Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates

The results of quantum chemical and experimental studies of the reaction of 2-bromomethyl-1,3-thiaselenole with 1,3-benzothiazole-2-thiol made it possible to discover the unprecedented pathway of this reaction, which proceeds stepwise at three different centers of seleniranium intermediates. The fir...

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Autores principales:	Svetlana V. Amosova, Vladimir A. Shagun, Nataliya A. Makhaeva, Irina A. Novokshonova, Vladimir A. Potapov
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	2-bromomethyl-1,3-thiaselenole 1,3-benzothiazole-2-thiol vinyl sulfides 2,3-dihydro-1,4-thiaselenine seleniranium cation rearrangement Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/ec9c1efb9b8448faae9c30f54274e1c8
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spelling	oai:doaj.org-article:ec9c1efb9b8448faae9c30f54274e1c82021-11-11T18:38:27ZQuantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates10.3390/molecules262166851420-3049https://doaj.org/article/ec9c1efb9b8448faae9c30f54274e1c82021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6685https://doaj.org/toc/1420-3049The results of quantum chemical and experimental studies of the reaction of 2-bromomethyl-1,3-thiaselenole with 1,3-benzothiazole-2-thiol made it possible to discover the unprecedented pathway of this reaction, which proceeds stepwise at three different centers of seleniranium intermediates. The first stage includes an attack of thiolate anion at the selenium atom of the seleniranium cation accompanied by ring opening with the formation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide, which is converted to six-membered heterocycle, 2-(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)-1,3-benzothiazole, in a 99% yield. The latter compound undergoes rearrangement with ring contraction producing five-membered heterocycle, 2-[(1,3-thiaselenol-2-ylmethyl)sulfanyl]-1,3-benzothiazole, in a 99% yield (the thermodynamic product). The formation of 1,2-bis[(<i>Z</i>)-2-(vinylsulfanyl)ethenyl] diselenide is the result of the disproportionation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide. Thus, based on the quantum chemical and experimental studies, a regioselective synthesis of the reaction products in high yields was developed.Svetlana V. AmosovaVladimir A. ShagunNataliya A. MakhaevaIrina A. NovokshonovaVladimir A. PotapovMDPI AGarticle2-bromomethyl-1,3-thiaselenole1,3-benzothiazole-2-thiolvinyl sulfides2,3-dihydro-1,4-thiaselenineseleniranium cationrearrangementOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6685, p 6685 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	2-bromomethyl-1,3-thiaselenole 1,3-benzothiazole-2-thiol vinyl sulfides 2,3-dihydro-1,4-thiaselenine seleniranium cation rearrangement Organic chemistry QD241-441
spellingShingle	2-bromomethyl-1,3-thiaselenole 1,3-benzothiazole-2-thiol vinyl sulfides 2,3-dihydro-1,4-thiaselenine seleniranium cation rearrangement Organic chemistry QD241-441 Svetlana V. Amosova Vladimir A. Shagun Nataliya A. Makhaeva Irina A. Novokshonova Vladimir A. Potapov Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
description	The results of quantum chemical and experimental studies of the reaction of 2-bromomethyl-1,3-thiaselenole with 1,3-benzothiazole-2-thiol made it possible to discover the unprecedented pathway of this reaction, which proceeds stepwise at three different centers of seleniranium intermediates. The first stage includes an attack of thiolate anion at the selenium atom of the seleniranium cation accompanied by ring opening with the formation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide, which is converted to six-membered heterocycle, 2-(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)-1,3-benzothiazole, in a 99% yield. The latter compound undergoes rearrangement with ring contraction producing five-membered heterocycle, 2-[(1,3-thiaselenol-2-ylmethyl)sulfanyl]-1,3-benzothiazole, in a 99% yield (the thermodynamic product). The formation of 1,2-bis[(<i>Z</i>)-2-(vinylsulfanyl)ethenyl] diselenide is the result of the disproportionation of (Z)-2-[(1,3-benzothiazol-2-ylsulfanyl)selanyl]ethenyl vinyl sulfide. Thus, based on the quantum chemical and experimental studies, a regioselective synthesis of the reaction products in high yields was developed.
format	article
author	Svetlana V. Amosova Vladimir A. Shagun Nataliya A. Makhaeva Irina A. Novokshonova Vladimir A. Potapov
author_facet	Svetlana V. Amosova Vladimir A. Shagun Nataliya A. Makhaeva Irina A. Novokshonova Vladimir A. Potapov
author_sort	Svetlana V. Amosova
title	Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
title_short	Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
title_full	Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
title_fullStr	Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
title_full_unstemmed	Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates
title_sort	quantum chemical and experimental studies of an unprecedented reaction pathway of nucleophilic substitution of 2-bromomethyl-1,3-thiaselenole with 1,3-benzothiazole-2-thiol proceeding stepwise at three different centers of seleniranium intermediates
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/ec9c1efb9b8448faae9c30f54274e1c8
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Quantum Chemical and Experimental Studies of an Unprecedented Reaction Pathway of Nucleophilic Substitution of 2-Bromomethyl-1,3-thiaselenole with 1,3-Benzothiazole-2-thiol Proceeding Stepwise at Three Different Centers of Seleniranium Intermediates

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