Nitro-, arylazo-, and amino-glyoxalines / by Robert George Fargher and Frank Lee Pyman.

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

Licence: In copyright

Credit: Nitro-, arylazo-, and amino-glyoxalines / by Robert George Fargher and Frank Lee Pyman. Source: Wellcome Collection.

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    These authors state that the yield of 4-/3-hydroxyethylglyoxaline, obtained by the action of barium nitrite on 4-jS-aminoethyl- glyoxaline hydrochloride, was so poor that the nitro-compound was not available in sufficient quantity for further study. It appeared to us, however, that this nitro-compound might be obtained by the action of nitric acid on other more readily accessible derivatives of glyoxaline containing a side-chain of carbon atoms in the 4-posi¬ tion, and in the first place we employed compounds containing two carbon atoms in the side-chains, like Windaus’s starting material. The results were disappointing; 4-j3-aminoethyl- glyoxaline, when boiled with 50 per cent, nitric acid for nine hours, was mainly recovered unchanged, whilst 4-cyanomethyl- glyoxaline was converted under the same conditions almost quanti¬ tatively into glyoxaline-4-acetic acid. Attempts to nitrate glyoxaline-4-carboxylic acid and glyoxaline-4:5-dicarboxylic acid were likewise unsuccessful. The prospect of nitrating 4-hydroxy- methylglyoxaline was not hopeful, for it has been shown previously (T., 1916, 109, 186) that hot concentrated nitric acid converts it into glyoxaline-4-formaldehyde and glyoxaline-4-carboxylic acid. It has now been found that the alcohol gives the same products when digested on the water-bath with fuming nitric acid, whilst it can be recovered almost quantitatively after boiling with ten parts of 25 per cent, nitric acid for four hours. On the other hand, the nitration of 4-hydroxymethylglyoxaline with nitric and sulphuric acids gave rise to a product which was not obtained in crystalline form, but further study of this was omitted in view of the peculiar behaviour of the simple nitroglyoxalines on reduction. (3) Arylazo glyoxaiines.—The constitution of the arylazo-deriv- atives of simple glyoxaiines has not been settled hitherto. Rung and Behrend (Annalen, 1892, 271, 28), who first isolated benzene- azoglyoxaline, considered it to be a diazoimino-compound (I), because boiling acids decomposed it with the formation of nitrogen CH>F(N:NPh) 11 CH ■N >CH, (I.) and glyoxaline, Burian (Ber., 1904, 37, 696), wno prepared many arylazoglyoxalines from diazobenzene-p-sulphonic acid and various glyoxaiines, adopted the same view of the constitution of these compounds on other grounds, namely, because all the glyoxaiines substituted in some or all of the 2-, 4-, and 5-positions which he examined coupled with the diazonium salt, whilst 1-substituted glyoxaiines did not. Pauly (Zeitsch. physiol. Chem., 1904, 42, 508), however, pointed out the possibility that the arylazo-
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