Thermal Deoxygenation Research Articles

ChemInform Abstract: Novel Thermal Deoxygenation in Bornyl α‐Azo Hydroperoxide to give Camphor Hydrazone. A Retro‐Ene Reaction Assisted by the Steric Compression Effect.

AbstractThermal deoxygenation of bornyl α‐azo hydroperoxide (I) gives the products (II) ‐ (VIII).

Novel Thermal Deoxygenation in Bornyl α-Azohydroperoxide to Give Camphor Hydrazone. A Retro-ene Reaction Assisted by the Steric Compression Effect

Abstract Camphor hydrazone, its dimer, and oxygen are generated from bornyl α-azohydroperoxide by thermal reaction accompanied by several other products. The retro-ene elimination mechanism is proposed.

Mass spectral fragmentation of benzofurazan‐1‐oxide

AbstractFragmentations in the mass spectrum of benzofurazan‐1‐oxide have been studied using linked scan, accelerating voltage scan and mass‐analysed ion kinetic energy spectrometric techniques. Major pathways involve NO·+ NO· and NO·+CO loss, these double losses occurring in such rapid succession as to appear ‘concerted’ in some experiments. Minor pathways are loss of CO2, C2N2O2, or C2HN2O2 from the molecular ion. The major fragment ion, m/z 76, in the conventional mass spectrum is not detected in a mass‐analysed ion kinetic energy spectrometric experiment with the molecular ion until collision activation is provided. The conventional electron impact spectrum invariably includes ions from benzofurazan which is produced by thermal deoxygenation in the source.

Heterocyclic polyfluoro-compounds. Part XXIII. Reaction of some 2-, 3-, and 4-substituted pyridine 1-oxides, 5-methylpyrimidine 1-oxide, and quinoline 1-oxide with perfluoropropene, and of pyridine 1-oxide with perfluoro-(2-methylpent-2-ene): synthesis of 2-(1,2,2,2-tetrafluoroethyl)-pyridines or -pyrimidines and their N-oxides and of 2,2,3-trifluoro-2,3-dihydro-3-trifluoromethylfuro[3,2-b]pyridine

Perfluoropropene reacts thermally with 2-chloro-, 2-cyano-, and 2-(1,2,2,2-tetrafluoroethyl)-pyridine 1-oxide and with 4-methyl-, 4-methoxy-, and 4-nitro-pyridine 1-oxide to yield carbonyl fluoride and the corresponding 2- or 4-substituted 6-(1,2,2,2-tetrafluoroethyl)pyridines. Thermal deoxygenation of 3-bromo-, 3-chloro-, or 3-fluoro-pyridine 1-oxide with perfluoropropene yields a mixture of the corresponding 3- and 5-halogeno-2-(1,2,2,2-tetrafluoroethyl)pyridines plus 2,2,3-trifluoro-2,3-dihydro-3-trifluoromethylfuro[3,2-b]pyridine and, in the cases of 3-bromo- and 3-chloro-pyridine 1-oxide, 3- and 5-fluoro-2-(1,2,2,2-tetrafluoroethyl)pyridine. Oxidation of the 2-(1,2,2,2-tetrafluoroethyl)pyridines 2-(CF3·CHF)C5H3NX (X = H, 3-Br, 3-Cl, 3-F, 4-Me, 4-NO2, 5-Br, 6-Cl, 6-CN, or 6-Me) with peroxy-acid yields the corresponding 1-oxides; 2,2,3-trifluoro-2,3-dihydro-3-trifluoromethylfuro[3,2-b]pyridine 4-oxide can be prepared similarly. Deoxygenation of pyridine 1-oxide with perfluoro-(2-methylpent-2-ene) yields 2-(2H-hexafluoroisopropyl)pyridine.Reaction of 5-methylpyrimidine 1-oxide with perfluoropropene yields 5-methyl-4- and 5-methyl-2-(1,2,2,2-tetrafluoroethyl)pyrimidine; oxidation of the former with peroxy-acid gives predominantly 5-methyl-4-(1,2,2,2-tetrafluoroethyl)pyrimidine 1-oxide.

The solid-state deoxygenation of dioxygencarbonylchlorobis(triphenylphosphine)iridium(I)

The thermal deoxygenation of solid IrO 2COCl(PPh 3) 2 in nitrogen has been studied, and the rate-controlling step between 379–397 K was found to be one of nucleation and growth of product, with an activation energy of 232 kJ mol −1. There is then a change of mechanism and between 405 and 425 K a phase boundary mechanism is rate-controlling, with an activation energy of 180 kJ mol −1. Some results obtained for the reaction under varying partial pressures of oxygen illustrate the balance between the known thermal and photochemical decompositions.

The thermal deoxygenation of 2‐alkylthiopyridine 1‐oxides

Journal of Heterocyclic ChemistryVolume 11, Issue 1 p. 101-102 Communication to the Editor The thermal deoxygenation of 2-alkylthiopyridine 1-oxides R. E. Kohrman, Corresponding Author R. E. Kohrman Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this authorD. X. West, D. X. West Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this authorM. A. Little, M. A. Little Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this author R. E. Kohrman, Corresponding Author R. E. Kohrman Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this authorD. X. West, D. X. West Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this authorM. A. Little, M. A. Little Department of Chemistry, Central Michigan University Mt. Pleasant, Michigan 48859Search for more papers by this author First published: February 1974 https://doi.org/10.1002/jhet.5570110126Citations: 3AboutPDF 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 onFacebookTwitterLinked InRedditWechat No abstract is available for this article.Citing Literature Volume11, Issue1February 1974Pages 101-102 RelatedInformation