Hydrochloric Acid → Methyl 3-hydroxy-4-(methylthio)benzoate

HRID 1489702Notes

Reaction equation

HRID 1489702 reaction equation
Cl.N[C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[S:13][CH3:14])[C:6]([O:8][CH3:9])=[O:7].N([O-])=[O:16].[Na+]>O>[OH:16][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:12]=1[S:13][CH3:14])[C:6]([O:8][CH3:9])=[O:7]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 21187837Methyl 3-amino-4-(methylthio)benzoateHCID 23668193Sodium Nitrite

Product 1

HCID 21187893Methyl 3-hydroxy-4-(methylthio)benzoateYield 30.3%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent3×

Procedure

A stirred solution of concentrated hydrochloric acid (3.2 mL) in water (3.6 mL) at from 0° C. to 5° C. is treated with methyl 3-amino-4-(methylthio)benzoate (1.97 g), followed by a solution of sodium nitrite (0.82 g) in water (2 mL), at such a rate that the temperature remained from 0° C. to 5° C. The mixture is then allowed to warm to room temperature and it is stirred for a further period of 1 hour. The reaction mixture is treated with water (30 mL) and then heated to 55°-60° C., until the evolution of nitrogen ceased (4 hours). The mixture is extracted with dichloromethane (2×100 mL) and the combined organic extracts are dried and concentrated. The resulting brown oil is subjected to flash chromatography, eluting with a mixture of diethyl ether and pentane (1:4 v/v), to give methyl 3-hydroxy-4-(methylthio)benzoate (0.6 g) in the form of a yellow solid.

Workup

  1. customremained from 0° C. to 5° C
  2. temperatureheated to 55°-60° C., until the evolution of nitrogen
  3. custom(4 hours)
  4. extractionThe mixture is extracted with dichloromethane (2×100 mL)
  5. customthe combined organic extracts are dried
  6. concentrationconcentrated
  7. washeluting with a mixture of diethyl ether and pentane (1:4 v/v)

Sources & evidence

ORD record
ord-d414ec39c47b4126b577da72b2f6b67b
Source dataset
uspto-grants-1997_10
Patent number
US05679696

Reaction notes

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