Sodium methanethiolate → 4-(Methylthio)-5-nitro-2-(pyridin-3-yl)thiazole

HRID 2199223Notes

Reaction equation

HRID 2199223 reaction equation
Cl[C:2]1[N:3]=[C:4]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[S:5][C:6]=1[N+:7]([O-:9])=[O:8].[CH3:16][S-:17].[Na+]>O1CCOCC1.C(OCC)(=O)C>[CH3:16][S:17][C:2]1[N:3]=[C:4]([C:10]2[CH:11]=[N:12][CH:13]=[CH:14][CH:15]=2)[S:5][C:6]=1[N+:7]([O-:9])=[O:8]

Participants

5

Reactant 2

HCID 4378561Sodium methanethiolateHCID 666452254-Chloro-5-nitro-2-(pyridin-3-yl)thiazole

Product 1

HCID 666452804-(Methylthio)-5-nitro-2-(pyridin-3-yl)thiazoleYield 68.3%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Procedure

To a solution of 4-chloro-5-nitro-2-(pyridin-3-yl)thiazole (500 mg, 2.07 mmol) in 1,4-dioxane (2 mL) was added in one portion solid sodium thiomethoxide (145 mg, 2.07 mmol). The orange-red mixture was stirred at room temperature for 3 hours. The mixture was diluted with ethyl acetate and rinsed with brine, dried over MgSO4 and concentrated in vacuo to give a yellow solid. This solid was purified by silica gel chromatography (ethyl acetate/hexanes) to give 4-(methylthio)-5-nitro-2-(pyridin-3-yl)thiazole (358 mg, 68%): 1H NMR (300 MHz, CDCl3) δ 9.21 (d, J=5.4 Hz, 1H), 8.79 (dd, J=4.8, 1.8 Hz, 1H), 8.24 (dt, J=7.8, 2.1 Hz, 1H), 7.46 (ddd, J=8.1, 4.8, 0.9 Hz, 1H), 2.81 (s, 3H); EIMS m/z 253.

Workup

  1. washrinsed with brine
  2. dry with materialdried over MgSO4
  3. concentrationconcentrated in vacuo
  4. customto give a yellow solid
  5. customThis solid was purified by silica gel chromatography (ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-d50ce3bdf41440698281d3d73eb43b93
Source dataset
uspto-grants-2016_06
Patent number
US09357780B2

Reaction notes

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