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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