D-Isolysergic Acid

To a freshly prepared solution of 2 parts of d-isolysergic acid azide in 300 parts of ether is added an ethereal solution of 2 parts of d-2-aminobutanol-1 and the mixture is left to stand at room temperature during 12 hours. The yellowish clear solution is then washed several times with some water, dried over sodium sulfate and the ether evaporated in vacuo. The crystallized residue is treated with a small quantity of acetone and filtered. Yield ... 

The alcoholic ethereal filtrate is then dried over calcined potassium carbonate and the solution evaporated, whereby 0.9 to 1 part of a mixture of d-lysergic acid-d-l-hydroxybutyl-amide-2 and of d-isolysergic acid-d-l-hvdroxvbutylamide-2 is obtained. In order to separate the isomers, the residue is dissolved in 15 parts of hot chloroform and filtered from the small quantity of inorganic salt, whereby on cooling down, the difficultly soluble chloroform compound of d-lysergic acid-d-l hvdroxvbutylamide-2 crystallizes out. Yield 0.4 part. This compound can be recrystallized from hot benzene, whereby crystals melting... 

According to the same procedure, the compound 14 2-bromo-D-isolysergic acid ethynylcyclohexylamide was obtained. The compound crystallizes from dichloro-methane C24H26BrN30 x 0.6 CH2CI2 m.p. = 154 - 157°C [a]o = +431.8°... 

The principle agent in this plant was found to be -lysergic acid amide, which had already been synthesized and was known as both ergine and LA-111. Other alkaloids of lesser importance found to be psychoactively influential in Turbina corymbosa were d-isolysergic acid amide (isoergine), chanodavine, elymoclavine and lysergol. 

Fig. 2. Rotation dispersion curves. 1 d-Isolysergic acid 2 d-lysergic acid 3 Mysergic acid 4 J-isolysergic acid.

The isomeric 6-methyl-8-amino-ergolenes (LXXVIa) and ergolines (LXXVIIa) were produced by a modified Curtius degradation of d-lysergic acid azide, of d-isolysergic acid azide, or of the isomeric d-di-hydrolysergic acid azides (149). 

After standing for about five minutes the solution is extracted about five times with 100 mL. portions of water. The aqueous extracts are combined and are saturated with sodium chloride. The saturated solution is extracted five times with 100 mL. portions of ethylene dichloride. The ethylene dichloride extracts are combined and are evaporated in vacuo leaving a residual syrup comprising, a mixture of the diethylamides of d-lysergic and d-isolysergic acids. 

The diethylamide of d-isolysergic aid passes though as a much more slowly moving zone. The residue of the chloroform solution thereof amounting to 0.8 to 1.2 grams, crystallises on taking up in acetone in beautiful prisms of m.p. 182° C (corr.) with decomposition and consists of the pure diethylamide of d-isolysergic acid [a] D20 = -i-217° (c=0.4 in pyridine). 

From the crystallization mother liquors, after concentration, neutralization, and re-extraction with ethylene dichloride, there can be obtained about 0.8 g. of amorphous d-isolysergic acid morpholide. This material can be isomerized to d-lysergic acid morpholide by the procedure disclosed by Smith and Timmis in J. Chem. Soc. 139, II, 1168 (1936). 

The ethylene dichloride extracts are combined and are evaporated in vacuo leaving a residual syrup comprising, a mixture of the diethyl amides of d-lysergic and d-isolysergic acids. 

Preparation of d-isoLysergic Acid Hydrazide d-iso-Lysergic Acid Azide From... 

Semonsky, M. Zikan, V. Beran, M. Preparing D-Lysergic and D-isolysergic Acid or Mixtures therof. Czech. 123,689 ... 

The dihydro-bases of type (I) yield on treatment with hydrazine the expected (—)-dihydro-d-isolysergic acid (I) hydrazide, but on hydrolysis with alkali the reduced isolysergic acid residue is irreversibly isomerised to the dihydrolysergic acid residue and the product obtained is (—)-dihydio-d-lysergic acid (c/. p. 532). 

The second type, dihydro-bases (II), hydrolyses with alkali or with hydrazine to (-f )-dihydro-d-isolysergic acid (II), which is probably identical with the y-dihydrolysergic acid of Jacobs and Craig. The principal characters of the dihydro-lysergic and wolysergic acids and their derivatives are summarised in the following table —... 

D-isolysergic acid derivatives) that are called ergopeptinins. The individual isomers differ in both biological and physico-chemical properties. Their amount increases with unsuitable conditions of grain storage. 

In addition to ergot, ergot alkaloids occur in some higher plants. For example, derivatives of D-lysergic and D-isolysergic acids were isolated from the seeds of beach moonflower Ipomoea violacea) and the related Christmas vine Turbina corymbosa (Convolvulaceae). The seeds of beach moonflower were used traditionally among Mexico s Zapotec Indians for ceremonial and curative purposes. 

The other groups of ergot alkaloids have a more complex structure and consist of five pairs. Each pair consists of one base which contains d-lysergic acid, while the other contains d-isolysergic acid, the other... 

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