Phenethyl bromide → HCID 68541258, compound

HRID 1441506Notes

Reaction equation

HRID 1441506 reaction equation
[ClH:1].[O:2]1[C@@H:14]2[C@@:15]34[CH2:17][CH2:18][NH:19][C@@H:9]([C@:10]3([O:21][CH2:22][CH2:23][CH2:24][C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[CH2:11][CH2:12][C:13]2=[O:20])[CH2:8][C:7]2=[C:16]4[C:3]1=[C:4]([O:31][CH3:32])[CH:5]=[CH:6]2.C(=O)([O-])[O-].[K+].[K+].[C:39]1([CH2:45][CH2:46]Br)[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1>O>[ClH:1].[O:2]1[C@@H:14]2[C@@:15]34[CH2:17][CH2:18][N:19]([CH2:46][CH2:45][C:39]5[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=5)[C@@H:9]([C@:10]3([O:21][CH2:22][CH2:23][CH2:24][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)[CH2:11][CH2:12][C:13]2=[O:20])[CH2:8][C:7]2=[C:16]4[C:3]1=[C:4]([O:31][CH3:32])[CH:5]=[CH:6]2

Participants

5

Reactant 3

HCID 7666Phenethyl bromideHCID 11430Potassium CarbonateHCID 68541097HCID 68541097, compound

Product 1

HCID 68541258HCID 68541258, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of 4,5α-epoxy-3-methoxy-14β-(3-phenylpropyloxy)morphinan-6-one hydrochloride (1.0 g, 2.38 mmol), potassium carbonate (3.00 g, 21.7 mmol) and 2-phenylethylbromide (1.19 ml, 8.8 mmol) in water-free N,N-dimethylformamide (10 ml) was stirred for 12 h under exclusion of moisture and under nitrogen at 80° C. (bath temperature). After filtration from the inorganic residue, which was washed three times each time with 50 ml dichloromethane, the filtrate was evaporated down under reduced pressure. The oily residue was dissolved in 300 ml dichloromethane, washed with water (3×200 ml) and saturated sodium chloride solution (4×200 ml), dried over sodium sulphate and evaporated down. The evaporation residue (960 mg of brown oil) was purified by column chromatography (silica gel; CH2Cl2/MeOH/conc. NH4OH 250:2:0.5), the oily evaporation residue dissolved in 50 ml ether and precipitated by the addition of etherial HCl up to the acidic reaction. Yield: 0.45 g (36%) of the compound 4.HCl as colourless crystals. Fp. 128-130° C.; MS (CI): 524 (M++1); IR (KBr): 1726 (C═O) cm−1; 1H-NMR (DMSO-d6, δ in ppm): δ 8.84 (s, wide, HN+), 7.39-7.17 (m, 10 arom. H), 6.89 (d, 1 arom. H, J=8.2 Hz), 6.79 (d, 1 arom. H, J=8.2 Hz), 4.95 (s, CH-5), 3.81 (s, CH3O).

Workup

  1. filtrationAfter filtration from the inorganic residue, which
  2. washwas washed three times each time with 50 ml dichloromethane
  3. customthe filtrate was evaporated down under reduced pressure
  4. dissolutionThe oily residue was dissolved in 300 ml dichloromethane
  5. washwashed with water (3×200 ml) and saturated sodium chloride solution (4×200 ml)
  6. dry with materialdried over sodium sulphate
  7. customevaporated down
  8. customThe evaporation residue (960 mg of brown oil) was purified by column chromatography (silica gel; CH2Cl2/MeOH/conc. NH4OH 250:2:0.5)
  9. dissolutionthe oily evaporation residue dissolved in 50 ml ether
  10. customprecipitated by the addition of etherial HCl up to the acidic reaction
  11. custom128-130° C.

Sources & evidence

ORD record
ord-0a39caf2c0114024b2ff713fcb095886
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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