A new synthesis of 4(or 5)-L-aminoethylglyoxaline, one of the active principles of ergot / by Frank Lee Pyman.

  • Pyman, Frank Lee.
Date:
[between 1910 and 1919?]
Catalogue details

Licence: In copyright

Credit: A new synthesis of 4(or 5)-L-aminoethylglyoxaline, one of the active principles of ergot / by Frank Lee Pyman. Source: Wellcome Collection.

    9/16 (page 676)
    carbonate, and evaporated to dryness under diminished pressure. The residue was extracted with warm ethyl acetate, and the extract distilled, when 16*3 grams of a brown oil remained. This began to crystallise, and after dissolution in a little warm water, 7*5 grams of pure 4(or 5)-cyanomefdiylglyoxaline separated, and a second crop of 1*0 gram of the cyano-base was obtained on concentrating the mother liquor. The oily liquor remaining was then converted into the acid oxalate by the addition of 9 grams of oxalic acid, and the resulting crops of mixed oxalates fractionally crystallised from water, when small quantities of 4 (or 5)-cyanomethylglyoxaline acid oxalate and a/3-6^s[4(or §)-gly oxaline\-fro'ipionitrile hydrogen oxalate were obtained. These oxalates, however, readily crystallise out side by side, and their separation is tedious. The total yield of 4(or 5)-cyanomethylglyoxaline amounts to about 50 per cent, of the theoretical. 4(or 5)-(7yanomethylglyoxaline, CH-NH H CN-CH2-C-' This base crystallises from water or ethyl acetate in stout, prismatic needles, which sinter at 136°, soften at 137°, and melt to a clear liquid at 138—140° (corr.). It is sparingly soluble in ether, chloroform, benzene, light petroleum, or cold water, but easily so in ethyl acetate, acetone, alcohol, or hot water: 0*1339 gave0*2755 C02 and 0*0573 H20. 0 = 56*1; H = 4*8. 0*0673 „ 22*5 c.c. N2 at 19° and 770 mm. N = 39*6. C5H5N3 requires C = 56*0; H = 4*7; N = 39*2 per cent. Aqueous solutions of this base give with mercuric chloride, ammoniacal silver nitrate, and ammoniacal solution of zinc hydroxide, white, amorphous precipitates; with sodium diazo- benzene-p-sulphonate, a dirty brownish-red colour, very much more intense than the beautiful red colour given by other glyoxalines con¬ taining a free imino-hydrogen atom, is produced; the difference is probably due to the product containing two chromophoric groups, one of which is attached to the imino-group as in other glyoxalines, and the second to the methylene group which is situated between the glyoxaline complex and the cyano-group. The hydrochloride crystallises from absolute alcohol in thin, glistening leaflets, which melt at 168—169° (corr.). It is very easily soluble in water, and fairly easily so in boiling absolute alcohol, but sparingly so in the latter when cold: 0*1514 gave 0*2315 C02 and 0*0585 H2Q. C = 41*7; H = 4*3. C5H5N3,H01 requires 0 = 41*8; 11 = 4*2 per cent.