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Monatshefte für Chemie / Chemical Monthly

, Volume 107, Issue 1, pp 155–170 | Cite as

Über 4-Alkylamino-bzw. 4-Arylamino-5,6-dihydro-2(1H)-pyridinthione

Über Heterocyclen, 45. Mitt.
  • Gustav Zigeuner
  • W.-Bernd Lintschinger
  • Alfred Fuchsgruber
  • Krystyna Kollmann
Organische Chemie und Biochemie

4-Alkylamino- and 4-arylamino-5,6-dihydro-2(1H)-pyridinethiones

Abstract

Heating 1-alkyl- or 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones5, 6 in an inert medium causes rearrangement to 4-alkylamino-(4-arylamino-)-5,6-dihydro-2(1H)-pyridinethiones11, 12, probably via the methylene form29, by thermal heterolysis of the N1/C2 bond and exchange of the alkylamino (arylamino) group 1 through the carbon atom of the methylene group 6. The aminodihydropyridinethiones11, which can be regarded as cyclic derivatives of 3-aminothiocrotonamide, react with bistrichlorophenylmalonate under diacylation, and with formaldehyde and primary amines to yield aminodialkylation products of the enamine system, tetrahydro-4-hydroxy-7,7-dimethyl-5-thioxopyrido[4,3-b]pyridine-2(1H)-ones13, 14 and hexahydro-7,7-dimethylpyrido[4,3-d]pyrimidine-5(6H)-thiones18, 19, 21 respectively. H2O2 converts11 to the corresponding 4-aminodihydro-2(1H)-pyridones22, which can be reconverted into11 with P4S10.11 reacts with alkyl halides to 2-alkylthiodihydropyridines23, 24, 25. The mechanism of the methylpyrimidine-pyridine rearrangement is discussed.

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Copyright information

© Springer-Verlag 1976

Authors and Affiliations

  • Gustav Zigeuner
    • 1
  • W.-Bernd Lintschinger
    • 1
  • Alfred Fuchsgruber
    • 1
  • Krystyna Kollmann
    • 1
  1. 1.Institut für Pharmazeutische Chemie der Universität GrazGrazÖsterreich

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