Aliphatic Ketoximes Research Articles

Hypervalent Iodine-Mediated Beckmann Rearrangement of Ketoximes

We developed a Beckmann rearrangement employing hypervalent iodine reagent under mild conditions. The reaction of ketoxime with hypervalent iodine afforded the corresponding ketone, but premixing of hypervalent iodine and a Lewis acid was effective for promoting Beckmann rearrangement. Aromatic and aliphatic ketoximes were converted into their corresponding amides in good to high yields.

ChemInform Abstract: Titanium Cation Exchanged Montmorillonite as an Active Heterogeneous Catalyst for the Beckmann Rearrangement under Mild Reaction Conditions.

AbstractThe rearrangement of aromatic and aliphatic ketoximes is efficiently promoted by the reusable title catalyst.

PYRIDINIUM FLUOROCHROMATE SUPPORTED ON WET ALUMINA: A MILD CONVENIENT REAGENT FOR THE FACILE DEPROTECTION OF ALDOXIMES

ABSTRACT A simple mild method of oxidative deoximation based on pyridinium fluorochromate (PFC) on wet alumina support is described. This method is particularly effective for rapid deprotection of aldoximes and aliphatic ketoximes. Sterically hindered ketoximes are resistant to the reagent.

Kinetics of uncatalyzed isomerization of aliphatic ketoximes

Three acyclic, aliphatic ketoximes studied show similar rates of isomerization at room temperature. From the rates of isomerization of one oxime at four temperatures, the thermodynamic activation parameters are calculated and a bimolecular transition state is postulated to account for the large negative entropy of activation.

Untersuchungen an quartären Pyridinium-Salzen, XIV Dihydropyridyl-oximether/Investigations of Quaternary Pyridinium Salts, XIV Dihydropyridyl-oxime-ethers

Abstract Pyridinium Salts with electron-withdrawing groups in the 3-position react with aliphatic ketoximes under basic conditions to lipophilic addition products, 6-(alkylideniminoxy)-1,6-dihydropyridines.

Kinetics and mechanism of oxidation of aliphatic ketoximes by thallium(III) acetate—part I

AbstractThe oxidative cleavage of some aliphatic ketoximes by thallium(III) acetate was studied in the temperature range of 20–40°C. The reactions were followed by determination of the rates of disappearance of thallium(III) acetate for variations in [substrate], [Tl(III)], [H+], ionic strength, temperature, etc. The reactions were found to be totally second order–first order with respect to each reactant. The second‐order rate constants and thermodynamic parameters were evaluated and discussed. The mechanism proposed involves one‐electron oxidation to the iminoxy radical followed by an another one‐electron oxidation to the hydroxynitroso compound which dimerizes and decomposes to give the carbonyl compounds and hyponitrous acid.

The Reactions of Oximes with Lead Tetraacetate. The Scope of the Reactions

Abstract A detailed study of the reaction of oximes by lead tetraacetate has been made. It has beers found that the reaction gave nitrogen and the respective aldehydes or ketones in good yields.. In the reaction, which can be applied to general oximes, the order of yields was: aliphatic aldoximes >aliphatic ketoximes>alicyclic ketoximes >aromatic ketoximes>aromatic aldoximes. Some limited mechanistic implications are presented and discussed on the basis of the results obtained. Stoichiometrically, it has been found that 2 moles of oxime react with 1 mole of lead tetraacetate to produce 2 moles of aldehyde or ketone and 1 mole of nitrogen.

THE BECKMANN REARRANGEMENT OF ALIPHATIC KETOXIMES. A COMPARISON OF THE INFLUENCE OF REAGENTS ON THE COURSE OF THE REARRANGEMENT1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTTHE BECKMANN REARRANGEMENT OF ALIPHATIC KETOXIMES. A COMPARISON OF THE INFLUENCE OF REAGENTS ON THE COURSE OF THE REARRANGEMENT1A. D. McLAREN and R. E. SCHACHATCite this: J. Org. Chem. 1949, 14, 2, 254–260Publication Date (Print):March 1, 1949Publication History Published online1 May 2002Published inissue 1 March 1949https://doi.org/10.1021/jo01154a010RIGHTS & PERMISSIONSArticle Views98Altmetric-Citations9LEARN 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 (407 KB) Get e-Alerts Get e-Alerts