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Synthesis 2009(15): 2616-2626  
DOI: 10.1055/s-0029-1217399
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Aryl Ring Migration Reaction in the Synthesis of 2,4-Diaryl-4H-3,1-benzothiazines

Alexander V. Butin*a, Fatima A. Tsiunchika, Vladimir T. Abaevb, Andrey V. Gutnovc, Dmitry A. Cheshkovd
a Research Institute of Heterocyclic Compounds Chemistry, Kuban State Technological University, Moskovskaya st. 2, Krasnodar 350072, Russian Federation
Fax: +7(861)2596592.; e-Mail: alexander_butin@mail.ru; e-Mail: av_butin@yahoo.com.;
b North-Ossetian State University, Vatutina St. 46, Vladikavkaz 362025, Russian Federation
c ChiroBlock GmbH, Andresenstr. 1a, 06766 Wolfen, Germany
d State Scientific Research Institute of Chemistry and Technology of Organoelement Compounds, Entuziastov Shosse 38, Moscow 111123, Russian Federation
Further Information

Publication History

Received 2 April 2009
Publication Date:
22 June 2009 (online)

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Abstract

A new rearrangement of 1-(diarylmethyl)-2-isothiocyanatobenzenes into 2,4-diaryl-4H-3,1-benzothiazine derivatives is described. Treatment of the starting compounds with aluminum trichloride under Friedel-Crafts conditions leads to migration of an aryl substituent by an electrophilic ipso-substitution mechanism, followed by cyclization to form a 3,1-benzothiazine ring. The expected intramolecular thiocarbamoylation reaction also takes place, and 5,11-dihydro-6H-dibenzo[b,e]azepine-5-thiones are isolated as byproducts. Factors influencing the mechanism and selectivity of the reaction are discussed. The corresponding 1-(arylmethyl)-2-isothiocyanatobenzene derivatives were also synthesized, and their behavior under Friedel-Crafts reaction conditions was investigated to confirm the crucial role of the stability of the intermediate benzhydryl/benzyl cations in determining the course of the reaction.

Key words

1-(diarylmethyl)-2-isothiocyanatobenzenes - Friedel-Crafts - rearrangement - aryl migration - 3,1-benzothiazines

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