Benzaldehyde Acetals Research Articles

ChemInform Abstract: KINETIC α SECONDARY DEUTERIUM ISOTOPE EFFECTS FOR O‐ETHYL S‐PHENYL BENZALDEHYDE ACETAL HYDROLYSIS

Chemischer InformationsdienstVolume 10, Issue 26 Preparative Organic Chemistry ChemInform Abstract: KINETIC α SECONDARY DEUTERIUM ISOTOPE EFFECTS FOR O-ETHYL S-PHENYL BENZALDEHYDE ACETAL HYDROLYSIS J. P. FERRAZ, J. P. FERRAZSearch for more papers by this authorE. H. CORDES, E. H. CORDESSearch for more papers by this author J. P. FERRAZ, J. P. FERRAZSearch for more papers by this authorE. H. CORDES, E. H. CORDESSearch for more papers by this author First published: June 26, 1979 https://doi.org/10.1002/chin.197926093AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume10, Issue26June 26, 1979 RelatedInformation

Mass Spectra of Substituted Benzaldehydes and Substituted Benzyl Ethers

Mass spectra of substituted benzaldehydes, substituted benzyl ethyl ethers, diethyl substituted benzaldehyde acetals and substituted benzaldehyde ethylene acetals were measured by electron impact ionization. The substituted group of compounds were H; o-, m-, p-CF3O;o-, m-, p-CH3, and o-, m-, p-CI. The fragmentation patterns were discussed on the basis of the metastable ions and the fragment of isomer.

PHOTOCHEMICAL REARRANGEMENT OF 1-METHOXYTRIPTYCENE. AN EFFICIENT RADICAL FRAGMENTATION OF A METHOXYCARBENE

Abstract Irradiation of 1-methoxytriptycene 1(X = OCH3) in alcohols gives 2-(9-fluorenyl)benzaldehyde acetals 3 in good yield, showing the formation of 2-(9-fluorenyl)phenylmethoxycarbene 2(X = OCH3). In cyclohexane the expected internal adduct 4 is not obtained, but the photoproduct is 2-(9-fluorenyl)benzaldehyde 5. A novel homolysis of the O–CH3 bond in less electrophilic methoxycarbene 2 has been demonstrated.

The reduction of acetals with cobalt carbonyl catalysts

When heated with a dicobalt octacarbonyl (Co2(CO)8) catalyst under synthesis gas, acetals of aromatic aldehydes (in contrast to aliphatic acetals) gave good yields of the products of reductive cleavage, but no products of hydroformylation. A mechanism is proposed to explain the products of cyclic acetals of benzaldehyde which yielded not only the expected hydroxy-ethers, but also considerable amounts of dibenzyl ethers. The room temperature reductive cleavage of aromatic acetals by pure HCo(CO)4 in organic solvents indicates that HCo(CO)4 might be the active species in the catalytic reductions. Since acetals of benzaldehyde para-substituted with electron-releasing groups cleaved faster than those substituted with electron-withdrawing groups, the mechanism probably involves a carbonium ion intermediate.The previously observed formation of dibenzyl ether during benzaldehyde reduction with cobalt carbonyl catalysts can now be explained via the reductive cleavage of hemiacetal or acetal intermediates.

Some reactions of benzaldehyde acetals with alkyl-lithium reagents; a stereospecific olefin synthesis from 1,2-diols

In certain cases the reaction of 2-phenyl-1,3-dioxolans with n-butyl-lithium gives olefins in a highly Stereospecific fragmentation reaction. In particular, the reaction constitutes the crucial step in a convenient preparation of trans-cyclo-octene from cis-cyclo-octene.A mechanism is proposed involving initial metallation of the dioxolan followed by concerted cycloelimination to olefin and benzoate ion. Support for this mechanism, in three instances, is provided by the isolation of products derived by in situ trapping of the lithium derivative of the dioxolan by benzoate ion.

Intermolecular general-acid catalysis in acetal hydrolysis

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.

Mixed Glycol Acetal Dimethylcarbamates via Transacetalation of Certain Di- and Trihydric Alcohols

Mixed acetals of a new type were synthesized by an acetal exchange reaction between the mono dimethylcarbamate of ethylene, propylene, and trimethylene glycols and the diethyl acetals of butyraldehyde, heptaldehyde, and benzaldehyde. The glycerol carbonate (followed by dimethylaminolysis) also underwent transacetalation and dimethylcarbamate esters of the dioxolane-type were synthesized.

The photochemistry of 1,2,3-triphenylaziridine

Photochemical behaviour of 1,2,3-triphenylaziridine has been investigated. Irradiation in alcoholic solvents induces a novel type of alcoholytic cleavage of the aziridine ring to give benzaldehyde acetals and N-benzylaniline. Competitively, fragmentation occurs to give rise to benzalaniline and phenylcarbene, the latter being trapped with alcohols as alkyl benzyl ethers. Photolysis in cyclohexene affords a 1,3-cycloaddition product, 1,2,3-triphenyloctahydroisoindole as a mixture of two stereoisomers.

The syntheses and infrared spectra of some acetals and ketals

Electrolyses of alkoxy(phenyl)acetic acids, in ethanol, give benzaldehyde and benzophenone simple and mixed acetals. The infrared spectra of a number of acetals and ketals are recorded in the 3000 and 1400 cm.–1 regions, and assignments are made for some frequencies. A method for differentiation of dimethyl, diethyl, and ethyl methyl acetals, as well as between benzaldehyde acetals and benzophenone ketals, is suggested.

Reactions of acetals with alkyl 2-bromovinyl ethers

A study was made of the condensation of benzaldehyde and acetaldehyde acetals with alkyl 2-bromovinyl ethers, as a result of which bromo ethoxy acetals of general formula RCH(OC2H5)CHBrCH(OR′)2 (R=C6H5 and CH3) were formed.

Peroxide-Induced Conversions of Cyclic Acetals of Benzaldehyde to Benzoate Esters1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPeroxide-Induced Conversions of Cyclic Acetals of Benzaldehyde to Benzoate Esters1Earl S. Huyser and Zenaida GarciaCite this: J. Org. Chem. 1962, 27, 8, 2716–2719Publication Date (Print):August 1, 1962Publication History Published online1 May 2002Published inissue 1 August 1962https://doi.org/10.1021/jo01055a002RIGHTS & PERMISSIONSArticle Views237Altmetric-Citations37LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (483 KB) Get e-Alerts Get e-Alerts