Methanesulfonic Acid → 4-Methylthio-N-(2-mercaptoethyl)pyridinium methanesulfonate

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.

1. temperatureby cooling in an ice-bath
2. temperaturethe mixture was heated at 50°-60° C. for 21 h
3. customAs reaction
4. temperatureAfter cooling
5. washwashed with Et2O (5×4 mL)
6. filtrationThe cloudy aqueous layer was filtered over Celite
7. customthe filtrate was purified by reverse phase silica gel column chromatography (C18 micro bondapack 10 g)
8. washeluting with H2O
9. customEach fraction of 10 mL was collected
10. customrepurified by the reverse phase column

ORDレコード

ord-48d9c4c9576249e5bf940598736e3d32

出典データセット

uspto-grants-1985_11

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US04552696