Reaktion #323234

Reaktionsgleichung

4-Methylthiopyridine

methanesulfonic acid

ethylene sulfide

→

title compound

4-Methylthio-N-(2-mercaptoethyl)pyridinium methanesulfonate

Lösungsmittel

H2O

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturby cooling in an ice-bath
2. 2
   Temperaturthe mixture was heated at 50°-60° C. for 21 h
3. 3
   SonstigeAs reaction
4. 4
   TemperaturAfter cooling
5. 5
   Waschenwashed with Et2O (5×4 mL)
6. 6
   FiltrationThe cloudy aqueous layer was filtered over Celite
7. 7
   Sonstigethe filtrate was purified by reverse phase silica gel column chromatography (C18 micro bondapack 10 g)
8. 8
   Wascheneluting with H2O
9. 9
   SonstigeEach fraction of 10 mL was collected
10. 10
    Sonstigerepurified by the reverse phase column

Vorschrift

4-Methylthiopyridine (2.75 g, 22.0 mmol) was added slowly to methanesulfonic acid* (0.65 mL, 10.5 mmol) by cooling in an ice-bath. To this solid was added ethylene sulfide* (0.66 mL, 11.0 mmol, Aldrich) and the mixture was heated at 50°-60° C. for 21 h. As reaction proceeds the solid went to solution. After cooling, the reaction mixture was dissolved in H2O (5 mL) and washed with Et2O (5×4 mL). The cloudy aqueous layer was filtered over Celite and the filtrate was purified by reverse phase silica gel column chromatography (C18 micro bondapack 10 g) eluting with H2O. Each fraction of 10 mL was collected. Fractions 2 and 3 were combined and repurified by the reverse phase column. Fraction 2 gave 1.258 g (4.48 mmol, y. 42.6%) of the title compound as a viscous oil: 1Hmr (DMSO-d6, CFT-20) δ: 2.32 (3H, s, MeSO3⃝), 2.72 (3H, s, --SMe), 2.68 (1H, m, SH), 2.9-3.2 (3H, m, --CH2S--), 4.59 (2H, t, J=6.4 Hz, --CH2N⊕), 7.97 (2H, "d", J=7.2 Hz, aromatic-Hs) and 8.72 ppm (2H, "d", J=7.2 Hz, aromatic-Hs); ir (neat) νmax : 1630, 1200 (br, --SO3⃝), 785 and 770 cm-1.

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