. Lower reaction temperatures, in the neighborhood of 600.degree. C., tend to produce high yields of liquid products. Higher temperatures encourage production of fuel gases of high calorific value. When fuel gases are a desired product, a feedstock containing water, in addition to the alcohol, produces increased yields due to the simultaneous catalysis of the water-gas shift reaction.

Abstract: One or more aldehydes or ketones, or both, are produced by pyrolyzing an alcohol having at least two carbon atoms or an aldehyde having at least two carbon atoms, or both, over a Group VIII metal oxide catalyst, preferably a catalyst composed predominantly of iron oxide, notably ferric oxide. Preferably, the catalyst additionally contains a minor proportion of a Group IV-A metal oxide, most preferably germanium dioxide. The process provides a good yield of lower molecular weight aldehydes, such as formaldehyde, or higher molecular weight ketones, such as acetone, 2-pentanone and the like. Selective manufacture of products enriched either in aldehyde or in ketone can be achieved by a simple adjustment in the reaction conditions employed.

Abstract: An improved process is provided for forming ketones from the corresponding olefins by vapor phase oxidation of the olefin in the presence of water vapor, and optionally in the additional presence of molecular oxygen employing a heterogeneous catalyst comprising at least one member selected from the group consisting of Ce, Nd and La and compounds and complexes thereof, optionally containing at least one metal compound or complex selected from the group consisting of Group VIB metals and Group VIII noble metals, and mixtures thereof. It has been surprisingly found that these catalysts effect the formation of ketones in high selectivities with minimal selectivities to the undesirable carbon dioxide and carbon monoxide by-products.

Abstract: .alpha.,.delta.-Diethylenic carbonyl compounds of the formula ##STR1## are made by an oxy-Cope rearrangement of an acetylenic alcohol of the formula ##STR2## in the presence of a catalyst based on a metal of Group Ib of the periodic table or palladium. In the formulae (I) and (II), R.sub.1, R.sub.2, R.sub.3 and R.sub.4, which may be identical or different, each denote a hydrogen atom or a hydrocarbon radical R.sub.2 and R.sub.3 being capable together of forming an alkylene radical (--CH.sub.2 --).sub.n in which one or more carbon atoms may be substituted by one or more alkyl radicals containing 1 to 4 carbon atoms, n is 3 to 20 inclusively and R.sub.5 denotes a hydrogen atom.

Abstract: The invention relates to a process of producing a carbonyl compound by dehydrogenating a linear aliphatic alcohol of 1 to 6 carbon atoms in the gas phase in the presence of a solid catalyst comprising a ruthenium catalyst supported on a carrier such as zinc oxide or magnesium oxide.

Abstract: Described is a process for preparing solanone and norsolanadione wherein in preparing solanone, the compound having the structure: ##STR1## or a mixture of compounds defined according to the structure: ##STR2## is reacted with methyl lithium and the resulting intermediate is hydrolyzed and the resulting compound is dehydrated and wherein in preparing norsolanadione this compound or mixture of compounds is reacted with ethylene glycol or propylene glycol thereby forming a ketal and the resulting ketal is reacted with methyl lithium and the resulting intermediate is then hydrolyzed in the presence of acid in which one of the dashed lines represents a carbon-carbon single bond and the other of the dashed lines represents a carbon-carbon double bond.

Abstract: The instant invention relates to a membrane solvent extraction and reaction system. More particularly it pertains to an improvement in the membrane solvent extraction system wherein a solute is extracted through a polymeric membrane from one solvent liquid phase to an extracting solvent liquid without direct contact between the liquid phases which are separated by the membrane and in which the extracting solvent has no greater solubility and usually substantially less solubility for the solute than the feed solvent. The impovement comprises converting the solute permeating across the membrane to a different chemical compound, whereby a high concentration gradient for the solute across the membrane is maintained to improve the separation of the solute from the feed solvent liquid phase.

