Water → 6-(Tert-butylthio)methyl-pyridine-3-carbonitrile

HRID 1190967Notes

Reaction equation

HRID 1190967 reaction equation
Br[CH2:2][C:3]1[N:8]=[CH:7][C:6]([C:9]#[N:10])=[CH:5][CH:4]=1.[CH3:11][C:12]([SH:15])([CH3:14])[CH3:13].C(=O)([O-])[O-].[Cs+].[Cs+].O>CN(C=O)C.C(Cl)Cl>[C:12]([S:15][CH2:2][C:3]1[N:8]=[CH:7][C:6]([C:9]#[N:10])=[CH:5][CH:4]=1)([CH3:14])([CH3:13])[CH3:11]

Participants

7

Reactant 4

HCID 962WaterHCID 6387tert-Butyl mercaptanHCID 10796Cesium carbonateHCID 219277766-(Bromomethyl)pyridine-3-carbonitrile

Product 1

HCID 584955036-(Tert-butylthio)methyl-pyridine-3-carbonitrileYield 76%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

Dissolve 6-bromomethyl-pyridine-3-carbonitrile (6.2 g, 31.4 mmol) in anhydrous DMF (60 mL) under nitrogen. Add tert-butylthiol (5.32 mL, 47.2 mmol) followed by cesium carbonate (15.3 g, 47.2 mmol) and stir the resulting suspension overnight. Dissolve the reaction mixture in DCM (200 mL) and add water (200 mL). Extract the aqueous phase with DCM (2×200 mL) and dry the combined organic extracts over MgSO4. Filter, add silica gel and concentrate the mixture in vacuo. Purify the residue by chromatography on silica gel (40 g) eluting with cyclohexane/EtOAc (98:2 to 65:35 gradient) to obtain the desired material as a yellow solid (4.92 g, 76%). MS (ES+) m/z: 207 (M+H)+.

Workup

  1. extractionExtract the aqueous phase with DCM (2×200 mL)
  2. dry with materialdry the combined organic extracts over MgSO4
  3. filtrationFilter
  4. additionadd silica gel
  5. concentrationconcentrate the mixture in vacuo
  6. customPurify the residue by chromatography on silica gel (40 g)
  7. washeluting with cyclohexane/EtOAc (98:2 to 65:35 gradient)

Sources & evidence

ORD record
ord-c31941f3b78f4f8c88108a028e0da764
Source dataset
uspto-grants-2014_03
Patent number
US08680091B2

Reaction notes

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