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, Sergii Buth, Alexander N. Chernega, Miron O. Lozinskii, Andrey A. Tolmachev

Research output: Contribution to journalArticle

6 Citations (Scopus)

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 languageEnglish (US)
Pages (from-to)4478-4485
Number of pages8
JournalTetrahedron
Volume64
Issue number19
DOIs
StatePublished - May 5 2008
Externally publishedYes

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Spiro Compounds
Hydrolysis
Carbon
Derivatives
Atoms
triethylamine
1,4-benzothiazine

Keywords

  • Chloro derivatives
  • Electrophilic substitution
  • Enamines
  • Rearrangement
  • Spiro heterocycles

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

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, Sergii; Chernega, Alexander N.; Lozinskii, Miron O.; Tolmachev, Andrey A.

In: Tetrahedron, Vol. 64, No. 19, 05.05.2008, p. 4478-4485.

Research output: Contribution to journalArticle

Nazarenko, Konstantin G. ; Shtil, Nataliya A. ; Buth, Sergii ; Chernega, Alexander N. ; Lozinskii, Miron O. ; Tolmachev, Andrey A. / 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. In: Tetrahedron. 2008 ; Vol. 64, No. 19. pp. 4478-4485.
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AU - Nazarenko, Konstantin G.

AU - Shtil, Nataliya A.

AU - Buth, Sergii

AU - Chernega, Alexander N.

AU - Lozinskii, Miron O.

AU - Tolmachev, Andrey A.

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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.

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KW - Enamines

KW - Rearrangement

KW - Spiro heterocycles

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