Benzyl Bromide → HCID 11773762, compound

HRID 1437526Notes

Reaction equation

HRID 1437526 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[N:11](S(C1C=CC=CC=1)(=O)=O)[C:10]1[CH:9]([OH:24])[CH2:8][CH2:7][CH2:6][C:5]2=1.[CH2:25](Br)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.[H-].[Na+].C(OCC1C=CC=CC=1)C1C=CC=CC=1.[OH-].[Na+]>CN(C)C=O.CO.O1CCCC1>[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[NH:11][C:10]1[CH:9]([O:24][CH2:25][C:26]3[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=3)[CH2:8][CH2:7][CH2:6][C:5]2=1

Participants

9

Reactant 5

HCID 7498Benzyl BromideHCID 7657Dibenzyl etherHCID 14798Sodium Hydroxide2×HCID 24758Sodium hydrideHCID 68935458HCID 68935458, compound

Product 1

HCID 11773762HCID 11773762, compoundYield 71%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 6-bromo-9-(phenylsulfonyl)-2,3,4,9-tetrahydro-1H-carbazol-1-ol (25 mg, 0.06 mmol) in N,N-dimethylformamide (2 mL) was added benzyl bromide (0.5 mL) and sodium hydride (60% in oil, 50 mg, 1.2 mmol). The reaction was stirred 1.0 min and quenched with water (1 mL). The reaction was diluted with ethyl acetate, washed with water, and concentrated to provide 6-bromo-1-[(phenylmethyl)oxy]-9-(phenylsulfonyl)-2,3,4,9-tetrahydro-1H-carbolzole: MS m/z (m−1) 494, 496. The crude benzyl ether was dissolved in methanol (5 mL) and tetrahydrofuran (3 mL) and aqueous sodium hydroxide (5N, 2 mL) and sodium hydroxide pellets (300 mg, 1.1 mmol) were added. The reaction was stirred at 70° C. for 16 h. The reaction was concentrated, diluted with ethyl acetate, washed with water and concentrated. The crude ether was purified by flash chromatography on silica (5% to 10% ethyl acetate/hexanes) to provide 6-bromo-1-[(phenylmethyl)oxy]-2,3,4,9-tetrahydro-1H-carbazole (15 mg, 71%). as an oily white solid: 1H-NMR (DMSO-d6): δ 11.10 (s, 1H), 7.57 (s, 1H), 7.39 (d, 2H), 7.33 (t, 2H), 7.29-7.24 (d, 2H), 7.13 (d, 1H), 4.72-4.61 (m, 3H), 2.69-2.63 (m, 1H), 2.55-2.50 (m, 1H), 1.99-1.91 (m, 3H), 1.78-1.71 (m, 1H); MS m/z (M−1) 354, 356.

Workup

  1. customquenched with water (1 mL)
  2. additionThe reaction was diluted with ethyl acetate
  3. washwashed with water
  4. concentrationconcentrated
  5. customto provide 6-bromo-1-[(phenylmethyl)oxy]-9-(phenylsulfonyl)-2,3,4,9-tetrahydro-1H-carbolzole
  6. stirringThe reaction was stirred at 70° C. for 16 h
  7. concentrationThe reaction was concentrated
  8. additiondiluted with ethyl acetate
  9. washwashed with water
  10. concentrationconcentrated
  11. customThe crude ether was purified by flash chromatography on silica (5% to 10% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-95932274867e419482751c2a94539765
Source dataset
uspto-grants-2009_11
Patent number
US07622494B2

Reaction notes

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