Synthesis 2006(9): 1427-1432  
DOI: 10.1055/s-2006-926445
PAPER
© Georg Thieme Verlag Stuttgart · New York

Boron Trifluoride Mediated Prins Reaction of Methylene Diacetate with Styrenes. One-Pot Synthesis of 3-Chloro-3-arylpropanols

Alper Isleyen, Özdemir Dogan*
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey
Fax: +90(312)2101280; e-Mail: dogano@metu.edu.tr;
Further Information

Publication History

Received 21 September 2005
Publication Date:
12 April 2006 (eFirst)

Abstract

A one-pot procedure was developed for the synthesis of 3-chloro-3-arylpropanols, which are important starting materials for the synthesis of biologically active benzanilide derivatives. Styrenes were reacted with methylene diacetate in the presence of boron trifluoride to give the corresponding 3-chloro-3-arylpropanols in 36-84% yield by the Prins reaction. A strongly electron-donating methoxy substituent at either the ortho or para position of the styrene did not give the expected 3-chloro-3-arylpropanols due to polymerization. Styrene with a strongly electron-withdrawing nitro substituent gave the corresponding 3-chloro-3-arylpropanol in very low yield. Under the same reaction conditions, substituted norbornene gave a tricyclic ether. A very easy procedure for the synthesis of methylene diacetate is also reported.

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8

Structural assignment of compound 2 was based on 1H, 13C NMR, COSY (W coupling between H-2 endo and H-6), and HMBC spectra (correlation between C-3 and H-8 endo , exo , C-3 and H-2 endo , C-9 and H-2 endo , exo , and C-2 and H-9).