Physical Alditols

In addition to these physical studies at the Bureau, Tipson was able to return to his synthetic interests, both alone and in collaboration with other staff members. He was especially pleased to prepare D-talose in crystalline form, an accomplishment that had eluded Emil Fischer. Pursuing his longstanding interest in the reaction of sulfonic esters with iodide and following an earlier observation that the tetratosyl ester of erythritol is converted into butadiene by the action of sodium iodide and zinc, he demonstrated (with A. Cohen) that nonterminal unsaturation may be conveniently introduced into alditol derivatives by reaction of contiguous secondary sulfonates with sodium iodide and zinc dust in boiling A.A-dimethylformamide. This Tipson-Cohen reaction subsequently proved of great utility in other hands for the conversion of more complex carbohydrate structures into vicinal dideoxy derivatives. 

Tables VI-XI show the physical properties of the alditol anhydrides and certain of their derivatives.

In view of this, a new overview of developments in this area is warranted, especially as no special summary on this subject has been published for some time. A comprehensive article2 in a previous volume of this series appeared in 1950. Subsequently, a brief discussion of 1,4 3,6-dianhydrohexitols was incorporated in a contribution on the stereochemistry of cyclic derivatives of carbohydrates,3 and they were treated exhaustively within a summary of alditol anhydrides that contained tables of physical properties of derivatives.4... 

From these findings with triols, it follows that, apart from the expectation that formation of five- and six-membered rings would be favored (see, however, the exceptional compound 19), no general conclusions can be drawn regarding the structures of boronates derived from more-complex polyhydric alcohols. In Table V, alditol boronates are listed with structures when these can be concluded either from the method of synthesis, from physical studies, or by deduction (as with the 1,2 5,6-diesters formed from 3,4-di-O-substi-tuted mannitols). 

The following Tables record some physical properties of boronates of sugars, glycosides, C- and N-glycosyl compounds including nucleosides, alditols, and anhydro sugars. 

Isomeric glucosylated amino-alditol derivatives, 17, derived from reaction of 2-amino-2-deoxy-mannit-6-yl and -glucit-6-yl a-D-glucopyranosides with methyl methacrylate, were co-polymerized and the physical properties of the resulting polymers were examined in water. 

M. Romina Marin, V. de Paz, N. Ittobane, J.-A. Galbis and S. Munoz-Guerra, Hydroxylated linear polyurethanes derived from sugar alditols, Macromol. Chem. Physic., 210 (6) 486-494, 2009. 

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