Process for the preparation of amines having the ring system of lysergic acid or dihydrolysergic acid

摘要

Amines of the general formula C15H15N2.NH2 or C15H17N2.NH2, in which the carboxylic groups of lysergic acid or dihydrolysergic acid or their isomers are replaced by amino groups, are prepared by heating the azides of the corresponding lysergic or dihydrolysergic acid isomers in aqueous acid solution. The process may be carried out by adding boiling dilute acid e.g. N-hydrochloric acid to the crystalline salts of the azides or by directly heating the acid solution of the azide hydrochloride resulting from the preparation of the azide from the hydrazide until evolution of gas ceases. In examples: (1) lysergic acid azide hydrochloride is heated with dilute hydrochloric acid and the products isolated by chromatography to give 6-methyl-8-aminoergoline and 6-methyl-8-aminoisoergolene; (2) isolysergic acid azide hydrochloride is heated with dilute sulphuric acid to give 6-methyl-8-aminoisoergolene; (3) dihydrolysergic acid azide hydrochloride is heated with dilute hydrochloric acid to give 6 - methyl - 8 - aminoergoline; (4) dihydroisolysergic acid azide hydrochloride is heated with dilute acetic acid to give 6-methyl-8-aminoisoergoline; and (5) dihydroisolysergic acid hydrazide is treated with sodium nitrite and dilute hydrochloric acid and the resultant solution is heated to give 6-methyl-8-amino isoergoline.