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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

    References

  • 1 Teobaldi P. Der Duft der Dinge   Verlagsbuchhandlung Liebeskind; München: 2001.  p.119 
    Google Scholar
  • 2 Kraft P. Chem. Unserer Zeit  2009,  43:  254 
    CrossrefGoogle Scholar
  • 3 Beereboom JJ, Cameron DP, and Stephens CR. inventors; Pfizer, US Patent  3799892.  ; Chem. Abstr. 1972, 76, 152326
  • 4 Kraft P. Eichenberger W. Eur. J. Org. Chem.  2003,  3735 
    CrossrefGoogle Scholar
  • 5a Hügel HM. Drevermann B. Lingham AR. Marriot PJ. In Current Topics in Flavor and Fragrance Research   Kraft P. Swift KAD. Verlag Helvetica Chimica Acta; Zürich: 2008.  p.199 
    Google Scholar
  • 5b Drevermann B. Lingham AR. Hügel HM. Marriot PJ. Helv. Chim. Acta  2007,  90:  1006 
    Google Scholar
  • 7 Gaudin J.-M. Nikolaenko O. de Saint Laumer J.-Y. Winter B. Blanc PA. Helv. Chim. Acta  2007,  90:  1245 
    CrossrefGoogle Scholar
  • 8 Ollis WD. Somanathan R. Sutherland IO. J. Chem. Soc., Chem. Commun.  1974,  492 
    Google Scholar
  • 9 Carlsen PHJ. Katsuki T. Martin VS. Sharpless KB. J. Org. Chem.  1981,  46:  3936 
    CrossrefGoogle Scholar
  • 10 Kraft P. Popaj K. Eur. J. Org. Chem.  2004,  4995 
    CrossrefGoogle Scholar
  • 11a Discovery Studio 2.5 - Advanced Software Package for Life Science Researchers   Accelrys, Inc.; San Diego: 2009. 
    Google Scholar
  • 11b

    For more information, see http://accelrys.com/

  • 12a Su T. Bao ZP. Zhang QY. Smith TJ. Hong JY. Ding X. Cancer Res.  2000,  60:  5074 
    Google Scholar
  • 12b Zhang X. Zhang QY. Liu D. Su T. Weng Y. Ling G. Chen Y. Gu J. Schilling B. Ding X. Drug. Metab. Disp.  2005,  33:  1423 
    Google Scholar
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].