The abnormal behaviour of glyoxaline-carboxylic esters and anilides towards diazonium salts / by Robert George Fargher and Frank Lee Pyman.

  • Fargher, Robert George.
Date:
[1919?]
Catalogue details

Licence: In copyright

Credit: The abnormal behaviour of glyoxaline-carboxylic esters and anilides towards diazonium salts / by Robert George Fargher and Frank Lee Pyman. Source: Wellcome Collection.

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    red coloration with sodium diazobenzene-p-sulphonate in sodium carbonate solution. Found, in air-dried material: loss at 110° = 12*7. 1JH20 requires 12'6 per cent. In substance dried at 110°, C = 63'5; H = 4-5; N = 14-8. C10H8O2N2 (188'1) requires C —63'8; H = 4'3; N = 14'9 per cent. Ethyl 2-ph enylglyoxaline-k-carb oxylate crystallises from ethyl acetate in minute needles, which melt at 189° (corr.), sintering above 183°. It is readily soluble in alcohol or hot ethyl acetate, less readily so in cold ethyl acetate, and very sparingly so in water. It gives no coloration with sodium diazobenzene-pLsulphonate in sodium carbonate solution. Found, in air-dried substance: loss at 100° = 9‘5. Found, in dried substance: C = 66-5; H.=5-7; N = 12'9. Ci2Hi202N2 (216*1) requires C = 66'6; H —5*6; N = 13*0 per cent. Ethyl Glyoxaline-k-acetate.—This was prepared previously by the action of alcoholic hydrogen chloride on 4-cyanomethyl- glyoxaline (T., 1911, 99, 681), and can also be obtained by the esterification of the corresponding acid or by the action of alcohol on the hydrochloride of glyoxaline-4-acetyl chloride. It gives a deep red colour when mixed with sodium diazobenzene-^'-sulphonate in aqueous sodium carbonate. Glyoxaline-^-acetyl chloride hydrochloride can be prepared in a crystalline state by the method given below. The crude product contains less than the theoretical amount of chlorine, and we have been unable to devise a satisfactory method of purifying it. Five grams of phosphorous pentachloride and 6 c.c. of thionyl chloride were heated on the water-bath to incipient ebullition (about 50°), and 4 grams of glyoxaline-4-acetic acid hydrochloride were added, the mixture being well stirred. Evolution of hydrogen chloride took place, and the pasty mass quickly became crystalline, forming minute leaflets. When the reaction had ended, the mass was diluted with chloroform, filtered, washed with chloroform, and dried in a vacuum over sulphuric acid and sodium hydroxide. The dry, crystalline powder obtained in this way was pale pink and amounted to 4'4 grams, that is, 97'7 per cent, of the theoretical. The specimen with the highest chlorine content melted and decom¬ posed .at 127° (corr.), the others at 125°'. Found: 0 = 33*2; H = 3'5; Cl = 35'5, 35'1, 36'8 (in different specimens). C5H50N2C1,HC1 (181-0) requires 0 = 33-2; H = 3-3; 01 = 39-2 per cent.
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