Sulfuric Acid → 6-(Methylthio)pyridin-3-OL

HRID 1685406Notes

Reaction equation

HRID 1685406 reaction equation
S(=O)(=O)(O)O.[CH3:6][S:7][C:8]1[N:13]=[CH:12][C:11](N)=[CH:10][CH:9]=1.N([O-])=[O:16].[Na+].C(=O)(O)[O-].[Na+]>O>[CH3:6][S:7][C:8]1[N:13]=[CH:12][C:11]([OH:16])=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 516892Sodium BicarbonateHCID 102611796-(Methylsulfanyl)pyridin-3-amineHCID 23668193Sodium Nitrite

Product 1

HCID 231452196-(Methylthio)pyridin-3-OLYield 60%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

A solution of 5.5 ml of concentrated sulfuric acid and 8 ml of water is added to 1.9 g (13.55 mM) of 6-(methylthio)-3-pyridinamine. The reaction medium is brought to −6° C. and a solution of 1.59 g (23.03 mM) of sodium nitrite in 3 ml of water is added dropwise without exceeding 0° C. The mixture is stirred for 1 hour 30 min between 0° C. and −4° C. and then refluxed for 1 hour. The cooled reaction medium is poured in the presence of sodium bicarbonate and the mixture is then extracted with ethyl acetate. The organic phase is concentrated under reduced pressure and the residue is then chromatographed on silica gel (dichloromethane/ethyl acetate, 90/10; v/v) to give the expected product in the form of a white powder with a yield of 60%.

Workup

  1. customis brought to −6° C.
  2. customwithout exceeding 0° C
  3. temperaturerefluxed for 1 hour
  4. customThe cooled reaction medium
  5. extractionthe mixture is then extracted with ethyl acetate
  6. concentrationThe organic phase is concentrated under reduced pressure
  7. customthe residue is then chromatographed on silica gel (dichloromethane/ethyl acetate, 90/10; v/v)

Sources & evidence

ORD record
ord-be0f6f5a1bda41c8ae1e1204bfb38f2c
Source dataset
uspto-grants-2012_04
Patent number
US08148407B2

Reaction notes

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