Water → HCID 178500902, compound

HRID 50103

Reaction equation

HRID 50103 reaction equation
[C:1]([CH2:6][C:7]([O:9][CH3:10])=[O:8])(=[O:5])[CH:2]([CH3:4])[CH3:3].[F:11][C:12]1[CH:19]=[CH:18][C:15]([C:16]#[N:17])=[CH:14][CH:13]=1.[Sn](Cl)(Cl)(Cl)Cl.O>C1(C)C=CC=CC=1.ClC(Cl)C.CCCCCC>[NH2:17][C:16](=[C:6]([C:1](=[O:5])[CH:2]([CH3:4])[CH3:3])[C:7]([O:9][CH3:10])=[O:8])[C:15]1[CH:18]=[CH:19][C:12]([F:11])=[CH:13][CH:14]=1

Participants

8

Reactant 4

HCID 962WaterHCID 145174-FluorobenzonitrileHCID 24287Tin tetrachlorideHCID 2759969Methyl 4-methyl-3-oxopentanoate

Product 1

HCID 178500902HCID 178500902, compoundYield 60.7%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolventHCID 63651,1-DichloroethaneSolventHCID 8058HexaneSolvent

Conditions

Temperature
80 °C

Procedure

75.09 g of methyl isobutyrylacetate (0.50 mol, concentration 96%) and 61.8 g of 4-fluorobenzonitrile (0.50 mol, concentration 98%) were dissolved in 500 ml of toluene and treated with 144.72 g of tin tetrachloride (0.55 mol, concentration 99%) at room temperature over the course of 15 min. After half an hour at room temperature, the mixture was heated to 80° C. After 3 h, the suspension was cooled to 10° C. and treated with 500 ml of water. The mixture was diluted with 100 ml of dichloroethane and the phases were separated. The organic phase was washed with 2×100 ml of 1N sodium hydroxide solution. After concentration in vacuo, 125.5 g of crude product were obtained in the form of a yellowish solid. The solid was dissolved in 160 ml of n-hexane under reflux and filtered hot. The product precipitated from the filtrate on cooling. By filtering through a frit and washing the filter cake with 130 ml of n-hexane, 79.8 g of methyl 2-[1-amino-1-(4-fluorophenyl)methylene]-4-methyl-3-oxopentanoate were obtained in the form of a spectroscopically pure solid.

Workup

  1. waitAfter half an hour at room temperature
  2. temperaturethe suspension was cooled to 10° C.
  3. customthe phases were separated
  4. washThe organic phase was washed with 2×100 ml of 1N sodium hydroxide solution
  5. concentrationAfter concentration in vacuo
  6. custom125.5 g of crude product were obtained in the form of a yellowish solid
  7. temperatureunder reflux
  8. filtrationfiltered hot
  9. customThe product precipitated from the filtrate
  10. temperatureon cooling
  11. filtrationBy filtering through a frit
  12. washwashing the filter cake with 130 ml of n-hexane

Sources & evidence

ORD record
ord-7791140929be4465b84d4a174af13562
Source dataset
uspto-grants-2004_03
Patent number
US06710178B2

Linked notes

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