Potassium Carbonate → HCID 68539027, compound

HRID 1441504Notes

Reaction equation

HRID 1441504 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([CH2:43]Br)[CH2:42][CH2:41][CH2:40]1>O>[ClH:1].[CH:39]1([CH2:43][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])[CH2:42][CH2:41][CH2:40]1

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 2734658(Bromomethyl)cyclobutaneHCID 68541097HCID 68541097, compound

Product 1

HCID 68539027HCID 68539027, 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 (500 mg, 1.19 mmol), potassium carbonate (1.00 g, 7.24 mmol) and cyclobutylmethylbromide (0.6 ml, 5.43 mmol) in water-free N,N-dimethylformamide (7 ml) was stirred for 24 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 20 ml dichloromethane, the filtrate was evaporated down under reduced pressure. The oily residue was dissolved in 100 ml dichloromethane, washed with water (3×100 ml) and saturated sodium chloride solution (4×100 ml), dried over sodium sulphate and evaporated down. The evaporation residue (520 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 10 ml ether and precipitated by the addition of etherial HCl. Yield: 0.40 g (69%) of the compound 2.HCl as colourless crystals. Fp. 128-133° C.; MS (CI): 488 (M++1); IR (KBr): 1728 (C═O) cm−1; 1H-NMR (DMSO-d6, δ in ppm): δ 8.48 (s, wide, HN+), 7.30-7.15 (m, 5 arom. H), 6.87 (d, 1 arom. H, J=8.4 Hz), 6.77 (d, 1 arom. H, J=8.4 Hz), 4.93 (s, CH-5), 3.81 (s, CH3O).

Workup

  1. filtrationAfter filtration from the inorganic residue, which
  2. washwas washed three times each time with 20 ml dichloromethane
  3. customthe filtrate was evaporated down under reduced pressure
  4. dissolutionThe oily residue was dissolved in 100 ml dichloromethane
  5. washwashed with water (3×100 ml) and saturated sodium chloride solution (4×100 ml)
  6. dry with materialdried over sodium sulphate
  7. customevaporated down
  8. customThe evaporation residue (520 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 10 ml ether
  10. customprecipitated by the addition of etherial HCl
  11. custom128-133° C.

Sources & evidence

ORD record
ord-9592a0f3088c45e39148d51cba14f163
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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