Triethylamine → Ethyl 1-(6-chloropyridin-2-yl)-5-(trifluoromethyl)-1h-pyrazole-4-carboxylate

HRID 1255159Notes

Reaction equation

HRID 1255159 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([NH:8][NH2:9])[N:3]=1.C(N(CC)CC)C.C(O[CH:20]=[C:21]([C:27](=O)[C:28]([F:31])([F:30])[F:29])[C:22]([O:24][CH2:25][CH3:26])=[O:23])C>C(#N)C>[CH2:25]([O:24][C:22]([C:21]1[CH:20]=[N:9][N:8]([C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[N:3]=2)[C:27]=1[C:28]([F:29])([F:30])[F:31])=[O:23])[CH3:26]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 3200042-Chloro-6-hydrazinopyridineHCID 4685753Ethyl 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutanoate

Product 1

HCID 73012968Ethyl 1-(6-chloropyridin-2-yl)-5-(trifluoromethyl)-1h-pyrazole-4-carboxylate

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution 2-chloro-6-hydrazinopyridine (1.00 g, 6.97 mmol) and triethylamine (0.971 mL, 6.97 mmol) in acetonitrile (35 mL) was added ethyl 2-(ethoxymethylene)-4,4,4-trifluoro-3-oxobutyrate (1.36 mL, 6.97 mmol). After 20 min, the reaction mixture was placed in a 60° C. oil bath. After 30 min, the reaction mixture was allowed to cool to ambient temperature, then was concentrated in vacuo. Purification by flash chromatography on silica gel (0 to 30% EtOAc in hexanes, then 30 to 100% EtOAc in hexanes) gave the title compound: LCMS m/z 319.9 [M+H]+; 1H NMR (500 MHz, CDCl3) δ 8.10 (s, 1H), 7.88 (t, J=7.5 Hz, 1H), 7.58 (d, J=8.0 Hz, 1H), 7.47 (d, J=8.0 Hz, 1H), 4.38 (q, J=7.0 Hz, 2H), 1.38 (t, J=7.0 Hz, 3H).

Workup

  1. customwas placed in a 60° C.
  2. waitAfter 30 min
  3. concentrationwas concentrated in vacuo
  4. customPurification by flash chromatography on silica gel (0 to 30% EtOAc in hexanes

Sources & evidence

ORD record
ord-663c67acc6dc489aa7ea1b219451739c
Source dataset
uspto-grants-2013_06
Patent number
US08455638B2

Reaction notes

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