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

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: [phone]; e-mail: [e-mail]].