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

HRID 523249Notes

Reaction equation

HRID 523249 reaction equation
[Br:1][C:2]1[C:14]([CH3:15])=[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[CH3:15]

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 1177754535-bromo-2-(ethoxycarbonyl)-6-methyl-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid

Product 1

HCID 1177712304-bromo-7-(ethoxycarbonyl)-3-methyl-9H-carbazole-1-carboxylic acidYield 88.4%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 5-bromo-2-(ethoxycarbonyl)-6-methyl-2,3,4,9-tetrahydro-1H-carbazole-8-carboxylic acid (1.60 g, 4.21 mmol) and 2,3-dichloro-5,6-dicyanobenzoquinone (2.10 g, 9.26 mmol) in THF (45 mL) was heated at 60° C. for 60 min. The cooled mixture was diluted with EtOAc (about 70 mL), stirred for 15 min, and the precipitate was collected by filtration, washed with EtOAc and dried. The filtrate was concentrated, and the residue was triturated with MeOH, filtered, and the collected precipitate was washed with MeOH. The two solids were combined to give 4-bromo-7-(ethoxycarbonyl)-3-methyl-9H-carbazole-1-carboxylic acid as a pale yellow solid (1.40 g, 88% yield). Mass spectrum m/z 376, 378 (M+H)+.

Workup

  1. filtrationthe precipitate was collected by filtration
  2. washwashed with EtOAc
  3. customdried
  4. concentrationThe filtrate was concentrated
  5. customthe residue was triturated with MeOH
  6. filtrationfiltered
  7. washthe collected precipitate was washed with MeOH

Sources & evidence

ORD record
ord-afba20e42adf432db4d86796ad11d127
Source dataset
uspto-grants-2016_05
Patent number
US09334290B2

Reaction notes

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