Methane, dichloromethoxy- → 3-Formyl-2-hydroxy-4-methoxy-benzoic acid methyl ester

HRID 1241242Notes

Reaction equation

HRID 1241242 reaction equation
[OH:1][C:2]1[CH:11]=[C:10]([O:12][CH3:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5].Cl[CH:15](Cl)[O:16]C>C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[OH:1][C:2]1[C:11]([CH:15]=[O:16])=[C:10]([O:12][CH3:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 2

HCID 21004Methane, dichloromethoxy-HCID 79523Methyl 4-methoxysalicylate

Product 1

HCID 219335993-Formyl-2-hydroxy-4-methoxy-benzoic acid methyl esterYield 42.4%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

At from 0 to 5° C., a solution of 209.0 g (1.1 mol) of titanium tetrachloride in 150 ml of methylene chloride was added dropwise to a solution of 50.1 g (0.275 mol) of methyl 2-hydroxy-4-methoxybenzoate and 88 g (0.725 mol) of dichloromethoxymethane in 400 ml of methylene chloride, and the mixture was stirred at room temperature overnight. The mixture was then stirred into ice-water and extracted with methylene chloride. The combined organic phases were washed with sodium bicarbonate solution, water and sodium chloride solution and dried, and the solvent was then removed. Silica gel chromatography using cyclohexane/ethyl acetate=1:1 gave 24.5 g (42%) of methyl 2-hydroxy-3-formyl-4-methoxybenzoate in the form of a colorless solid of m.p.: 123–1240° C.

Workup

  1. extractionextracted with methylene chloride
  2. washThe combined organic phases were washed with sodium bicarbonate solution, water and sodium chloride solution
  3. customdried
  4. customthe solvent was then removed

Sources & evidence

ORD record
ord-da332f17749b401ebf1f485b3d9364a6
Source dataset
uspto-grants-2006_10
Patent number
US07115545B1

Reaction notes

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