Sodium hydride → 9-[(Phenyl)methyl]-4-hydroxy-5-carbomethoxy carbazole

HRID 51353

Reaction equation

HRID 51353 reaction equation
[C:1]1([CH2:7][N:8]2[C:20]3[CH2:19][CH2:18][CH2:17][C:16](=[O:21])[C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][C:13]=3[C:22]([O:24][CH3:25])=[O:23])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[H-].[Na+].C1(S(OC)=O)C=CC=CC=1>O1CCOCC1.C(O)(=O)C.C(OCC)(=O)C>[C:1]1([CH2:7][N:8]2[C:20]3[CH:19]=[CH:18][CH:17]=[C:16]([OH:21])[C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][C:13]=3[C:22]([O:24][CH3:25])=[O:23])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 24758Sodium hydrideHCID 2759784Methyl benzenesulfinateHCID 223377289-[(phenyl)methyl]-5-carbomethoxy-1,2-dihydrocarbazol-4(3H)-one

Product 1

HCID 223377169-[(Phenyl)methyl]-4-hydroxy-5-carbomethoxy carbazoleYield 81%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent2×

Procedure

To a solution of the 9-[(phenyl)methyl]-5-carbomethoxy-1,2-dihydrocarbazol-4(3H)-one (2.87 g, 8.61 mM) in 29 ml dioxane was added 60% sodium hydride in mineral oil (0.79 g, 19.8 mM). The reaction was stirred 8 minutes, then methyl benzenesulfinate (1.80 ml, 13.8 mM) was added. The reaction was stirred an additional 1.5 h, then diluted with 43 ml dioxane and 1.13 ml acetic acid. The mixture was refluxed 1 h, diluted with ethyl acetate, and extracted with sat'd NaHCO3 two times, then with brine. After drying (NaSO4), evaporation in vacuo afforded 4.90 g. The mixture was purified by column chromatography on silica gel (elution with toluene/methylene chloride) to afford 2.31 g (81%) of the 9-[(phenyl)methyl]-4-hydroxy-5-carbomethoxy carbazole. 1H NMR (DMSO-d6) δ10.25 (s, 1H), 7.7 (d, 1H, J=8 Hz), 7.4 (t, 1H, J=8 Hz), 7.4-7.0 (m, 8H), 6.6 (d, 1H, J=8 Hz), 5.6 (s, 2H), and 3.8 (s, 3H). IR (CHCl3, cm−1) 1723, 1685, 1621, 1597, 1568, 1496, 1453, 1442, 1392, 1286, 1267, 1156, and 1138. MS (ES) m/e 330, 332.

Workup

  1. stirringThe reaction was stirred an additional 1.5 h
  2. temperatureThe mixture was refluxed 1 h
  3. extractionextracted with sat'd NaHCO3 two times
  4. customAfter drying
  5. custom(NaSO4), evaporation in vacuo
  6. customafforded 4.90 g
  7. customThe mixture was purified by column chromatography on silica gel (elution with toluene/methylene chloride)

Sources & evidence

ORD record
ord-3a58cb9f8b6244a1913f22f246e58f8a
Source dataset
uspto-grants-2004_03
Patent number
US06713645B1

Linked notes

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