Regiodirected Synthesis and Stereochemistry of 2,4,8‐Trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes and α,ω‐Bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes |
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| Authors: | Vnira R. Akhmetova Ruslan A. Vagapov Tat'yana V. Tyumkina Guzel R. Khabibullina Zoya A. Starikova Alexander H. Lobov Yuliya V. Nelyubina Raikhana V. Kunakova Usein M. Dzhemilev |
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| Affiliation: | 1. Institute of Petrochemistry and Catalysis, Russian Academy of Science, Ufa, Russia;2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia;3. Ufa State Academy of Economics and Service, Ufa, Russia |
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| Abstract: | 2,4,8‐Trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes have been obtained by the regioselective and stereoselective cyclocondensation of 1,2‐ethanediamine with aldehydes RCHO (R═Me, Et, Prn, Bun, Pentn) and H2S at molar ratio 1:3:2 at 0°C. The increase in molar ratio of thiomethylation mixture RCHO–H2S (6:4) at 40°C resulted in selective formation of bis‐(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)ethanes. Cyclothiomethylation of aliphatic α,ω‐diamines with aldehydes RCHO (R═Me, Et) and H2S at molar ratio 1:6:4 and at 40°С led to α,ω‐bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes. Stereochemistry of 2,4,8‐trialkyl‐3‐thia‐1,5‐diazabicyclo[3.2.1]octanes have been determined by means of 1H and 13С NMR spectroscopy and further supported by DFT calculations at the B3LYP/6‐31G(d,p) level. The structure of α,ω‐bis(2,4,6‐trialkyl‐1,3,5‐dithiazinane‐5‐yl)alkanes was confirmed by single‐crystal X‐ray diffraction study. |
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