Ammonia → HCID 13374940, compound

HRID 2309541Notes

Reaction equation

HRID 2309541 reaction equation
Br[C:2]1[NH:16][C:15]2[C:17]3[C:3]=1[CH2:4][C@@H:5]1[C:10]([C:11]=3[CH:12]=[CH:13][CH:14]=2)=[CH:9][C@H:8]([NH:18][C:19](=[O:25])[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:7][N:6]1[CH3:26].[BH4-].[Na+].N>FC(F)(F)C(O)=O>[CH3:26][N:6]1[C@H:5]2[C:10]([C:11]3[CH:12]=[CH:13][CH:14]=[C:15]4[C:17]=3[C@H:3]([CH2:4]2)[CH2:2][NH:16]4)=[CH:9][C@H:8]([NH:18][C:19](=[O:25])[N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH2:7]1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 71266BromergurideHCID 4311764Sodium borohydride2×

Product 1

HCID 13374940HCID 13374940, compoundYield 62.2%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

In an ice bath, 280 ml of trifluoroacetic acid is cooled and then successively combined, under inert gas, with 12.5 g of 3-(2-bromo-9,10-didehydro-6-methyl-8α-ergolinyl)-1,1-diethylurea (30 millimoles) and 7 g of sodium borohydride in tablet form. The mixture is stirred under ice cooling for 4 hours and, during this time, 2×3 g of sodium borohydride is added. Then the reaction mixture is poured on about 200 ml. of ice and, under ice cooling, gently neutralized with concentrated aqueous ammonia solution (32%). The mixture is extracted with methylene chloride, and the organic phase is then dried with magnesium sulfate and evaporated. The residue is crystallized from ethyl acetate and diisopropyl ether, thus obtaining 6.35 g of 3-(9,10-didehydro-2,3β-dihydro-6-methyl-8α-ergolinyl)-1,1-diethylurea (62% of theoretical). From the mother liquor, another 1.0 g of compound is additionally crystallized. According to NMR analysis, the compound is solely a 3βH-compound.

Workup

  1. additionis added
  2. additionThen the reaction mixture is poured on about 200 ml
  3. extractionThe mixture is extracted with methylene chloride
  4. dry with materialthe organic phase is then dried with magnesium sulfate
  5. customevaporated
  6. customThe residue is crystallized from ethyl acetate and diisopropyl ether

Sources & evidence

ORD record
ord-a9ff102363094136b8139cd41ee3ed92
Source dataset
uspto-grants-1987_09
Patent number
US04695635

Reaction notes

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