Propargyl bromide → HCID 131727871, compound

HRID 1441507Notes

Reaction equation

HRID 1441507 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:28]=[CH:29][CH:30]=1)[CH2:5][O:6][C@:7]12[C@@H:20]3[N:21]([CH3:24])[CH2:22][CH2:23][C@:12]41[C:13]1[C:14]([O:26][C@H:11]4[C:10](=[O:27])[CH2:9][CH2:8]2)=[C:15]([OH:25])[CH:16]=[CH:17][C:18]=1[CH2:19]3.C([O-])([O-])=O.[K+].[K+].[CH2:37](Br)[C:38]#[CH:39]>CC(C)=O>[ClH:1].[Cl:1][C:2]1[CH:3]=[C:4]([CH:28]=[CH:29][CH:30]=1)[CH2:5][O:6][C@:7]12[C@@H:20]3[N:21]([CH3:24])[CH2:22][CH2:23][C@:12]41[C:13]1[C:14]([O:26][C@H:11]4[C:10](=[O:27])[CH2:9][CH2:8]2)=[C:15]([O:25][CH2:39][C:38]#[CH:37])[CH:16]=[CH:17][C:18]=1[CH2:19]3

Participants

5

Reactant 3

HCID 7842Propargyl bromideHCID 11430Potassium CarbonateHCID 68535808HCID 68535808, compound

Product 1

HCID 131727871HCID 131727871, compound

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

A mixture of unpurified 14β-[(3-chlorobenzyl)oxy]-4,5α-epoxy-3-hydroxy-17-methylmorphinan-6-one (500 mg of brown foamy resin), K2CO3 (485 mg, 3.51 mmol) and propargylbromide (0.26 ml, 3.51 mmol) and 40 ml acetone (with 0.5% H2O) was reflux heated under N2 for 3 h. After cooling the inorganic material was filtered off, washed with CH2Cl2 and the filtrate evaporated down. The evaporation residue (538 mg of brown oil) was purified using column chromatography (silica gel; CH2Cl2/MeOH/conc. NH4OH (250:2:0.5)). The evaporation residue (337 mg of yellow oil) was dissolved in ether and 18.HCl was precipitated as a pure substance by the addition of etherial HCl. Yield: 347 mg (74%). Fp. 145-150° C.; IR (KBr): 1717 (CO), 2118 (C═C) cm−1; 1H-NMR (DMSO-d6): δ 9.21 (s, wide, +NH), 7.71-7.32 (m, 4 arom. H), 6.96 (d, 1 arom. H, J=8.4 Hz), 6.82 (d, 1 arom. H, J=8.4 Hz), 5.20 (s, C5—H), 4.89 (d, 1H, C14OCH2, J=12.1 Hz), 4.69 (d, 1H, C14OCH2, J=12.1 Hz), 4.84 (d, 2H, C3OCH2, J=2.2 Hz), 3.58 (t, 1H, C═CH, J=2.2 Hz), 2.94 (d, +NCH3, J=4.4 Hz); MS (CI): m/z 465 (M++1).

Workup

  1. temperaturewas reflux
  2. temperatureheated under N2 for 3 h
  3. temperatureAfter cooling the inorganic material
  4. filtrationwas filtered off
  5. washwashed with CH2Cl2
  6. customthe filtrate evaporated down
  7. customThe evaporation residue (538 mg of brown oil) was purified
  8. dissolutionThe evaporation residue (337 mg of yellow oil) was dissolved in ether
  9. customHCl was precipitated as a pure substance by the addition of etherial HCl
  10. custom145-150° C.

Sources & evidence

ORD record
ord-62a687a80afe49b8b7f241edc2e92fe1
Source dataset
uspto-grants-2010_02
Patent number
US07655671B2

Reaction notes

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