Dithiobiuretes in reactions with electrophilic acetylenes. New derivatives of 1,3,5-dithiazines,-thiadiazines and-triazines as the products of competing reactions of nucleophilic cycloaddition

Tatýana Glotova 1 , Nadezhda Protsuk 1 , Alexander Albanov 1 , Valentin Lopyrev 1 , and Gennadii Dolgushin 1
  • 1 A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of Russian Academy of Sciences, 1 ul. Favorsky, Irkutsk, Russian Federation


The nucleophilic addition of 2,4-dithiobiurete, 1- and 1,4-substituted 2,4-dithiobiuretes (2 a-e) with benzoylacetylene (1) has been studied. 2-(Benzoylmethyl)-4-(R1-imino)-6-(R2-imino)dihydro-4H-1,3,5-dithiazinium perchlorates (3 a-e) are obtained in glacial acetic acid (AcOH) in the presence of equimolar quantities of HClO4. The reaction of benzoylacetylene with 1,5-diphenyl-2,4-dithiobiurete in either of MeOH, C6H6, or MeCN solvents proceeds non-selectively to give a mixture of products such as 2-(benzoylmethyl)-4,6-di(phenylimino)dihydro-4H-1,3,5-dithiazine (5), 2-(benzoylmethyl)-4-(β-benzoylvinyl)thio-3-phenyl-6-(phenylimino)-3,6-dihydro-2H-1,3,5-thiadiazine (8), 2-(benzoylmethyl)-1,3-diphenylhexahydro-1,3,5-triazine-4,6-dithione (7) and N-(β-benzoylvinyl)-N-phenylthioureas (6).

If the inline PDF is not rendering correctly, you can download the PDF file here.

  • [1] P.P. Pathe and M.G. Paranjpe: “A New Synthesis of 5-Aryl-2,3-dihydro-2,6-dimercapto-4-phenylimino-1,3,5-triazines”, Indian J. Chem., Vol. 20B, (1981), pp. 824–825.

  • [2] P.P. Pathe and M.G. Paranjpe: “Preparation of 5-Aryl-4-Arylimino-6-Benzylimino-2-Phenylimino-1,3,5-Dithiazine”, J. Indian Chem. Soc., Vol. 61, (1984), pp. 149–150.

  • [3] A.E.S. Fairfull and D.A. Peak: “Dithiobiurets. Part II. Some Cyclic Derivatives”, J. Chem. Soc., Vol. 3, (1955), pp. 803–808. http://dx.doi.org/10.1039/jr9550000803

  • [4] M.S. Chande and N.P. Shetgiri: “Reaction of Ethylchloroformate with 1-Alkyl/Aryl-2,4-dithiobiurets in Presence of Ketohes”, J. Indian Chem. Soc., Vol. 67, (1990), pp. 849–852.

  • [5] A.S. Nakhmanovich, T.E. Glotova, T.N. Komarova, V.A. Lopyrev: “A New Route of Synthesis of Substituted 5,6-Dihydro-1,3,5-dithiazinium hydrobromides by the Reaction of 1-Acyl-2-bromoacetylenes with Dithiobiurete”, Khim. Geterotsikl. Soed., No. 3, (1998), pp. 417–418 (Rus).

  • [6] A.S. Nakhmanovich, T.E. Glotova, G.G. Skvortsova: “On the Reaction of Dithiobiuret with α-Acetylenic Ketones”, Izv. Akad. Nauk. Ser. Khim., No. 2, (1985), pp. 113–116 (Rus).

  • [7] J. Goerdeler and R. Losch: “Darstellung und Reaktionen von (Thiocarbamoyl) carbodiimiden”, Chem. Ber.-Recl., Vol. 113, (1980), pp. 79–89.

  • [8] C.P. Joshua and V.P. Rajan: “Reaction of Isothiocyanates with Thiourea and Amidinothioureas: Formation of S-(N-Substituted thiocarbamyl)isothioureas and 1-Alkyl(or aryl)-4-imino(or arylimino)-6-iminohexahydro-1,3,5-triazine-2-thiones”, Aust. J. Chem., Vol. 29, (1976), pp. 415–425. http://dx.doi.org/10.1071/CH9760415

  • [9] C.P. Joshua, E. Prasannan, S.K. Thomas: “Reaction of Isothiocyanates with Thiourea—a Correction”, Aust. J. Chem., Vol. 34, (1981), pp. 917–921. http://dx.doi.org/10.1071/CH9810917

  • [10] A.S. Nakhmanovich, T.E. Glotova, T.N. Komarova, G.G. Skvortsova, M.V. Sigalov, V.B. Modonov: “On the Reaction of Thiobenzamide with α-Acetylenic Ketones”, Zh. Org. Khim., Vol. 19, (1983), pp. 1428–1431 (Rus).


Journal + Issues