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.

    3/16 (page 670)
    of a/3-bis(o-nitrophenyl)propionitrile when o-nitrobenzyl chloride and potassium cyanide are boiled together for several hours in aqueous alcoholic solution (Bamberger, Ber., 1886, 19, 2635). The conditions under which the latter reaction takes place are, of course, more severe, and it may be pointed out that in the preparation of phenylacetonitrile from benzyl chloride and potassium cyanide prolonged boiling in aqueous alcoholic solution is also necessary. The extraordinary reactivity of 4(or 5)-chloromethylglyoxaline, indi¬ cated by the ease with which the halogen is replaced, emphasises the marked influence of the glyoxaline complex on the side-chain. An attempt w^as made to effect the replacement of the chloro- by the cyano-group in absolute alcoholic solution, but after several hours' boiling of the hydrochloride of the chloro-compound with finely powdered potassium cyanide in this solvent, a complex mixture was obtained, from which a certain amount of 4(or b)-ethoxymethylglyoxaline, CgHgN^CBVOEt, but none of the cyano-compound, could be isolated. The last stage of the synthesis of 4(or 5)-/6-aminoethylglyoxaline (VII) was accomplished by the reduction of 4(or 5)-cyanomethyl- glyoxaline by means of sodium and alcohol: CH*NH\ h /)0H ii >CH C-—> C-N'T CH2-cisr UH2-CH2‘1stH2 (v.) (VII). when there were also obtained as by-products a large amount of glyoxaline-4(or 5)-acetic acid (VIII) and a small quantity of 4(or 5)-methylglyoxaline (IX): CH*NH' O -JS’/' CH CH-NH ii c— yen (JH2-C02H (VIII.) CHc (IX.) Glyoxaline-4(or 5)-acetic acid, which is thus prepared synthetically for the first time, has previously been obtained by Knoop (Beitr. chem. Physiol. Path., 1907, 10, 119) by the oxidation of oxy- deaminohistidine (a-hydroxy-/3-glyoxaline-4(or 5)-propionic acid). It has now been further characterised by the preparation of a number of salts, and its ester, ethyl glyoxalineA(ov b)-acetate, has been prepared by the action of alcoholic hydrogen chloride on 4 (or 5)-cyanomethylglyoxaline. The occurrence of 4(or 5)-methylglyoxaline amongst the reduc¬ tion products of 4(or 5)-cyanomethylglyoxaline is probably due to the loss of carbon dioxide on the part of glyoxaline-4(or 5)-acetie acid.