Showing papers on "Benzaldehyde published in 1969"
TL;DR: In this paper, the Tishchenko reaction of benzaldehyde with various aluminium alkoxides has been studied kinetically in benzene at 20° and the initial rate of reaction is decreased in the order: aluminium benzyl oxide > di-t-butoxyaluminium benzyloxide [a reaction mixture of PhCHOAl(O-T-Bu) 3 ] > aluminium isopropoxide > aluminium t-butoxide.
45 citations
TL;DR: A number of aldehyde arylhydrazones have been oxidised with lead tetra-acetate in methanol as mentioned in this paper, and they have been trapped with acrylonitrile, to form 1,3-diphenylpyrazole-5-carbonitrile together with a small quantity of the isomeric 4-caroline.
Abstract: A number of aldehyde arylhydrazones have been oxidised with lead tetra-acetate. In many cases diacylhydrazines, RCO·NH·NAcAr, can be isolated in good yield. With benzaldehyde phenylhydrazone, provided that precautions are taken to avoid autoxidation, α-phenylazobenzyl acetate can be isolated in up to 27% yield. Evidence has been obtained that this compound is not the main precursor of the diacyl derivative PhCO·NH·NAcPh or of further oxidation products, but that these arise via the nitrilimine PhC[graphic omitted]Ph; this 1,3-dipolar compound has been trapped with acrylonitrile, to form 1,3-diphenylpyrazole-5-carbonitrile together with a small quantity of the isomeric 4-carbonitrile. Analogous nitrilimines have been similarly trapped during the oxidation of the p-nitrophenylhydrazones of benzaldehyde, propionaldehyde, benzoin, and benzil. Oxidations with lead tetrabenzoate, and with lead tetra-acetate in methanol, have also been carried out; they lead to azo-dibenzoates and azo-dimethyl ethers, respectively, and benzaldehyde phenylhydrazone also forms an azo-benzoate.The acylhydrazones PhCH:N·NH·COR (R = Ph or NPh2) undergo oxidative cyclisation with lead tetra-acetate to give high yields of the corresponding oxadiazoles. Likewise, the phenyl- and p-nitrophenyl-hydrazones of o-nitrobenzaldehyde are cyclised to 3-arylazoanthranil 1-oxides. Nitrilimines, by implication, mediate in each case.
36 citations
TL;DR: Darzens type condensation of chloromethyl p-tolyl sulfone with benzaldehyde, acetaldehyde, and cyclohexanone, with potassium tert-butoxide as base, gave good yields of the corresponding α,β-epoxy sulfones as mentioned in this paper.
Abstract: Darzens type condensation of chloromethyl p-tolyl sulfone with benzaldehyde, acetaldehyde, acetone, benzophenone, and cyclohexanone, with potassium tert-butoxide as base, gave good to excellent yields of the corresponding α,β-epoxy sulfones (1). The condensation of α-chloroethyl p-tolyl sulfone and bromomethyl p-tolyl sulfone with benzaldehyde also gave excellent yields. With the aldehydes only the trans-epoxides were formed, which is shown by nuclear magnetic resonance spectroscopy. The mechanism and stereochemistry are discussed.
34 citations
Patent•
25 Mar 1969TL;DR: In this article, the authors describe compounds of the formula in which R represents an optionally substituted hydrocarbon radical, X represents oxygen or sulphur and Ph a phenylene radical, are useful for the treatment of cardiac insuffiency and as antihypertensive agents.
Abstract: Compounds of the formula IN WHICH R represents an optionally substituted hydrocarbon radical, X represents oxygen or sulphur and Ph a phenylene radical, are useful for the treatment of cardiac insuffiency and as antihypertensive agents.
33 citations
TL;DR: The solubility of toluene and benzaldehyde was measured in NaBr and (n-Pr)4NBr aqueous solutions at 25 °C, and benzoic acid and nitrobenzene were measured in the same systems at 10°C.
Abstract: The solubility of toluene and benzaldehyde was measured in NaBr and (n-Pr)4NBr aqueous solutions at 25 °C, and the solubility of benzoic acid and nitrobenzene was measured in the same systems at 10...
30 citations
25 citations
TL;DR: In this article, the co-oxidation of cis-and trans-2-butene and benzaldehyde at 110 °C has been carried out in benzene and the mechanism of epoxide formation has been investigated by examining the ratio of cis to trans-epoxides.
