Reaction Of N-oxide Research Articles

Mechanisms of the reactions of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides

The rearrangements of substituted iso-quinoline and quinoline N-oxides with arenesulfonyl chlorides have been carried out to clarify the mode of migration of the arenesulfonoxy group by means of both 18O tracer and kinetic experiments. In the rearrangements of N-arenesulfonoxy-iso-carbostyril and carbostyril, the main migration route of the arenesulfonoxy group is via the solvent separated ion pair path with a minor portionpassing throug step appears to be NO bond cleavage. For 1-amino-iso-quinoline N-oxide the migration of tosyloxy group to 1-amino-4-tosyloxyiso-quinoline through the oxygen-bridged ion pair pathway is so fast that the presence of the anhydro base cannot be detected. Reaction of 2-aminoquinoline N-oxide to afford 2-amino-6-tosyloxyquinoline which involves migration to a distant position proceeds rapidly, apparently through the solvent separated ion pair path.

Isoxazoles from nitrile oxides and arylacetylenes. Kinetics of the reaction of p-chlorobenzonitrile N-oxide with phenyl- and mesityl-acetylene

The reactions between p-chlorobenzonitrile N-oxide and phenyl- and mesityl-acetylene lead to isomeric 3,5-diarylisoxazoles and acetylenic oximes. The rates of formation of these isomers in carbon tetrachloride solution, and the rate of isomerization of the acetylenic oximes to the corresponding isoxazoles have been measured. In both cases, the results show that the acetylenic oxime is not the precursor of the isoxazole isolated from the reaction.

Keten. Part X. The reaction of dimethylketen with pyridine N-oxide

The reaction of dimethylketen with pyridine N-oxide gives acetone, pyridine, 4-isopropylpyridine and a bicyclic compound for which two alternative structures are suggested, which may arise by reaction of pyridine N-oxide with an α-lactone.

Reaction of sym-octahydroacridine N-oxide with acetic anhydride in the presence of an aromatic aldehyde

Reaction of sym-octahydroacridine N-oxide with acetic anhydride in the presence of an aromatic aldehyde

Mechanism of the reaction of 4-picoline N-oxide with acetic anhydride studied by nuclear magnetic resonance spectroscopy

Mechanism of the reaction of 4-picoline N-oxide with acetic anhydride studied by nuclear magnetic resonance spectroscopy

Rearrangement of aromatic N-oxides. IV. Reaction of acridine N-oxide with acetyl sulfide

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRearrangement of aromatic N-oxides. IV. Reaction of acridine N-oxide with acetyl sulfideJ. Hodge Markgraf, Myong-Ku Ahn, Charles G. Carson III, and George A. LeeCite this: J. Org. Chem. 1970, 35, 11, 3983–3985Publication Date (Print):November 1, 1970Publication History Published online1 May 2002Published inissue 1 November 1970https://doi.org/10.1021/jo00836a098RIGHTS & PERMISSIONSArticle Views125Altmetric-Citations4LEARN 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 (433 KB) Get e-Alerts Get e-Alerts

Aromatic N-oxides. VI. Anhydro base intermediate and the rate-controlling step in the reaction of 4-alkylpyridine N-oxide with acid anhydrides

Aromatic N-oxides. VI. Anhydro base intermediate and the rate-controlling step in the reaction of 4-alkylpyridine N-oxide with acid anhydrides

Isoxazoles from nitrile oxides and arylacetylenes. The role of the α-acetylenic oxime in the isoxazole synthesis from the reaction of p-chlorobenzonitrile n-oxide with phenylacetylene

Isoxazoles from nitrile oxides and arylacetylenes. The role of the α-acetylenic oxime in the isoxazole synthesis from the reaction of p-chlorobenzonitrile n-oxide with phenylacetylene

Studies on Tertiary Amine Oxides. XXXVII. Reactions of Aromatic N-Oxides with Enol Ethers in the Presence of Benzoyl Chloride

Reaction of aromatic N-oxide with enol ether in the presence of benzoyl chloride was examined. 2-Ethoxycyclohexene (II) reacted readily with quinoline 1-oxides (I, IV) and isoquinoline 2-oxide (VI), producing α-2-cyclohexanonyl derivatives (III, V, VII) in fairly good yields. Similarly, the reaction of I with 2-ethoxypropene (IX), methyl vinyl ether (XI) and dihydropyrane (XIV) gave 2-acetonyl-(X), 2-(2-methoxyvinyl)-(XII) and 2-(5-dihydropyranyl)-quinolines (XV), respectively. Nucleophilic reactivity of enol ether in this reaction was considerably lower compared with that of enamine ; no satisfactory result was obtained with II and pyridine 1-oxide and also with I and furan, thiophene and anisole under similar conditions.

Donor properties of acridine N-oxide

The co-ordination of acridine N-oxide (aco) with Lewis acids has been studied. Heats of reaction of acridine N-oxide with the reference acids, phenol and bis-(pentane-2,4-dionato)oxovanadium(IV) have been determined. The relative basicity and steric effects of acridine N-oxide, quinoline N-oxide, and pyridine N-oxide are compared. Transition-metal complexes of acridine N-oxide with cobalt(II), nickel(II), and zinc(II) perchlorates have been prepared and characterized. They have the general formula M(aco)4(ClO4)2,nH2O; the nickel complex is assigned a tetragonally distorted octahedral structure and the cobalt complex a tetrahedral structure.

