Pyridine → HCID 20159240, compound

HRID 986102Notes

Reaction equation

HRID 986102 reaction equation
[CH3:1][S:2]([OH:5])(=[O:4])=[O:3].[N:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[CH2:12]1[S:15][CH:13]1[CH3:14]>>[CH3:1][S:2]([O-:5])(=[O:4])=[O:3].[SH:15][CH:13]([CH3:14])[CH2:12][N+:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

4

Reactant 3

HCID 1049PyridineHCID 6395Methanesulfonic AcidHCID 14072Thiirane, 2-methyl-

Product 1

HCID 20159240HCID 20159240, compoundYield 15.2%

Conditions

Temperature
40 °C

Procedure

Methanesulfonic acid (1.95 mL, 0.030 mol) was added slowly to cold pyridine (7.83 mL, 0.097 mol) and the resulting mixture was stirred at 40° C. for 15 min, treated with dl-propylenesulfide (2.59 mL, 0.033 mol) and stirred at 60° C. under a nitrogen atmosphere for 90 h. Pyridine was removed under vacuum; the residue was mixed with water and purified by chromatography (hplc, Prep. Bondapak C-18). The appropriate fractions were combined and lyophilized giving dl-1-(2-mercapto-2-methylethyl)pyridinium methanesulfonate 1.14 g (15%) as a colorless syrup; ir (film) νmax : 2520 (SH), 1640 (pyridinium), 1180 (s, CH3SO3-), 1040 (CH3SO3-)cm-1, 1Hmr (DMSO d6) δ: 1.35 (d; J=6.8 Hz, 3H, CH3CHS), 2.30 (s, 3H, CH3SO3-), 2.90 (d, J=8.5 Hz, 1H, SH), 3.2-3.7 (m, CHSH), 4.52 (dd, Jgem =12.9 Hz, J=8.4 Hz, CHCH2N+), 4.87 (dd, Jgem =12.9 Hz, J=6.0 Hz, CHCH2N+), 8.0-8.4 (m, 2H, Hm of pyridinium), 8.5-8.8 (m, 1H, Hp of pyridinium), 9.04 (dd, J=1.4 Hz, J=6.7 Hz, 2H, Ho of pyridinium), uv(H2O) λmax : 208 (ε5267), 259 (ε3338), Anal. calcd for C9H15NO3S2.2H2O; C 37.88, H 6.71, N 4.91, S 22.47; found: C 37.49, H 6.85, N 4.86, S 22.09 and dl-1-(2-mercapto-1-methylethyl) pyridinium methanesulfonate 0.82 g (11%) as a colourless syrup; ir (film) νmax : 2500 (SH), 1628 (pyridinium), 1180 (sulfonate, 1035 (sulfonate) cm-1, 1Hmr (DMSO d6) δ: 1.69 (d, J=6.8 Hz, 3H, CH3CHN+), 2.31 (s, 3H, CH3SO3-), 3.0-3.3 (m, 2H, CH2S), 4.2-5.2 (m, 1H, CHN+), 8.0-8.4 (m, 2H, Hm of pyridinium), 8.5-8.8 (m, 1H, Hp of pyridinium), 9.0-9.2 (m, 2H, Ho of pyridinium), uv (H2O) λmax : 209 (ε4987), 258 (ε3838). Anal. calcd. for C9H15NO3S2.1.5H2O: C 39.11, H 6.56, N 5.07; found: C 39.13, H 5.92, N 5.20.

Workup

  1. stirringstirred at 60° C. under a nitrogen atmosphere for 90 h
  2. customPyridine was removed under vacuum
  3. additionthe residue was mixed with water
  4. custompurified by chromatography (hplc, Prep. Bondapak C-18)

Sources & evidence

ORD record
ord-9191e42fbf524c5285b3aa5d5ff4c8e0
Source dataset
uspto-grants-1987_12
Patent number
US04710568

Reaction notes

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