Diisopropylethylamine → Impurity E of MESOTRIONE

HRID 1367683Notes

Reaction equation

HRID 1367683 reaction equation
Cl[C:2]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[CH:3]=1.[N+:9]([C:12]1[CH:20]=[C:19]([S:21]([CH3:24])(=[O:23])=[O:22])[CH:18]=[CH:17][C:13]=1[C:14]([OH:16])=[O:15])([O-:11])=[O:10].C(N(C(C)C)CC)(C)C>[Cl-].[Cl-].[Zn+2].C(#N)C>[N+:9]([C:12]1[CH:20]=[C:19]([S:21]([CH3:24])(=[O:23])=[O:22])[CH:18]=[CH:17][C:13]=1[C:14]([O:16][C:2]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[CH:3]=1)=[O:15])([O-:11])=[O:10]

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 184292Benzoic acid, 4-(methylsulfonyl)-2-nitro-HCID 5683453-Chlorocyclohex-2-en-1-one

Product 1

HCID 22005919Impurity E of MESOTRIONEYield 50.5%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
45 °C

Procedure

To a mixture of 157 mg (1.15 mmol) of 3-chlorocyclohex-2-en-1-one (prepared as described in Synthesis (1974), (1), 47-8), 16 mg (0.12 mmol) of ZnCl2, 297 mg (1.15 mmol) of 2-nitro-4-methylsulfonylbenzoic acid and 3 ml of anhydrous acetonitrile there are added dropwise, under a nitrogen atmosphere, over the course of 15 minutes, 166 mg (1.27 mmol) of diisopropylethylamine. A further 2 ml of acetonitrile are then added and the reaction mixture is maintained at a temperature of 45° C. for 18 hours in an oil bath, with stirring. The reaction mixture is then heated up again and maintained at reflux temperature for 40 hours. The reaction mixture is then brought to ambient temperature and the solvent is removed in vacuo. 25 ml of dichloromethane and 0.35 g of 36% hydrochloric acid in 5 ml of water are then added and the phases are separated. The organic phase is washed twice with 10 ml of water, dried using magnesium sulfate and concentrated in vacuo. 197 mg of 3-(2-nitro-4-methylsulfonyl-phenylcarbonyloxy)-cyclohex-2-en-1-one are obtained in the form of a brown oil.

Workup

  1. temperatureThe reaction mixture is then heated up again
  2. temperaturemaintained
  3. temperatureat reflux temperature for 40 hours
  4. customis then brought to ambient temperature
  5. customthe solvent is removed in vacuo
  6. addition25 ml of dichloromethane and 0.35 g of 36% hydrochloric acid in 5 ml of water are then added
  7. customthe phases are separated
  8. washThe organic phase is washed twice with 10 ml of water
  9. customdried
  10. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-42a88dda8b5d44ab9d7821fdeaa94fde
Source dataset
uspto-grants-2011_02
Patent number
US07893270B2

Reaction notes

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