Benzyl mercaptan → 3-Methyl-2-(phenylmethylthio)-pyridine

HRID 414034Notes

Reaction equation

HRID 414034 reaction equation
[H-].[Na+].[CH2:3]([SH:10])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.F[C:12]1[C:17]([CH3:18])=[CH:16][CH:15]=[CH:14][N:13]=1>CN(C=O)C.O>[CH3:18][C:17]1[C:12]([S:10][CH2:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)=[N:13][CH:14]=[CH:15][CH:16]=1

Participants

6

Reactant 3

HCID 7509Benzyl mercaptanHCID 24758Sodium hydrideHCID 2427222-Fluoro-3-methylpyridine

Product 1

HCID 146531873-Methyl-2-(phenylmethylthio)-pyridine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

To a solution of NaH (2.4 g, 99 mmol) in 100 mL of DMF cooled to 0° C. is added benzylmercaptan (12.3 g, 99 mmol). The solution was allowed to warm to room temperature then recooled to 0° C. 2-Fluoro-3-methylpyridine in 10 mL DMF was added dropwise and stirred at room temperature overnight. The solution was diluted with H2O, extracted twice with Et2O, twice with EtOAc, and the combined organics washed twice with saturated NaHCO3, dried and concentrated. The resulting oil was flash chromatographed (10% Et2O/hexane (v/v)) to yield 16.3 g of the desired product. NMR (200 MHz, CDCl3) δ 2.24 (s, 3H), 4.50 (s, 2H), 6.9 (dd, 1H), 7.2 (m, 5H), 7.4 (d, 1H) and 8.3 (d, 1H).

Workup

  1. customthen recooled to 0° C
  2. extractionextracted twice with Et2O, twice with EtOAc
  3. washthe combined organics washed twice with saturated NaHCO3
  4. customdried
  5. concentrationconcentrated
  6. customchromatographed (10% Et2O/hexane (v/v))

Sources & evidence

ORD record
ord-38583ede8ae94ed893f3b7fb57925287
Source dataset
uspto-grants-1988_12
Patent number
US04789465

Reaction notes

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