D-Glucitol l,5:3,6-dianhydro

Treatment of l,4 3,6-dianhydro-D-glucitol with boron trichloride gives l,6-dichloro-l,6-dideoxy-D-glucitol (20). Although methyl 6-chloro-6-deoxy-a-D-glucopyranoside (isolated as the tribenzoate) could be isolated from the reaction of methyl 3,6-anhydro-a-D-glucopyranoside with boron trichloride (21), the application to the isomeric furanoside derivative led to complex results. 

That steric factors alone cannot account for the reactivity of hydroxyl groups was indicated by the unimolar p-toluenesulfonylation of l,4 3,6-dianhydro-D-glucitol.23 The major product, the 5-p-toluenesulfonate (45%), is derived by reaction at the sterically hindered endo-hydroxyl group, and the exo-2-p-toluenesulfonate was isolated in only 12% yield. Although the more reactive HO-5 (es-... 

Jackson and Hayward59hydroxyl group in l,4 3,6-dianhydro-D-glucitol is preferentially sulfonylated prior to conversion into the mixed ester is incorrect. They based their conclusions on studies of the rate of replacement of p-tolylsulfonyloxy group by iodide in the three dianhydro stereoisomers. However, their proof of structure was questioned by Lemieux and Mclnnes59acetoxonium intermediate prior to attack by the iodide ion. 

Frequencies (cm-1) of Absorption Bands of 3,6-Anhydro-D-glucitol (1), 1,4-Anhydro-D-mannitol (2), 1,4 3,6-Dianhydro-2,5-di-0-methyl-D-mannitol (3), and l,4 3,6-Dianhydro-D-glucitol (4)... 

Circular dichroism of the nitrato (ONO) chromophore of the mono- and di-nitric esters of l,4 3,6-dianhydrohexitols was found to consist of two dichroic bands, one weak and positive, at about 265 nm, and a stronger band at —228 nm, which was positive for the endo-(R)-nitrato chromophore and negative for the exo-(S)-nitrato group.68 However, for l,4 3,6-dianhydro-D-glucitol dinitrate, which has both an endo and an exo nitrato group, both bands were positive, but [ ]ma r (+ 7,260) for the band at 225 nm was about half of the algebraic sum of this band for the di-endo (+ 18,400) and di-exo (—4,460) compounds. 

Interest has developed in the use of l,4 3,6-dianhydro-D-glucitol as an orally administered, osmotic diuretic. It has been examined in the laboratory," 1 and clinically"5 in patients having cirrhosis of the liver. It was found to be similar in effectiveness to intravenous D-mannitol."5 Its use in diuretic compositions has been patented.116... 

The structure of l,4 3,6-dianhydro-D-glucitol (see Structure 5, taken from Ref. 40 atom numbering as in formula 33) is well established. An X-ray analysis of the molecular structure of the molecule, recorded at 100 K (R = 0.026), has been published.40... 

Diammonium Aquabis(peroxotartratovanadate)(2-), 3065b l,4 3,6-Dianhydro-D-glucitol dinitrate, see Isosorbide dinitrate, 2373 Dianilineoxodiperoxochromium(VI), 3517 Dianilinium dichromate, 3531... 

An aqueous syrup of l,4 3,6-dianhydro-D-glucitol is slowly added to a cooled mixture of HN03 and H2S04. After standing a few minutes the mixture is poured into cold water and the precipitated product is collected and recrystallized from ethanol. 

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