Showing papers on "Benzaldehyde published in 1970"
TL;DR: In this article, the reaction between pyrroles and benzaldehyde in refluxing acetic acid gives meso-tetraphenylporphins and chlorins.
122 citations
Patent•
05 Oct 1970
TL;DR: In this article, a method of adding cyclohexane to the reaction system in an amount of five to 20 weight parts based on one weight part of the benzaldehyde was proposed.
Abstract: In reacting an aqueous solution of sorbitol with benzaldehyde in the presence of a dehydrating catalyst to produce a benzylidene sorbitol, a method of this invention comprises adding cyclohexane to the reaction system in an amount of five to 20 weight parts based on one weight part of the benzaldehyde, heating with stirring the reaction system to effect the reaction between sorbitol and benzaldehyde while boiling an azeotropic mixture of cyclohexane and water, said azeotropic mixture being condensed and separated to remove the water from the reaction system and recycle the cyclohexane to the system, and recovering the resultant benzylidene sorbitol thus produced.
47 citations
TL;DR: Substituted carboxamide hydrazones have been condensed with 2,3-butanedione and with glyoxal to form 1,2,4-triazines as mentioned in this paper.
37 citations
29 citations
17 citations
TL;DR: In this article, a cyclic four-membered transition state is proposed in which the polarity of both the silicon-aromatic bond and the attacking reagent are stressed, and a new pathway to heterocyclic ketones, keto-acids, esters and alcohols is proposed.
16 citations
TL;DR: The reaction of benzaldehyde with ethyl chloracetate is stereoselective in benzene-NaH ethanol-sodium ethylate but is non-stereoselectively in HMPT, and the intermediate threo- and erythro-halohydrins (ethyl-2-chloro-3-hydroxy-3phenyl-propionates) are cyclized under Darzens' conditions as discussed by the authors.
15 citations
13 citations
TL;DR: A novel cleavage reaction of thiamin to give 4-amino-2, 5-dimethylpyrimidine (III) and 2-benzoyl-5-(2-hydroxyethyl)-4-methylthiazole (IV) has been discovered as mentioned in this paper.
Abstract: A novel cleavage reaction of thiamin to give 4-amino-2, 5-dimethylpyrimidine (III) and 2-benzoyl-5-(2-hydroxyethyl)-4-methylthiazole (IV) has been discovered. The reaction involves the treatment of thiamin chloride hydrochloride (I) with two mole equivalents of triethylamine and an excess of benzaldehyde in methanol. The finding was further extended to the reactions of thiamin and its homologs with a variety of aromatic aldehydes to give several new 2-acylthiazoles. The pyrimidine moiety of thiamin was indispensable for these reactions. On the other hand, the reaction of thiamin with cinnamaldehyde gave 2, 9a-dimethyl-9-(2-hydroxyethyl)-7-(3-methoxy-3-phenylpropionyl)-5, 9, 9a, -10-tetrahydro-7H-pyrimido [4, 5-d] thiazolo [3, 4-a] pyrimidine (XV).
12 citations
Patent•
16 Mar 1970
TL;DR: In this article, a catalytic process for the preparation of benzoyl chlorides and benzaldehydes was provided for a tin-closeted catalytic environment.
Abstract: A catalytic process is provided for the preparation of benzoyl chlorides and benzaldehydes comprising reacting benzo polychloromethanes with an organic carboxylic acid to produce the corresponding benzoyl chloride or benzaldehyde plus the acyl chloride corresponding to the organic carboxylic acid, the reaction being carried out in the presence of a tin chloride catalyst.
11 citations
Patent•
25 Sep 1970TL;DR: In this article, the authors describe a scenario where either a ring-substituted Benzaldehyde or a N,N-DIALKYLANILINE is used in the presence of a CATALYTICALLY EFFECTIVE AMOUNT of an ORGANIC SULFONIC ACID.
