Hexitols oxidation

It may be mentioned at this point that the synthesis of hexitols from Griner s liquid iB more easily accomplished if the mixture of isomeric divinyl-glycols is oxidized directly, since their separation is more difficult than the separation of the resulting hexitols. 

Oxidation of l,2,5,6-tetraacetoxyhexene-3 led to the formation of dulcitol tetraacetate. In a typical experiment 22 g. of the tetraacetate was oxidized with 4.4 g. of silver chlorate and 0.1 g. of osmic acid and yielded a sirujj which did not crystallize. The sirup was acetylated again and yielded the corresponding hexitol hexaacetate. The crystals which deposited first were collected and recrystallized from methanol, in which they are difficultly soluble in the cold. The product melted at 166-166.5° and analyzed correctly for a hexitol hexaacetate. Now there was found in the collections of the Ecole Normale Sup rieure an old bottle containing dulcitol hexaacetate, m. p. 167-168°. A mixture of the new and the old hexaacetates was found to melt at 166.5-167.5° the identity of the two compounds was thus beyond doubt. 

As a corollary to this work, oxidation with periodate constitutes the basis of analytical procedures for the determination of 6-deoxyhexoses ( methylpentoses ),88 calcium gluconate89 and gluconic acid,90 hexitols,91 94... 

Crystalline 1,4-anhydro-D-sorbitol is of much more recent origin than 1,4-anhydro-D-mannitol, inasmuch as its preparation was first recorded in 1946.10 It was obtained by the restricted dehydration of D-sorbitol and has been given the trivial name arlitan. Two groups of workers simultaneously effected proof of its constitution. Hockett and coworkers11 treated the anhydride with lead tetraacetate and since its rate of oxidation coincided with that of ethyl D-galactofuranoside and since one molecular proportion of formaldehyde was formed, the authors concluded that the ring must involve Cl and C4 of a hexitol chain. Assuming that no other carbon atoms are involved, sorbitan is either 1,4-anhydro-D-sorbitol or 1,4-anhydro-D-dulcitol (Walden inversion at C4 of the sorbitol molecule). They therefore synthesized 3,6-anhydro-D-dulcitol (enantio-morphous with 1,4-anhydro-L-dulcitol) but found it to be different from arlitan. 

Ethylene oxide rings have as yet been introduced only at the ends of hexitol molecules by hydrolysis of suitable substituents attached to primary carbon atoms, so no question of Walden inversion has arisen. 

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,... 

Commercially, the polyalkylene oxide derivatives made by reacting ethylene oxide or propylene oxide with hexitols, or their partial esters, are the most important ethers. 

Soluble complexes are formed with metallic oxides, especially in the presence of alkali hydroxides. The strong tendency of hexitols to dissolve metallic oxides presents considerable technical difficulty in their manufacture and for this reason glass, rubber or stainless-steel equipment is used. In some instances well defined complexes can be isolated, particularly with alkaline earth oxides or mixtures with ferric oxide. These complexes absorb carbon dioxide and water and are unstable in dilute aqueous solution. Their structures are not established, but are inferred from analytical and physical measurements. Diehl has reviewed the subject. 

By far the most important oxidation of the hexitols is their specific biochemical transformation to ketoses. The history of this reaction dates from the fortuitous discovery of L-sorbose in mountain ash berries by Pelouze in 1852. It was not until twenty years later that Boussin-gault showed that it had arisen by bacterial oxidation of sorbitol. 

Oxidation of the hexitols to saccharic acids is accomplished in the same manner as the oxidation of the aldohexoses. This is mainly of theoretical interest since the same products are obtained from the generally more... 

The hexitols may be determined quantitatively by periodate oxidation. Either the amount of oxidant consumed or the amount of acid or formaldehyde liberated may be determined. This method will not... 

Oxepane (seven-membered) rings (1,6-anhydrohexitols)52 have been prepared from the 3,4-isopropylidene acetals of D-mannitol, D-glucitol, and L-iditol, by way of alkaline hydrolysis of the corresponding 1,2 5,6-dianhydrides. The ring structures of the products were established through periodate oxidation and lead tetraacetate oxidation the requisite amount of formic acid was produced, and 3 equivalents of lead tetraacetate were consumed. No inversions at any of the asymmetric centers were involved in the reactions conducted, so the oxepanes had retained the configurations of the starting hexitols. 

Alditols are oxidized by alkaline solutions of some halogens, and the main product seems to be the 1,2-dicarbonyl derivative. However, in further studies on the oxidation of pentitols and hexitols with bromine in the presence of calcium carbonate, 2- and 3-uloses and 2,5-hexodiuloses were... 

Manganese(III) has been employed for the oxidation of aldoses, and a general mechanism for the oxidation has been proposed.167 The oxidation of hexoses, pentoses, hexitols, and pentitols by Mn(III), as well as by other cations, was proposed to proceed via a free-radical mechanism,168 as shown in Scheme 26. Oxidation of alditols produces the corresponding aldoses, which are further oxidized in the presence of an excess of oxidant to the lower monosaccharides and thence to formaldehyde, formic acid, and even carbon dioxide. The kinetics for the oxidation of aldoses and ketoses by Mn(III) in sulfuric acid medium have been reported.169... 

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