‘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; Kasim Popaj; Peter Müller; Michael Schär

doi:10.1055/s-0030-1258142

PAPER

‘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 Popaj^a, Peter Müller^a, Michael Schär^b
^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

Abstract

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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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References

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