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

HRID 35208

Reaction equation

HRID 35208 reaction equation
[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

Participants

5

Reactant 3

HCID 222AmmoniaHCID 28864LisurideHCID 4311764Sodium borohydride

Product 1

HCID 867423423-(9,10-Didehydro-2,3-dihydro-6-methyl-8alpha-ergolinyl)-1,1-diethylureaYield 53.8%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

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.

Workup

  1. additionThe mixture is then poured on ice
  2. extractionextracted with methylene chloride
  3. customThe organic phase is dried
  4. concentrationconcentrated
  5. customchromatographed on silica gel with methylene chloride/methanol

Sources & evidence

ORD record
ord-89628022f31d4c1cb80c087367553939
Source dataset
uspto-grants-1988_08
Patent number
US04766128

Linked notes

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