Abstract: Process for the preparation of .delta.-ethylenic carbonyl compounds of the formula: ##STR1## by the oxy-Cope rearrangement of a diethylenic alcohol of the formula: ##STR2## in which the transformation is carried out in the presence of a catalytic amount of a divalent palladium compound.In the depicted formulae R.sub.1, R.sub.4 and R.sub.6 each represent a hydrogen atom or a hydrocarbon radical, R.sub.2 represents a hydrogen atom and R.sub.3 and R.sub.5 each represent a hydrocarbon radical, or R.sub.3 and R.sub.4 together represent an alkylene radical (--CH.sub.2 --).sub.n (wherein n is an integer from 3 to 20 inclusive) in which one or more carbon atoms can optionally carry as substituent(s) one or more alkyl radicals containing 1 to 4 carbon atoms.The carbonyl products are useful as starting materials for the preparation of compounds intended for use in pharmacy, in agriculture or perfumery.

Abstract: A process for the production of secondary butyl alcohol by the direct hydration of n-butenes in the presence of an acidic cation exchange resin catalyst which comprises depressurizing the vaporous product stream from a reactor to a pressure ranging from 15 to 40 bar and cooling the depressurizing product stream to a temperature of 120.degree. C. or below to liquefy the product stream, separating an aqueous fraction from said stream leaving an alcohol-butene/butane organic mixture, vaporizing said organic mixture, depressurizing said organic mixture to a pressure ranging from 3 to 30 bar and including a pressure of from 3 to 8 bar and introducing said depressurized organic mixture into a separation column to separate secondary butyl alcohol from said mixture.

Abstract: New unsaturated fatty alcohols of the formula: ##STR1## in which n=2 or 4 are provided and are prepared by the novel process of reacting butadiene with water in the presence of a palladium salt and orthoboric acid, B(OH).sub.3, in a polar aprotic solvent.

Abstract: .alpha.,.beta.-and .beta.,.gamma.-unsaturated ketones of formula ##STR1## possessing a double bond in one of the positions indicated by the dashed lines and wherein R and R.sup.1 have the meaning given above and index n stands for integer 1 or 2, are obtained by a process which consists in treating with a strong base in an inert organic solvent a diallyl carbinol of formula ##STR2## wherein symbol R represents a primary, secondary or tertiary alkyl radical, or a substituted or unsubstituted phenyl radical, and symbol R.sup.1 represents a hydrogen atom or an alkyl radical.

Abstract: Hydroxy-ketones having formula ##STR1## possessing a double bond in one of the positions indicated by the dotted lines, are prepared starting from a diallyl carbinol of formula ##STR2## Hydroxy-ketones (Ia, b) are useful as intermediates for the preparation of rose oxide.

Abstract: Process for the co-production of ketones and mono-olefins from secondary alcohols and conjugated di-olefins in which dehydrogenation of the secondary alcohol and hydrogenation of the conjugated di-olefin are effected by contacting a mixture of the secondary alcohol and the conjugated di-olefin with a heterogeneous copper-containing catalytic system. The process is very useful for the co-production of methyl ethyl ketone and n-butenes from sec-butanol and butadiene at low temperatures (e.g. between 90.degree. C. and 130.degree. C.).

Abstract: A process for removing alkynes from hydrocarbon mixtures, particularly those containing butadiene by reacting the alkynes with hydroxyl group containing organic compounds in the presence of a silver exchanged ion-exchange resin and separating the products formed from the unreacted components of said mixture.

Abstract: Alkyl and aryl hydroxy compounds are converted to aldehydes, alcohols, and ketones in the presence of hydrogen using a catalyst comprised of the oxides of manganese, nickel and magnesium.

Abstract: Novel cyano substituted diphenoquinones of the formula, ##STR1## wherein X is a bromine atom or a cyano group, are useful as oxidizing agents and electron acceptors in charge-transfer complex formation owing to their high redox potentials. They may be easily prepared by oxidizing the corresponding cyano substituted biphenols with dinitrogen tetraoxide in an inert organic solvent.

Abstract: Primary and secondary unsaturated alcohols are converted to their corresponding aldehydes and/or carboxylic acids and ketones respectively with alkali metal (per) halate, preferably sodium periodate, in the presence of ruthenium catalyst. The process is particularly useful in the oxidation of chrysanthemyl alcohol. Any unconverted intermediate aldehyde formed may be converted to the acid by recycling or by a separate oxidation step.