Showing papers on "Carboxylic acid published in 1968"

Chemistry of Sodium Borohydride and Diborane. IV. Reduction of Carboxylic Acids to Alcohols with Sodium Borohydride through Mixed Carbonic-Carboxylic Acid Anhydrides

Abstract: Mixed carbonic-carboxylic acid anhydrides, prepared in situ from carboxylic acids and ethyl chloroformate, were reduced with sodium borohydride in aqueous tetrahydrofuran to the corresponding alcohols in fair yields. Under the reaction condition examined, it was possible to reduce carboxyl group selectively to hydroxymethyl group in carboxylic acids having functional groups such as nitro-, cyano-, amido-, ester-group, and conjugated double bond. The general procedure for this reaction is given.

Ashless lubricating oil detergents

Abstract: ASHLESS LUBRICATING OIL DETERGENTS ARE PROVIDED BY THE REACTION PRODUCT OF: (A) A CARBOXYLIC ACID OR ACID ANHYDRIDE CONTAINING ADDITION COPOLYMER HAVING AT LEAST TWO ACID OR ANHYDRIDE GROUPS, OPTIONALLY COMPOSED IN PART OF MONOMERIC CARBOXYLIC ACID OR ANHYDRIDE, (B) AN AMINE, AND (C) AN AMINOPHENL.

Electron spin resonance spectra of carboxylic acid radical anions at 77°K

Abstract: Sodium atoms have been deposited on a series of monocarboxylic acids, R—COOH, at 77° K in the rotating cryostat and the deposits examined by electron spin resonance (e.s.r.) spectroscopy. The spectra show that the primary paramagnetic species in each case is the corresponding radical O– anion, [graphic omitted]. The spectra are similar to those observed for the primary radicals formed by X-, β- or γ- irradiation of mono-or di-carboxylic acids at 77° K and thus confirm that these radicals are the radical anions, and not cations, of the corresponding acids. The carbon-13 hyperfine coupling constants have been determined for the radical anion, [graphic omitted], of fully deuterated acetic acid. The results show that the free valence centre has a pyramidal configuration, in contrast to the planar structure found in many alkyl radicals. The radical anions are able to abstract hydrogen from adjacent neutral molecules at 77° K to give secondary radicals. The extent of reaction depends on the strength of the CH bonds in the acid. Negligible reaction occurs with acetic acid which possesses only primary hydrogens, whereas the radical anion reacts completely with the tertiary hydrogen in isobutyric acid to give the radical (CH3)2CCOOH.

Studies on co-ordination compounds of silver(II). Part I. Magnetic and spectral properties of complexes with pyridine carboxylic acids

Abstract: The magnetic susceptibility of seven pyridine carboxylic acid complexes of silver(II) have been measured over the temperature range 300–80°K. All the complexes show Curie or Curie–Weiss behaviour but silver(II) nicotinate (θ= 52°) is believed to be antiferromagnetic. I.r. and electronic spectronic spectral data are also reported and correlated with the structures of the complexes. Silver(II) dipicolinate tetrahydrate (dipicolinic acid = pyridine-2,6-dicarboxylic acid) probably has a pseudo-tetrahedral configuration. The spectral and magnetic properties of related copper(II) and silver(II) complexes with pyridine monocarboxylic acids are compared.

Derivatives of orthoacids. IV. Acid-catalysed thermal eliminations and baseinduced eliminations of some 2-Ethoxy-1,3-dioxolans

Abstract: A series of phenyl substituted 2-ethoxy-1,3-dioxolans (orthoformates) has been prepared and their stereochemistry assigned. When heated in the presence of a carboxylic acid they underwent a stereospecific cis elimination to form the corresponding olefins, carbon dioxide, and ethanol. Provided that one 4 or 5 position in these dioxolans was unsubstituted, they reacted with butyllithium through elimination of the elements of ethyl formate and the formation of a carbonyl compound. The eliminated portion was always converted by the butyllithium into nonan-5-ol. A simple preparative method for cis-stilbene is described.

Process for preparing molybdenum acid salts

Abstract: This invention relates to the preparation of molybdenum acid salts by directly reacting the carboxylic acid with a molybdenum compound while removing the water that is formed. These molybdenum acid salts are useful as catalysts in such processes as in the epoxidation of olefins.

Infrared spectroscopic studies of polystyrene emulsion polymers: Effect of oxidation during polymerization

Abstract: Infrared spectroscopy was empolyed to study the nature of the structural changes which occurred through oxidation during the emulsion polymerization of styrene. Aliphatic carboxylic, amino, and phosphate emulsifiers and hydrogen peroxide and potassium persulfate initiators were empolyed for polymer preparation. In addition, a polystyrene dispersion prepared in the absence of any emulsifier or stabilizer was examined. Irrespective of the nature of the initiator–emulsifier combination employed, all of the polymer spectra revealed bands at 1705 and 1770 cm.−1. The band at 1705 cm.−1 was assigned in part to the carbonyl stretching mode of dimertic carboxylic acid, formed by oxidation, in the polystyrene chains. Absorption at 1770 cm.−1, which was very weak, was tentatively attributed to the carbonyl stretching mode of the monomeric form of this acid. The structure of the acid endgroup was not established, but the results obtained suggest that it was possibly a phenylacetic acid residue or a residue with a similar structure.

