Sodium hydride → 9-[(3-Methylphenyl)methyl]-2-methyl-4-hydroxy-5-carbomethoxy carbazole

HRID 51328

Reaction equation

HRID 51328 reaction equation
[CH3:1][C:2]1[CH:3]=[C:4]([CH2:8][N:9]2[C:21]3[CH2:20][CH:19]([CH3:22])[CH2:18][C:17](=[O:23])[C:16]=3[C:15]3[C:10]2=[CH:11][CH:12]=[CH:13][C:14]=3[C:24]([O:26][CH3:27])=[O:25])[CH:5]=[CH:6][CH:7]=1.[H-].[Na+].C1(S(OC)=O)C=CC=CC=1>O1CCOCC1.C(O)(=O)C.C(OCC)(=O)C>[CH3:1][C:2]1[CH:3]=[C:4]([CH2:8][N:9]2[C:21]3[CH:20]=[C:19]([CH3:22])[CH:18]=[C:17]([OH:23])[C:16]=3[C:15]3[C:10]2=[CH:11][CH:12]=[CH:13][C:14]=3[C:24]([O:26][CH3:27])=[O:25])[CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 3

HCID 24758Sodium hydrideHCID 2759784Methyl benzenesulfinateHCID 227383569-[(3-methylphenyl)methyl]-5-carbomethoxy-2-methyl-1,2-dihydrocarbazol-4(3H)-one

Product 1

HCID 227381449-[(3-Methylphenyl)methyl]-2-methyl-4-hydroxy-5-carbomethoxy carbazoleYield 66%

Reagents, catalysts & solvents 3

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

Procedure

To a solution of 9-[(3-methylphenyl)methyl]-5-carbomethoxy-2-methyl-1,2-dihydrocarbazol-4(3H)-one (1.41 g, 3.89 mM) in 13 ml dioxane was added 60% sodium hydride in mineral oil (0.36 g, 8.95 mM). The reaction was stirred 6 minutes, then methyl benzenesulfinate (0.81 ml, 6.22 mM) was added. The reaction was stirred an additional 6 hours, then diluted with 20 ml dioxane and 0.51 ml acetic acid. The mixture was refluxed 30 minutes, diluted with ethyl acetate, and extracted with saturated NaHCO3, brine, then water. After drying (NaSO4), evaporation in vacuo afforded 2.30 g. The mixture was purified by column chromatography on silica gel (elution with toluene/methylene chloride) to afford 0.92 g (66%) of 9-[(3-methylphenyl)methyl]-2-methyl-4-hydroxy-5-carbomethoxy carbazole. 1H NMR (CDCl3) δ10.45 (s, 1H), 8.0 (d, J=8 Hz, 1H), 7.55 (d, J=8 Hz, 1H), 7.4 (dd, J=8 and 8 Hz, 1H), 7.4 (dd, J=8 and 8 Hz, 1H), 7.05 (d, J=8 HZ, 1H), 6.9 (s, 1H), 6.85 (d, J=8 Hz, 1H), 6.75 (s, 1H), 6.7 (s, 1H), 5.45 (s, 2H), 4.1 (s, 3H), 2.4 (s, 3H), 2.25 (s, 3H). MS (ES) m/e 328, 360.

Workup

  1. stirringThe reaction was stirred an additional 6 hours
  2. temperatureThe mixture was refluxed 30 minutes
  3. extractionextracted with saturated NaHCO3, brine
  4. customAfter drying
  5. custom(NaSO4), evaporation in vacuo
  6. customafforded 2.30 g
  7. customThe mixture was purified by column chromatography on silica gel (elution with toluene/methylene chloride)

Sources & evidence

ORD record
ord-8dffb545419a4274b353c8d029d0778a
Source dataset
uspto-grants-2004_03
Patent number
US06713645B1

Linked notes

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