Potassium Carbonate → HCID 68540912, compound

HRID 1441505Notes

Reaction equation

HRID 1441505 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+].[CH:39]1([CH2:42]Br)[CH2:41][CH2:40]1>O>[ClH:1].[CH:39]1([CH2:42][N:19]2[CH2:18][CH2:17][C@:15]34[C:16]5[C:3]6[O:2][C@H:14]3[C:13](=[O:20])[CH2:12][CH2:11][C@@:10]4([O:21][CH2:22][CH2:23][CH2:24][C:25]3[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=3)[C@H:9]2[CH2:8][C:7]=5[CH:6]=[CH:5][C:4]=6[O:31][CH3:32])[CH2:41][CH2:40]1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 81503BromomethylcyclopropaneHCID 68541097HCID 68541097, compound

Product 1

HCID 68540912HCID 68540912, 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 (1.5 g, 3.57 mmol), potassium carbonate (3.00 g, 21.7 mmol) and cyclopropylmethylbromide (1.0 ml, 6.62 mmol) in water-free N,N-dimethylformamide (10 ml) was stirred for 4 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 10 ml dichloromethane, the filtrate was evaporated down under reduced pressure. The oily residue was dissolved in 50 ml dichloromethane, washed with water (3×50 ml) and saturated sodium chloride solution (4×50 ml), dried over sodium sulphate and evaporated down. The evaporation residue (1.42 g of yellow 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: 0.60 g (53%) of the compound 3.HCl as colourless crystals. Fp. 130-133° C.; MS (EI): 473 (M+); IR (KBr): 1725 (C═O) cm−1; 1H-NMR (DMSO-d6, δ in ppm): δ 8.30 (s, wide, HN+), 7.31-7.18 (m, 5 arom. H), 6.88 (d, 1 arom. H, J=8.4 Hz), 6.78 (d, 1 arom. H, J=8.4 Hz), 4.96 (s, CH-5), 3.81 (s, CH3O), 0.80-0.40 (m, 5 cyclopropyl H).

Workup

  1. filtrationAfter filtration from the inorganic residue, which
  2. washwas washed three times each time with 10 ml dichloromethane
  3. customthe filtrate was evaporated down under reduced pressure
  4. dissolutionThe oily residue was dissolved in 50 ml dichloromethane
  5. washwashed with water (3×50 ml) and saturated sodium chloride solution (4×50 ml)
  6. dry with materialdried over sodium sulphate
  7. customevaporated down
  8. customThe evaporation residue (1.42 g of yellow 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. custom130-133° C.

Sources & evidence

ORD record
ord-74f6f87937304935899601fcedcb0aca
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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