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Über die Reaktionen von 2-Cyclohexenonen mit Ammoniumthiocyanat bzw. Thioharnstoff Über Heterocyclen, 59. Mitteilung

The reactions of 2-cyclohexenones with ammoniumthiocyanate and thiourea

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Abstract

The 2-cyclohexenones1 a, b andc react with NH4SCN to give 3,5,5-trimethyl-, 3-methyl-5-phenyl- and 3-methyl-2-cyclohexeniminiumthiocyanates8 a, b andc resp. (i.e. salts of α,β-unsaturated imines) and not the expected diazabicyclononane-thiones5 a, b andc. Alternative formulae for the1—NH4SCN-condensates are discussed and rejected on the basis of IR- and NMR-spectra and the chemical properties of5 a-c.

By action of thiourea inMeOH/NaOMe the 2-cyclohexenones1a, d ande are transformed into 1-hydroxy-5,7,7-trimethyl-, 1-hydroxy-5-methyl- and 1-hydroxy-2,4-diazabicyclo[3.3.1]nonane-3-thiones5 a, d ande resp. The structure of the diazabicyclononane-thiones5 a, d ande is established by means of NMR-, IR- and MS-spectra.

8 a-c and5 e showed no significant herbicidal and only small fungicidal (8 b, c) and insecticidal (8 a-c) activities in screening tests.

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Wendelin, W., Kern, W. Über die Reaktionen von 2-Cyclohexenonen mit Ammoniumthiocyanat bzw. Thioharnstoff Über Heterocyclen, 59. Mitteilung. Monatshefte für Chemie 110, 1345–1355 (1979). https://doi.org/10.1007/BF00938291

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Keywords

  • 2-Cyclohexeniminium thiocyanates
  • 2-Cyclohexenones, reactions with thiocyanate and thiourea
  • 2,4-Diazabicyclo[3.3.1]nonane-3-thiones
  • 2-Pyrimidinthiones, bicyclic