Sodium Chloride → 3-hydroxy-N-(benzyloxycarbonyl)morphinan

HRID 639504Notes

Reaction equation

HRID 639504 reaction equation
[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:6][C@H:7]3[NH:18][CH2:17][CH2:16][C@@:13]4([C:14]=2[CH:15]=1)[C@H:8]3[CH2:9][CH2:10][CH2:11][CH2:12]4.C(N(CC)CC)C.Cl[C:27]([O:29][CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1)=[O:28].[Na+].[Cl-]>ClCCl>[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[CH2:6][C@H:7]3[N:18]([C:27]([O:29][CH2:30][C:31]4[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=4)=[O:28])[CH2:17][CH2:16][C@@:13]4([C:14]=2[CH:15]=1)[C@H:8]3[CH2:9][CH2:10][CH2:11][CH2:12]4

Participants

6

Reactant 4

HCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 10387Benzyl chloroformateHCID 5463854(-)-3-Hydroxymorphinan

Product 1

HCID 538511903-hydroxy-N-(benzyloxycarbonyl)morphinanYield 52.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 3-hydroxymorphinan (20 mg, 0.061 mmol) and triethylamine (26 μL, 0.183 mmol) in dry Dichloromethane (0.3 mL) was added benzyl chloroformate (10.5 μL, 0.073 mmol) at 0° C. The mixture was stirred for 2 h, and to the mixture was added sat aq NaCl solution (2 mL) and the mixture was extracted with EtOAc (3 mL×3). The combined organic layer was dried over anhydrous MgSO4, filtered, and concentrated, after column chromatography of the crude product gave 12 mg (51%) of title compound: 1H NMR (300 MHz, CDCl3) δ7.3˜7.5 (5H, m) 6.9 (1H, t); 6.8 (1H, d); 6.6 (1H, t); 5.1 (2H, s); 4.3 (1H, dd); 3.9 (1H, m); 3.1 (1H, m); 2.7 (2H, m); 2.3 (1H, d); 1.0˜1.8 (10H, m).

Workup

  1. additionto the mixture was added
  2. extractionthe mixture was extracted with EtOAc (3 mL×3)
  3. dry with materialThe combined organic layer was dried over anhydrous MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-6490f55ab9804a49b16eefa6d88d7880
Source dataset
uspto-grants-2010_04
Patent number
US07691874B2

Reaction notes

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