ALICYCLIC CARBOHYDRATES .36. PARTICIPATION BY NEIGHBORING METHOXYL IN A DISPLACEMENT OF HYDROXYL BY HALOGEN . CONVERSION OF (-)-INOSITOL INTO MESO-(1,3,5/2,4)-CYCLOHEXANEPENTOL

A neighboring methoxyl group appears to participate in the reaction of phosphorus pentachloride with the one free hydroxyl group in (-)-inositol 2,3,4,5,6-pentamethyl ether (9). The reaction product was the all-trans diastereomer (13, X = CI) of chloropentamethoxycyclohexane identified by conversion into the previously known cyclohexanepentol (“scyllo-quercitol”) (11), and to the chloropentol (10) pentaacetate. Tetramethyl ether 2 derived from (-)-inositol was selectively benzoylated at the (equatorial) position 2. The resulting tetramethyl ether monobenzoate (7) reacted with methyl iodide and silver oxide to give a mixture consisting mainly of 1-monobenzoate pentamethyl ether 8, owing to acyl migration.4-6 Similar reaction of tetramethyl ether monobenzoate 7 with phosphorus pentachloride gave chloropentol tetramethyl ether monobenzoate 14, which was identified by conversion into the same chloropentol (10). © 1969, American Chemical Society. All rights reserved.