Abstract: AMINO-TRIPHENYLMETHANE LEUCO BASES ARE PREPARED BY REACTING BENZALDEHYDE OR A RING-SUBSTITUTED BENZALDEHYDE WITH AN N,N-DIALKYLANILINE IN THE PRESENCE OF A CATALYTICALLY EFFECTIVE AMOUNT OF AN ORGANIC SULFONIC ACID. THE REACTION IS ADVANTAGEOUSLY CARRIED OUT BY EMPLOYING A POLAR SOLVENT WHICH FORMS AN AZEOTROPE WITH WATER AND CONTINUOUSLY REMOVING THE WATER PRODUCED IN THE REACTION BY AZEOTROPIC DISTILLATION.
TL;DR: In this paper, the tin(IV)chloride and bromide with benzaldehyde, salicyldehyde, furanaldehyde, cinnamaldehyde, naphthaldehyde and phthalaldehyde have been isolated.
TL;DR: In this article, it was shown that the bivalent sulfur compounds such as benzaldehyde diethylmercaptal, benzophenone diethrmcaptole, ethyl orthotrithioformate and benzyl methylsulfide, react with copper(II) salts of 1,3-dicarbonyl compounds, active methylene compounds or anisole, in the presence of cupric chloride, to give condensation or substitution products in good yields accompanied with carbon-sulfur bond cleavage.
Abstract: It was found that the bivalent sulfur compounds such as benzaldehyde diethylmercaptal, benzophenone diethylmercaptole, ethyl orthotrithioformate and benzyl methylsulfide, react with copper(II) salts of 1,3-dicarbonyl compounds, active methylene compounds or anisole, in the presence of cupric chloride, to give condensation or substitution products in good yields accompanied with carbon-sulfur bond cleavage. On the other hand, in the absence of cupric chloride, the bivalent sulfur compounds underwent no reaction and the starting materials were recovered. These results can be explained by assuming initial formation of active complexes from the bivalent sulfur compounds and copper(II).
TL;DR: In this paper, it was found that a pseudo-equilibrium between benzyl alcohol and benzaldehyde was attained during the reaction in a closed system and the formation of CO2, CH4, and other hydrocarbons as gaseous products was also observed.
Abstract: Benzyl alcohol was dehydrogenated to benzaldehyde when it was heated in the presence of various metal catalysts. It was found that the dehydrogenation was accompanied by a reductive dehydroxylation and dehydroxymethylation which led to the production of toluene and benzene respectively. The compositions of the products, which mainly consisted of benzaldehyde, toluene, and benzene, were greatly affected by the chemical nature of the catalysts used. The results of the reactions in a sealed tube or in an authoclave suggested that a pseudo-equilibrium between benzyl alcohol and benzaldehyde was attained during the reaction in a closed system. The formation of CO2, CH4, and other hydrocarbons as gaseous products was also observed. From these results, the catalytic dehydrogenation, dehydroxylation, and dehydroxymethylation were assumed to proceed competitively via a certain metal benzyl complex which is formed as an adsorbed transition complex upon the catalyst metal.
TL;DR: The decomposition of erythro- and threo-β-hydroxyphosphonates in basic medium shows that they partly revert to benzaldehyde and the anion to an extent which is solvent-dependent, and partly interconvert directly as mentioned in this paper.
Abstract: The decomposition of erythro- and threo-β-hydroxyphosphonates in basic medium shows that they partly revert to benzaldehyde and the anion (1) to an extent which is solvent-dependent, and partly inter-convert directly; the ratios of cis- to trans-cinnamonitrile formed from the two β-hydroxyphosphonates are very similar.
TL;DR: In this paper, a procedure suitable for the synthesis of methyl-labeled methyl d -glucuronate from d-glucuronic acid was devised, and the intermediates prepared during the synthesis, 1,2:3,5-di- O -benzylidene-α- d -gluco-furanuronic acids and its methyl ester, were determined to exist in an O-inside conformation by examination of their n.m. and g.l.c. spectra.
