Derivatives mucic acid

The Synthesis of Some Galactaric (Mucic) Acid Derivatives, K. Butler, D. R. Lawrence, and M. Stacey,/. Chem. Soc., (1958) 740-743. 

Calcium gluconate is well known for its insolubility in wine and the turbidity it causes. Mucic acid, derived from galactose by oxidation, both of the aldehyde function of carbon 1 and the primary alcohol function of carbon 6, is just as undesirable. Also known as galactaric acid, it is therefore both... 

In practice, eluents of widely varying polarity have been used. Very weakly polar steroids (oestrenols) can be quantitatively eluted with hydrophobic solvents like methylene dichloride (cf Table 14) [217], whereas difficulties are reported in the elution of the more polar progesterone under the same conditions [691]. Chloroform has been used to elute dinitrophenylhydrazones from silica gel and opium alkaloids from alumina [470, 535]. Methanol and ethanol are often used for elution of substances of all types of compound class from silica gel [213, 215, 259, 434] or alumina [122, 437]. Butyl acetate has been chosen as the most suitable eluent for penicillin V [486]. Acetone has proved suitable for recovering ubiquinones [733]. Polar neutral, acid and basic aqueous eluents have also been employed, e.g., water for mucic acid derivatives [451] (cf Table 14), 1% Tween 80 solution for cobalamin [128], 0.2 N sulphuric acid for Vitamin Bg factors [702], 34% ammonium persulphate solution for nicotinic acid [702] and ammonium hydroxide for azo dyes [638]. Nitro-4-acetaminophenetoles have been extracted from alumina with the highly polar dimethylformamide [489]. 

Like the pentoses, mucic acid loses three molecules of water and is converted, as described on p. 386, into derivatives of furane with concentrated hydrochloric acid the product is furane-a d-dicarboxylic acid. Dry distillation yields furane-a-carboxylic or pyromucic acid. 

The origins of furan chemistry have been outlined by Partington (B-64MI31000). When Scheele subjected mucic acid to dry distillation in 1780 he obtained the first furan derivative,... 

Furan is a colorless liquid, boiling point 32°C. insoluble in water, soluble in alcohol or ether. Furan vapor produces a green coloration on pine wood moistened with hydrochloric acid. Furan may he made from mucic acid. COOHtCHOHLCOOH. by dry distillation into pyromneie acid, C4H1O - COOH. and then heating the latter under pressure at 270 C. Furan derivatives arc known, namely, methyl, primary alcohol, aldehyde, carboxylic acid, in which the group attachment is at carbon number 2 ... 

Ethylidene-Methylglucosides and Derivatives. Mucic Acid Trinitrate. See in Vol 8, M160-R... 

Pyrrole and N-substituted pyrroles are formed by a reaction analogous to the conversion of sugars to furan aldehydes. Ammonium and substituted ammonium salts of mucic acid, H02C(CH0H)4C0jH, are cyclized and de-carboxylated by pyrolysis. The yields of pyrrole and its N-phenyl and N-methyl derivatives are about 40%. Tetrahydropyrroles (pyrrolidines) are formed from various 4-substituted amines by elimination of water, ammonia, or hydrogen halide. ... 

Panzer obtained a gel-like carbohydrate substance from defatted bacilli (human strain) by successive extraction with water, hydrochloric acid, sodium carbonate, sodium nitrate, hot water and potassium hydroxide. The resulting liquors each yielded a gum-like substance which was sulfur-, nitrogen- and phosphorus-free. Oxidation of this derivative with nitric acid gave oxalic acid but no mucic acid. Panzer concluded that the substance was probably a pectin but not a galactan. It is now known that drastic oxidation of this nature would give oxalic acid from any sugar derivative. It is possible that by using controlled oxidation, mucic acid could be obtained from this carbohydrate. 

I omucic Acid.—When mucic acid is heated three molecules of water and one of carbon dioxide are lost and a monobasic acid is obtained known as pyromucic acid, and this acid by loss of CO2 goes to furfuran thus proving it to be the acid derived from furfuran. The acid is also obtained by oxidizing furfural. The reactions and relationships are as follows ... 

Pyrrole and the simple alkyl-pyrroles are colourless liquids, with relatively weak odours rather like that of aniline, which, also like the anilines, darken by autoxidation. Pyrrole itself is readily available commercially, and is manufactured by alumina-catalysed gas-phase interaction of furan and ammonia. Pyrrole was first isolated from coal tar in 1834 and then in 1857 from the pyrolysate of bone, the chemistry of which is similar to an early laboratory method for the preparation of pyrrole - the pyrolysis of the ammonium salt of the sugar acid, mucic acid. The word pyrrole is derived from the Greek for red, which refers to the bright red colour which pyrrole imparts to a pinewood shaving moistened with concentrated hydrochloric acid. 

An early pyrrole synthesis, which was originally useful on the laboratory scale, involves the pyrolysis of the ammonium salt of the glucose-derived mucic acid (9.1, Scheme 9.2). 

Mucic Acid.—Galactose and its derivatives (lactose, galac-tosides, etc.), jfield the insoluble mucic acid upon oxidation with... 

Oxidation Tests.—Galactose and its derivatives (lactose, and galactosides) on oxidation by hot nitric acid yield mucic acid which is almost insoluble in cold water. Other saccharides yield saccharic acid which is much more soluble, but forms an identifiable acid potassium salt. The following test, which must be carried out in a fume chamber, will detect both galactose and glucose, or sugars giving rise to them. It is not applicable to dilute solutions, which must be concentrated to syrups before oxidation. 

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