3,5-DIALKYLTETRAHYDRO-4<i>H</i>-THIOPYRAN-4-ONES UNDER THE CONDITIONS OF MANNICH REACTION

Authors

  • Лариса А. Баева Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054
  • Ляйсан Ф. Бикташева Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054
  • Ахнэф А. Фатыхов Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054
  • Нафиса К. Ляпина Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054

DOI:

https://doi.org/10.1007/2702

Keywords:

3, 5-dialkyltetrahydro-4H-thiopyranone, sodium sulfide, 3-thia-7-azabicyclo[3.3.1]nonan-9-one, Mannich condensation, thiomethylation

Abstract

Thiomethylation of pentan-3-one, 5-methylhexan-3-one, and heptan-4-one with a mixture of formaldehyde and sodium sulfide gave the respective 3,5-dialkyltetrahydro-4H-thiopyran-4-ones, while 3,5-dihydroxymethyl- or 3,5-dialkyl-5-hydroxymethyltetrahydro-4H-thiopyran-4-ols were formed in the presence of primary amines. The oxidation of 3,5-dimethyltetrahydro-4H-thiopyran-4-one with an equivalent amount of hydrogen peroxide in tetrahydrofuran and chloroform led to the sulfoxide and sulfone, respectively, while aminomethylation with a mixture of formaldehyde and methylamine, hexylamine, monoethanolamine, or hydrochlorides of methyl, ethyl, and 2-propyl esters of aminoacetic acid at рH 7–8 produced the respective 1,5-dimethyl-3-thia-7-azabicyclo[3.3.1]nonanes. An equilibrium between the chair and boat conformations in the thiopyranone ring was found in CDCl3 solutions of 7-(2-hydroxyethyl)-1,5-dimethyl-3-thia-7-azabicyclo[3.3.1]nonan-9-one at 50°С and DMSO-d6 solutions of 1,5,7-trimethyl-3-thia-7-azabicyclo[3.3.1]nonan-9-one monoperchlorate at 20°С.

How to Cite
Baeva, L. A.; Biktasheva, L. F.; Fatykhov, A. A.; Lyapina, N. K. Chem. Heterocycl. Compd. 2015, 51, 969. [Khim. Geterotsikl. Soedin. 2015, 51, 969.]

For this article in the English edition see DOI 10.1007/s10593-016-1806-x

Author Biographies

Лариса А. Баева, Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054

Лариса Асхатовна Баева

лаборатория химической кинетики, ст.н.с., доцент

Ляйсан Ф. Бикташева, Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054

Ляйсан Фаритовна Бикташева

лаборатория химической кинетики, м.н.с.

Ахнэф А. Фатыхов, Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054

Ахнэф Амирович Фатыхов

лаборатория физико-химических методов анализа, ст.н.с.

Нафиса К. Ляпина, Ufa Institute of Chemistry, Russian Academy of Sciences, 71 Oktyabrya Ave., Ufa 450054

Нафиса Кабировна Ляпина

лаборатория химической кинетики, гл.н.с., проф.

Published

2015-11-18

Issue

Section

Original Papers