TL;DR: In this paper, photolysis of 2-phenyl-3,1-benzoxanthian-4-one results in formation of benzaldehyde and dibenzo [c,g]-[1,2]-dithiocan-5,6-dione.
TL;DR: The diastereoisomeric ethyl 2-chloro-3-hydroxy 3-phenyl-propionates were synthesized in three different ways; the reaction of hypochlorous acid or N-chlorosuccinimide on cinnamic acid derivatives, the condensation of benzaldehyde with magnesium enolates of ethyl chloracetate, and the conditional addition of the organozinc derivative of the ethyl dichloracetate as mentioned in this paper.
Patent•
11 Feb 1970
TL;DR: In this paper, the 3-Imino-pyrazolidines of the formula R and R 1 represent hydrogen or alkyl, polyhydroxyalkyl, #-carboxyalkyl and #-alkoxycarbonyl-alkyl are prepared by hydrogenating a 1 : 1 molar mixture of a pyrazolidine and a carbonyl compound.
Abstract: 1,180,876. 3 - Imino - pyrazolidine; pyrazolidinones. DEUTSCHE AKADEMIE DER WISSENSCHAFTEN ZU BERLIN. 15 Aug., 1968, No. 39033/68. Heading C2C. 3-Imino-pyrazolidines of the formula wherein R and R 1 represent hydrogen or alkyl, polyhydroxyalkyl, #-carboxyalkyl, #-alkoxycarbonyl-alkyl, phenyl, substituted phenyl or heterocyclic radicals, or R and R 1 together form a cycloalkyl ring and R 11 is hydrogen or an alkyl radical, or the acid addition salts thereof, are prepared by hydrogenating a 1 : 1 molar mixture of a pyrazolidine of the formula or an acid addition salt thereof, and a carbonyl compound R.CO.R 1 in a solvent at 0-40‹ C. in the presence of a metallic hydrogenation catalyst until 1 mol. of hydrogen has been taken up. When the starting pyrazolidine is the free base, the reaction is preferably effected in the presence of 1-2 mols. of an acid, per mol. pyrazolidine. The starting pyrazolidines may be prepared by reacting aqueous hydrazine with the required α,#-unsaturated nitrile to obtain the corresponding #-hydrazinopropionitrile which cyclizes under acidic conditions to the 3-imino-pyrazolidine. The 1-substituted- 3-imino pyrazolidines obtained by the hydrogenation process may be hydrolysed by heating with an acid, e.g. H 2 SO 4 , to the corresponding 1-substituted pyrazolidin-3-ones. Examples describe the preparation of 1-iso-propyl-, 1- cyclohexyl-, 1-desoxy-D-mannite-, 1-benzyl- and 1 - # - phenylethyl - 3 - imino - pyrazolidines, and the corresponding pyrazolidinones, from acetone, cyclohexanone, D-mannose, benzaldehyde and phenylacetaldehyde.
TL;DR: In this article, the effect of additives on the grafting of styrene to cellulose has been studied for the system cellulose-styrene-methanol irradiated in air at dose rates ranging from 0.045-0.77 Mrad/hr in a cobalt-60 facility.
Abstract: The effect of additives upon the grafting of styrene to cellulose has been studied for the system cellulose-styrene-methanol irradiated in air at dose-rates ranging from 0.045-0.77 Mrad/hr in a cobalt-60 facility. The additives included glycol, acetic acid, ethyl acetate, chloroform, acetone, aniline, benzaldehyde, hydroquinone, thiourea, thiophen, pyridine, benzene, naphthalene, pyrene, phenanthrene, durene, hexamethylbenzene, stilbene, acridine, and fluoro-, chloro-and bromo-benzene. At a low concentration (10-2M) of the non-aromatic additives, a reduction in grafting yields is observed whereas at a higher concentration (10-1M) of the same additives sensitization is common. Radical scavengers such as hydroquinone and thiourea suppress grafting provided their concentration in the grafting solution is sufficiently high. With the aromatic additives, little change in grafting yields is observed except for anthracene and acridine. Possible reaction mechanisms are discussed. Preliminary studies are also reported for the effect on grafting of chemically bound lignin and non-cellulosic material present in the trunk polymer.
