Hydrochloric Acid → alpha-Ethoxyimino-2-phenoxymethylbenzyl chloride

HRID 1004347Notes

Reaction equation

HRID 1004347 reaction equation
[Cl:1][CH:2](Cl)[CH3:3].S(Cl)(Cl)=O.[O:9]([CH2:16][C:17]1[CH:25]=[CH:24][CH:23]=[CH:22]C=1C(O)=O)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.Cl.[CH2:27]([O:29][NH2:30])[CH3:28].N1C=CC=CC=1.Cl.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Cl)(Cl)(Cl)Cl>C(#N)C.O.ClCCl.CN(C)C=O>[CH2:27]([O:29][N:30]=[C:2]([Cl:1])[C:3]1[CH:22]=[CH:23][CH:24]=[CH:25][C:17]=1[CH2:16][O:9][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1)[CH3:28]

Participants

13

Reactant 8

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 5943Carbon TetrachlorideHCID 63651,1-DichloroethaneHCID 11776TriphenylphosphineHCID 24386Thionyl ChlorideHCID 697612-(Phenoxymethyl)benzoic acidHCID 76850O-ethylhydroxylamine hydrochloride

Product 1

HCID 54544981alpha-Ethoxyimino-2-phenoxymethylbenzyl chlorideYield 93.2%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
80 °C

Procedure

Dichloroethane (50 ml), thionyl chloride (6.54 g, 0.055 mol) and N,N-dimethylformamide (0.25 ml) were added to 2-phenoxymethylbenzoic acid (11.41 g, 0.05 mol), and the mixture was stirred at 80° C. for 2 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was dissolved in dichloromethane (25 ml). The solution was added to a mixture of ethoxyamine hydrochloride (5.85 g, 0.06 mol), pyridine (9.89 g, 0.125 mol) and dry dichloromethane (50 ml) under ice-cooling over 20 minutes, and then the resulting mixture was stirred at room temperature for 2 hours. After completion of the reaction, water (200 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. Acetonitrile (150 ml), triphenylphosphine (20.98 g, 0.08 mol) and carbon tetrachloride (24.61 g, 0.16 mol) were added to the residue, and the mixture was stirred under reflux for 1.5 hours. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (ethyl acetate/n-hexane) to give α-ethoxyimino-2-phenoxymethylbenzyl chloride (13.51 g, 93.2%) as a colorless oil.

Workup

  1. customAfter completion of the reaction
  2. concentrationthe mixture was concentrated under reduced pressure
  3. dissolutionthe residue was dissolved in dichloromethane (25 ml)
  4. temperaturecooling over 20 minutes
  5. stirringthe resulting mixture was stirred at room temperature for 2 hours
  6. additionwas added
  7. extractionextracted with dichloromethane
  8. dry with materialThe dichloromethane layer was dried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. stirringthe mixture was stirred
  11. temperatureunder reflux for 1.5 hours
  12. customAfter completion of the reaction
  13. concentrationthe mixture was concentrated under reduced pressure
  14. customthe residue was purified by silica gel chromatography (ethyl acetate/n-hexane)

Sources & evidence

ORD record
ord-0b2d0c78224441429b50698357a963cd
Source dataset
uspto-grants-2000_04
Patent number
US06048885

Reaction notes

Loading…