Ethyl Acetoacetate → 5-Methyl-3-pyrimidin-5-yl-1-(3-trifluoromethoxy-phenyl)-1h-pyrazole-4-carboxylic acid ethyl ester

HRID 1011987Notes

Reaction equation

HRID 1011987 reaction equation
[N:1]1[CH:6]=[C:5](/[CH:7]=[N:8]/[NH:9][C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([O:16][C:17]([F:20])([F:19])[F:18])[CH:11]=2)[CH:4]=[N:3][CH:2]=1.[C:21]([O:27][CH2:28][CH3:29])(=[O:26])[CH2:22][C:23]([CH3:25])=O>[Cl-].[Zn+2].[Cl-]>[CH2:28]([O:27][C:21]([C:22]1[C:7]([C:5]2[CH:6]=[N:1][CH:2]=[N:3][CH:4]=2)=[N:8][N:9]([C:10]2[CH:15]=[CH:14][CH:13]=[C:12]([O:16][C:17]([F:18])([F:19])[F:20])[CH:11]=2)[C:23]=1[CH3:25])=[O:26])[CH3:29]

Participants

4

Reactant 2

HCID 8868Ethyl AcetoacetateHCID 87352512N-[(E)-pyrimidin-5-ylmethylideneamino]-3-(trifluoromethoxy)aniline

Product 1

HCID 673154735-Methyl-3-pyrimidin-5-yl-1-(3-trifluoromethoxy-phenyl)-1h-pyrazole-4-carboxylic acid ethyl esterYield 30%

Reagents, catalysts & solvents 1

HCID 3007855ZincchlorideCatalyst

Conditions

Temperature
170 °C

Procedure

A mixture of N-[1-pyrimidin-5-yl-meth-(E)-ylidene]-N′-(3-trifluoromethoxy-phenyl)-hydrazine (215 mg, 0.76 mmol) and zinc chloride (208 mg, 1.52 mmol) in 2 ml ethyl acetoacetate was heated at 170° C. for 3 h and stirring was continued for 20 h at room temperature. Ethyl acetoacetate was distilled (Kugelrohr distillation, 90° C., 10-40 mbar) and the residue was purified by column chromatography (EtOAc:n-heptane 4:1) to afford the title compound as a yellow oil (89 mg, 30%). MS: 393.0 (MH+).

Workup

  1. distillationEthyl acetoacetate was distilled
  2. distillation(Kugelrohr distillation, 90° C., 10-40 mbar)
  3. customthe residue was purified by column chromatography (EtOAc:n-heptane 4:1)

Sources & evidence

ORD record
ord-83a7ba65924643008f2e87761cea6199
Source dataset
uspto-grants-2011_07
Patent number
US07977358B2

Reaction notes

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