(4-Chloro-2-fluoro-5-propan-2-yloxyphenyl)hydrazine → 2-(2-Fluoro-4-chloro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one

HRID 324255

Reaction equation

HRID 324255 reaction equation
C([O-])(=O)C.[Na+].Br[CH:7](Br)[C:8]([C:10]([F:13])([F:12])[F:11])=O.[F:15][C:16]1[CH:21]=[C:20]([Cl:22])[C:19]([O:23][CH:24]([CH3:26])[CH3:25])=[CH:18][C:17]=1[NH:27][NH2:28].[C:29]([CH2:34][CH:35]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)(OCC)=[O:30]>C(OCC)C.O>[F:15][C:16]1[CH:21]=[C:20]([Cl:22])[C:19]([O:23][CH:24]([CH3:26])[CH3:25])=[CH:18][C:17]=1[N:27]1[C:29](=[O:30])[C:34]([CH3:35])=[C:8]([C:10]([F:13])([F:12])[F:11])[CH:7]=[N:28]1

Participants

7

Reactant 4

HCID 185080(4-Chloro-2-fluoro-5-propan-2-yloxyphenyl)hydrazineHCID 517045Sodium AcetateHCID 5505231,1-Dibromo-3,3,3-trifluoroacetoneHCID 12607919Ethyl 3-(triphenyl-lambda~5~-phosphanylidene)propanoate

Product 1

HCID 110898282-(2-Fluoro-4-chloro-5-isopropoxyphenyl)-4-methyl-5-trifluoromethylpyridazin-3-one

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 5.3 g (53.3 mmol) of sodium acetate mixed with about 100 ml of water was added under ice cooling 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone, and the mixture was stirred at 70° C. for 20 minutes. The reaction mixture was cooled to room temperature, to which a solution of 5.8 g (21.5 mmol) of 2-fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the mixture was stirred at room temperature for 1 hour. The ether layer was separated and then concentrated. About 60 ml of tetrahydrofuran (hereinafter referred to as THF) was added to the residue, to which 8.3 g (23.0 mmol) of (carbethoxyethylidene)triphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. The THF was distilled out under reduced pressure, and the residue was subjected to silica gel column chromatography, which afforded 3.8 g (10.5 mmol) of 2-[2-fluoro-4-chloro-5-isopropoxyphenyl]-4-methyl-5-trifluoromethylpyridazin-3-one.

Workup

  1. additionwas added
  2. stirringthe mixture was stirred at room temperature for 1 hour
  3. customThe ether layer was separated
  4. concentrationconcentrated
  5. additionwas added
  6. temperaturethe mixture was heated
  7. temperatureunder reflux for 2 hours
  8. distillationThe THF was distilled out under reduced pressure

Sources & evidence

ORD record
ord-4c56b8cd4c0d4cbdaaa92068ee2b995b
Source dataset
uspto-grants-2001_04
Patent number
US06218338B1

Linked notes

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