Sodium hydride → tert-butyl 2-(benzyloxy)-7-(N-methylformamido)-9H-carbazole-9-carboxylate

HRID 1425573

Reaction equation

HRID 1425573 reaction equation
[CH2:1]([O:8][C:9]1[CH:21]=[C:20]2[C:12]([C:13]3[CH:14]=[CH:15][C:16]([N:22]([CH3:25])[CH:23]=[O:24])=[CH:17][C:18]=3[NH:19]2)=[CH:11][CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Na+].[C:28](=O)([O:34]C1C=CC=CC=1)[O:29][C:30]([CH3:33])([CH3:32])[CH3:31]>C1COCC1>[CH2:1]([O:8][C:9]1[CH:10]=[CH:11][C:12]2[C:13]3[C:18](=[CH:17][C:16]([N:22]([CH3:25])[CH:23]=[O:24])=[CH:15][CH:14]=3)[N:19]([C:28]([O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[O:34])[C:20]=2[CH:21]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 81113Carbonic acid, 1,1-dimethylethyl phenyl esterHCID 86651370N-(7-(benzyloxy)-9H-carbazol-2-yl)-N-methylformamide

Product 1

HCID 86651372tert-butyl 2-(benzyloxy)-7-(N-methylformamido)-9H-carbazole-9-carboxylateYield 66.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To N-(7-(benzyloxy)-9H-carbazol-2-yl)-N-methylformamide (140 mg, 0.42 mmol) in 5 mL dry THF at 0° C. under Ar atmosphere was added NaH (50 mg, 60% in oil, 1.26 mmol) in 4 portions. The mixture was then stirred at rt for 20 min followed by the addition of tert-butyl phenyl carbonate (244 mg, 1.26 mmol) with a syringe. The reaction was allowed to stir at rt for 3 h and quenched onto ice (30 g). The mixture was extracted with EtOAc (2×40 mL) and the combined organic phase was dried over MgSO4. After solvent removal, the residue was chromatographed to afford tert-butyl 2-(benzyloxy)-7-(N-methylformamido)-9H-carbazole-9-carboxylate as a white solid (120 mg, 66%). 1H NMR (400 MHz, CDCl3) δ 8.56 (s, 1H), 8.15 (s, 1H), 7.98 (s, 1H), 7.86 (d, J=8.4 Hz, 1H), 7.83 (d, J=8.4 Hz, 1H), 7.50-7.49 (m, 2H), 7.43-7.39 (m., 2H), 7.37-7.32 (m, 1H), 7.13 (dd, J=8.4, 2.0 Hz, 1H), 7.05 (dd, J=8.8, 2.4 Hz, 1H), 5.18 (s, 2H), 3.41 (s, 3H), 1.75 (s, 9H); MS (ESI) m/z 431 (M+H+).

Workup

  1. stirringto stir at rt for 3 h
  2. customquenched onto ice (30 g)
  3. extractionThe mixture was extracted with EtOAc (2×40 mL)
  4. dry with materialthe combined organic phase was dried over MgSO4
  5. customAfter solvent removal
  6. customthe residue was chromatographed

Sources & evidence

ORD record
ord-3b05886ed49148c781d91d954738e768
Source dataset
uspto-grants-2015_01
Patent number
US08932557B2

Linked notes

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