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Showing papers on "Benzaldehyde published in 1979"


Journal ArticleDOI
TL;DR: In this article, the addition of lithium trimethylsilylacetylide (LSL) to benzaldehyde afforded the corresponding alkynyl alcohol in 92% optical yield, which was achieved by using a chiral ligand (2S, 2′S)-2-hydroxymethyl-1-[(1-methylpyrrolidin-2-yl)methyl]pyrroleidin as a ligand.
Abstract: Enantioselective addition of acetylene to aldehyde was investigated by the use of (2S, 2′S)-2-hydroxymethyl-1-[(1-methylpyrrolidin-2-yl)methyl]pyrrolidine as a chiral ligand. The addition of lithium trimethylsilylacetylide to benzaldehyde afforded the corresponding alkynyl alcohol in 92% optical yield.

53 citations



Journal ArticleDOI
TL;DR: In this article, a new method for synthesizing phenylacetic esters starting from benzaldehyde was proposed, which was shown to be also applicable to the production of (2-thienyl)acetic Esters from corresponding aromatic aldehydes.
Abstract: Methyl (methylthio) methyl sulfoxide was found to react with benzaldehyde in the presence of benzyl tri-methylammonium hydroxide (Triton B), sodium hydroxide, or potassium hydroxide, affording 1-(methylsulfinyl)1-(methylthio)-2-phenylethylene. Treatment of this product with hydrogen chloride in an alcohol gave the corresponding alkyl phenylacetate in high yield. The whole reaction sequence provides a new method for synthesizing phenylacetic esters starting from benzaldehyde. In a similar manner, (alkoxy-, halogen-, or alkyl-substituted phenyl)acetic esters could be synthesized from the corresponding aromatic aldehydes. The present method was shown to be also applicable to the production of (2-thienyl)acetic esters.

38 citations


Journal ArticleDOI
TL;DR: In this paper, the vapor phase oxidation of benzyl alcohol catalyzed by Y-type zeolite has been investigated in a flow system with reaction temperature between 300 to 390 °C.

35 citations


Journal ArticleDOI
TL;DR: In this article, Malonitrile (I) reacted with thioglycolic acid to yield the thiazolin-4-one derivatives II or III depending on the molar ratio of the reactants.

32 citations


Journal ArticleDOI
D. Y. Tang1, A. Lipman1, G.-J. Meyer1, C-N. Wan1, Alfred P. Wolf1 
TL;DR: In this article, the synthesis of octanal and benzaldehyde, labeled with 11C in the carbonyl position, is reported. But the synthesis time was 50 ± 10 min for each compound.
Abstract: The synthesis of octanal and benzaldehyde, labeled with 11C in the carbonyl position, is reported. Octanal was prepared via an insertion reaction of 11CO into the boroncarbon bond of B-heptyl-9-BBN, followed by oxidative hydrolysis. Benzaldehyde was synthesized by the reaction of phenyl magnesium bromide with 11CO2, and subsequent reduction of the labeled benzoic acid to benzylalcohol which was then oxidized to the final product by CrO2Cl2. Both aldehydes were purified via GLPC, leading to radiochemical purities of > 99.5% in each case. The radiochemical yield for octanal and benzaldehyde was 30 ± 5% and 15 ± 5%, respectively. The overall synthesis time was 50 ± 10 min for each compound.

30 citations


Journal ArticleDOI
TL;DR: Normal and Simian virus 40-transformed cells were treated with benzaldehyde which has been found in figs as a potent carcinostatic element and the reaction of benzaldehyde with cellular proteins was limited mainly to exposed membrane proteins.

29 citations


Journal ArticleDOI
TL;DR: The dimethylacetal of benzaldehyde and some 3, 3, 4, 4 and 3,4, 5 oxygenated derivatives thereof are regiospecifically deprotonated at the 2-position by alkyl lithiums as discussed by the authors.