Structure‐mechanical property relationships in ethylene methacrylic acid copolymers and their salts

Abstract: A dynamic mechanical study has been made of an ethylenemethacrylic acid copolymer containing 4.1 mole per cent of methacrylic acid units and its sodium, lithium and calcium salts. On the basis of the results and related physical chemical studies it is proposed that the structures of the ionized copolymers consist of three distinct phases—a crystalline polyethylene phase, an amorphous polyethylene phase, and an ionic phase consisting of ionic domains. It is further proposed that the unionized acid copolymer consists of two phases—a crystalline polyethylene phase and an amorphous phase consisting of polyethylene crosslined with hydrogen bonded, carboxylic acid dimers.

Paint stripping composition and process

Abstract: WHERE R IS AN ALIPHATIC GROUP HAVING FROM 8 TO 18 CARBONS AND R'' IS AN ALKYL GROUP HAVING FROM 1 TO 8 CARBONS, OR ALKYLBENZENE SULFONIC ACID OR SALTS THEREOF, FROM 0.1 TO 10 PARTS OF AMMONIUM BIFLUORIDE DISSOLVED IN FROM ABOUT 3 UP TO 20 PARTS OF WATER, AND OPTIONALLY, EVAPORATION RETARDERS AND THICKENERS. RNHR''COOH PAINTS ARE REMOVED FROM SURFACES USING A PAINT STRIPPER COMPRISING FROM 50 TO 90 PARTS OF A CHLORINATED LIQUID HYDROCARBON SOLVENT, 2 TO 15 PARTS OF A LOWER ALIPHATIC ALCOHOL OR THEIR GLYCOL ETHERS, 0.1 TO 15 PARTS OF A LOWER CARBOXYLIC ACID, 2 TO 30 PARTS OF HYDROXYBENZENES SUCH AS PHENOLS OR THEIR DERIVATIVES, 2 TO 10 PARTS FATTY ACID SULFONATE OR A SALT OF A FATTY AMINE CARBOXYLIC ACID HAVING THE FORMULA

Acylating agents,their salts,and lubricants and fuels containing the same

Abstract: Oil-soluble carboxylic acid acylating agents are prepared by reacting a high molecular weight mono- or polycarboxylic acid with a sulfonating agent. The resulting acylating agents can be converted to acidic, neutral, or basic metal salts. Both the novel acylating agents and the salts are useful additives for lubricants and fuels and as intermediates for the preparation of other useful lubricant and fuel additives, particularly high molecular weight oil-soluble acylated nitrogen compositions and esters. The latter are prepared by reacting the acylating agents with, for example, alkylene polyamines or mono- or polyhydric alcohols.

Priming composition comprising a coupling agent and a polyfunctional azide for bonding polymers to glass,metal and metal oxide substrates

Abstract: IT HAS BEEN FOUND THAT POLYMERS CAN BE MADE TO ADHERE MORE FIRMLY TO GLASS, METAL AND METAL OXIDES BY FIRST CONJOINTLY TREATING THE SUBSTRATE WITH (1) A COUPLING AGENT SELECTED FROM THE GROUP CONSISTING OF ORGANOSILANES, ETHYLENICALLY UNSATURATED CARBOXYLIC ACID CHROMIUM CHLORIDE COMPLEXES, UNSATURATED CARBOXYLIC ACIDS AND ANHYDRIDES, AND UNSATURATED ORGANOPHOSPHORUS COMPOUNDS, AND (2) A POLYFUNCTIONAL AZIDE. A POLYMER MAY BE BONDED TO THE THUS TREATED GLASS, METAL OR METAL OXIDE IMMEDIATELY AFTER SUCH TREATMENT OR AT SOME LATER DATE.

Cationic electrodeposition system

Abstract: A cross-linkable coating composition derived from an unsaturated compound containing a carboxylic acid group, an epoxidized material and a compound which contains a pendant amine group is dispersed in water by means of an acid such as phosphoric acid. The composition may be a blend of an epoxidized material with a copolymer having free carboxylic acid and amine groups, or a partially reacted precondensate thereof, or a condensate of a drying oil carboxylic acid, an epoxidized material and an amino acid. An article immersed in the dispersion as cathode is coated by electrodeposition and thereafter the coating cross linked by heating. The dispersion is replenished by a concentrate of coating composition.

