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Synthesis 2010(17): 3029-3036  
DOI: 10.1055/s-0030-1258142
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

‘Vanilla Oceanics’: Synthesis and Olfactory Properties of (1′E)-7-(Prop-1′-enyl)-2H-benzo[b][1,4]dioxepin-3(4H)-ones and Homologues

Philip Kraft*a, Kasim Popaja, Peter Müllera, Michael Schärb
a Givaudan Schweiz AG, Fragrance Research, Überlandstr. 138, 8600 Dübendorf, Switzerland
Fax: +41(44)8242926; e-Mail: philip.kraft@givaudan.com;
b Laboratorium für Organische Chemie, ETH Zürich, Hönggerberg, HCI, 8093 Zürich, Switzerland
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Publication History

Received 22 March 2010
Publication Date:
01 July 2010 (online)

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Abstract

(1′E)-7-(Prop-1′-enyl)-2H-benzo[b][1,4]dioxepin-3(4H)-one was synthesized from dimethyl 2,2′-[(4-allyl-1,2-phenyl­ene)­bis(oxy)]diacetate by isomerization of the double bond and Dieckmann condensation followed by saponification and decarboxylation. It possessed an intense marine, spicy-vanillic odor, and served as starting material for the synthesis of homologues by protection as 1,3-dioxolane, Katsuki-Sharpless oxidation of the benz­ylic double bond, Grignard reaction, and dehydration/deprotection with 50% aqueous sulfuric acid. The olfactory properties and the extremely low odor thresholds of these resulting homologues are rationalized with an improved olfactophore model.

Key words

benzodioxepinones - Grignard reaction - heterocycles - isomerization - odorants

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6

The crystallographic data (excluding structure factors) for structure 9 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-730162. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223)336033; e-mail: deposit@ccdc.cam.ac.uk].