Benzyl mercaptan → 3-Bromo-5-[(phenylmethyl)thio]pyridine

HRID 1774479Notes

Reaction equation

HRID 1774479 reaction equation
[CH2:1]([SH:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].[Na+].[Br:11][C:12]1[CH:13]=[N:14][CH:15]=[C:16](Br)[CH:17]=1>CN(C=O)C.CCOC(C)=O>[CH2:1]([S:8][C:16]1[CH:15]=[N:14][CH:13]=[C:12]([Br:11])[CH:17]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 7509Benzyl mercaptanHCID 24758Sodium hydrideHCID 693693,5-Dibromopyridine

Product 1

HCID 710766893-Bromo-5-[(phenylmethyl)thio]pyridine

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Benzyl mercaptan (1 g, 7.35 mmol) was dissolved in DMF (10 mL) and cooled to 0° C. Sodium hydride (60% in mineral oil, 0.294 g, 7.35 mmol) was added, the ice bath was removed, and the reaction stirred for 15 minutes. 3,5-Dibromopyridine (1.74 g, 7.35 mmol) was added and the reaction was heated to 130° C. After heating for 1 hour the reaction was cooled then diluted with EtOAc and hexanes (1:1) and washed with 4× H2O and brine, with back-extraction. The combined organics were dried over MgSO4, filtered and concentrated. The crude material was purified on silica gel (0-40% EtOAc in hexanes) to yield the title compound.

Workup

  1. customthe ice bath was removed
  2. temperaturethe reaction was heated to 130° C
  3. temperatureAfter heating for 1 hour the reaction
  4. temperaturewas cooled
  5. washwashed with 4× H2O and brine, with back-extraction
  6. dry with materialThe combined organics were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude material was purified on silica gel (0-40% EtOAc in hexanes)

Sources & evidence

ORD record
ord-867204aaf927467ebc5adafd479ff195
Source dataset
uspto-grants-2016_02
Patent number
US09260416B2

Reaction notes

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