Pentane → HCID 12044736, compound

HRID 1057604Notes

Reaction equation

HRID 1057604 reaction equation
[CH3:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:14]=1[NH:13][C:12]1[CH2:11][CH2:10][CH2:9][C:8](=[O:15])[C:7]2=1.CCCCC.[H-].[Na+].[F:23][C:24]1[CH:31]=[CH:30][C:27]([CH2:28]Br)=[CH:26][CH:25]=1>CN(C=O)C>[F:23][C:24]1[CH:31]=[CH:30][C:27]([CH2:28][N:13]2[C:12]3[CH2:11][CH2:10][CH2:9][C:8](=[O:15])[C:7]=3[C:6]3[C:14]2=[C:2]([CH3:1])[CH:3]=[CH:4][CH:5]=3)=[CH:26][CH:25]=1

Participants

6

Reactant 4

HCID 8003PentaneHCID 24758Sodium hydrideHCID 680214-Fluorobenzyl bromide2×HCID 11830419HCID 11830419, compound

Product 1

HCID 12044736HCID 12044736, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

8-Methyl-1,2,3,9-tetrahydro-4H-carbazol-4-one (0.1967 g, 0.99 mmol) is added to a slurry of pentane-washed NaH (0.0449 g, 0.0011 mol) in DMF (2 mL). After stirring for 30 min, p-fluorobenzyl bromide (0.15 mL, 0.0012 mol) is added. Starting material is still present after 3 h, so additional p-fluorobenzyl bromide (0.015 mL, 0.12 mmol) is added and the mixture is stirred overnight. The mixture is then partitioned between aq. sodium bicarbonate and ethyl acetate and the organic layer is dried over sodium sulfate and concentrated to dryness. The resulting solids are chromatographed on silica gel (75 mL) using methanol/dichloromethane (2/98). The impure fractions are rechromatographed on silica gel (60 mL) using methanol/dichloromethane (2/98). The pure fractions are combined and recrystallized from ethyl acetate/hexane/dichloromethane to give 0.1021 g (34%) of the title compound; mp 154-155° C.; MS (ESI+) for C20H18FNO m/z 308.2 (M+H)+; IR (drift) 1635, 1602, 1539, 1510, 1462, 1449, 1414, 1226, 1159, 835, 826, 801, 786, 756, 747 cm−1; 1H NMR (CDCl3) δ2.21, 2.51, 2.59, 2.81, 5.55, 6.87, 6.98, 7.17, 8.23. Anal. Calcd for C20H18FNO: C, 78.15; H, 5.90; N, 4.56. Found: C, 77.72; H, 5.95; N, 4.64.

Workup

  1. waitStarting material is still present after 3 h
  2. stirringthe mixture is stirred overnight
  3. customThe mixture is then partitioned between aq. sodium bicarbonate and ethyl acetate
  4. dry with materialthe organic layer is dried over sodium sulfate
  5. concentrationconcentrated to dryness
  6. customThe resulting solids are chromatographed on silica gel (75 mL)
  7. customThe impure fractions are rechromatographed on silica gel (60 mL)
  8. customrecrystallized from ethyl acetate/hexane/dichloromethane

Sources & evidence

ORD record
ord-eade1fb126304bd299aaa493c6b8d193
Source dataset
uspto-grants-2003_02
Patent number
US06514968B1

Reaction notes

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