2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 4-bromo-7-(ethoxycarbonyl)-3-fluoro-9H-carbazole-1-carboxylic acid

HRID 523239Notes

Reaction equation

HRID 523239 reaction equation
[Br:1][C:2]1[C:14]([F:15])=[CH:13][C:12]([C:16]([OH:18])=[O:17])=[C:11]2[C:3]=1[C:4]1[CH2:5][CH2:6][CH:7]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH2:8][C:9]=1[NH:10]2.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1COCC1.CCOC(C)=O>[Br:1][C:2]1[C:3]2[C:4]3[C:9](=[CH:8][C:7]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:6][CH:5]=3)[NH:10][C:11]=2[C:12]([C:16]([OH:18])=[O:17])=[CH:13][C:14]=1[F:15]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 1177608064-bromo-7-ethoxycarbonyl-3-fluoro-6,7,8,9-tetrahydro-5H-carbazole-1-carboxylic acid

Product 1

HCID 1177608524-bromo-7-(ethoxycarbonyl)-3-fluoro-9H-carbazole-1-carboxylic acidYield 84.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 5-bromo-2-(ethoxycarbonyl)-6-fluoro-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid (2.87 g, 7.47 mmol) and 2,3-dichloro-5,6-dicyanobenzoquinone (3.73 g, 16.4 mmol) in THF (45 mL) was heated at 60° C. for 90 min. The cooled mixture was diluted with EtOAc (about 50 mL) and stirred for 60 min. The resulting precipitate was collected by filtration, washed with EtOAc and dried. The filtrate was concentrated, and the residue was triturated with MeOH with sonication, filtered, and the precipitate was washed with MeOH and dried. The two precipitates were combined to give 4-bromo-7-ethoxycarbonyl-3-fluoro-9H-carbazole-1-carboxylic acid as a pale yellow solid (2.39 g, 84% yield). Mass spectrum m/z 380, 382 (M+H)+.

Workup

  1. filtrationThe resulting precipitate was collected by filtration
  2. washwashed with EtOAc
  3. customdried
  4. concentrationThe filtrate was concentrated
  5. customthe residue was triturated with MeOH with sonication
  6. filtrationfiltered
  7. washthe precipitate was washed with MeOH
  8. customdried
  9. customThe two precipitates

Sources & evidence

ORD record
ord-43bec32b56b2485487a801832950296c
Source dataset
uspto-grants-2016_05
Patent number
US09334290B2

Reaction notes

Loading…