Hydrochloric Acid → HCID 19780818, compound

HRID 2081143Notes

Reaction equation

HRID 2081143 reaction equation
[H-].[Na+].[NH2:3]/[C:4](/[C:11]([F:14])([F:13])[F:12])=[CH:5]\[C:6]([O:8]CC)=O.[Cl:15][C:16]1[CH:32]=[CH:31][C:30]([N:33]=[C:34]=[O:35])=[CH:29][C:17]=1[C:18]([O:20][C:21]([CH3:28])([CH3:27])[C:22]([O:24][CH2:25][CH3:26])=[O:23])=[O:19].Cl>C(OCC)C.CN(C)C=O>[Cl:15][C:16]1[CH:32]=[CH:31][C:30]([N:33]2[C:6](=[O:8])[CH:5]=[C:4]([C:11]([F:12])([F:13])[F:14])[NH:3][C:34]2=[O:35])=[CH:29][C:17]=1[C:18]([O:20][C:21]([CH3:27])([CH3:28])[C:22]([O:24][CH2:25][CH3:26])=[O:23])=[O:19]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 24758Sodium hydrideHCID 5702529Ethyl 3-amino-4,4,4-trifluorocrotonateHCID 19780807HCID 19780807, compound

Product 1

HCID 19780818HCID 19780818, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
-5 °C

Procedure

4.9 g of sodium hydride (50% dispersion in white oil) are added to 120 ml of dimethylformamide while stirring and the mixture is cooled to -5° C. At this temperature a solution of 22.4 g of ethyl 3-amino-4,4,4-trifluorocrotonate in 180 ml of diethyl ether is added dropwise during 30 minutes. The reaction mixture is stirred at room temperature for one hour and thereafter cooled to -65° C. A solution of 28 g of ethyl 2-(2-chloro-5-isocyanato-benzoyloxy)-2-methylpropionate in 100 ml of dimethylformamide is now added dropwise during 30 minutes. The reaction mixture is stirred at -65° C. for 2 hours; thereafter it is left to warm to room temperature. The reaction mixture is introduced into 300 ml of 1N hydrochloric acid at 0° C. The mixture is extracted twice with 300 ml of ethyl acetate each time. The organic phases are back-washed once with 200 ml of water and once with 200 ml of saturated sodium chloride solution, dried over anhydrous sodium sulphate and concentrated under reduced pressure. The residue is recrystallized from ethyl acetate/n-hexane. There is obtained ethyl 2-{2-chloro-5-[3,6-dihydro-2,6-dioxo-4-trifluoromethyl-1(2H)-pyrimidinyl]-benzoyloxy}-2-methylpropionate, m.p. 176°-177° C.

Workup

  1. stirringThe reaction mixture is stirred at room temperature for one hour
  2. temperaturecooled to -65° C
  3. stirringThe reaction mixture is stirred at -65° C. for 2 hours
  4. waitthereafter it is left
  5. temperatureto warm to room temperature
  6. extractionThe mixture is extracted twice with 300 ml of ethyl acetate each time
  7. washThe organic phases are back-washed once with 200 ml of water and once with 200 ml of saturated sodium chloride solution
  8. dry with materialdried over anhydrous sodium sulphate
  9. concentrationconcentrated under reduced pressure
  10. customThe residue is recrystallized from ethyl acetate/n-hexane

Sources & evidence

ORD record
ord-9a3e83c21ebb4d13a3a158978d54bea0
Source dataset
uspto-grants-1993_02
Patent number
US05183492

Reaction notes

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