Abstract: The co-oxidation of cis- and trans-2-butene and benzaldehyde at 110 °C has been carried out in benzene and the mechanism of epoxide formation has been investigated by examining the ratio of cis- to trans-epoxides. The results indicate that epoxides were formed by two mechanisms, one involving the benzoylperoxy radical to give about half cis and half trans epoxides and the other by stereospecific epoxidation with perbenzoic acid. Experimental results show that the stereospecific character of epoxidation increases with the reaction time and the concentration of benzaldehyde, but does not depend on the concentration of 2-butene.
22 citations
TL;DR: In this paper, the ketonization of acetic acid has been studied on a chromia catalyst at 460 °C and at a contact time of 0.7 sec at various partial pressures in presence of tertiary butyl alcohol and benzyl alcohol.
20 citations
19 citations
TL;DR: A rapid, simple spectrophotometric method which can be used to determine microgram quantities of pemoline and mandelic acid in biological fluids is described and should be capable of determining many other compoundsWhich can be converted to benzaldehyde.
16 citations
TL;DR: In this article, the authors studied the radical reactivity of basic hydrogen peroxide and Fenton's reagent for the oxidation of the 1-and 2-phenylethane-boronic esters.
TL;DR: Treatment of the ester of 2-(2-chloroacetamido)-2-alkenoic acid with ammonia led to the formation of 3-alkylidene-2,5-piperazinedione, and its physical constants are virtually identical with those recorded for the natural albonoursin.
Abstract: Treatment of the ester of 2-(2-chloroacetamido)-2-alkenoic acid with ammonia led to the formation of 3-alkylidene-2,5-piperazinedione. By using this method, total synthesis of albonoursin was accomplished. 2-(2-Chloroacetamido)-4-methyl-2-pentenoic acid, derived from the condensation of 4-methyl-2-oxopentanoic acid with chloroacetonitrile or the pyrolysis of 2,2-bis(2-chloroacetamido)-4-methylpentanoic acid, was converted to the ethyl ester, which was treated with ammonia to give 3-isobutylidene-2,5-piperazinedione. The piperazinedione was also synthesized by the esterification of 2-(2-aminoacetamido)-4-methylpentenoic acid, followed by a cyclization of the ester. Condensation of the piperazinedione with benzaldehyde yielded 3-benzylidene-6-isobutylidene-2,5-piperazinedione, and its physical constants are virtually identical with those recorded for the natural albonoursin.
TL;DR: A variety of Nα-amidobenzyl compounds attached to secondary amines have been newly prepared advantageously by reactions of N, N'-benzylidenebisamines with amides.
Abstract: A variety of N-α-amidobenzyl compounds attached to secondary amines have been newly prepared advantageously by reactions of N, N'-benzylidenebisamines with amides. Also the known procedures for preparation of N, N'-benzylidenebisamines from benzaldehyde was best improved in yield using a dehydrating agent, boron trioxide.
TL;DR: Using a selective catalyst consisting of molybdenum oxide doped with tungstic oxide on alumina, the kinetics of the vapour-phase oxidation of toluene by air has been studied as mentioned in this paper.
TL;DR: In this article, 1,2,3,4-tetrahydrole-pidine was shown to be easily autoxidized forming lepidine and hydrogen peroxide in the presence of HCl.
TL;DR: Triethylindium reacted with thiobenzophenone, benzophenone and benzonitrile, forming colored complexes at low temperature as mentioned in this paper, but with elevation of temperature, these complexes, except that of benzoneitrile (V), rearranged, giving hydrogen migration products (I) and (II) and ethyl group migration products(III and (IV) exclusively.
TL;DR: In this paper, the structural requirements for the hydrolysis of an acetal to be general-acid catalysed are discussed and a concerted A-SE2 mechanism is preferred to a slow proton transfer followed by a rapid breakdown of the resulting conjugate acid.
Abstract: The structural requirements for the hydrolysis of an acetal to be general-acid catalysed are discussed. It is concluded that the hydrolysis of mixed aryl alkyl acetals of benzaldehyde should show general-acid catalysis. This is confirmed by showing that the hydrolysis of benzaldehyde methyl phenyl acetal is general-acid catalysed in acetate, formate, chloroacetate, and phosphate buffers. The α-value of the Bronsted equation is calculated from the results of the first three of these buffers to be 0·60 at 20°. The solvent isotope effect of the acetic acid-catalysed reaction is k(HOAc)/k(DOAc)= 2·11 and of the hydronium ion-catalysed reaction k(H3O+)/k(D3O+)= 1·02 at 20°. The ρ-value for the acetic acid-catalysed hydrolyses of a series of benzaldehyde methyl aryl acetals is +0·98. A concerted A–SE2 mechanism is preferred to one involving a slow proton transfer followed by a rapid breakdown of the resulting conjugate acid.
