HCID 90391163, compound → HCID 90391033, compound

HRID 1485369Notes

Reaction equation

HRID 1485369 reaction equation
[OH:1][C:2]12[CH:11]3[CH2:12][C:13]4[C:18]5[C:7]1([CH2:8][CH2:9][N:10]3[CH3:22])[C:6]([CH2:23][OH:24])([O:19][C:17]=5[C:16]([O:20][CH3:21])=[CH:15][CH:14]=4)[C:5](=[O:25])[CH:4]=[CH:3]2>C(O)C>[OH:1][C:2]12[CH:11]3[CH2:12][C:13]4[C:18]5[C:7]1([CH2:8][CH2:9][N:10]3[CH3:22])[C:6]([CH2:23][OH:24])([O:19][C:17]=5[C:16]([O:20][CH3:21])=[CH:15][CH:14]=4)[C:5](=[O:25])[CH2:4][CH2:3]2

Participants

3

Reactant 1

HCID 90391163HCID 90391163, compound

Product 1

HCID 90391033HCID 90391033, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 5-(hydroxymethyl)-14-hydroxycodeinone 4 (0.13 g, 0.379 mmol) in 5 mL of 1:1 ethanol-glacial acetic acid Pd/C (10%, 15 mg) was added. The mixture was evacuated and filled with H2 gas in a hydrogenation flask and maintained under 40 psi H2 pressure for 4 h. The reaction mixture was filtered through celite, the solvent was evaporated and the residue was basified with aqueous ammonia prior to CHCl3 extraction. Organic phases were combined, washed with brine, dried over anhydrous Na2SO4 and the solvent was evaporated. The residue was subjected to column chromatography (7:93 methanol-dichloromethane) to give the pure olefin reduced compound 5 as white foam (0.0915 g, 70%). 1H NMR (CDCl3, 400 MHz): δ 6.7 d (1H, J=8.6 Hz), 6.65 d (1H, J=8.6 Hz), 4.16 d (1H, J=10.9 Hz), 4.01 d (1H, J=11.7 Hz), 3.86 s (3H), 3.16 d (1H, J=18.7 Hz), 3.07 td (1H, J=5.4, 14.8 Hz), 2.96 d (1H, J=5.4 Hz), 2.67-2.51 m (2H), 2.43 s (3H), 2.40-2.29 m (2H), 2.25-2.15 m (1H), 1.96-1.87 m (1H), 1.74-1.63 m (1H), 1.47 d (1H, J=12.5 Hz). 13C NMR (CDCl3, 100 MHz): δ 210.47, 144.17, 142.88, 129.60, 124.43, 119.64, 114.49, 96.26, 70.29, 64.20, 61.74, 56.53, 50.58, 44.67, 42.65, 37.31, 31.21, 26.88, 21.91. MS (ESI): m/z 346.1 (M+1)+.

Workup

  1. customThe mixture was evacuated
  2. additionfilled with H2 gas in a hydrogenation flask
  3. temperaturemaintained under 40 psi H2 pressure for 4 h
  4. filtrationThe reaction mixture was filtered through celite
  5. customthe solvent was evaporated
  6. extractionto CHCl3 extraction
  7. washwashed with brine
  8. dry with materialdried over anhydrous Na2SO4
  9. customthe solvent was evaporated

Sources & evidence

ORD record
ord-e5459dca9d68408fa384e5b38e8205fe
Source dataset
uspto-grants-2016_08
Patent number
US09422302B2

Reaction notes

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