Ammonia → 3-(9,10-Didehydro-2,3-dihydro-6-methyl-8alpha-ergolinyl)-1,1-diethylurea

反応式

[CH3:1][N:2]1[C@H:16]2[C:6]([C:7]3[CH:8]=[CH:9][CH:10]=[C:11]4[C:17]=3[C:14]([CH2:15]2)=[CH:13][NH:12]4)=[CH:5][C@H:4]([NH:18][C:19](=[O:25])[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:3]1.[BH4-].[Na+].N>FC(F)(F)C(O)=O>[CH3:1][N:2]1[C@H:16]2[C:6]([C:7]3[CH:8]=[CH:9][CH:10]=[C:11]4[C:17]=3[CH:14]([CH2:15]2)[CH2:13][NH:12]4)=[CH:5][C@H:4]([NH:18][C:19](=[O:25])[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:3]1

参加物

実験手順

At -20° C., 19.6 g of 3-(9,10-didehydro-6-methyl-8α-ergolinyl)-1,1-diethylurea is dissolved in 80 ml of trifluoroacetic acid, and 8 portions of respectively 500 mg of sodium borohydride are added at intervals of 3-4 minutes. The mixture is then poured on ice, made alkaline under ice cooling with 90 ml of 26% ammonia solution, and extracted with methylene chloride. The organic phase is dried, concentrated, and chromatographed on silica gel with methylene chloride/methanol, thus isolating 10.6 g of 3-(9,10-didehydro-2,3-dihydro-6-methyl-8α-ergolinyl)-1,1-diethylurea as a mixture of isomers of the 3α and 3β-H-compounds. Crystallization from ethyl acetate yields 6.5 g of the 3β-H-compound.