2-Mercapto-3-butanol → 4-(3-Hydroxy-2-butylthiomethyl)pyridine

HRID 1389786Notes

Reaction equation

HRID 1389786 reaction equation
C[O-].[Na+].Cl.[N:5]1[CH:10]=[CH:9][C:8]([CH2:11]Cl)=[CH:7][CH:6]=1.[SH:13][CH:14]([CH3:18])[CH:15]([OH:17])[CH3:16]>C(O)C>[OH:17][CH:15]([CH3:16])[CH:14]([S:13][CH2:11][C:8]1[CH:9]=[CH:10][N:5]=[CH:6][CH:7]=1)[CH3:18]

Participants

5

Reactant 3

HCID 620872-Mercapto-3-butanolHCID 745704-(Chloromethyl)pyridinium chlorideHCID 10942334Sodium Methoxide

Product 1

HCID 536720964-(3-Hydroxy-2-butylthiomethyl)pyridine

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent3×

Procedure

Sodium methoxide (3.40 g., 63 mmoles) was dissolved in 30 ml. of absolute ethanol under nitrogen and cooled in an ice bath. To the chilled solution there was added a suspension of finely ground 4-picolyl chloride hydrochloride (5.07 g., 30 mmoles) suspended in approximately 30 ml. of absolute ethanol over 15 minutes, followed by the addition of a solution of 3-mercapto-2-butanol [3.19 g., 30 mmoles, Price et al., J. Am. Chem. Soc. 75, 2396 (1953)] in 6 ml. of absolute ethanol over 5 minutes. The reaction mixture was warmed to room temperature and allowed to stir for 14 hours. The reaction mixture was filtered, the solids being extracted with additional ethanol. The ethanol solutions were combined and evaporated to an oil containing solids (6.31 g.), which was taken up in chloroform, solids removed by filtration and concentrated to an oil. The resuling oil was chromatographed on 200 g. of silica gel with chloroform as eluant. Product fractions were combined and stripped to an oil (5.03 g.). Dissolution in approximately 50 ml. of ethyl acetate, filtration through diatomaceous earth and removal of solvent gave purified 4-(3-hydroxy-2-butylthiomethyl)pyridine [oil; ir (film: 3.08, 3.40, 3.45, 6.24, 7.08, 9.20, 12.27μ; m/e calcd: 197, found: 197; pnmr/CDCl3 /TMS/δ: 8.57 (m, 2H), 7.30 (m, 2H), 3.85 (m, 1H), 3.76 (s, 2H), 3.12 (s, broad, 1H, exchanges with D2O), 2.75 (m, 1H) and 1.20 (d, 6H)].

Workup

  1. additionTo the chilled solution there was added
  2. filtrationThe reaction mixture was filtered
  3. extractionthe solids being extracted with additional ethanol
  4. customevaporated to an oil containing solids (6.31 g.), which
  5. customsolids removed by filtration
  6. concentrationconcentrated to an oil
  7. customThe resuling oil was chromatographed on 200 g
  8. dissolutionDissolution in approximately 50 ml
  9. filtrationof ethyl acetate, filtration
  10. customthrough diatomaceous earth and removal of solvent
  11. customgave
  12. custompurified 4-(3-hydroxy-2-butylthiomethyl)pyridine [oil

Sources & evidence

ORD record
ord-33f7197aef744086bf840211c63c5c17
Source dataset
uspto-grants-1981_01
Patent number
US04246263

Reaction notes

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