Derivatives of glyoxaline-4 (or 5)-formaldehyde and glyoxaline -4 (or 5)-carboxylic acid. A new synthesis of histidine / by Frank Lee Pyman.

  • Pyman, Frank Lee.
Date:
[1916]
Catalogue details

Licence: Public Domain Mark

Credit: Derivatives of glyoxaline-4 (or 5)-formaldehyde and glyoxaline -4 (or 5)-carboxylic acid. A new synthesis of histidine / by Frank Lee Pyman. Source: Wellcome Collection.

    15/18 (page 200)
    Ethyl GlyoxalineA{ox b)-carboxylcite, C3H3N2*C02Et. Five grams of glyoxalinecarboxylic acid hydrochloride were boiled with 25 c.c. of absolute alcohol for six hours under a reflux condenser, the liquor being saturated from time to time with dry hydrogen chloride. The salt gradually passed into solution, and at the end of this time the alcohol was removed by distillation. The residue was dissolved in a small quantity of water and precipitated with a saturated solution of potassium carbonate, when, on stirring, 3'6 grams of the ester were obtained as a sandv precipitate melt¬ ing at 158°. Ethyl glyoxalineA{or b)-ccirboxylate crystallises from alcohol in clusters of plates which melt at 162° (corr.). It is sparingly soluble in cold, more readily so in hot water, fairly readily soluble in cold alcohol and readily so in ether or chloroform. It is anhydrous: Found, C=51*2; H = 57. CgH802N2 (140T) requires C = 51'4; II = 5'7 per cent. On hydrolysis by boiling with 10 per cent, aqueous hydro¬ chloric acid, the acid is formed in quantitative yield. Methyl GlyoxalineA(ov b)-carboxylcite, C3H3N2*C02Me. • This ester was prepared in a similar manner. It crystallises from methyl alcohol in clusters of plates which melt at 156° (corr.). Its solubilities are similar to those of the ethyl ester, except that it is more' sparingly soluble in cold methyl and ethyl alcohols : Found, C = 47'6 ; H = 4'8. C5II0O2N2 (126T) requires C~47'6; IT = 4'8 per cent. 4(or 5)-[ Glyo ralineA{ox b)-meth yl]-gly oxali n e-b (oi: 4)-methyl Alcohol, c3h3n2-ch2-c3ii2n2-cii2-oh. This base was obtained as a by-product in the preparation of 4-(or 5)-hydroxymethylglyoxaline by the action of nitric acid on 2-thiol-4(or 5)-aminomethylglyoxaline (T., 1911, 99, 673). After the crystallisation of a large quantity of hydroxymethylglyoxaline as hydrogen oxalate in well-formed crystals, the mother liquors deposited a powdery salt which melted at 80—120°. Forty grams of this salt were mixed with an excess of aqueous barium hydroxide, filtered, saturated with carbon dioxide, and again filtered. The liquor was acidified with hydrochloric acid, evaporated to a syrup, and stirred with absolute alcohol, when 7'2 grams of the hydro¬ chloride of glyoxalinemethylglyoxalinemethyl alcohol were obtained