Hydrochloric Acid → 2-Chloromethyl-alpha-methoxyiminobenzyl chloride

HRID 1004348Notes

Reaction equation

HRID 1004348 reaction equation
[Cl:1][CH2:2][C:3]1[CH:11]=[CH:10][CH:9]=[CH:8][C:4]=1[C:5]([Cl:7])=O.Cl.[CH3:13][O:14][NH2:15].N1C=CC=CC=1.Cl.P(Cl)(Cl)(Cl)(Cl)Cl.C(=O)(O)[O-].[Na+]>ClCCl.O>[Cl:1][CH2:2][C:3]1[CH:11]=[CH:10][CH:9]=[CH:8][C:4]=1[C:5]([Cl:7])=[N:15][O:14][CH3:13]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 24819Phosphorus pentachlorideHCID 516892Sodium BicarbonateHCID 521874O-Methylhydroxylamine hydrochlorideHCID 30163952-(Chloromethyl)benzoyl chloride

Product 1

HCID 539269502-Chloromethyl-alpha-methoxyiminobenzyl chlorideYield 83.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

2-Chloromethylbenzoyl chloride (18.90 g, 0.1 mol) was dissolved in dichloromethane (50 ml). The solution was added to a mixture of methoxyamine hydrochloride (12.53 g, 0.15 mol), pyridine (19.78 g, 0.25 mol) and dry dichloromethane (150 ml) under ice-cooling over 1 hour, and then the resulting mixture was stirred at 0° C. for 2 hours. After completion of the reaction, water (300 ml) was added, adjusted to pH<2 with conc. hydrochloric acid, and extracted with dichloromethane. The dichloromethane layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in dichloromethane (200 ml), and phosphorus pentachloride (20.82 g, 0.1 mol) was added under ice-cooling over 5 minutes. The mixture was stirred at 0° C. for 1 hour. After completion of the reaction, saturated aqueous sodium bicarbonate solution (400 ml) was added, and the mixture was extracted with dichloromethane. The dichloromethane layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel chromatography (ethyl acetate/n-hexane) to give 2-chloromethyl-α-methoxyiminobenzyl chloride (18.15 g, 83.2%) as a colorless oil.

Workup

  1. temperaturecooling over 1 hour
  2. additionwas added
  3. extractionextracted with dichloromethane
  4. dry with materialThe dichloromethane layer was dried over anhydrous magnesium sulfate
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue was dissolved in dichloromethane (200 ml)
  7. temperaturecooling over 5 minutes
  8. stirringThe mixture was stirred at 0° C. for 1 hour
  9. additionwas added
  10. extractionthe mixture was extracted with dichloromethane
  11. dry with materialThe dichloromethane layer was dried over anhydrous magnesium sulfate
  12. concentrationconcentrated under reduced pressure
  13. customthe residue was purified by silica gel chromatography (ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-651488af4f9d4c7ab93159e675e12074
Source dataset
uspto-grants-2000_04
Patent number
US06048885

Reaction notes

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