Water → 2-Chloro-4-fluoro-5-(6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl)benzaldehyde (O-methyl)oxime

HRID 566600Notes

Reaction equation

HRID 566600 reaction equation
[NH2:1]/[C:2](/[C:9]([F:12])([F:11])[F:10])=[CH:3]\[C:4]([O:6]CC)=O.[H-].[Na+].[CH3:15][O:16][N:17]=[CH:18][C:19]1[CH:24]=[C:23]([N:25]=[C:26]=[O:27])[C:22]([F:28])=[CH:21][C:20]=1[Cl:29].O>CN(C)C=O.O1CCCC1.ClCCl>[CH3:15][O:16][N:17]=[CH:18][C:19]1[CH:24]=[C:23]([N:25]2[C:4](=[O:6])[CH:3]=[C:2]([C:9]([F:10])([F:11])[F:12])[NH:1][C:26]2=[O:27])[C:22]([F:28])=[CH:21][C:20]=1[Cl:29]

Participants

8

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 5702529Ethyl 3-amino-4,4,4-trifluorocrotonateHCID 542049932-Chloro-4-fluoro-5-isocyanatobenzaldehyde (O-methyl)oxime

Product 1

HCID 570273782-Chloro-4-fluoro-5-(6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl)benzaldehyde (O-methyl)oxime

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 168.5 g (0.92 mol) of ethyl 3-amino-4,4,4-trifluorocrotonate in 0.1 l of dimethylformamide was added dropwise with ice-cooling to 30.4 g (1.01 mol) of 80% by weight sodium hydride in 0.5 l of dimethylformamide. After one hour at this temperature, the mixture was cooled to (−30) to (−35)° C., and a solution of 210.3 g (0.92 mol) of 2-chloro-4-fluoro-5-isocyanatobenzaldehyde (O-methyl)oxime in 0.15 l of tetrahydrofuran was added dropwise. The reaction mixture was then stirred for 20 hours at approximately 20° C., and 1.5 l of water were subsequently added with ice-cooling. Undissolved matter in the mixture formed was removed and washed using 300 ml of water. The combined filtrates were acidified using dilute hydrochloric acid. The product of value was then extracted from the solution obtained using dichloromethane. The extract was washed with water, dried over sodium sulfate and finally concentrated. Yield: 289 g; m.p.: 176-177° C. (diisopropyl ether/petroleum ether).

Workup

  1. temperaturecooling
  2. customUndissolved matter in the mixture formed
  3. customwas removed
  4. washwashed
  5. extractionThe product of value was then extracted from the solution
  6. customobtained
  7. washThe extract was washed with water
  8. dry with materialdried over sodium sulfate
  9. concentrationfinally concentrated

Sources & evidence

ORD record
ord-f45abe62a40e43639a860c920e30e445
Source dataset
uspto-grants-2001_01
Patent number
US06175007B1

Reaction notes

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