Cyclization of Pentitols in Pyridine Via Their O-Tosyl Derivatives

Abstract Heating of equimolar quantities of pentitols with p-toluenesulfonyl (tosyl) chloride in pyridine at 60 °C for 4 h afforded 1, 4- or 2, 5-mono-anhydropentitols, which retained configuration of the asymmetric carbon atoms 2 or 4, together with small amounts of products with altered configuration at these centers. Variation of the reaction conditions by using a triple-molar excess of tosyl chloride and elevation of the temperature up to 115 °C gave mainly 1, 4-anhydro-5-chloro-5-deoxy-pentitols and small amounts of 1, 4-anhydro-2, 5- and 3, 5-dichloro-2, 5- and 3, 5-dideoxy-pentitols. The stereochemistry of the molecule of D-arabinitol was shown to favor the formation of 1, 4: 2, 5-dianhydro-D-arabinitol, a compound with two tetrahydrofuran rings. All mixtures were separated by capillary GC, and their components were identified by co-injection of standards by GC-MS.

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