Proton Chemical Polarisation, Autocatalysis and Frontal Kinetics of the Oxidation of Dialkylsulphides with Nitric Acid Full article
Conference |
International Symposium on Chemical Induced Dynamic Polarisation of Nuclei and Electrons 13-16 Aug 1972 , Tallinn |
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Journal |
Magnetic Resonance in Chemistry
ISSN: 0749-1581 , E-ISSN: 1097-458X |
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Output data | Year: 1973, Volume: 5, Number: 7, Pages: 343-346 Pages count : 4 DOI: 10.1002/mrc.1270050708 | ||
Tags | oxidation alkyl sulfide nitric acid; nuclear polarization oxidation alkyl sulfide; frontal reaction oxidation alkyl sulfide | ||
Authors |
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Affiliations |
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Abstract:
The oxidation of dimethyl sulphide to dimethylsulphoxide with nitric acid displays CIDNP effects of protons and the
phenomenon of frontal kinetics. The process is autocatalytic, with N2O4 as the catalyst and the primary oxidant of sulphide. In the presence of the inhibitor (methylmercaptan) the frontal reaction takes place: in purified samples - the usual volume reaction. The interaction of ethyl, n-propyl and n-butyl sulphides with NOZ is accompanied by integral polarisation of the a-CH,-protons. In all the cases sulphide is negatively polarised and sulphoxide positively polarised. The reaction mechanism proposed includes the formation of a radical pair during the interaction of sulphide
with N2O4. Disproportionation of the radical pair leads to the formation of polarised sulphoxide and the decay results in regeneration of sulphide. The rate of oxidation of sulphide during the volume reaction is proportional to the product polarisation.
Cite:
Rudakov E.S.
, Mastikhin V.M.
, Popov S.G.
, Rudakova R.I.
Proton Chemical Polarisation, Autocatalysis and Frontal Kinetics of the Oxidation of Dialkylsulphides with Nitric Acid
Magnetic Resonance in Chemistry. 1973. V.5. N7. P.343-346. DOI: 10.1002/mrc.1270050708 Scopus РИНЦ
Proton Chemical Polarisation, Autocatalysis and Frontal Kinetics of the Oxidation of Dialkylsulphides with Nitric Acid
Magnetic Resonance in Chemistry. 1973. V.5. N7. P.343-346. DOI: 10.1002/mrc.1270050708 Scopus РИНЦ
Dates:
Submitted: | Oct 31, 1972 |
Accepted: | Dec 11, 1972 |
Published print: | Jul 1, 1973 |
Identifiers:
Scopus | 2-s2.0-84994988653 |
Elibrary | 47283974 |
Chemical Abstracts | 1973:491340 |
Chemical Abstracts (print) | 79:91340 |
OpenAlex | W1977393432 |