Methyl iodide → HCID 67378219, compound

HRID 877496Notes

Reaction equation

HRID 877496 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][C:14]=1[Cl:15])[N:11]([S:16]([C:19]1[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=1)(=[O:18])=[O:17])[C:10]1[C:9](=[O:26])[CH2:8][CH2:7][CH2:6][C:5]2=1.[Li+].[CH3:28][Si]([N-][Si](C)(C)C)(C)C.CI.[NH4+].[Cl-]>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][C:14]=1[Cl:15])[N:11]([S:16]([C:19]1[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=1)(=[O:18])=[O:17])[C:10]1[C:9](=[O:26])[CH:8]([CH3:28])[CH2:7][CH2:6][C:5]2=1

Participants

6

Reactant 4

HCID 6328Methyl iodideHCID 25517Ammonium ChlorideHCID 2733832Lithium HexamethyldisilazideHCID 67362572HCID 67362572, compound

Product 1

HCID 67378219HCID 67378219, compoundYield 394.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

6,7-Dichloro-9-tosyl-2,3,4,9-tetrahydro-1H-carbazol-1-one 0.1 g, 0.024 mmol) was dissolved in dry THF, cooled to −78° C. and LiHMDS (0.6 mL, 0.61 mmol) was added dropwise. The reaction mixture was slowly warmed to 0° C. and stirred for an additional 30 min. The reaction mixture was cooled to −78° C. and MeI (0.040 mL, 0.61 mmol) was added slowly, warmed to room temperature and stirred for 4 h. Saturated NH4Cl (10 mL) was added to the reaction mixture and extracted with EtOAc (2×50 mL). The combined organic extracts were dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified by column chromatography [EtOAc-hexane (1:9) as eluant] to obtain the title compound (0.04 g, 40%). 1H NMR (500 MHz, CDCl3, δ in ppm) 8.49 (s, 1H), 8.03 (d, J=8.0 Hz, 2H), 7.67 (s, 1H), 7.32 (d, J=8.0 Hz, 2H), 2.98-2.85 (m, 2H), 2.71-2.66 (m, 1H), 2.43 (s, 3H), 2.27-2.23 (m, 1H), 1.96-1.89 (m, 1H), 1.25-1.17 (m, 3H).

Workup

  1. temperatureThe reaction mixture was slowly warmed to 0° C.
  2. temperatureThe reaction mixture was cooled to −78° C.
  3. temperaturewarmed to room temperature
  4. stirringstirred for 4 h
  5. extractionextracted with EtOAc (2×50 mL)
  6. dry with materialThe combined organic extracts were dried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe crude residue was purified by column chromatography [EtOAc-hexane (1:9) as eluant]

Sources & evidence

ORD record
ord-fd3bd2faff3c47caaf48b72b586208f4
Source dataset
uspto-grants-2015_03
Patent number
US08987319B2

Reaction notes

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