Tetritols

The fourth group in ascending the series of sugar alcohols is the tetritols, of which the most available compound is erythritol. This compound is meso-butanetetrol-1,2,3,4 and was assigned the name, ery-thrite, by Berthelot in 1860. The present names of the compound, erythrol and erythritol, are modifications of erythrite. Erythritol is a white crystalline powder, with a sweetness more than twice that of sucrose.  

Other than an early report by PflUger that erythritol feeding lowered the liver-glycogen content of chickens, no reports on the fate of erythritol in the animal body have appeared until the studies of Beck, Carr and Krantz in 1938. These investigators studied extensively the fate of 

Erythritol is a white crystalline solid with a melting point of 121 C. (uncorrected). The anhydride, erythritan, prepared from erythritol by treatment with sulfuric acid is an almost colorless, mobile liquid which is water-soluble. 

Beck studied the acute toxicity, upon intraperitoneal injection, to mice of each compound. The anhydride was definitely less toxic. Erythritol in doses of 0.8 to 0.9 g. per 100 g. of mouse caused definite hypersensitivity, later convulsions, followed by death in two to three hours. Doses of 1.8 g. per 100 g. of mouse of erythritan produced convulsions followed by a lingering depression, ending usually in the death of the animal. 

The tetranitrate of erythritol like the trinitrate of glycerol is a potent vasodilator and enjoys widespread use in the treatment of hypertension. 

Das Glykogen und seine Beziehung zur Zuckerkrankheit. PflUger, Bohn (1905). 

D-Threitol (I), m.p. 88 , [a] +4.3 (H2O) dibenzylidene derivative, m.p. 231 is not found in nature. It was synthesized by Maquenne 2) from D-xylose by way of the Wohl degradation and sodium amalgam reduction. 

L-Threitol, like its enantiomorph, is purely synthetic. It was obtained by Bertrand 3) from erythritol by bacterial oxidation to L-erythrulose followed by reduction with sodium amalgam. 

DL-Threitol, tetraacetate m.p. 54-55 dibenzylidene derivative m.p. 217-219 was synthesized by novel means starting from 3,4-epoxy 1-butene (4). The steps required are given as follows  

A somewhat different synthesis is based on the cis and trans forms of 

2-butene-l,4-diol diacetate (5). In this synthesis the separation of the CIS and trans forms of the ethylenic precursor makes fractionation of the tetritols unnecessary. 

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The other tetritols were formerly called d-and /-erythritol, but have been renamed L-and D-threitol respectively. A racemic form can also be prepared,... 

Fig. 1. Stmctures of the tetritols (a) erythritol, (b) D-threitol, and (c) L-threitol and the pentitols (d) ribitol, (e) D-arabinitol, (f) L-arabinitol, and (g) xyhtol.

Polarimetric analysis of sorbitol and mannitol in the presence of each other and of sugars is possible because of their enhanced optical rotation when molybdate complexes are formed and the higher rotation of the mannitol molybdate complex under conditions of low acidity (194). The concentration of a pure solution of sorbitol may be determined by means of the refractometer (195). Mass spectra of trimethylsilyl ethers of sugar alcohols provide unambiguous identification of tetritols, pentitols, and hexitols and permit determination of molecular weight (196). 

Another main subject of research of Garcia Gonzalez, with the collaboration of J. Femandez-Bolanos, was the reaction of amino sugars with isothiocyanic acid derivatives. 2-Amino-2-deoxy-D-glucose hydrochloride and potassium thiocyanate were shown to give rise to 4-(D-arabino-tetritol-l-... 

Barker, S. A., and Bourne, E. J., Acetals and Ketals of the Tetritols, Pentitols and Hexitols, VII, 137-207 Barrett, Elliott P., Trends in the Development of Granular Adsorbents for Sugar Refining, VI, 205-230 Barry, C. P., and Honeyman, John, Fructose and its Derivatives, VII, 53-98... 

Scheme 4-20 exemplifies PhS- attack mediated by a Payne rearrangement. The selective ring-opening product can be applied to prepare tetritols.37... 

This approach provides a new method for carbohydrate synthesis. In the synthesis of tetritols, pentitols, and hexitols, for example, titanium-catalyzed asymmetric epoxidation and the subsequent ring opening of the thus formed 2,3-epoxy alcohols can play an essential role. 

Tetritols, especially erythritol, have been included in model studies on the separation of alditol acetates (see, for example, Refs. 217 and 417), and a commercial analysis of glycerol as its acetate has been proposed.597... 

TETRILE, Tetranitrometilanilina, Trinitrofenil-metilnitroammine o Tetralite (Tetryl, Amer and CE, British). It is described in Belgrano (Ref 31, pp 272-75). He lists its uses in Gt-Britain and the USA but says nothing about its uses in Italy. In Ref 28, p 349 it is stated that it is used as a component of some expl mixtures, as with TNT, such as Tetritol... 

Tetritol (Tetrytol). Accdg to Belgrano (Ref 31, p 246), the mixture used in Italy consisted of Tetryl 75 TNT 25% and was colored yellow. 

An article on the anhydrides of polyhydric alcohols appeared in Volume 5 of this Series,1 and it is the purpose of the present article to bring the subject up to date. Wiggins article1 was limited to the anhydrides of the pentitols and hexitols the present article will include the anhydrides of tetritols and of alditols higher than the hexitols. However, anhydrides having the three-membered (oxirane) ring will not be considered, as they are discussed elsewhere in this Volume.13 2,5-Anhydrides of aldoses are also treated in this Volume.lb... 

However, saponification of 2-O-p-tolylsulfonyl-L-erythritol or of 2-O-p-tolylsulfonyl-D-threitol did not furnish any 1,4-anhydro compounds, but only the respective tetritol. 

In the course of studies on the reactivity30 of fluoro carbohydrates, the 3,4-isopropylidene acetals of 2-deoxy-2-fluorotetritols were obtained. These react with the Pnrdie reagents under mild conditions, to give the corresponding O-methyl derivatives. More-vigorous reaction-conditions cause expulsion of the fluorine atom, leading to 3,4-0-isopropylidene-l,2-di-0-methyl-DL-tetritols. Mild oxidation of 2-de oxy-2-fluoro-3,4-0 -isopropyl ide ne-DL-ery thritol with barium... 

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