Synthesis 2005(14): 2426-2432  
DOI: 10.1055/s-2005-870015
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 2-Substituted 4H-3,1-Benzoxazin-4-ones by Thermally Induced Cyclization of N-(2-Benzyloxycarbonyl)phenyl Ketenimines; Oxygen-to-Carbon­ Migration of a Benzyl Group

Mateo Alajarín*a, Ángel Vidal*a, María-Mar Ortína, Delia Bautistab
a Departamento de Química Orgánica, Facultad de Química, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain
b Servicio Universitario de Instrumentación Científica, Universidad de Murcia, Campus de Espinardo, 30100 Murcia, Spain
Fax: +34(968)364149; e-Mail: alajarin@um.es;
Further Information

Publication History

Received 18 March 2005
Publication Date:
13 July 2005 (eFirst)

Abstract

N-(2-Benzyloxycarbonyl)phenyl ketenimines undergo a thermally induced cyclization to give 2-substituted 4H-3,1-benzoxazin-4-ones. These processes involve the formation of a new carbon-oxygen bond and the migration of the benzyl group from the oxygen atom of the benzyloxy unit at the ester function to the terminal carbon atom of the ketenimine fragment.

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29

Ketenimines 5 and 7 remained unaltered when heated in boiling toluene or boiling ortho-xylene.

30

In the thermal treatment of the N-(2-benzyloxycarbo­-nyl)phenyl ketenimines 5 small amounts of the corres­-ponding 4H-3,1-benzoxazin-4-ones 9 (Figure [3] ) were always formed (8-13%).
Probably, compounds 9 resulted from the hydrolysis of the ketenimine function in the N-(2-benzyloxycarbonyl)phenyl ketenimines 5 to yield the corresponding amides, followed by intramolecular nucleophilic displacement of the benzyloxy group from the ester group by the carbonyl oxygen of the amide function. We tried very hard to exclude water from the reaction mixtures, but probably we did not succeed as the results were invariable, and small amounts of benzoxazinones 9 were always formed.
Compounds 9a (R1 = H) and 9b (R1 = Cl) could not be separated from the 4H-3,1-benzoxazin-4-ones 6c [R1 = H; R2 = Ph; Ar = 4-MeOC6H4] and 6f [R1 = Cl; R2 = Ph; Ar = 4-MeOC6H3], respectively.

31

CCDC 264507 contains the supplementary crystallographic data for 6g. The data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; e-mail:deposit@ccdc.cam.ac.uk).