Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines

Konstantin G. Nazarenko; Nataliya A. Shtil; Sergey A. Buth; Alexander N. Chernega; Miron O. Lozinskii; Andrey A. Tolmachev

doi:10.1016/j.tet.2008.02.049

Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines

Konstantin G. Nazarenko, Nataliya A. Shtil, Sergey A. Buth, Alexander N. Chernega, Miron O. Lozinskii, Andrey A. Tolmachev

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

The reaction of 2-chloro-3-oxo-3,4-dihydro-2H-1,4-benzothiazines with 'push-pull' enamines was investigated. The reaction with the enamines occurs at the β-carbon atom in the presence of a small excess of triethylamine. As a result, a set of 3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives was prepared. On acidic hydrolysis of ethyl 2-ethyl-3-(methylimino)-2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl)butanoate, a new rearrangement affording ethyl 11-ethyl-2,3-dimethyl-4-oxo-2,3,4,5-tetrahydro-1H-2,5-methano-6,1,3-benzothiadiazocine-11-carboxylate was discovered. A plausible mechanism and factors influencing the course of the reaction are discussed.

Original language	English (US)
Pages (from-to)	4478-4485
Number of pages	8
Journal	Tetrahedron
Volume	64
Issue number	19
DOIs	https://doi.org/10.1016/j.tet.2008.02.049
State	Published - May 5 2008
Externally published	Yes

Keywords

Chloro derivatives
Electrophilic substitution
Enamines
Rearrangement
Spiro heterocycles

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2008.02.049

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Nazarenko, K. G., Shtil, N. A., Buth, S. A., Chernega, A. N., Lozinskii, M. O., & Tolmachev, A. A. (2008). Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines. Tetrahedron, 64(19), 4478-4485. https://doi.org/10.1016/j.tet.2008.02.049

Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines. / Nazarenko, Konstantin G.; Shtil, Nataliya A.; Buth, Sergey A. et al.
In: Tetrahedron, Vol. 64, No. 19, 05.05.2008, p. 4478-4485.

Research output: Contribution to journal › Article › peer-review

@article{5686219468e642d6b4cff9416d5f13fc,

title = "Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines",

abstract = "The reaction of 2-chloro-3-oxo-3,4-dihydro-2H-1,4-benzothiazines with 'push-pull' enamines was investigated. The reaction with the enamines occurs at the β-carbon atom in the presence of a small excess of triethylamine. As a result, a set of 3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives was prepared. On acidic hydrolysis of ethyl 2-ethyl-3-(methylimino)-2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl)butanoate, a new rearrangement affording ethyl 11-ethyl-2,3-dimethyl-4-oxo-2,3,4,5-tetrahydro-1H-2,5-methano-6,1,3-benzothiadiazocine-11-carboxylate was discovered. A plausible mechanism and factors influencing the course of the reaction are discussed.",

keywords = "Chloro derivatives, Electrophilic substitution, Enamines, Rearrangement, Spiro heterocycles",

author = "Nazarenko, {Konstantin G.} and Shtil, {Nataliya A.} and Buth, {Sergey A.} and Chernega, {Alexander N.} and Lozinskii, {Miron O.} and Tolmachev, {Andrey A.}",

note = "Funding Information: We thank Enamine Co, Ukraine for the financial support of this work and Prof. Kostyuk, A.N. for his help in the preparation of this paper. Copyright: Copyright 2009 Elsevier B.V., All rights reserved.",

year = "2008",

month = may,

day = "5",

doi = "10.1016/j.tet.2008.02.049",

language = "English (US)",

volume = "64",

pages = "4478--4485",

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T1 - Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines

AU - Nazarenko, Konstantin G.

AU - Shtil, Nataliya A.

AU - Buth, Sergey A.

AU - Chernega, Alexander N.

AU - Lozinskii, Miron O.

AU - Tolmachev, Andrey A.

N1 - Funding Information: We thank Enamine Co, Ukraine for the financial support of this work and Prof. Kostyuk, A.N. for his help in the preparation of this paper. Copyright: Copyright 2009 Elsevier B.V., All rights reserved.

PY - 2008/5/5

Y1 - 2008/5/5

N2 - The reaction of 2-chloro-3-oxo-3,4-dihydro-2H-1,4-benzothiazines with 'push-pull' enamines was investigated. The reaction with the enamines occurs at the β-carbon atom in the presence of a small excess of triethylamine. As a result, a set of 3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives was prepared. On acidic hydrolysis of ethyl 2-ethyl-3-(methylimino)-2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl)butanoate, a new rearrangement affording ethyl 11-ethyl-2,3-dimethyl-4-oxo-2,3,4,5-tetrahydro-1H-2,5-methano-6,1,3-benzothiadiazocine-11-carboxylate was discovered. A plausible mechanism and factors influencing the course of the reaction are discussed.

AB - The reaction of 2-chloro-3-oxo-3,4-dihydro-2H-1,4-benzothiazines with 'push-pull' enamines was investigated. The reaction with the enamines occurs at the β-carbon atom in the presence of a small excess of triethylamine. As a result, a set of 3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives was prepared. On acidic hydrolysis of ethyl 2-ethyl-3-(methylimino)-2-(3-oxo-3,4-dihydro-2H-1,4-benzothiazin-2-yl)butanoate, a new rearrangement affording ethyl 11-ethyl-2,3-dimethyl-4-oxo-2,3,4,5-tetrahydro-1H-2,5-methano-6,1,3-benzothiadiazocine-11-carboxylate was discovered. A plausible mechanism and factors influencing the course of the reaction are discussed.

KW - Chloro derivatives

KW - Electrophilic substitution

KW - Enamines

KW - Rearrangement

KW - Spiro heterocycles

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Synthesis of 1,4-benzothiazin-2-yl derivatives of 1,3-dicarbonyl compounds and benzothiazinone spiro derivatives by the reaction of 2-chloro-1,4-benzothiazin-3-ones with 'push-pull' enamines

Abstract

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