TL;DR: Condensation of acyclic or cyclic β-nitroalcohols with aldehydes was examined in this article, where the reaction of 2methoxy-1-nitropentane or non-protected 2nitrocyclohexanol and reactive aldehyde (formaldehyde, acetaldehyde and n-butyl glyoxylate) in the presence of sodium hydrogen carbonate gave the corresponding condensation products.
Abstract: Condensation of acyclic or cyclic β-nitroalcohols with aldehydes was examined. In the case of non-protected 1-deoxy-1-C-nitro-D-glycitols and benzaldehyde, products caused by aldehyde-exchange reaction were obtained. However, the reaction of 2-methoxy-1-nitropentane or non-protected 2-nitrocyclohexanol and reactive aldehydes (formaldehyde, acetaldehyde and n-butyl glyoxylate) in the presence of sodium hydrogencarbonate gave the corresponding condensation products.
Patent•
26 Aug 1970
TL;DR: In a continuous process, the reaction mixture is allowed to separate in a settling tank, the layers separated and recovered solvent and regenerated reagent recycled as mentioned in this paper. But the reagent is not regenerated by electrolysis.
Abstract: 1,203,434. Oxidation and reduction of organic substrates. IMPERIAL CHEMICAL INDUSTRIES Ltd. 9 Oct., 1968 [23 Oct., 1967], No. 48091/67. Headings B1F and B1X. [Also in Divisions C2 and C7] Substantially water-immiscible organic substrates are reduced or oxidised by a process comprising contacting a solution of the substrate in a non-reactive, water-immiscible solvent with a reagent comprising an aqueous solution of a compound of a variable valency element, separating the two phases after reaction and regenerating the reagent by electrolysis. In a continuous process the reaction mixture is allowed to separate in a settling tank, the layers separated and recovered solvent and regenerated reagent recycled. Examples refer to oxidation of toluene to benzaldehyde and of pxylene to p-tolualdehyde with ceric ammonium nitrate in nitric acid and oxidation of 2, 6 dit-butyl alcohol to 2, 2 1 , 6, 6 1 - tetrabutyldiphenoquinone with ceric ammonium nitrate, reduction of 5, 6-dicholesterol to cholesterol with acidified chromous chloride, and oxidation of naphthalene to 1, 4 napthaquinone and 1-nitronaphthalene using ceric ammonium nitrate in nitric acid.
TL;DR: In this article, the authors investigated the kinetics of the oxidation of benzaldehyde to benzoic acid with bromine in buffers of pH 1−5 and in aqueous acetic acid.
Abstract: The kinetics of the oxidation of benzaldehyde to benzoic acid with bromine have been investigated in buffers of pH 1–5 and in aqueous acetic acid. The substituents of ten substituted benzaldehydes have little effect on the rate of oxidation and there is a poor Hammett correlation. Benzaldehyde is oxidised 2·5 times faster than [2H1]-benzaldehyde at 70°. There is little difference of solvent isotope effect in the oxidation of benzaldehyde and acetaldehyde measured in normal water and deuterium oxide, contrary to the findings of other authors. The evidence presented is in favour of a similar mechanism for the oxidation of both aliphatic and aromatic aldehydes.
TL;DR: In this article, it was shown that benzaldehyde reacts with 1-pyrrolidin-1-ylcyclohexene (1-piperidin) and 1-polycyclic cyclohexenes to give xanthene derivatives identical to the products of reaction of dibenzylidenecyclohexanone with the enamines.
Abstract: Benzaldehyde reacts with 1-pyrrolidin-1-ylcyclohexene and 1-piperidin-1-ylcyclohexene to give xanthene derivatives identical to the products of reaction of dibenzylidenecyclohexanone with the enamines : 1-morpholinocyclohexene behaves differently. Benzylidenecyclohexanone with 1-pyrrolidin-1-ylcyclohexene gives an analogous adduct the hydrolysis of which has been investigated.
