Methanesulfonyl chloride → HCID 86642950, compound

HRID 661932Notes

Reaction equation

HRID 661932 reaction equation
[Br:1][C:2]1[C:14]2[C:13]3[C:8](=[CH:9][C:10]([CH2:15][OH:16])=[CH:11][CH:12]=3)[NH:7][C:6]=2[C:5]([C:17]([NH2:19])=[O:18])=[CH:4][CH:3]=1.[CH3:20][S:21](Cl)(=[O:23])=[O:22].C([O-])(O)=O.[Na+]>C1COCC1>[CH3:20][S:21]([O:16][CH2:15][C:10]1[CH:11]=[CH:12][C:13]2[C:14]3[C:6](=[C:5]([C:17](=[O:18])[NH2:19])[CH:4]=[CH:3][C:2]=3[Br:1])[NH:7][C:8]=2[CH:9]=1)(=[O:23])=[O:22]

Participants

5

Reactant 3

HCID 31297Methanesulfonyl chlorideHCID 516892Sodium BicarbonateHCID 66606607HCID 66606607, compound

Product 1

HCID 86642950HCID 86642950, compoundYield 104.4%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Step 1 A suspension of 4-bromo-7-(hydroxymethyl)-9H-carbazole-1-carboxamide (Example 30-2, 300 mg, 0.940 mmol) and TEA (0.262 mL, 1.880 mmol) in THF (9.4 mL) was treated dropwise with methanesulfonyl chloride (0.077 mL, 0.987 mmol) and the mixture was stirred at rt for 1 hr. It was treated with NaHCO3 (aq) and extracted with EtOAc. The organic phase was washed with brine, dried and concentrated to provide crude (5-bromo-8-carbamoyl-9H-carbazol-2-yl)methyl methanesulfonate as a light yellow solid (390 mg, 89%). This material was suspended in DMF (8.3 mL) and treated with sodium azide (271 mg, 4.17 mmol). After being stirred overnight at rt, the mixture was diluted with water and extracted with EtOAc. The organic phase was washed with brine, dried and concentrated to provide crude 7-(azidomethyl)-4-bromo-9H-carbazole-1-carboxamide as a light yellow solid (350 mg, 97%). 1H NMR (400 MHz, DMSO-d6) δ 11.80 (1H, s), 8.62 (1H, d, J=8.4 Hz), 8.22 (1H, br. s.), 7.88 (1H, d, J=8.1 Hz), 7.83 (1H, s), 7.58 (1H, br. s.), 7.46 (1H, d, J=8.4 Hz), 7.28 (1H, dd, J=8.1, 1.5 Hz), 4.63 (2H, s).

Workup

  1. extractionextracted with EtOAc
  2. washThe organic phase was washed with brine
  3. customdried
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-10a993d5aeb947b0b9a0cb6adc61fe45
Source dataset
uspto-grants-2011_12
Patent number
US08084620B2

Reaction notes

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