1,3-Dibromo-5,5-dimethylhydantoin → 1-Benzenesulfonyl-5-fluoro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

HRID 60222

Reaction equation

HRID 60222 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([F: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].[Br:25]N1C(C)(C)C(=O)N(Br)C1=O>ClCCCl>[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([F: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:25])=[O:4]

Participants

4

Reactant 2

HCID 64791,3-Dibromo-5,5-dimethylhydantoinHCID 583651851-Benzenesulfonyl-5-fluoro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

Product 1

HCID 583650121-Benzenesulfonyl-5-fluoro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl esterYield 93.3%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of 1-benzenesulfonyl-5-fluoro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (13.9 g, 39.9 mmol), 1,3-dibromo-5,5-dimethylhydantoin (12.6 g, 39.9 mmol) and 1,1-azobis(cyclohexanecarbonitrile) (1.95 g, 8.0 mmol) in 1,2-dichloroethane (150 mL) was heated under reflux for 90 minutes then stirred at ambient temperature for 16 hours. The reaction mixture was 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 cream solid (15.9 g, 93%). 1H NMR (400 MHz, CDCl3): 8.47-8.44 (m, 2H), 8.32 (dd, J=2.8, 1.1 Hz, 1H), 8.04 (dd, J=8.5, 2.8 Hz, 1H), 7.64-7.64 (m, 1H), 7.54-7.53 (m, 2H), 5.68 (s, 2H), 4.00 (s, 3H).

Workup

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

Sources & evidence

ORD record
ord-50494b488cbe4e83a33254f9337a10b1
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Linked notes

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