TL;DR: In this paper, it was shown that 2-Benzothiazole-carbaldehyde is transformed into di-O-acetyl-enol-(benzothiazolescarboxyl-2)-oin in the presence of acetic anhydride and of pyridine as catalyst.
Abstract: 2-Benzothiazole-carbaldehyde is transformed into di-O-acetyl-enol-(benzothiazolecarboxyl-2)-oin in the presence of acetic anhydride and of pyridine as catalyst. Without pyridine or with 2,6-lutidine no reaction occurs. A mechanism of this reaction is proposed. No reaction was observed in the case of benzaldehyde.
Choral reacts with acetic anhydride in the presence of pyridine as well as of 2,6-lutidine as catalyst to give 1,1-diacetoxy-2,2,2-trichloro-ethane. A mechanism is proposed, in which in an intermediate state the acetate ion (and not pyridine, for steric reasons) attacks the carbon of the carbonyl function of the conjugate acid with the acetylium cation to yield 1,1-diacetoxy-2,2,2-trichloro-ethane.
These two reactions occur only with aldehydes whose carbonyl is very electrophilic, and seem to be a possible way to point out the presence of an acylium cation in pyridine medium.
TL;DR: In this article, it was shown that the major primary reaction product is a benzyl nitrate ester, and that the outcome of the reaction is dependent on the rate of hydrolysis of this nitrate, which is followed by rapid oxidation of the substituted benzyl alcohol.
Abstract: Reports have appeared that substituted toluenes can be oxidised by ammonium cerium(IV) nitrate in dilute nitric acid solution to the corresponding benzaldehydes in high yield. We find that the major primary reaction product is a benzyl nitrate ester, and that the outcome of the reaction is dependent on the rate of hydrolysis of this nitrate ester, which is followed by rapid oxidation of the substituted benzyl alcohol. Aliphatic hydrocarbon solvents greatly reduce the concentration of nitrate ester in the aqueous phase and prevent hydrolysis. In the absence of solvents toluene is eventually oxidised to benzaldehyde but o-xylene gives 2-methylbenzyl nitrate as the major oxidation product. The nitrate insertion reaction acts in parallel with a hydroxide insertion reaction which yields a substituted benzyl alcohol as an alternative primary reaction product : the small amount of o-tolualdehyde obtained from the oxidation of o-xylene is probably formed from this latter reaction rather than by hydrolysis and further oxidation of the nitrate ester.
TL;DR: In this article, Dimethylsulfonium 2-oxo-3, 4-diphenyl-cis-3-butenylide derivatives (IVa-e) were prepared from dimethyl 3-phenyl-2-propynylsulfoneium bromide and benzaldehyde derivatives and its addition mechanism were considered.
Abstract: Dimethylsulfonium 2-oxo-3, 4-diphenyl-cis-3-butenylide derivatives (IVa-e) were prepared from dimethyl 3-phenyl-2-propynylsulfonium bromide (III) and benzaldehyde derivatives and its addition mechanism were considered.
TL;DR: The formation of Schiff bases by treatment of benzaldehyde with o-nitroaniline and its derivatives proceeds best in the presence of an excess of aldehyde, under conditions which permit removal of water as soon as it is formed as discussed by the authors.
Abstract: The formation of Schiff bases by treatment of benzaldehyde with o-nitroaniline and its derivatives proceeds best in the presence of an excess of aldehyde, under conditions which permit removal of water as soon as it is formed. The products obtained from the corresponding reactions with substituted benzaldehydes depend on the nature of the substituents.
TL;DR: In this paper, the relative rates of chlorination of substituted benzaldehydes with CCl 3 SO 2 Cl (I) have been determined in dilute CCl 4 solution at 80° by means of competitive reactions using p -diethylbenzene as reference standard.