Phenethyl bromide → HCID 10874002, compound

HRID 369000Notes

Reaction equation

HRID 369000 reaction equation
Cl.[O:2]1[C@:14]2([CH3:20])[C@@:15]34[CH2:17][CH2:18][NH:19][C@@H:9]([C@:10]3([O:22][CH2:23][CH3:24])[CH2:11][CH2:12][C:13]2=[O:21])[CH2:8][C:7]2=[C:16]4[C:3]1=[C:4]([O:25][CH3:26])[CH:5]=[CH:6]2.C(=O)([O-])[O-].[K+].[K+].[C:33]1([CH2:39][CH2:40]Br)[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1>O>[O:2]1[C@:14]2([CH3:20])[C@@:15]34[CH2:17][CH2:18][N:19]([CH2:40][CH2:39][C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)[C@@H:9]([C@:10]3([O:22][CH2:23][CH3:24])[CH2:11][CH2:12][C:13]2=[O:21])[CH2:8][C:7]2=[C:16]4[C:3]1=[C:4]([O:25][CH3:26])[CH:5]=[CH:6]2

Participants

5

Reactant 3

HCID 7666Phenethyl bromideHCID 11430Potassium CarbonateHCID 69036130HCID 69036130, compound

Product 1

HCID 10874002HCID 10874002, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A mixture of 4,5α-epoxy-14-ethoxy-3-methoxy-5-methylmorphinan-6-one hydrochloride (H. Schmidhammer et al., Helv. Chim. Acta Vol. 76, 476-480,1993) (3.0 g, 7.88 mmol), potassium carbonate (3.9 g, 28.2 mmol), 2-phenylethyl bromide (1.41 ml, 10.4 mmol), and of 20 ml anhydrous NN-dimethyl formamide was stirred at 80° C. (bath temperature) for 2h. After cooling and addition of 130 ml of H2O, the mixture was extracted with diethyl ether (3×60 ml). The combined organic layers were washed with H2O(3×70 ml), dried over Na2SO4 and evaporated. The residue (3.6 yellow oil) was crystallized from MeOH to afford 2.1 g (70%) of 4,5α-epoxy-14-ethoxy-3-methoxy-5-methyl-17-(2-phenyl)ethylmorphinan-6-one (compound 3). M.p. 86-89° C. IR (KBr): 1725 (CO) cm-1. CI-MS: m/z 448 (M+ +1). 1H-NMR (CDCl3): δ 7.21 (m, 5 arom. H), 6.64 (d,J=8.2 Hz, 1 arom. H, 6.54 (d, J=8.2 Hz, 1 arom. H.), 3.85 (s, OCH3), 1.60 (s, CH3 --C(5)), 1.12 (t, J=6.8 Hz, CH3). Analysis calculated for C28H33NO4 (447.55): C 75.14, H 7.43, N 3.13; found: C 75.04, H 7.69, N 3.26.

Workup

  1. temperatureAfter cooling
  2. extractionthe mixture was extracted with diethyl ether (3×60 ml)
  3. washThe combined organic layers were washed with H2O(3×70 ml)
  4. dry with materialdried over Na2SO4
  5. customevaporated
  6. customThe residue (3.6 yellow oil) was crystallized from MeOH

Sources & evidence

ORD record
ord-062216822be84f4c963b1895900999e6
Source dataset
uspto-grants-2000_10
Patent number
US06136817

Reaction notes

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