Dimethyl Sulfoxide → Ammonium Hydroxide

HRID 840105Notes

Reaction equation

HRID 840105 reaction equation
CS(C)=[O:3].C(Cl)(=O)C(Cl)=O.[Br:11][C:12]1[CH:13]=[CH:14][C:15]2[CH2:16][C@H:17]3[N:29]([CH3:30])[CH2:28][CH2:27][C@:23]45[C:24]=2[C:25]=1[O:26][CH:22]4[CH:21]([OH:31])[CH2:20][CH2:19][C@@H:18]35.CCN(CC)CC>C(Cl)Cl>[NH4+:29].[OH-:3].[Br:11][C:12]1[CH:13]=[CH:14][C:15]2[CH2:16][C@H:17]3[N:29]([CH3:30])[CH2:28][CH2:27][C@:23]45[C:24]=2[C:25]=1[O:26][CH:22]4[C:21](=[O:31])[CH2:20][CH2:19][C@@H:18]35

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 53700356HCID 53700356, compound

Product 2

HCID 14923Ammonium HydroxideHCID 54485567HCID 54485567, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

A solution of 1.6 ml of DMSO in 4.8 ml of CH2Cl2 was added slowly, under a nitrogen atmosphere and at −55° C., to a solution of 0.9 ml of oxalyl chloride in 21 ml of CH2Cl2. After 2 min. 3.6 g (10.3 mmol) of 3-bromo-4,5-epoxy-17-methylmorphinan-6-ol in 20 ml of CH2Cl2 were added, followed, after 15 min. by 6.6 ml of Et3N. The reaction mixture was allowed to warm up to room temperature in 2 h, then it was quenched with 50 ml of H2O. The phases were separated, the organic phase was dried over NA2SO4 and the solvent was removed in vacuo. The crude reaction mixture was purified by flash chromatography, eluting with a mixture CH2Cl2/MeOH/conc. NH4OH 90:7:0.7 respectively, yielding 2.87 g of the title product.

Workup

  1. customit was quenched with 50 ml of H2O
  2. customThe phases were separated
  3. customthe organic phase was dried over NA2SO4
  4. customthe solvent was removed in vacuo
  5. customThe crude reaction mixture
  6. customwas purified by flash chromatography
  7. washeluting with a mixture CH2Cl2/MeOH/conc

Sources & evidence

ORD record
ord-a24194220486427daeb712b9b1287b22
Source dataset
uspto-grants-2002_04
Patent number
US06365594B1

Reaction notes

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