Nitrile N-oxides Research Articles

The Reaction Nitrile Oxides with Alkyl- and Alkyl-halo-substituted p-Benzoquinones

Abstract Various aromatic nitrile N-oxides, sterically stabilized and unstabilized ones, were allowed to react with several alkyl- and alkyl-halo-substituted p-benzoquinones with a view to studying the influence of quinone substituents on the mode of the addition reaction. Mono-, di-, and tri-substituted quinones with such substituents gave isoxazoline derivatives formed through addition of nitrile oxides to the C=C bond of the quinones. 2-Chloro-5- and -6-methyl-p-benzoquinones gave two kinds of C=C adducts, one formed through the addition to the C=C of methyl-substituted side and the other to that of chlorine-substituted side, and the latter adducts were not isolable due to the prompt dehydrochlorination forming the fully-conjugated isoxazoloquinones and subsequent C=O addition of another nitrile N-oxide forming spirodioxazole derivatives.

Theoretical discussion of cyclodimerization of nitrile N-oxides to furoxans

1. Based on the data of quantum-chemical calculations the cyclodimerization of nitrile N-oxides is a two-step reaction with the formation of cis-dinitrosoethylene as an intermediate product, whose structure is determined by the stereospecificity of the reaction. 2. In the first transition state two molecules of the nitrile N-oxides are found in perpendicular planes, forming a molecular system with a C2 symmetry, whose structure is determined by the regioselectivity of the reaction.

The Reaction of Aromatic Nitrile N-Oxides with Tetrahalo-p-benzoquinones

Abstract Cycloaddition reaction of aromatic nitrile N-oxides, such as benzonitrile N-oxide, 2,4,6-trimethylbenzonitrile N-oxide, and 2,3,5,6-tetramethylbenzonitrile N-oxide, with tetrahalo-p-benzoquinones was studied. The reaction gave 1:1- and/or 2:1-adducts of a nitrile N-oxide and a tetrahalobenzoquinone according to the conditions, especially the mole ratios of each reactant. The 2:1-adducts are formed via 1:1-adducts, each having two stereoisomers. The structures of these adducts were determined to be dioxazole derivatives formed by the addition of nitrile N-oxides to the carbonyl bonds of the tetrahalobenzoquinones.

Formation of 1,4,2-oxathiazole derivatives in the reaction of 3-amino-2-arylindene-1-thiones with nitrile n-oxides

Formation of 1,4,2-oxathiazole derivatives in the reaction of 3-amino-2-arylindene-1-thiones with nitrile n-oxides

The Reactions of Nitrile N-Oxides

The Reactions of Nitrile N-Oxides

Reactions of aromatic nitrile N-oxides with organic radicals. New type of spin-trapping reagent

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of aromatic nitrile N-oxides with organic radicals. New type of spin-trapping reagentB. C. Gilbert, V. Malatesta, and R. O. C. NormanCite this: J. Am. Chem. Soc. 1971, 93, 13, 3290–3291Publication Date (Print):June 1, 1971Publication History Published online1 May 2002Published inissue 1 June 1971https://doi.org/10.1021/ja00742a036RIGHTS & PERMISSIONSArticle Views152Altmetric-Citations17LEARN 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 (262 KB) Get e-Alerts Get e-Alerts

Cycloaddition of nitrile N-oxides to bis(trifluoromethyl)ketene

The cycloaddition of nitrile N-oxides to bis(trifluoromethyl)ketene leads to 2-hexafluoroisopropylidene-1,3,4-dioxazoles.

Electronic structures of aromatic amine N-oxides

The electronic structures of heterocyclic amine N-oxides, nitrones, and nitrile N-oxides were systematically studied by the Pariser-Parr-Pople method. In addition, the intensity of n- π * transition pertinent to conjugated N-oxide systems has been calculated. The results of these calculations were compared with the experimental ones reported hitherto and also carried out in the present work. The electronic structure and spectra of aromatic amine N-oxides were thus discussed in detail.

Electronic Spectra and Electronic Structures of Benzonitrile N-Oxide and Its Derivatives

Abstract The electronic spectra of 2,6-dimethylbenzonitrile N-oxide and its some derivatives were recorded in n-heptane and were compared with those of benzonitrile and phenylacetylene. The analyses of the electronic spectra of aromatic nitrile N-oxides were done by the following procedures. First, simple molecular orbitals (SMO) of benzonitrile and phenylacetylene were calculated using some parameters determined by the use of the overlap integrals and valence state ionization potentials. Then, by comparing the eigenvalues of the SMO thus obtained with the observed spectra the spectroscopic exchange integrals have been obtained for 1A1 and 1B1 bands, where interactions between two configurations were taken into consideration for the 1B1 bands. The SMO of benzonitrile N-oxide was next calculated on reference to the physicochemical nature of aromatic nitrile N-oxides studied before. The parameters were chosen so as to fit with the observed values of dipole moments of benzonitrile N-oxide and its some methyl derivatives. Electronic spectra of the nitrile N-oxides were then analyzed using the above SMO’s and spectroscopic exchange integrals. The substituent effect on the electronic spectrum of benzonitrile N-oxide was also discussed by the similar treatment. Characteristic strong band appearing in the near UV region was assigned to the 1A1 band having a change transfer (CT) nature, where the CT from the oxygen atom to the residual conjugated system makes a larger contribution than that of the reverse direction. In addition, the physicochemical nature and reactivity of nitrile N-oxides were discussed on the basis of their molecular diagrams, which were obtained from the SMO’s mentioned above.

Molecular complexes of aromatic nitrile N-oxides with iodine, .beta.-naphthol, and phenol

Molecular complexes of aromatic nitrile N-oxides with iodine, .beta.-naphthol, and phenol

The Electronic Spectra of Nitrile N-Oxides and the Solvent Effect on Them

Abstract The electronic spectra of several substituted benzonitrile N-oxides and 9-anthronitrile N-oxide were recorded in various solvents and compared with those of the corresponding nitriles. The following results were thus obtained. (1) Substituted benzonitrile N-oxides showed a characteristic strong π–π* band at wavelengths much longer than those of the 1La band of the corresponding nitriles. (2) The π–π* band showed a blue shift with an increase in the polarity of the solvents. Quantitative analyses of the solvent effect led to the result of the decreasing dipole moment at π–π* state. (3) The hydrogen-bonding ability of the nitrile N-oxides was found to be weak from experiments on three-component systems and from analyses of the above solvent effect. (4) The electronic structures of the nitrile N-oxides were discussed on the basis of the above-mentioned findings and the measurements of the infrared spectra. It was suggested that the interaction of oxygen 2pπ electrons with the rest of the π electron system should be taken into consideration.

Infrared Spectra of the Nitrile N-Oxides: Some New Furoxans

Infrared Spectra of the Nitrile N-Oxides: Some New Furoxans