Mannitol 1,2:3,0-dianhydro-4,5-0-isopropylidene

The dimethyl derivative of isomannide was synthesized by Wiggins as follows. l,6-Dichloro-l,6-didesoxy-3,4-isopropylidene-D-mannitol was converted i nto 1,6-dichloro-l, 6-didesoxy-2,5-dimethyl-3,4-isopr opylidene-D-mannitol (LVI). This on mild acid hydrolysis gave 1,6-dichloro-l,6-didesoxy-2,5-dimethyl-D-mannitol (LVII) which with cold sodium methoxide furnished 2,5-dimethyl-l,4 3,6-dianhydro-D-mannitol (LVIII), identical with the product of methylation of isomannide itself. Further... 

The most interesting ethylene oxide derivative of the hexitols encountered hitherto is 1,2 5,6-dianhydro-D-mannitol. This was obtained in the form of its 3,4-isopropylidene (LXXXVIII) and 3,4-ethylidene (LXXXIX) derivatives.72 The isopropylidene compound was synthesized from l,6-dichloro-l,6-didesoxy-D-mannitol through its conversion first into l,6-dichloro-l,6-didesoxy-3,4-isopropylidene-D-mannitol. This,... 

One would also think that saccharides are more attractive starting raw materials for direct preparation of epoxy resins than hydrocarbons since they already possess oxygen atoms needed for the epoxy rings. Such diepoxy derivatives of hexitols are known compounds, for instance 1,2 5,6-dianhydro-3,4-0-isopropylidene-D-mannitol (XIX). Their preparation, however is difficult and requires 15 to 18 steps which proceed in very low overall yield (17-19). 

As a first step in this direction, we have been able to prepare 1,2 5,6-dianhydro-3,4-0-isopropylidene-D-mannitol as a model diepoxy hexitol derivative in four steps with overall 50% yield according to the following scheme ... 

Finally, epoxy ring formation has been carried out in methanol at room temperature with sodium methoxide as a catalyst (24). 1,2 5,6-Dianhydro-3,4-0-isopropylidene-D-mannitol (XIX) has been obtained in near quantitative yield. 

Wiggins57" reported that the physical constants of a product that he had obtained from l,2 5,6-di-0-isopropylidene-3,4-di-0-p-tolylsul-fonyl-D-mannitol by deacetalation with 70% acetic acid followed by acetylation and saponification with sodium methoxide were those of l,4 3,6-dianhydro-D-iditol. Tipson and Cohen576 have presented evi-... 

To the submitters knowledge, 04,05-isopropylidene-1-iodo-3,6-anhydro-1-deoxy-D-glucitol and 04,05-isopropylidene-1,2 3,6-dianhydro-D-glucitol have not been prepared before. However, the corresponding isomannide derivatives have been obtained in five steps from mannitol in low overall yield by Foster and Overend in 1951.6 7 The present method is a simple, rapid and inexpensive route to multigram amounts of these tetrahydrofuran derivatives in reasonable yields. 

Wolfram u. a. (106, 107) stellten aus l,2 5,6-Dianhydro-3,4-O-isopropyliden-D-mannitol (LXVII)... 

The preparation of a number of a,b>-dimethanesuIfonates of alditols has been described. For example, by treating l,2 5,6-dianhydro-3,4-di-O-isopropylidene-D-mannitol with methanesulfonic acid, 1,6-di-0-(methylsulfonyl)-D-mannitol was formed. It is noteworthy that treatment of l,2-anhydro-3-deoxy-DL-glycerol with p-toluenesulfonic acid gave 3-deoxy-l-O-p-tolylsulfonyl-DL-glycerol and 3-deoxy-2-O-p-tolylsulfonyl-DL-glycerol. 

A range of C2-symmetric cyclic 1,6- and 2,5-diamino-hexitols have been prepared as potential glycosidase inhibitors. Reaction of guanidine with the known bis-epoxides, l,2 5,6-dianhydro-3,4-0-isopropylidene-D-mannitol and -L-iditol, yields 21 and 22 respectively. The 2,5-diamino compounds 23 and 24 were derived from thiourea 25 by reaction with various amines, including methyl 6-amino-6-deoxy-a-D-glucopyranoside, in the presence of mercuric chloride. ... 

A standard sequence of conversions has been used to convert 1,6-dibromo-1,6-dideoxy-3,4-0-isopropylidene-D-mannitol by chain elongation to the 3,6-diamino-l,4 5,8-dianhydro-L-manno- and L-ido-22... 

Alditols, Cyclitols and Derivatives Thereof. - 2,5 3,4-Dianhydro-D-altritol, 2,5-aohydro-3,4-0-(l,2-ethanediyl)-D mannitol, pentaerythritol tetraacetate, ribitol tetraacetate, xylitol tetraacetate, D-arabinitol tetraacetate, D, L-arabinitol tetraacetate, 2,4 3,5-di-0-isopropylidene-D-mannitol, 2 hexa-O-acetyl-D-mannitol, allitol hexaacetate, D-mannitol hexaacetate, D, L-mannitol hexaacetate, D-iditol hexaacetate, D, L-iditol hexaacetate, D, L-glucitol hexaacetate, D, L-altritol hexaacetate, L-galacto-D-galacto-decitol (which is C2-symmetric), 5 6-0-benzyl-2,3-0-[(S)-caniphanylidene]-l,4,5-tris-0-pivaloyl-D-myo-inositol, 6D-3,6-di-0-benzyl-l-0-[(S)-camphanyl]-2-deoxy-2,2-difluoro-4,5-0-isopropylidene- y< -inositol, cyclopentane 28. ... 

Treatment of 2,5-anhydro-3,4-di-0-benzyl-1 -deoxy-1 -tritylamino-D-glucitol with mesyl chloride, tosic acid-methanol, triethylamine then hydrogen-palladium catalyst affords the 1,6-imino-bridged derivative The reaction of l,2 5,6-dianhydro-3,4-0-isopropylidene-D-mannitol with ben-zylamine followed by deprotection leads only to the seven-membered azepane 52 in high yield. Other l,2 5,6-dianhydro-3,4-0-isopropylidene hexitols gave similar results. No six-membered ring products were detected as is the case with 1,2 5,6-dianhydro-3,4-di-( -benzyl-D-mannitol (see Vol. 28, p. 230, ref. 63). ... 

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