• Medientyp: E-Artikel
  • Titel: Synthesis and Crystal Structures of New 1,4-Disubstituted 1,2,4-Triazoline-5-thiones
  • Beteiligte: Laus, Gerhard; Kahlenberg, Volker; Wurst, Klaus; Schottenberger, Herwig
  • Quelle: Zeitschrift für Naturforschung B ; 69 ( 2014 ) S. 950-964
  • Erschienen: Walter de Gruyter GmbH, 2014
  • Sprache: Englisch
  • DOI: 10.5560/znb.2014-4145
  • ISSN: 1865-7117; 0932-0776
  • Schlagwörter: General Chemistry
  • Zusammenfassung: <jats:title>Abstract</jats:title> <jats:p>Introduction of sulfur into the 5-position of 1,4-disubstituted quaternary 1,2,4-triazolium salts (1-9; Cl, Br, I, BF<jats:sub>4</jats:sub>, PF<jats:sub>6</jats:sub>, CH<jats:sub>3</jats:sub>OSO<jats:sub>3</jats:sub> were used as anions) by two methods was investigated. The syntheses of nine 1,4-disubstituted 1,2,4-triazoline-5-thiones 10-18 are reported (1, 10: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 2, 11: R<jats:sup>1</jats:sup> = NH<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 3, 12: R<jats:sup>1</jats:sup> = NH<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>; 4, 13: R<jats:sup>1</jats:sup> = N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 5, 14: R<jats:sup>1</jats:sup> = N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>; 6, 15: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = NH<jats:sub>2</jats:sub>; 7, 16: R<jats:sup>1</jats:sup> = OCH<jats:sub>2</jats:sub>Ph, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 8, 17: R<jats:sup>1</jats:sup> = OCH<jats:sub>2</jats:sub>Ph, R<jats:sup>2</jats:sup> = CH<jats:sub>2</jats:sub>CH<jats:sub>3</jats:sub>; 9, 18: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>2</jats:sub>Ph). Compounds 11-17 represent 1-amino, 4-amino, 4-dimethylamino, and 4-benzyloxy-1,2,4-triazoline-5- thiones, whereas 10 served as a reference compound. Thione 18 was identified as an unexpected by-product in the synthesis of 16 and was also prepared independently. Thermolysis of 10 in air gave 1,4-dimethyl-1,2,4-triazolium hydrogensulfate. Crystal structures of eight 1,4-disubstituted 1,2,4- triazoline-5-thiones were determined by single-crystal X-ray diffraction. Intermolecular hydrogen bonds (C-H···S, C-H···N, N-H···N, N-H···S) were observed in the solid state. The solvent-dependent <jats:sup>1</jats:sup>H NMR chemical shifts of signals of 10 and 13 were satisfactorily correlated with the Kamlet- Abboud-Taft π* and b parameters in ten solvents. From the lack of correlation with the a parameter and from the C=S bond length (average 1.67 Å) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely </jats:p>
  • Beschreibung: <jats:title>Abstract</jats:title>
    <jats:p>Introduction of sulfur into the 5-position of 1,4-disubstituted quaternary 1,2,4-triazolium salts (1-9; Cl, Br, I, BF<jats:sub>4</jats:sub>, PF<jats:sub>6</jats:sub>, CH<jats:sub>3</jats:sub>OSO<jats:sub>3</jats:sub> were used as anions) by two methods was investigated. The syntheses of nine 1,4-disubstituted 1,2,4-triazoline-5-thiones 10-18 are reported (1, 10: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 2, 11: R<jats:sup>1</jats:sup> = NH<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 3, 12: R<jats:sup>1</jats:sup> = NH<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>; 4, 13: R<jats:sup>1</jats:sup> = N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 5, 14: R<jats:sup>1</jats:sup> = N(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, R<jats:sup>2</jats:sup> = CH(CH<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>; 6, 15: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = NH<jats:sub>2</jats:sub>; 7, 16: R<jats:sup>1</jats:sup> = OCH<jats:sub>2</jats:sub>Ph, R<jats:sup>2</jats:sup> = CH<jats:sub>3</jats:sub>; 8, 17: R<jats:sup>1</jats:sup> = OCH<jats:sub>2</jats:sub>Ph, R<jats:sup>2</jats:sup> = CH<jats:sub>2</jats:sub>CH<jats:sub>3</jats:sub>; 9, 18: R<jats:sup>1</jats:sup> = CH<jats:sub>3</jats:sub>, R<jats:sup>2</jats:sup> = CH<jats:sub>2</jats:sub>Ph). Compounds 11-17 represent 1-amino, 4-amino, 4-dimethylamino, and 4-benzyloxy-1,2,4-triazoline-5- thiones, whereas 10 served as a reference compound. Thione 18 was identified as an unexpected by-product in the synthesis of 16 and was also prepared independently. Thermolysis of 10 in air gave 1,4-dimethyl-1,2,4-triazolium hydrogensulfate. Crystal structures of eight 1,4-disubstituted 1,2,4- triazoline-5-thiones were determined by single-crystal X-ray diffraction. Intermolecular hydrogen bonds (C-H···S, C-H···N, N-H···N, N-H···S) were observed in the solid state. The solvent-dependent <jats:sup>1</jats:sup>H NMR chemical shifts of signals of 10 and 13 were satisfactorily correlated with the Kamlet- Abboud-Taft π* and b parameters in ten solvents. From the lack of correlation with the a parameter and from the C=S bond length (average 1.67 Å) a significant contribution of a mesoionic imidazolium-2-thiolate resonance structure seems unlikely </jats:p>