Chlorosuccinimide → ethyl 5-bromo-8-carbamoyl-6-chloro-9H-carbazole-2-carboxylate

HRID 523202Notes

Reaction equation

HRID 523202 reaction equation
[Br:1][C:2]1[CH:14]=[CH:13][C:12]([C:15](=[O:17])[NH2:16])=[C:11]2[C:3]=1[C:4]1[CH:5]=[CH:6][C:7]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:8][C:9]=1[NH:10]2.C1C(=O)N([Cl:30])C(=O)C1>C(Cl)(Cl)(Cl)Cl.CN(C=O)C>[Br:1][C:2]1[C:14]([Cl:30])=[CH:13][C:12]([C:15](=[O:17])[NH2:16])=[C:11]2[C:3]=1[C:4]1[CH:5]=[CH:6][C:7]([C:18]([O:20][CH2:21][CH3:22])=[O:19])=[CH:8][C:9]=1[NH:10]2

Participants

5

Reactant 2

HCID 31398ChlorosuccinimideHCID 59375100ethyl 5-bromo-8-carbamoyl-9H-carbazole-2-carboxylate

Product 1

HCID 117760738ethyl 5-bromo-8-carbamoyl-6-chloro-9H-carbazole-2-carboxylateYield 65%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of ethyl 5-bromo-8-carbamoyl-9H-carbazole-2-carboxylate [synthesized according to the procedure described in U.S. Pat. No. 8,084,620, Intermediate 48-1] (0.100 g, 0.277 mmol) and NCS (recrystallized from toluene; 0.037 g, 0.277 mmol) in CCl4 (10 mL) and DMF (2 mL) was stirred at room temperature for 112 h. The mixture was filtered, and the collected precipitate was washed with CCl4 and dried overnight under vacuum. The residue was purified by column chromatography on silica gel (40 g), eluting with hexanes, then with EtOAc-hexanes (30%, then 50%), to give ethyl 5-bromo-8-carbamoyl-6-chloro-9H-carbazole-2-carboxylate as a fluffy white solid (0.071 g, 65% yield). Mass spectrum m/z 395, 397, (M+H)+. 1H NMR (400 MHz, DMSO-d6) δ 12.13 (s, 1H), 8.77 (d, J=8.6 Hz, 1H), 8.53 (d, J=1.1 Hz, 1H), 8.36 (br. s., 1H), 8.29 (s, 1H), 7.89 (dd, J=8.4, 1.5 Hz, 1H), 7.74 (br. s., 1H), 4.38 (q, J=7.0 Hz, 2H), 1.38 (t, J=7.0 Hz, 3H).

Workup

  1. customsynthesized
  2. filtrationThe mixture was filtered
  3. washthe collected precipitate was washed with CCl4
  4. customdried overnight under vacuum
  5. customThe residue was purified by column chromatography on silica gel (40 g)
  6. washeluting with hexanes

Sources & evidence

ORD record
ord-9b4ab54bc5aa42f6b6ac2853e883a322
Source dataset
uspto-grants-2016_05
Patent number
US09334290B2

Reaction notes

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