23 citations


Journal ArticleDOI
TL;DR: Condensation of a chiral dithioacetal mono-Soxide anion with benzaldehyde leads to α-methoxytolualdehyde with high chemical and optical yield as discussed by the authors.
Abstract: Condensation of a chiral dithioacetal mono-S-oxide anion with benzaldehyde leads to α-methoxytolualdehyde with high chemical and optical yield.

22 citations


Journal ArticleDOI
TL;DR: In contrast to previous studies of the Cannizzaro reaction using isotopically labeled reactants, the benzyl alcohol from reaction of 0.60 M benzaldehyde-cap alpha..-d and 0.25 M NaOH in 74% CH/sub 3/OH to 26% H/sub 2/O solution at 100/sup 0/C includes a substantial percentage of benzyl-..cap alpha.
Abstract: In contrast to previous studies of the Cannizzaro reaction using isotopically labeled reactants, the benzyl alcohol from reaction of 0.60 M benzaldehyde-..cap alpha..-d and 0.25 M NaOH in 74% CH/sub 3/OH to 26% H/sub 2/O solution at 100/sup 0/C includes a substantial percentage of benzyl-..cap alpha..-d/sub 1/ alcohol (21% after half consumption of hydroxide ion) rather than only benzyl-..cap alpha..-d/sub 2/ alcohol. Products from C/sub 6/H/sub 5/CHO in CH/sub 3/OH, CH/sub 3/OH solutions indicate that the side reactions responsible for hydrogen exchanges and adding to the yield of benzyl alcohol are (1) bimolecular hydride transfer to benzaldehyde from methoxide ion, (2) a nearly equal amount of crossed Cannizzaro reaction from the resulting formaldehyde, (3) a smaller amount of hydride transfer to benzaldehyde from the resulting sodium formate leading to sodium carbonate, and (4) a less frequent combination of two benzaldehydes plus methoxide ion leading to benzaldehyde dimethyl acetal. Decreasing the initial concentration of C/sub 6/H/sub 5/CHO to 5 x 10/sup -4/ M decreases the relative contributions of the three termolecular reactions and causes the bimolecular hydride transfer (1) to become the dominant reaction. Its k/sub CH/sub 3/O/sup -///k/sub CD/sub 3/O/sup -// isotope effect is 2.2 +- 0.2. 1 table.

19 citations



Journal ArticleDOI
TL;DR: In this paper, it is suggested that both reactions proceed via 1,2,3,4,4-tetrahydro-1, 2, 4, 4-benzotriazines (III), formed by addition of the amino group on the hydrazone double bond.

Journal ArticleDOI
TL;DR: Asymmetric alkylation of benzaldehyde and acetophenone by modified aluminium “ate” complexes is reported in this paper, where a wide range of new asymmetric reagents has been obtained from aluminium ‰ate· complexes and chiral compounds, it can be assumed that the method described could be useful to synthetise chiral alcohols with high optical yield.

Journal ArticleDOI
TL;DR: In this article, the P-C bond cleavage reaction of triphenylphosphine to give benzaldehyde and benzyl alcohol was studied and shown to be necessary for attaining high yield of benzaldehyde.
Abstract: Rh4(CO)12, Rh6(CO)16, and Rh12(CO)302− cluster complexes catalyze the P–C bond cleavage reaction of triphenylphosphine to give benzaldehyde and benzyl alcohol. Formaldehyde is necessary for attaining high yield of benzaldehyde.

