Dimethylformamide → 9-Benzyl-1,2,3,9-tetrahydro-4H-carbazol-4-one

HRID 1057592Notes

Reaction equation

HRID 1057592 reaction equation
[H-].[Na+].[CH3:3][N:4]([CH:6]=O)[CH3:5].[CH2:8]1[CH2:12][O:11][CH2:10][CH2:9]1.C(Br)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>CCCCCC>[CH2:6]([N:4]1[C:3]2[CH2:12][CH2:8][CH2:9][C:10](=[O:11])[C:17]=2[C:16]2[C:5]1=[CH:18][CH:19]=[CH:14][CH:15]=2)[C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

6

Reactant 4

HCID 6228DimethylformamideHCID 7498Benzyl Bromide2×HCID 8028TetrahydrofuranHCID 24758Sodium hydride

Product 1

HCID 27279169-Benzyl-1,2,3,9-tetrahydro-4H-carbazol-4-oneYield 79%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent

Procedure

Sodium hydride (60% in oil; 0.207 g, 5.18 mmol) is washed three times with hexane. DMF (3 mL) is added, followed by 36B added in portions. A moderate exotherm ensued; THF (3 mL) is added. After ten minutes benzyl bromide (1.047 g, 6.12 mmol) is added. After stirring for 4 h, an additional 0.1 g of benzyl bromide is added. The mixture is stirred overnight and then the solvents are removed; the residue is partitioned between CH2C2 and aq. sodium bicarbonate. The organic layers are dried over sodium sulfate. Chromatography on silica gel (150 mL) using CH3OH—CH2Cl2 (1/99) as eluent, followed by re-chromatography of mixed fractions using EtOAc-hexane (30/70), gave 1.023 g (79%) of the title compound; mp 157.0-157.5° C.; IR (drift) 2940, 1636, 1610, 1530, 1484, 1464, 1445, 1399, 1357, 1187, 1133, 749, 742, 731, 698 cm−1; 1H NMR (CDCl3) δ2.23, 2.60, 2.88, 5.34, 7.03, 7.2-7.3, 8.30. Anal. Calcd for C19H17NO: C, 82.88; H, 6.22; N, 5.09. Found: C, 82.51; H, 6.21; N, 5.13.

Workup

  1. additionadded in portions
  2. stirringThe mixture is stirred overnight
  3. customthe solvents are removed
  4. customthe residue is partitioned between CH2C2 and aq. sodium bicarbonate
  5. dry with materialThe organic layers are dried over sodium sulfate

Sources & evidence

ORD record
ord-773a6d17802c4c259224c5c87064aea0
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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