Sodium methanethiolate → 2-[Chloro(difluoro)methyl]-5-[1-(methylthio)ethyl]pyridine

HRID 1472761Notes

Reaction equation

HRID 1472761 reaction equation
[Cl:1][C:2]([F:13])([F:12])[C:3]1[CH:8]=[CH:7][C:6]([CH:9](Cl)[CH3:10])=[CH:5][N:4]=1.[CH3:14][S-:15].[Na+]>C(O)C>[Cl:1][C:2]([F:13])([F:12])[C:3]1[CH:8]=[CH:7][C:6]([CH:9]([S:15][CH3:14])[CH3:10])=[CH:5][N:4]=1

Participants

4

Reactant 2

HCID 4378561Sodium methanethiolateHCID 59218619Pyridine, 2-(chlorodifluoromethyl)-5-(1-chloroethyl)-

Product 1

HCID 592185952-[Chloro(difluoro)methyl]-5-[1-(methylthio)ethyl]pyridineYield 40.7%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To a solution of 2-[chloro(difluoro)methyl]-5-(1-chloroethyl)pyridine (D) (0.81 g, 3.6 mmol) in ethanol (10 mL) was added sodium thiomethoxide (0.52 g, 7.4 mmol) under stiffing in one portion at 0° C. After 10 min, the mixture was allowed to warm to room temperature and stirred overnight. The solvent ethanol was then removed under reduced pressure and the residue was re-taken into ether/CH2Cl2 and brine. The two phases were separated and the organic layer was extracted with CH2Cl2 one more time. The combined organic layer was dried over anhydrous Na2SO4, filtered, concentrated, purified on silica gel using 5% ethyl acetate in hexane to give 0.348 g of the 2-[chloro(difluoro)methyl]-5-[1-(methylthio)ethyl]pyridine (E) in 40% yield GC-MS: mass calcd for C9H10ClF2NS [M]+ 237. Found 237.

Workup

  1. customunder stiffing in one portion at 0° C
  2. customThe solvent ethanol was then removed under reduced pressure
  3. customThe two phases were separated
  4. extractionthe organic layer was extracted with CH2Cl2 one more time
  5. dry with materialThe combined organic layer was dried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. custompurified on silica gel using 5% ethyl acetate in hexane

Sources & evidence

ORD record
ord-8ebb4df7f15041a9b73ea252c0e68a95
Source dataset
uspto-grants-2015_04
Patent number
US09012654B2

Reaction notes

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