Chloromethyl Methyl Ether → HCID 54502953, compound

HRID 324952Notes

Reaction equation

HRID 324952 reaction equation
[C:1]1([CH3:10])[C:2]([C:7]([OH:9])=[O:8])=[CH:3][CH:4]=[CH:5][CH:6]=1.Cl[CH2:12][O:13][CH3:14].C(N(CC)CC)C.[Br:22]N1C(=O)CCC1=O>ClCCl.C(Cl)(Cl)(Cl)Cl.N(C(C)(C)C#N)=NC(C)(C)C#N.C(OCC)(=O)C>[CH3:12][O:13][CH2:14][O:8][C:7](=[O:9])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=1[CH2:10][Br:22]

Participants

9

Reactant 4

HCID 7864Chloromethyl Methyl EtherHCID 83732-Methylbenzoic acidHCID 8471TriethylamineHCID 67184N-bromobutanimide

Product 1

HCID 54502953HCID 54502953, compound

Reagents, catalysts & solvents 4

HCID 6547AzobisisobutyronitrileCatalystHCID 5943Carbon TetrachlorideSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

After o-toluic acid (500 mg, produced by Wako Pure Chemical Industries) was dissolved in dichloromethane (10 ml), chloromethylmethyl ether (360 μl) and triethylamine (665 μl) were added, followed by stirring at room temperature for 2 hours. After ethyl acetate (50 ml) was added, the reaction mixture was washed with 0.01M hydrochloric acid, 2% aqueous sodium hydrogen carbonate and water, each in an amount of (2×30 ml). The organic layer obtained was dried over anhydrous sodium sulfate, after which it was concentrated under reduced pressure to yield a colorless oily substance (600 mg). This oily substance (200 mg) was dissolved in carbon tetrachloride (10 ml); N-bromosuccinimide (198 mg) and 2,2′-azobisisobutyronitrile (1.8 mg) were added, followed by stirring at 90° C. for 3 hours. After filtration to remove the succinimide, the reaction mixture was concentrated. The residue obtained was subjected to silica gel column chromatography, washed with hexane and hexane/ethyl acetate (50:1), then eluted and fractionated with hexane/ethyl acetate (20:1). The eluate was concentrated under reduced pressure to yield 2-(bromomethyl)benzoic acid methoxymethyl ester (65 mg) as a colorless oily substance.

Workup

  1. washthe reaction mixture was washed with 0.01M hydrochloric acid, 2% aqueous sodium hydrogen carbonate and water
  2. customThe organic layer obtained
  3. dry with materialwas dried over anhydrous sodium sulfate
  4. concentrationafter which it was concentrated under reduced pressure
  5. customto yield a colorless oily substance (600 mg)
  6. stirringby stirring at 90° C. for 3 hours
  7. filtrationAfter filtration
  8. customto remove the succinimide
  9. concentrationthe reaction mixture was concentrated
  10. customThe residue obtained
  11. washwashed with hexane and hexane/ethyl acetate (50:1)
  12. washeluted
  13. concentrationThe eluate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-6f9cd877cf4c44eaa56e4970fdcfa879
Source dataset
uspto-grants-2001_04
Patent number
US06221637B1

Reaction notes

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