Journal ArticleDOI
TL;DR: In this paper, the title compound (1) reacts with one equivalent of primary alcohols to give good yields of nitrogen and 1-alkoxycarbonyl-2-Nphenylcarbamoyl-4-phenyl-1,2,4-triazolidine-3,5-di ones.
Abstract: Two equivalents of the title compound (1) react with one equivalent of primary alcohols to give good yields of nitrogen and 1-alkoxycarbonyl-2-N-phenylcarbamoyl-4-phenyl-1,2,4-triazolidine-3,5-di ones (3). With secondary alcohols or benzyl alcohol the major products are the ketone or benzaldehyde, while 3 are minor products. The latter can, however, be made the major products if pyridine is used to catalyze the reaction. Compound 3a dissociates on heating or in pyridine solution into the 1-methoxycarbonyltriazolidinedione 4.If alcohols are absent 1 is converted by pyridine or other tertiary amines into nitrogen and the bicyclic compound 9; if diethyl azodicarboxylate is present in the reaction compound 13 can be trapped.Primary and secondary amines react very rapidly with 1 to give nitrogen and complex products. It is likely that these are 1,2-dicarbamoyl-4-phenyltriazolidine diones, analogous to 3, and that they are very prone to dissociate in solution.

Journal ArticleDOI
TL;DR: In this article, the authors studied the liquid phase oxidation of toluene catalyzed by the cobalt ion and the bromide ion in the presence of the copper(II) ion and found that the product distribution was greatly dependent on the NaBr concentration.
Abstract: The liquid-phase oxidation of toluene catalyzed by the cobalt(II) ion and the bromide ion in the presence of the copper(II) ion has been studied. Benzyl acetate was obtained in a good yield (50–70%) with mixed catalysts of metal acetates and sodium bromide in acetic acid at 100–150 °C, accompanied by small amounts of benzaldehyde and benzoic acid. The product distribution was greatly dependent on the NaBr concentration, which can be explained in terms of the high oxidizing ability of the copper(II) ion coordinated by the bromide ion. A synergistic effect was found on the yield of benzyl acetate upon the addition of copper(II) acetate with a high NaBr concentration, the maximum yield being obtained at the Co:Cu:NaBr ratio of 1:1:5–10. A change in the oxygen partial pressure also varied the product distribution, suggesting that the competitive reaction of the copper(II) ion with the oxygen molecule for the benzyl radical was simultaneously taking place at a diffusion-controlled rate. Benzyl acetate was cons...

Patent
31 Oct 1979
TL;DR: In this article, a process for the electrochemical preparation of benzaldehyde-dialkylacetals of the formula "STR1" is described. But the process is not described.
Abstract: 4-substituted benzaldehyde-dialkylacetals of the formula ##STR1## where R1 is one of the radicals CH2 ═CH--CH2 --, ##STR2## R2 is alkyl and R3 and R4 are hydrogen or alkyl, and a process for the electrochemical preparation of these compounds.

Patent
11 Jan 1979
TL;DR: N-benzhydryl-N'-hydroxybenzyl-piperazine derivs of formula (I) and their acid addn salts are new In as discussed by the authors.
Abstract: N-benzhydryl-N'-hydroxybenzyl-piperazine derivs of formula (I) and their acid addn salts are new In (I) R' is H, F, Cl or Br in the 2-, 3- or 4-position and R2 is F or Br in the 2-, 3- or 4-position Cl in the 2-, or 3-position or, when R' is other than H, Cl in the 4-position (I) have marked psychotropic activity, eg good antidepressant properties

Patent
Carl Andrew Renner1
08 Jan 1979
TL;DR: In this article, a process for formylating an alkyl-substituted benzene using carbon monoxide and hydrogen chloride, in the presence of aluminum chloride catalyst, in a reaction mixture which includes chlorobenzene as a solvent, was described.
Abstract: Process for formylating an alkyl-substituted benzene using carbon monoxide and hydrogen chloride, in the presence of aluminum chloride catalyst, in a reaction mixture which includes chlorobenzene as a solvent, and process for oxidizing an alkyl-substituted benzaldehyde using oxygen, in the presence of an autoxidation initiator, in a reaction mixture which includes cyclohexanone as a reductant.