TL;DR: The phenylhydrazones of benzophenone, acetophenone and benzaldehyde were converted by a molecular equivalent of an alkali amide in liquid ammonia to their mono-alkali derivatives as discussed by the authors.
Abstract: The phenylhydrazones of benzophenone, acetophenone, and benzaldehyde were converted by a molecular equivalent of an alkali amide in liquid ammonia to their mono-alkali derivatives, which underwent ...
TL;DR: In this paper, a column chromatography was used to isolate dibenzyl ether hydroperoxide (4) in a purity of 95 and 92.5% resp·.
TL;DR: The mass spectra of α-d-all-trans-hepta-2,4-dien-6-yn-1-ol (3) and α-D-benzyl alcohol (4) are remarkably similar to benzyl alcohol and benzaldehyde respectively as discussed by the authors.
Abstract: The mass spectra of all-trans-hepta-2,4-dien-6-yn-1-ol (3) and all-trans-hepta-2,4-dien-6-yn-1-al (6) are remarkably similar to benzyl alcohol and benzaldehyde respectively. Comparison of α-d-all-trans-hepta-2,4-dien-6-yn-1-ol (5) and α-d-benzyl alcohol shows that the deuterium in the C7H7+ tropylium ion is randomized in both compounds.
TL;DR: In this article, the effect of carboxylic acids and anhydrides on the Tishchenko reaction of benzaldehyde with aluminum benzyloxide have been studied kinetically by means of GLC.
Patent•
17 Dec 1969TL;DR: In this paper, a process for preparing orthochlorobenzaldehyde which comprises chlorinating the side chains of a mixture of ortho- and para-chlorotoluene containing from about 50 to about 85 percent by weight of the orthoisomer in the liquid phase with chlorine gas was described.
Abstract: This invention discloses a process for preparing orthochlorobenzaldehyde which comprises chlorinating the side chains of a mixture of ortho- and para-chlorotoluene containing from about 50 to about 85 percent by weight of the orthoisomer in the liquid phase with chlorine gas until the ratio of orthochlorobenzal chloride to parachlorobenzal chloride in the reaction mixture is at least about 10 to 1 by weight, hydrolyzing the resulting mixture to the corresponding benzaldehyde and benzoic acids and thereafter recovering the orthochlorobenzaldehyde therefrom.
TL;DR: In this article, the reaction of α-diazoacetophenone with carbonyl compounds such as benzaldehyde, acetophenone and p-phenylacetphenone, has been studied in the presence of bis(acetylacetonato) copper (II).
Abstract: The reaction of α-diazoacetophenone with carbonyl compounds such as benzaldehyde, acetophenone and p-phenylacetophenone, has been studied in the presence of bis(acetylacetonato) copper (II). The reaction gave the corresponding tetrahydrofurans and dioxolanes accompanied by some by-products derived from benzoylcarbene. The mechanism of the reaction has been discussed in terms of an intermediate with a structure of betaine type, produced by the reaction of a ketocarbene-metal chelate complex with carbonyl compounds.
Patent•
29 Jan 1969
TL;DR: In this paper, the authors describe a set of chemotherapeutic compositions useful for the prevention and control of COCCIDIOSIS in the aromatic ring.
Abstract: CHEMOTHERAPEUTIC COMPOSITIONS USEFUL FOR THE PREVENTION AND CONTROL OF COCCIDIOSIS COMPRISING ADDUCTS BETWEEN A BENZALDEHYDE OR A CINNAMALDEHYDE AND AN AMINOTRIAZOLE OR BETWEEN AN ALKYL ARYL KETONE AND AN AMINOTRIAZOLE, OPTIONALLY SUBSTITUTED IN THE AROMATIC RING, ARE DESCRIBED AS SPECIFIC AND NOVEL COMPOUNDS USEFUL FOR THE PREVENTION AND CONTROL OF COCCIDIOSIS.
TL;DR: Little interference was observed from compounds with structure similar to mandelic acid, although a small constant value for apparent mandelIC acid in normal horse urine was found.
Abstract: A method is described for the indirect determination of low concentrations of mandelic acid in urine by using gas-liquid chromatography. The method can also be used with ultraviolet spectrophotometry in place of gas chromatography when samples containing no interfering compounds are to be analysed. The mandelic acid is oxidised by potassium periodate, in dilute sulphuric acid solution, to benzaldehyde, which is separated by simultaneous steam-distillation from interfering compounds before being determined; 395-µg amounts in aqueous solution were determined with accuracies of ±0·62 per cent. (ultraviolet spectrophotometry) and ±3·1 per cent. (gas chromatography). Little interference was observed from compounds with structure similar to mandelic acid, although a small constant value for apparent mandelic acid in normal horse urine was found.