CIDNP in the reaction of 2-picoline N-oxide with acetic anhydride

CIDNP in the reaction of 2-picoline N-oxide with acetic anhydride

Rearrangement of tertiary amine N-oxides—XXVII : Mechanism of the reaction of isoquinoline N-oxide with substituted benzenesulfonyl chlorides

Kinetic experiments have been carried out on the reactions of isoquinoline N-oxide with p-toluenesulfonyl and other substituted benzenesulfonyl chlorides, varying solvent and salt compositions. The rate was correlated by the second-order equation, i.e., v = [N → O] × [ArSO 2Cl], and was found to be accelerated in polar media. The addition of chloride ion was found to increase the rate considerably, while the rates of the over-all reaction became greater with arenesulfonyl chlorides bearing stronger electron-withdrawing substituents (ϱ = +2·0). By the use of 1-deuterated isoquinoline N-oxide a small kinetic isotope effect ( k H/ k D = 1·2) was observed for this reaction. Based on these kinetic observations the rate-determining step of this reaction is considered to be the cleavage of NO bond. Meanwhile, from the 18O-tracer experiments in several solvents using uniformly 18O-labelled p-toluenesulfonyl or p-bromobenzenesulfonyl chloride the migration of arenesulfonate was found to proceed mainly via oxygen-bridged ion pair pathway.

Polyhalogenoaromatic compounds. Part VI. Nucleophilic reactions of polyfluoronaphthalenes, NN-disubstituted aminopolyfluoronaphthalene N-oxides, and NN-disubstituted aminopentafluorobenzene N-oxides

Nucleophilic substitution of octafluoronaphthalene by various secondary amines to give 2-mono- and 2,6-di-(NN-disubstituted amino) fluoronaphthalenes is described. Oxidation of the NN-disubstituted 2-aminoheptafluoronaphthalenes to the corresponding N-oxides was readily brought about with performic acid. These N-oxides react with secondary amines (1 mol.) to give, after deoxygenation, 1,2- and 2,3-di-(NN-disubstituted amino)-hexafluoronaphthalenes and with an excess of nucleophile to give 1,2,3-tri-(NN-disubstituted amino)pentafluoronaphthalenes. Hydrazine causes defluorination and deoxygenation of the N-oxides; a mechanism for this reaction is advanced. The products were assigned structures on the basis of their 19F n.m.r. spectra. Reaction of N-pentafluorophenylpiperidine N-oxide with hydrazine likewise results in monodefluorination and deoxygenation as well as cyclisation to a benzimidazole.

Studies on the synthesis of aminoquinoline derivatives. V. Reaction of alkylquinoline N-oxide with tosyl chloride

Studies on the synthesis of aminoquinoline derivatives. V. Reaction of alkylquinoline N-oxide with tosyl chloride

Uneven distribution of 18O in the resulting esters formed in the reaction of 2-picoline, 2,6-lutidine and quinaldine N-oxide with acetic anhydride

Uneven distribution of 18O in the resulting esters formed in the reaction of 2-picoline, 2,6-lutidine and quinaldine N-oxide with acetic anhydride

Keten. Part V. The reaction of dimethylketen with heteroaromatic N-oxides

Phenanthridine N-oxide forms an adduct with two molecules of dimethylketen, which has been shown to be a phenanthridino[5,6-b][1,2]oxazepinedione (I). Isoquinoline N-oxide forms a similar adduct (VI). The reaction of phenanthridine N-oxide with dimethylketen in various solvents also produces phenanthridine and phenanthridone. Isoquinoline N-oxide reacts with dimethylketen in methanolic solution to form isoquinoline, 1-(1-methoxycarbonyl-1-methylethyl)-1,2-dihydro-2-isobutyrylisoquinoline (XVIII), and 2-methoxyisobutyric acid, the last compound indicating that deoxygenation occurs by formation of an α-lactone.

Reaction of 4-picoline N-oxide with acetic anhydride. Trapping of the cationic intermediate

Reaction of 4-picoline N-oxide with acetic anhydride. Trapping of the cationic intermediate

The Reaction of 2-Picoline N-Oxide with Substituted Acetic Anhydrides

The Reaction of 2-Picoline N-Oxide with Substituted Acetic Anhydrides

Rearrangements of Tertiary Amine Oxide. XV. The Reaction of Heterocyclic N-Oxides with p-Nitrobenzenesulfinyl Chloride

Abstract In the reaction of pyridine and α-picoline N-oxide with p-nitrobenzenesulfinyl chloride, the N–O bond of the intermediate salt appears to cleave homolytically, as in the case of N-oxide with p-nitrobenzenesulfenyl chloride, and the p-nitrosulfonyl radical which arises from the homolytic cleavage of the N–O bond is considered to be so stable that only the secondary reaction products from the sulfonyl radical, and no heteroring-substituted products, are obtained. It is the same in the case of unsubstituted benzenesulfinyl chloride.

Rearrangement of tertiary amine N-oxide—XVI : The mechanism of the reaction of acridine N-oxide with acetic anhydride

The mechanism of the reaction of acridine N-oxide with acetic anhydride giving acridone was investigated using oxygen-18 as a tracer. Acridine N-oxide was allowed to react with 18O-labelled acetic anhydride under various conditions and the amount of 18O incorporation in the product was analysed. It was shown that the amount of 18O incorporation in the product was affected not by the molarity of the acetic anhydride but mainly by the amount and the nature of the solvent used. These results clearly reject the intermolecular path, and seems to favor an intramolecular mechanism involving two competing processes, for this rearrangement.