Substitution with Sulfur at the Sterically Hindered Neopentyl Position: Preparation of 9-Mercaptocamphor and 9,10-Epithiocamphor

Bernhard Koppenhoefer; Horst Völlenkle; Hans-Georg Brendle; Marc Schwierskott

doi:10.1055/s-1997-1223

Synthesis 1997; 1997(5): 515-517
DOI: 10.1055/s-1997-1223

short paper

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Substitution with Sulfur at the Sterically Hindered Neopentyl Position: Preparation of 9-Mercaptocamphor and 9,10-Epithiocamphor

Bernhard Koppenhoefer¹ , Horst Völlenkle² , Hans-Georg Brendle³ , Marc Schwierskott³

¹Institut für Organische Chemie der Universität, Auf der Morgenstelle 18, D-72076 Tübingen, Germany, Fax +49(7071)292037
²Institut für Mineralogie, Kristallographie und Strukturchemie der TU Wien, Getreidemarkt 9, A-1000 Vienna, Austria
³Institut für Organische Chemie der Universität, Auf der Morgenstelle 18, D-72076 Tübingen, Germany

Abstract

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A variety of methods for S_N2 substitution at sterically hindered 9-bromocamphor (2) was tested for the preparation of 9-mercaptocamphor (1), a fragrant compound with a roasty note reminiscent of onion. All reagents failed, with the notable exception of potassium thioacetate in N-methylpyrrolidone (for 3 days at 180°C). The peculiar reactivity pattern of both neopentyl-type 2 and 9,10-dibromocamphor (9) involves surprisingly smooth substitution reactions where strain is released. Thus, 9 was transformed into tricyclic 9,10-epithiocamphor 12, as established by X-ray analysis.

nucleophilic displacement - neopentyl system - camphor - mercaptan - thioether

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