Beckmann Rearrangement Using Indium(III) Chloride: Synthesis of Substituted Oxazoloquinolines from the Corresponding Ketoximes of 3-Acyl-1H-quinolin-4-ones

Abstract

Nitrilium ion intermediates in the Beckmann rearrangement of 3-acyl-4-quinolinone ketoximes, in the presence of InCl₃, were trapped by the β-hydroxy group of the tautomeric form of the ketoxime giving, predominantly, the corresponding oxazoloquinolines with isooxazoloquinolines formed as minor products.

Key words

indium(III) chloride - Beckmann rearrangement - β-hydroxy ketoxime - cyclization - oxazoloquinoline

References

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19

We could not reproduce the result claimed by Barman et al. in ref. 11a. When the same substrate, o-hydroxyaceto-phenone ketoxime, was subjected to the reaction conditions described therein, a mixture of benzoxazole (68%), benzisooxazole (6%), and 2-hydroxy acetanilide (20%) were obtained within 2 hours. However, 2-hydroxyacetanilide, prepared separately, was converted only sluggishly to benzoxazole (47%) under the same reaction condition in 30 hours. Additionally, 3-chloro- and 3,5-dichloro-2-hydroxy acetophenone ketoxime resulted in a mixture of the corresponding benzoxazole (81% and 73%) and benzisooxazole (7% and 8%) respectively without any corresponding acetanilide.

27

X-ray crystal structure analysis of 2e and 3i: atomic coordinates, bond lengths [Å] and angles [deg], anisotropic displacement parameters, hydrogen coordinates, torsion angles [deg] have been deposited at Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK, under deposition number CCDC 273870 for 2e, CCDC 273871 for 3i [fax: [phone]], E-mail: [e-mail]).