Synthesis, NMR Spectroscopy, and Molecular Modeling of 2-Methyl-2,3,4,5-tetrahydro-1H-[1]benzothieno[2,3-c]azepine

被引：1

作者：

Eresko, A. B. ^{[1
]}

Raksha, E. V. ^{[1
]}

Berestneva, Yu. V. ^{[2
]}

Muratov, A. V. ^{[1
]}

Voitash, A. A. ^{[1
]}

Tolkunov, V. S. ^{[3
]}

Tolkunov, S. V. ^{[3
]}

机构：

[1] Litvinenko Inst Phys Organ & Coal Chem, UA-83114 Donetsk, Ukraine

[2] Russian Acad Sci, Fed Res Ctr Agroecol Complex Meliorat & Protect A, Volgograd 400062, Russia

[3] Natl Acad Sci Ukraine, Litvinenko Inst Phys Organ & Coal Chem, UA-02160 Kiev, Ukraine

来源：

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY | 2020年 / 56卷 / 11期

关键词：

fused azepines; Eschweiler-Clark reaction; chemical shift; coalescence; inversion barrier; GIAO; INVERSION;

D O I：

10.1134/S1070428020110068

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new synthetic approach to fused azepines was demonstrated on an example of the synthesis of 2-methyl-2,3,4,5-tetrahydro-H-1-[1]benzothieno[2,3-c]azepine. The key stage of the synthesis is the formation of the azepine ring under the Eschweiler-Clark reaction conditions. The Gibbs energy of activation for the inversion of the azepine ring was determined by dynamic H-1 NMR spectroscopy. Molecular modeling of the structure and estimation of the H-1 and C-13 NMR chemical shifts were performed for 2-methyl-2,3,4,5-tetrahydro-1H-[1]benzothieno[2,3-c]azepine. The magnetic shielding tensors were calculated by the standard GIAO method using the B3LYP/6-31G(d,p)-optimized molecular geometry parameters. The solvent effect was taken into account in the PCM approximation. The calculated H-1 and C-13 NMR chemical shifts of 2-methyl-2,3,4,5-tetrahydro-1H-[1]benzothieno[2,3-c]azepine are in good agreement with the experimental values observed in the spectra of its DMSO-d(6) solution.

引用

页码：1929 / 1936

页数：8

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