Ammonia → Bromocriptine

HRID 1195078Notes

Reaction equation

HRID 1195078 reaction equation
C[Si](C)(C)[Br:3].[CH3:6][CH:7]([CH2:9][C@@H:10]1[N:19]2[C:20]([C@@:22]([NH:27][C:28]([C@@H:30]3[CH:45]=[C:44]4[C@@H:33]([CH2:34][C:35]5[C:39]6[C:40]4=[CH:41][CH:42]=[CH:43][C:38]=6[NH:37][CH:36]=5)[N:32]([CH3:46])[CH2:31]3)=[O:29])([CH:24]([CH3:26])[CH3:25])[O:23][C@@:18]2([OH:47])[C@H:17]2[N:13]([CH2:14][CH2:15][CH2:16]2)[C:11]1=[O:12])=[O:21])[CH3:8].CC(C[C@@H]1N2C([C@@](NC([C@@H]3C=C4[C@@H](CC5C6C(=CC=CC=64)NC=5)N(C)C3)=O)(C)O[C@@]2(O)[C@H]2N(CCC2)C1=O)=O)C.CC(C[C@@H]1N2C([C@@](NC([C@@H]3C=C4[C@H](CC5C6C(=CC=CC=64)NC=5)N(C)C3)=O)(C(C)C)O[C@@]2(O)[C@H]2N(CCC2)C1=O)=O)C.N>CS(C)=O>[CH3:8][CH:7]([CH2:9][C@@H:10]1[N:19]2[C:20]([C@@:22]([NH:27][C:28]([C@@H:30]3[CH:45]=[C:44]4[C@@H:33]([CH2:34][C:35]5[C:39]6[C:38](=[CH:43][CH:42]=[CH:41][C:40]=64)[NH:37][C:36]=5[Br:3])[N:32]([CH3:46])[CH2:31]3)=[O:29])([CH:24]([CH3:25])[CH3:26])[O:23][C@@:18]2([OH:47])[C@H:17]2[N:13]([CH2:14][CH2:15][CH2:16]2)[C:11]1=[O:12])=[O:21])[CH3:6]

Participants

7

Reactant 5

HCID 222AmmoniaHCID 76113BromotrimethylsilaneHCID 105137Ergosine3×HCID 134551Ergocryptine2×HCID 54502730HCID 54502730, compound

Product 1

HCID 31101Bromocriptine

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

9.1 ml of trimethylbromosilane are added to 1000 ml of anhydrous dimethylsulfoxide and the solution is stirred at room temperature for 15 minutes, then 10 g of a base mixture of α-ergocryptine and ergosine are added, which contains 64.2% of α-ergocryptine base, 28.46% of ergosine base, 2.78% of α-ergocryptinine base and 1.96% of ergosinine base. After stirring for 20 minutes, the mixture is poured into 5 liters of ice-water and the pH is made alkaline up to a value of 8 to 9 by adding aqueous ammonia. The mixture is extracted 3 times with 500 ml of dichloromethane each, the organic phases are combined and washed 3 times with 200 ml of 10% sodium chloride solution each. The dichloromethane phase is dried over anhydrous sodium sulfate, filtered and evaporated under reduced pressure. The residue is purified on a Kieselgel column by using ethyl acetate as eluant to give the title compound in a yield of 6.3 g (0.00967 mole, 87%) (as calculated for the starting base mixture), m.p.: 218° C.; as well as 2.9 g (0.0046 mole, 89%) of 2-bromoergosine, m.p.: 183°-185° C.

Workup

  1. additionare added
  2. stirringAfter stirring for 20 minutes
  3. extractionThe mixture is extracted 3 times with 500 ml of dichloromethane each, the organic phases
  4. washwashed 3 times with 200 ml of 10% sodium chloride solution each
  5. dry with materialThe dichloromethane phase is dried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. customevaporated under reduced pressure
  8. customThe residue is purified on a Kieselgel column

Sources & evidence

ORD record
ord-0bae6df6e2484a4dace8bf8b814be546
Source dataset
uspto-grants-1989_03
Patent number
US04816587

Reaction notes

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