Allyl bromide → HCID 131727870, compound

HRID 1441503Notes

Reaction equation

HRID 1441503 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+].[CH2:39](Br)[CH:40]=[CH2:41]>O>[Cl:1][OH:2].[CH2:41]([N:19]1[CH2:18][CH2:17][C@:15]23[C:16]4[C:3]5[O:2][C@H:14]2[C:13](=[O:20])[CH2:12][CH2:11][C@@:10]3([O:21][CH2:22][CH2:23][CH2:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[C@H:9]1[CH2:8][C:7]=4[CH:6]=[CH:5][C:4]=5[O:31][CH3:32])[CH:40]=[CH2:39]

Participants

5

Reactant 3

HCID 7841Allyl bromideHCID 11430Potassium CarbonateHCID 68541097HCID 68541097, compound

Product 1

HCID 131727870HCID 131727870, 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 (2.00 g, 4.76 mmol), potassium carbonate (4.00 g, 28.9 mmol) and allyl bromide (0.56 ml, 6.62 mmol) in water-free N,N-dimethylformamide (15 ml) was stirred for 7 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 obtained 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 acid reaction. The product was recrystallised from isopropanol. Yield: 1.50 g (69%) of the compound 1.HCl as colourless crystals. Fp. 129-130° C.; MS (CI): 460 (M++1); IR (KBr): 1725 (C═O) cm−1; 1H-NMR (DMSO-d6, δ in ppm): δ 8.98 (s, wide, HN+), 7.30-7.18 (m, 5 arom. H), 6.89 (d, 1 arom. H, J=8.4 Hz), 6.83 (d, 1 arom. H, J=8.4 Hz), 5.89 (m, 1 olef. H), 5.69 (m, 2 olef. H), 4.94 (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 obtained 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 acid reaction
  11. customThe product was recrystallised from isopropanol
  12. custom129-130° C.

Sources & evidence

ORD record
ord-0ec075725f5340e998a757934a043620
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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