N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement

Lev M. Yagupolskii, Irina I. Maletina, Liubov V. Sokolenko, Yurii G. Vlasenko, Sergii Buth

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The analogues of carboxamides in which the sp2-hybridized oxygen atom is replaced by more electron-withdrawing groups, {double bond, long}NSO2CF3 and {double bond, long}NSO2C4F9, have been synthesized. The resulting N-perfluoroalkylsulfonyl arenecarboxamidines ArC({double bond, long}NSO2Rf)NH2 (Rf = CF3, C4F9) undergo an oxidative Hofmann-type rearrangement to the corresponding carbodiimides ArN{double bond, long}C{double bond, long}NSO2Rf under the action of (diacyloxyiodo)arenes. Rearrangement of related compounds ArC({double bond, long}NSO2R)NH2 (R = CH3, Ph) containing fluorine-free substituents at the sulfonyl group also occurs in similar conditions. It was found that the reactivity of amidines rises with the increasing electron-withdrawing ability of the substituent R.

Original languageEnglish (US)
Pages (from-to)486-492
Number of pages7
JournalJournal of Fluorine Chemistry
Volume129
Issue number6
DOIs
StatePublished - Jun 2008
Externally publishedYes

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Amides
amides
Amidines
Electrons
Derivatives
Carbodiimides
electron
acids
Acids
Fluorine
acid
fluorine
oxygen atoms
electrons
reactivity
analogs
Oxygen
Atoms
oxygen

Keywords

  • Amidines
  • Carbodiimides
  • Rearrangements
  • X-ray structure

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics

Cite this

N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement. / Yagupolskii, Lev M.; Maletina, Irina I.; Sokolenko, Liubov V.; Vlasenko, Yurii G.; Buth, Sergii.

In: Journal of Fluorine Chemistry, Vol. 129, No. 6, 06.2008, p. 486-492.

Research output: Contribution to journalArticle

Yagupolskii, Lev M. ; Maletina, Irina I. ; Sokolenko, Liubov V. ; Vlasenko, Yurii G. ; Buth, Sergii. / N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement. In: Journal of Fluorine Chemistry. 2008 ; Vol. 129, No. 6. pp. 486-492.
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T1 - N-Perfluoroalkylsulfonylimido derivatives of arenecarboxylic acid amides and their oxidative aza Hofmann rearrangement

AU - Yagupolskii, Lev M.

AU - Maletina, Irina I.

AU - Sokolenko, Liubov V.

AU - Vlasenko, Yurii G.

AU - Buth, Sergii

PY - 2008/6

Y1 - 2008/6

N2 - The analogues of carboxamides in which the sp2-hybridized oxygen atom is replaced by more electron-withdrawing groups, {double bond, long}NSO2CF3 and {double bond, long}NSO2C4F9, have been synthesized. The resulting N-perfluoroalkylsulfonyl arenecarboxamidines ArC({double bond, long}NSO2Rf)NH2 (Rf = CF3, C4F9) undergo an oxidative Hofmann-type rearrangement to the corresponding carbodiimides ArN{double bond, long}C{double bond, long}NSO2Rf under the action of (diacyloxyiodo)arenes. Rearrangement of related compounds ArC({double bond, long}NSO2R)NH2 (R = CH3, Ph) containing fluorine-free substituents at the sulfonyl group also occurs in similar conditions. It was found that the reactivity of amidines rises with the increasing electron-withdrawing ability of the substituent R.

AB - The analogues of carboxamides in which the sp2-hybridized oxygen atom is replaced by more electron-withdrawing groups, {double bond, long}NSO2CF3 and {double bond, long}NSO2C4F9, have been synthesized. The resulting N-perfluoroalkylsulfonyl arenecarboxamidines ArC({double bond, long}NSO2Rf)NH2 (Rf = CF3, C4F9) undergo an oxidative Hofmann-type rearrangement to the corresponding carbodiimides ArN{double bond, long}C{double bond, long}NSO2Rf under the action of (diacyloxyiodo)arenes. Rearrangement of related compounds ArC({double bond, long}NSO2R)NH2 (R = CH3, Ph) containing fluorine-free substituents at the sulfonyl group also occurs in similar conditions. It was found that the reactivity of amidines rises with the increasing electron-withdrawing ability of the substituent R.

KW - Amidines

KW - Carbodiimides

KW - Rearrangements

KW - X-ray structure

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