Water → HCID 66606813, compound

HRID 661987Notes

Reaction equation

HRID 661987 reaction equation
[CH3:1]C(C)([O-])C.[K+].[Br:7][C:8]1[C:20]2[C:19]3[C:14](=[CH:15][C:16]([CH:21]=O)=[CH:17][CH:18]=3)[NH:13][C:12]=2[C:11]([C:23]([NH2:25])=[O:24])=[CH:10][CH:9]=1.O>C1COCC1.[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:7][C:8]1[C:20]2[C:19]3[C:14](=[CH:15][C:16]([CH:21]=[CH2:1])=[CH:17][CH:18]=3)[NH:13][C:12]=2[C:11]([C:23]([NH2:25])=[O:24])=[CH:10][CH:9]=1

Participants

6

Reactant 3

HCID 962WaterHCID 23665647Potassium tert-butoxideHCID 86642954HCID 86642954, compound

Product 1

HCID 66606813HCID 66606813, compound

Reagents, catalysts & solvents 2

HCID 74505Methyltriphenyliphosphonium bromideCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Step 1 A solution of potassium tert-butoxide (3.40 g, 30.3 mmol) in THF (249 mL) at 0° C. was treated with methyltriphenylphosphonium bromide (8.79 g, 24.60 mmol), forming a bright yellow suspension. After 1 h, 4-bromo-7-formyl-9H-carbazole-1-carboxamide (prepared according to the procedure of Step 1 of Example 41-1, 4 g, 9.46 mmol) was added, and the resulting suspension was warmed to rt and stirred for 3 h. Water was added and the mixture was extracted with EtOAc. The organic phase was washed with brine, dried and concentrated. The residue was purified by column chromatography (eluting with a gradient from 70:30 hexane-EtOAc to EtOAc). The crude material was suspended in methanol, and the precipitate was collected by filtration and dried. The filtrate was concentrated to provide additional solid which was collected by filtration, dried and combined with the first crop to provide 4-bromo-7-vinyl-9H-carbazole-1-carboxamide as a light brown solid (1.66 g, ca. 90% purity, 50%). 1H NMR (400 MHz, DMSO-d6) δ 11.68 (1H, s), 8.52 (1H, d, J=8.3 Hz), 8.06-8.29 (1H, m), 7.79-7.88 (2H, m), 7.58 (1H, br. s.), 7.35-7.45 (2H, m), 6.78-6.98 (1H, m), 5.88 (1H, d, J=17.6 Hz), 5.32 (1H, d). Mass spectrum m/z 344, 346 (M+H)+.

Workup

  1. customforming a bright yellow suspension
  2. additionwas added
  3. extractionthe mixture was extracted with EtOAc
  4. washThe organic phase was washed with brine
  5. customdried
  6. concentrationconcentrated
  7. customThe residue was purified by column chromatography (
  8. washeluting with a gradient from 70:30 hexane-EtOAc to EtOAc)
  9. filtrationthe precipitate was collected by filtration
  10. customdried
  11. concentrationThe filtrate was concentrated
  12. customto provide additional solid which
  13. filtrationwas collected by filtration
  14. customdried

Sources & evidence

ORD record
ord-3339dbf6e154435eac826c2957463fa3
Source dataset
uspto-grants-2011_12
Patent number
US08084620B2

Reaction notes

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