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Cyclothiomethylation of aryl hydrazines with formaldehyde and hydrogen sulfide

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Abstract

Cyclothiomethylation of phenyl hydrazine with CH2O and H2S in a ratio of 1: 3: 2 in an acidic medium (HCl) afforded previously unknown 3-phenyl-1,3,4-thiadiazolidine (35% yield) and N-phenyl(perhydro-1,3,5-dithiazin-5-yl)amine (35% yield). The analogous reaction in an alkaline medium (BuONa) produced N-phenyl(perhydro-1,3-thiazetidin-3-yl)amine (22% yield). The reaction of 1,2-diphenyl hydrazine with CH2O and H2S in an alkaline medium gave 1,2,4,5-tetraphenylhexahydro-1,2,4,5-tetrazine and previously unknown 3,4-diphenyl-1,3,4-thiadiazolidine and 5,6-diphenyltetrahydro-1,3,5,6-dithiadiazepine in 39 and 22% yields, respectively. Cyclothiomethylation of benzyl hydrazine afforded previously unknown bis[(6-benzyl-4,2,6-thiadiazolidin-2-yl)methyl] sulfide (60% yield) and N-benzyl(perhydro-1,3,5-dithiazin-5-yl)amine (19% yield). The reaction of tosyl hydrazine produced 3-[(p-tolyl)sulfonyl]-1,3,4-thiadiazolidine, N-(perhydro-1,3,5-dithiazin-5-yl)-p-tolylsulfonamide, and 3,7-bis(p-tolylsulfonylamino)-1,5-dithia-3,7-diazacyclooctane in 21, 38, and 41% yields, respectively.

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Authors and Affiliations

  1. Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 prosp. Oktyabrya, 450075, Ufa, Russian Federation

    V. R. Akhmetova, G. R. Nadyrgulova, T. V. Tyumkina & U. M. Dzhemilev

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    Z. A. Starikova, D. G. Golovanov & M. Yu. Antipin

  3. Ufa State Academy of Economics and Service, 145 ul. Chernyshevskogo, 450077, Ufa, Russian Federation

    R. V. Kunakova

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  1. V. R. Akhmetova
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  2. G. R. Nadyrgulova
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  3. T. V. Tyumkina
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  4. Z. A. Starikova
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  5. D. G. Golovanov
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  7. R. V. Kunakova
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  8. U. M. Dzhemilev
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1758–1767, October, 2006.

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Akhmetova, V.R., Nadyrgulova, G.R., Tyumkina, T.V. et al. Cyclothiomethylation of aryl hydrazines with formaldehyde and hydrogen sulfide. Russ Chem Bull 55, 1824–1834 (2006). https://doi.org/10.1007/s11172-006-0493-7

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  • DOI: https://doi.org/10.1007/s11172-006-0493-7

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