Ethanethiol → 6-Chloro-2-ethylsulfanyl-4-methyl-pyridine-3-carboxylic acid

HRID 922007Notes

Reaction equation

HRID 922007 reaction equation
[H-].[Na+].[CH2:3]([SH:5])[CH3:4].Cl[C:7]1[C:12]([C:13]([OH:15])=[O:14])=[C:11]([CH3:16])[CH:10]=[C:9]([Cl:17])[N:8]=1>C1COCC1>[Cl:17][C:9]1[N:8]=[C:7]([S:5][CH2:3][CH3:4])[C:12]([C:13]([OH:15])=[O:14])=[C:11]([CH3:16])[CH:10]=1

Participants

5

Reactant 3

HCID 6343EthanethiolHCID 24758Sodium hydrideHCID 6761212,6-Dichloro-4-methylpyridine-3-carboxylic acid

Product 1

HCID 866643126-Chloro-2-ethylsulfanyl-4-methyl-pyridine-3-carboxylic acidYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

6.1 g (153 mmol, 60% w/w in mineral oil) NaH were dissolved in THF (90 ml) at 0° C. At this temperature 3.4 g (54.7 mmol) ethane thiol were added. After stirring for 15 min at 0° C., 12.4 g (60.2 mmol) 2,6-dichloro-4-methyl-pyridine-3-carboxylic acid were added portionwise. The RM was allowed to warm to RT and stirring was continued at RT for 16 h. Then the reaction was quenched with a 2M aq. HCl and diluted with EtOAc. The organic layer was separated, dried over MgSO4 and concentrated in vacuo. Crystallisation (DCM/hexane) of the residue yielded 12.0 g (51.7 mmol, 95%) 6-chloro-2-ethylsulfanyl-4-methyl-pyridine-3-carboxylic acid.

Workup

  1. temperatureto warm to RT
  2. stirringstirring
  3. waitwas continued at RT for 16 h
  4. customThen the reaction was quenched with a 2M aq. HCl
  5. additiondiluted with EtOAc
  6. customThe organic layer was separated
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated in vacuo
  9. customCrystallisation (DCM/hexane) of the residue

Sources & evidence

ORD record
ord-0a21c894d81c41a19c4eb8895f8969d1
Source dataset
uspto-grants-2016_03
Patent number
US09278103B2

Reaction notes

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