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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 33, 2003 - Issue 4
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Original Articles

Propylene Glycol Cyclic Sulfate as a Substitute for Propylene Oxide in Reactions with Acetylides

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Pages 633-640 | Received 03 Dec 2001, Published online: 16 Aug 2006

References

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  • Berridge , M.S. , Franceschini , M.P. , Rosenfield , E. and Tewson , T.J. 1990 . J. Org. Chem. , 55 : 1211 Preparation by the method of Gao and Sharpless[8] is higher yielding and more convenient. Propylene glycol is appreciably hygroscopic, but it may be conveniently dried by azeotropic removal of water with toluene
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  • Prepared by bromination of triethyl orthopropionate (Beyerstedt, F.; McElvain, S.M. J. Am. Chem. Soc. 1937, 59, 1273; Walters, P.M.; McElvain, S.M. J. Am. Chem. Soc. 1940, 62, 1482), then elimination, bromination and elimination again (Stetter, H.; Uerdingen, W.; Synthesis 1973, 207; Gassman, P.G.; Chavan, S.P. Tetrahedron Lett. 1988, 29, 3407). For both elimination reactions, powdered KOH in DMSO was used in place of KOt-Bu. An alternative method has been described.[14]
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  • For numerous examples, see Ref.7
  • The rapid formation of a cloudy precipitate indicates that sufficient acid has been added. If the mixture is not opaque, hydrolysis of the hemisulfate does not occur and more acid is required

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