2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → ethyl 6-bromo-8-carbamoyl-9H-carbazole-2-carboxylate

HRID 2410668Notes

Reaction equation

HRID 2410668 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[C:13]([C:15](=[O:17])[NH2:16])[CH:14]=1)[NH:11][C:10]1[CH2:9][CH:8]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH2:7][CH2:6][C:5]2=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[C:13]([C:15](=[O:17])[NH2:16])[CH:14]=1)[NH:11][C:10]1[CH:9]=[C:8]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:7]=[CH:6][C:5]2=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 66605605ethyl 6-bromo-8-carbamoyl-2,3,4,9-tetrahydro-1H-carbazole-2-carboxylate

Product 1

HCID 66604694ethyl 6-bromo-8-carbamoyl-9H-carbazole-2-carboxylateYield 118.4%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A stirred suspension of ethyl 6-bromo-8-carbamoyl-2,3,4,9-tetrahydro-1H-carbazole-2-carboxylate (3.93 g, 10.76 mmol) and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.37 g, 23.67 mmol) in toluene (60 mL) was heated at reflux for 4 h. The reaction mixture was cooled to room temperature and the solid was filtered, washed with toluene, and air-dried. The solid was suspended in ethyl acetate, the solid filtered, washed with MeOH and air-dried to furnish 4.6 g of ethyl 6-bromo-8-carbamoyl-9H-carbazole-2-carboxylate which was taken as such to the next reaction. MS (ESI) m/z 361.1/363.1 (M+H)+. 1H NMR (DMSO-d6) δ ppm 11.76 (s, 1H), 8.60 (d, J=1.76 Hz, 1H), 8.36 (d, J=0.88 Hz, 1H), 8.25 (d, J=8.35 Hz, 1H), 8.23 (br. s., 1H), 8.13 (d, J=1.76 Hz, 1H), 7.73 (dd, J=8.24, 1.43 Hz, 1H), 7.59 (br. s., 1H), 4.29 (q, J=7.18 Hz, 2H), 1.30 (t, J=7.14 Hz, 3H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 4 h
  3. filtrationthe solid was filtered
  4. washwashed with toluene
  5. customair-dried
  6. filtrationthe solid filtered
  7. washwashed with MeOH
  8. customair-dried

Sources & evidence

ORD record
ord-2fbce074752d4b868b9bd89052c56f95
Source dataset
uspto-grants-2014_08
Patent number
US08815840B2

Reaction notes

Loading…