On the synthesis of 3,4-dihydroxyprolines. I. cis-Glycolation of 3,4-dehydroproline derivatives

Abstract: The interaction of OsO4 and protected derivatives of 3,4-dehydro-DL-proline gives high yields of 2,3-trans-3,4-cis-3,4-dihydroxy-DL-proline derivatives, with only traces of the 2,3-cis-3,4-cis diastereoisomers. Corresponding α-glycolation with KMnO4 gives mixtures of the 2,3-trans-3,4-cis and 2,3-cis-3,4-cis isomers in the ratio 1 : 1. Separation of the components of such mixtures is extremely difficult. The free amino acids in these two families of the 3,4-dihydroxy-DL-prolines have been characterized. Epimerization at C2 of 2,3-cis derivatives occurs readily. O-Tosylation of the 2,3-cis series occurs more readily than for other hydroxyprolines. Esters of N,O,O-tritosyl-2,3-trans-3,4-cis-3,4-dihydroxyproline are converted very rapidly by mild alkali into the equivalent esters of X-tosylpyrrole-2-carboxylic acid. For the corresponding N,O,O-tritosyl carboxylic acid, decarboxylation also takes place during aromatization, to yield N-tosylpyrrole.

Process for the manufacture of unsaturated esters of carboxylic acids

Abstract: PRODUCTION OF UNSATURATED ESTERS OF ARBOXYLIC ACIDS BY REACTION OF AN OLEFINIC COMPOUND AND AN ALIPHATIC OR AROMATIC CARBOXYLIC ACID, WHICH EACH CONTAIN FROM 2 TO 20 CARBON ATOMS, WITH MOLECULAR OXYGEN, OR AIR, IN THE GAS PHASE, AT ELEVATED TEMPERATURE AND IN CONTACT WITH A CARRIER CATALYST, THE REACTION BEING CARRIED OUT IN CONTACT WITH A CARRIER CATALYST CONTAINING PALLADIUM ACETATE, ALKALI METAL ACETATE AND ONE OR MORE VANADIUM COMPOUNDS AS ITS ACTIVE CONSTITUENTS, THE DRY, POWDERY CARRIER CATALYST BEING IRRADIATED WITH ULTRAVIOLET AND/OR VISIBLE LIGHT, PRIOR TO USING IT.

Conversion of ethylenically unsaturated compounds using heteropoly-molybdic and heteropolytungstic acids as catalysts

Abstract: PROCESS FOR THE CONVERSION OF ETHYLENICALLY UNSATURATED COMPOUNDS TO ESTER AND ALCOHOLS WHEREIN THE ETHYLENCIALLY UNSATURATED COMPOUND AND A CARBOXYLIC ACID ARE REACTED IN TEH PRSENCE OF A FREE HETEROPOLYACID OF MOLYBDENUM OR TUNGSTEN. ESTERS ARE THE MAIN PRODUCT WHEN ANHYDROUS CONDITION ARE USED WHILE A MIXTURE OF ESTERS AND ALCOHOLS MAY BE PRODUCED WHEN WATER IS PRESENT.

Process for the preparation of Tetrahydrofuran and/or Homologues thereof

Abstract: 1,170,222. Tetrahydrofurans. SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ N.V. 10 June, 1968, No. 27444/68. Heading C2C. A tetrahydrofuran of the general formula in which each R represents a hydrogen atom or a C 1 -C 5 alkyl group is prepared by (a) contacting a conjugated diolefin of general formula in an anhydrous, or substantially anhydrous, liquid medium, with a metal salt of an aliphatic carboxylic acid having 2-6 carbon atoms, together with a compound of divalent palladium, or with a divalent palladium salt of such a carboxylic acid alone; (b) separating from the reaction mixture one or more olefinically unsaturated 1,4-glycol acylates having the general formula in which at least one of the radicals R 1 and R 2 represents an acyl group having 2-6 carbon atoms, the other being the same or a hydrogen atom; (c) hydrogenating the ester obtained in (b) to give a saturated 1,4-glycol mono- and/or diacylate; and (d) converting the 1,4-glycol mono- and/or diacylate into the desired tetrahydrofuran, either directly by the action of an acidic catalyst in the presence of water or indirectly by first hydrolysing the mono- and/or diacylate and subsequently allowing the cyclization into the desired tetrahydrofuran to take place by methods known per se.

A nuclear magnetic resonance study of some platinum hydrides

Abstract: The complexes trans-PtHL(PEt3)2, where L is an o-, m-, or p- substituted benzoato-ligand or a substituted acetato-ligand, have been prepared and their 1H n.m.r. spectra have been determined. Linear correlations are found between the chemical shift of the hydrido-ligand, the platinum–hydrogen coupling constant, the platinum–hydrogen stretching frequency, and the pKa of the parent carboxylic acid. These are discussed.