Journal ArticleDOI
TL;DR: In this article, the reaction of buta-1,3-diene with acetaldehyde, benzaldehyde, and acrolein in the presence of bis(1,5-cyclooctadiene)nickel and an organophosphorus ligand has been demonstrated to yield 2 : 1 adducts.
Abstract: The reaction of buta-1,3-diene with acetaldehyde, benzaldehyde, and acrolein in the presence of bis(1,5-cyclooctadiene)nickel and an organophosphorus ligand has been demonstrated to yield 2 : 1 adducts. With triphenylphosphine as ligand high selectivity to 1-substituted-3,6,8-nonatrien-1-ols was found. A similar reaction between isoprene and acetaldehyde in the presence of (cyclododecatriene) nickel and triphenylphosphine gave mainly 2 : 1 adducts in which the isoprene was dimerised in a head-tail manner. The major products were 3,7-dimethyl-3-vinylocta-7-en-2-ol and its isomer 3,7-dimethyl-3-vinylocta-6-en-2-ol. The selectivity of this reaction is discussed in terms of the σ,η character of the bis(η-allyl)nickel intermediate.

Journal ArticleDOI
TL;DR: In this article, a nucleophilic attack of peroxomonophosphoric acid species on the carbonyl carbon centre has been discussed in terms of the Hammett relationship, unlike the oxidation in the acid medium.
Abstract: The oxidation of benzaldehydes by peroxomonophosphoric acid has been found to proceed by(i) −d[peroxomonophosphoric acid]⁄dt∝ [benzaldehyde][peroxomonophosphoric acid][H+]xwhere x=a fraction at [H+] 0.5 M and(ii) −d[peroxomonophosphate]⁄dt∝ [benzaldehyde][peroxomonophosphate][OH−]ywhere y=a fraction at [OH−] 0.1 M.In the alkaline oxidation Hammett relationship is obeyed excellently, unlike the oxidation in the acid medium. The oxidation mechanisms are discussed in terms of a nucleophilic attack of the peroxomonophosphoric acid species on the carbonyl carbon centre. Thermodynamic parameters have been evaluated to substantiate the mechanisms.

Patent
02 Jul 1979
TL;DR: In this paper, a one-step method of converting 2,6-disubstituted benzaldehydes to 2, 6-dissubstitized benzonitriles was proposed.
Abstract: A one step method of converting 2,6-disubstituted benzaldehydes to 2,6-disubstituted benzonitriles which comprises heating benzaldehyde in the presence of a hydroxylamine and a dehydrating agent for about 1 to 40 hours at a temperature of 110°-250° and then separating out the resultant 2,6-disubstituted benzonitrile.

Patent
14 Nov 1979
TL;DR: An electrochemical oxidation process of optionally substituted toluene dissolved in an alcohol in the presence of a conducting salt is described in this article, where the electrochemical oxidization is carried out at a current density of 0.1 to 50 A/dm 2 using oxidation-resistant anodes.
Abstract: An electrochemical oxidation process of optionally substituted toluene dissolved in an alcohol in the presence of a conducting salt is described wherein the electrochemical oxidation is carried out at a current density of 0.1 to 50 A/dm 2 using oxidation-resistant anodes. According to the disclosure, the reaction product can be distillatively worked up to obtain secondary products which can be recycled to electrochemical oxidation optionally after treatment of at least some of the secondary products with hydrogen in the presence of a catalyst.

Journal ArticleDOI
TL;DR: In this paper, the U.U.v. irradiation of acetaldehyde in the presence of styrene or methylstyrenes yields oxetans in a reaction which is both regio-and stereo-selective.
Abstract: U.v. irradiation of acetaldehyde in the presence of styrene or methylstyrenes yields oxetans in a reaction which is both regio- and stereo-selective; benzaldehyde also reacts, but in a less selective manner.

