4-Toluenesulfonyl chloride → Carbamic acid, N-[3-bromo-1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridin-5-yl]-, phenylmethyl ester

HRID 887363Notes

Reaction equation

HRID 887363 reaction equation
[Br:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([NH:11][C:12](=[O:21])[O:13][CH2:14][C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[CH:9]=2)[NH:4][CH:3]=1.[H-].[Na+].[S:24](Cl)([C:27]1[CH:33]=[CH:32][C:30]([CH3:31])=[CH:29][CH:28]=1)(=[O:26])=[O:25]>C1COCC1>[Br:1][C:2]1[C:10]2[C:5](=[N:6][CH:7]=[C:8]([NH:11][C:12](=[O:21])[O:13][CH2:14][C:15]3[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=3)[CH:9]=2)[N:4]([S:24]([C:27]2[CH:33]=[CH:32][C:30]([CH3:31])=[CH:29][CH:28]=2)(=[O:26])=[O:25])[CH:3]=1

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 24758Sodium hydrideHCID 57471661Benzyl 3-bromo-1H-pyrrolo[2,3-b]pyridin-5-ylcarbamate

Product 1

HCID 59414519Carbamic acid, N-[3-bromo-1-[(4-methylphenyl)sulfonyl]-1H-pyrrolo[2,3-b]pyridin-5-yl]-, phenylmethyl esterYield 75.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Benzyl 3-bromo-1H-pyrrolo[2,3-b]pyridin-5-ylcarbamate (10.22 g, 29.53 mmol) in dry THF (120 mL) was cooled to 0° C. and treated portionwise with sodium hydride (1.193 g, 29.83 mmol, 1.01 Eq). The mixture was allowed to stir at this temperature for 1 hour and then treated with tosyl chloride (5.744 g, 30.13 mmol, 1.02 Eq) in THF (15 mL) over a period of 10 minutes. The mixture was left to stir at room temperature for a further 4 hours and then quenched with sat. aq. ammonium chloride. The mixture was diluted with EtOAc and the organic layer separated, washed with brine, dried over magnesium sulphate, filtered and evaporated to dryness. The crude product was purified by column chromatography (5% MeOH/DCM) to give 11.09 g (75%) of brown solid.

Workup

  1. waitThe mixture was left
  2. stirringto stir at room temperature for a further 4 hours
  3. customquenched with sat. aq. ammonium chloride
  4. additionThe mixture was diluted with EtOAc
  5. customthe organic layer separated
  6. washwashed with brine
  7. dry with materialdried over magnesium sulphate
  8. filtrationfiltered
  9. customevaporated to dryness
  10. customThe crude product was purified by column chromatography (5% MeOH/DCM)

Sources & evidence

ORD record
ord-f49a148a1b124a17852206ef816785bc
Source dataset
uspto-grants-2012_08
Patent number
US08247421B2

Reaction notes

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