N-bromobutanimide → 1H-Pyrrolo[2,3-b]pyridine-3-carboxylic acid, 5-bromo-2-(bromomethyl)-1-(phenylsulfonyl)-, methyl ester

HRID 60213Notes

Reaction equation

HRID 60213 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([Br:14])[CH:12]=2)[N:7]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:17])=[O:16])[C:6]=1[CH3:24])=[O:4].C1C(=O)N([Br:32])C(=O)C1>ClCCCl>[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([Br:14])[CH:12]=2)[N:7]([S:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)(=[O:17])=[O:16])[C:6]=1[CH2:24][Br:32])=[O:4]

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 582665641H-Pyrrolo[2,3-b]pyridine-3-carboxylic acid, 5-bromo-2-methyl-1-(phenylsulfonyl)-, methyl ester

Product 1

HCID 582663771H-Pyrrolo[2,3-b]pyridine-3-carboxylic acid, 5-bromo-2-(bromomethyl)-1-(phenylsulfonyl)-, methyl esterYield 90%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of 1-benzenesulfonyl-5-bromo-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (121 g, 296 mmol), NBS (63 g, 354 mmol) and 1,1-azobis(cyclohexanecarbonitrile) (14.4 g, 59 mmol) in 1,2-dichloroethane (1.2 L) was heated under reflux for 90 minutes. The reaction mixture was allowed to cool to ambient temperature and washed with saturated aqueous sodium thiosulfate solution. The organic layer was dried (Na2SO4) then filtered. The filtrate was stirred with flash silica gel, filtered and the filtrate evaporated under reduced pressure. The resultant residue was triturated with diethyl ether/pentane (1:1) to afford the title compound as a white solid (130 g, 90%). 1H NMR (400 MHz, CDCl3): 8.47-8.46 (m, 4H), 7.64-7.64 (m, 1H), 7.54-7.53 (m, 2H), 5.67 (s, 2H), 4.00 (s, 3H).

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 90 minutes
  3. washwashed with saturated aqueous sodium thiosulfate solution
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. filtrationthen filtered
  6. filtrationfiltered
  7. customthe filtrate evaporated under reduced pressure
  8. customThe resultant residue was triturated with diethyl ether/pentane (1:1)

Sources & evidence

ORD record
ord-1c1fa94386cc4b398289e14baec804c3
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Reaction notes

Loading…