Diethyl Ether → 2-(N-methyl-N-(methoxycarbonyl)amino)-4'-difluoromethoxyacetophenone

HRID 1657156Notes

Reaction equation

HRID 1657156 reaction equation
[CH3:1][N:2](C)[CH2:3][C:4]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH:13]([F:15])[F:14])=[CH:8][CH:7]=1)=[O:5].Cl[C:18]([O:20][CH3:21])=[O:19].C(OCC)C>C(Cl)Cl>[CH3:1][N:2]([CH2:3][C:4]([C:6]1[CH:11]=[CH:10][C:9]([O:12][CH:13]([F:14])[F:15])=[CH:8][CH:7]=1)=[O:5])[C:18]([O:20][CH3:21])=[O:19]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 6586Methyl chloroformateHCID 189809272-Dimethylamino-4'-difluoromethoxyacetophenone

Product 1

HCID 189809882-(N-methyl-N-(methoxycarbonyl)amino)-4'-difluoromethoxyacetophenoneYield 60.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
20 °C

Procedure

To 16.8 g (73 mmole) of 2-dimethylamino-4'-difluoromethoxyacetophenone in 100 ml of methylene chloride cooled to 0° C. was added 7.6 g (81 mmole) of methyl chloroformate. After the addition was complete the reaction mixture was allowed to warm to 20° C. and stirred overnight. Concentration in vacuo, partitioning between diethyl ether and 1M aqueous hydrochloric acid, washing with brine, drying over anhydrous magnesium sulfate, and reconcentration in vacuo gave a crude oil. Chromatography of this oil on silica gel using diethyl ether in hexanes gave 12 g of 2-(N-methyl-N-(methoxycarbonyl)amino)-4'-difluoromethoxyacetophenone an oil, bp 150°-190° C. at 0.7 torr.

Workup

  1. additionAfter the addition
  2. concentrationConcentration in vacuo
  3. custompartitioning between diethyl ether and 1M aqueous hydrochloric acid
  4. washwashing with brine
  5. dry with materialdrying over anhydrous magnesium sulfate, and reconcentration in vacuo
  6. customgave a crude oil

Sources & evidence

ORD record
ord-e176169ac19b400691050555d9c81841
Source dataset
uspto-grants-1993_10
Patent number
US05256670

Reaction notes

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