Journal ArticleDOI
TL;DR: In this article, the binding of anilines with lanthanide shift reagents has been studied in the context of a series of aldehydes and ketones related to benzaldehyde and acetophenone.
Abstract: We have recently extended our Infrared studies of the binding of anilines with lanthanide shift reagents1 to an NMR examination of hindered phenyl-carbinols2 and a series of aldehydes and ketones related to benzaldehyde and acetophenone3.

Journal ArticleDOI
TL;DR: In this paper, a comparison between the reactions of mercuric acetate and lead tetra-acetate with phenyl-hydrazone systems is discussed, and it is shown that the ortho-mercuriation occurred by an internal cyclometallation process involving the hydrazone imino-moiety.
Abstract: Treatment of substituted benzaldehyde phenylhydrazones with mercury(II) acetate in acetic acid resulted in exclusive mercuriation at the ortho-site of the N-phenyl ring. Kinetic measurements at 25 °C in acetic acid gave Hammett ρ values for methine phenyl substituents of –0.81 for the p-bromophenylhydrazone series and –1.02 for the p-nitrophenylhydrazone series (σ+ correlation). The ρ values for amino-N-phenyl substituents were –2.30 for the p-tolualdehyde series and –2.99 for the p-nitrobenzaldehyde series (σn correlation). Thermodynamic parameters ΔEact 17.5, ΔHact 16.9 kcal mol–1, and ΔSact–14.1 cal K–1 mol–1 were measured for benzaldehyde p-bromophenylhydrazone. The ortho-mercuriation occurred by an internal cyclometallation process involving the hydrazone imino-moiety. The comparison between the reactions of mercuric acetate and lead tetra-acetate with phenyl-hydrazone systems is discussed.


Journal ArticleDOI
TL;DR: The high temperature reaction of hydrogen sulfide with chloro-and bromosubstituted aromatic and heteroaromatic compounds is a convenient method for synthesis of the corresponding thiols and sulfides as mentioned in this paper.
Abstract: The high temperature reaction of hydrogen sulfide with chloro- and bromosubstituted aromatic and heteroaromatic compounds is a convenient method for synthesis of the corresponding thiols and sulfides. The reaction of hydrogen sulfide with ortho-dihalosubstituted aromatic compounds may be directed toward the formation of thianthrene or dibenzo thiophene and their derivatives. The high temperature reaction of thiophenol with chloro- and bromoderivatives of aromatic and heteroaromatic compounds affords the corresponding mixed sulfides. The reaction with ortho-substituted halogen derivatives leads to formation of the sulfur heterocycles of the thianthrene, thioxanthene and dibenzothiophenene series. The high temperature reaction of hydrogen sulfide with vinyl chloride gives vinylthiol and thiophene. Hydrogen sulfide initiates pyrolytic transformations of thiophene, aniline and benzaldehyde into dithienyls, 5.10-dihydrophenazine and stilbene, respectively. The reaction mechanism has been discussed.

Journal ArticleDOI
TL;DR: The fluorescent product formed from benzaldehyde or p-hydroxybenzaldehyde with the reagent in the presence of tri-n-butylphosphine, phosphine, and sulphite has been characterized by elemental and structural analysis as the corresponding 2-arylnaphtho [1,2-d ] thiazole as discussed by the authors.

Journal ArticleDOI
TL;DR: In this article, N-chloronylon 66 (NCN) was used to oxidize tertiary amines with N-methylaniline with 15-50% yield, depending on the solvents used.
Abstract: Oxidation of tertiary amines with N-chloronylon 66 (NCN) was investigated in several organic solvents. NCN was found to oxidize N,N-dimethylaniline (DMA) at room temperature to give N-methylaniline with 15–50% yield, depending on the solvents used. Oxidation of N,N-dimethylbenzylamine (DMBA) gave benzaldehyde with 15–30% yield and a small amount of N-methylbenzylamine. A mechanism was discussed. For comparison, N-chlorosuccinimide, a low molecular N-chloro-compound, was also used for oxidation of DMA and DMBA.