Chloromethyl Methyl Ether → Methyl 2-(methoxymethoxy)-4-methylbenzoate

HRID 2081881Notes

Reaction equation

HRID 2081881 reaction equation
[H-].[Na+].[CH3:3][C:4]1[CH:5]=[C:6]([OH:14])[C:7](=[CH:12][CH:13]=1)[C:8]([O:10][CH3:11])=[O:9].[CH3:15][O:16][CH2:17]Cl>CN(C)C=O.C(OCC)C>[CH3:15][O:16][CH2:17][O:14][C:6]1[CH:5]=[C:4]([CH3:3])[CH:13]=[CH:12][C:7]=1[C:8]([O:10][CH3:11])=[O:9]

Participants

6

Reactant 3

HCID 7864Chloromethyl Methyl EtherHCID 24758Sodium hydrideHCID 78400Benzoic acid, 2-hydroxy-4-methyl-, methyl ester

Product 1

HCID 13149247Methyl 2-(methoxymethoxy)-4-methylbenzoateYield 112.3%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent2×HCID 6228DimethylformamideSolvent

Procedure

To a suspension of sodium hydride (1.62 g, 0.0675 mol) in 90 mL of dimethylformamide was added dropwise a solution of methyl 4-methylsalicylate (10.2 g, 0.0614 mol) in 20 mL of diethyl ether. After stirring for 15 minutes, a solution of chloromethyl methyl ether (5.6 mL, 0.0737 mol) in 10 mL of diethyl ether was added. The reaction mixture was stirred at room temperature for 18 hours and then it was partitioned between water and diethyl ether. The layers were separated and the aqueous layer was extracted an additional three times with diethyl ether. The combined organic extracts were washed with brine, dried with magnesium sulfate, and concentrated in vacuo to give 14.5 g of an oil. The product was purified by flash chromatography on silica gel eluting with 10%-15% ethyl acetate in hexane to give 9.41 g (73%) of product as an oil.

Workup

  1. stirringThe reaction mixture was stirred at room temperature for 18 hours
  2. customit was partitioned between water and diethyl ether
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted an additional three times with diethyl ether
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried with magnesium sulfate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ee01908decce46dcb176dab8f0d81314
Source dataset
uspto-grants-1993_02
Patent number
US05185351

Reaction notes

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