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

HRID 60230

Reaction equation

HRID 60230 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:13]2[C:8](=[N:9][CH:10]=[C:11]([Cl: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]([Cl: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 583649861-Benzenesulfonyl-5-chloro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester

Product 1

HCID 583651731-Benzenesulfonyl-5-chloro-2-bromomethyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl esterYield 66.8%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of 1-benzenesulfonyl-5-chloro-2-methyl-1H-pyrrolo[2,3-b]pyridine-3-carboxylic acid methyl ester (16.9 g, 46.2 mmol), 1,3-dibromo-5,5-dimethylhydantoin (13.21 g, 46.2 mmol) and 1,1-azobis(cyclohexanecarbonitrile) (1.52 g, 9.3 mmol) in 1,2-dichloroethane (200 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 white solid (13.7 g, 61%). LCMS (Method B): RT=4.35 min, M+H+=443/445/447. 1H NMR (400 MHz, CDCl3): 8.46-8.46 (m, 2H), 8.39 (d, J=2.4 Hz, 1H), 8.32 (d, J=2.4 Hz, 1H), 7.64-7.64 (m, 1H), 7.55-7.52 (m, 2H), 5.67 (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-21c54ea8a39c465cb72954c01e742bd1
Source dataset
uspto-grants-2016_09
Patent number
US09440976B2

Linked notes

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