5(10 ? 9)abeo-Ergolines from 9-hydroxyergolines

Abstract

Treatment of 9-hydroxyergolines with POC1,pyridine yields 5( 10 +-9)abeo-9,1O-didehydroergolines.LYSERGIC ACID (5 g) in tetrahydrofuran (200 ml) was treated overnight with diborane (0.55111; 135 ml), and 5% methanolic KOH (250ml) was then added followed by 35% H20, (25 ml). The solution was diluted with water and extracted with ether. The extract was evaporated in vucuo and the residue boiled for 3 h with methanol; on dilution with water the diol (1) (2.8 g ) , m.p. 275-278 "C, separated.l When a sample of (1) (2 g) was treated at 70 "C for 2 h with POC1,-HC1-pyridine (3 : 3 : 20) a compound (A), m.p. 184 "C, [ o r ] :-148" (pyridine), resulting from the replacement of a hydroxy-group by chlorine and loss of one molecule of H20, was obtained. Since its U.V. spectrum showed Amax 323 nm as in lysergic acid, (A) was assumed to have structure (2). However treatment of lysergol (3)