Pentanenitrile, 4,4-dimethyl-3-oxo- → 5-Amino-3-tert-butyl-1-(2-methylpyridine-5-yl)pyrazole

HRID 1930335Notes

Reaction equation

HRID 1930335 reaction equation
Cl.[NH:2]([C:4]1[CH:5]=[CH:6][C:7]([CH3:10])=[N:8][CH:9]=1)[NH2:3].[CH3:11][C:12]([CH3:19])([CH3:18])[C:13](=O)[CH2:14][C:15]#[N:16]>CCO>[C:12]([C:13]1[CH:14]=[C:15]([NH2:16])[N:2]([C:4]2[CH:9]=[N:8][C:7]([CH3:10])=[CH:6][CH:5]=2)[N:3]=1)([CH3:19])([CH3:18])[CH3:11]

Participants

4

Reactant 2

HCID 108871Pentanenitrile, 4,4-dimethyl-3-oxo-HCID 248205115-Hydrazinyl-2-methylpyridine--hydrogen chloride (1/1)

Product 1

HCID 114019745-Amino-3-tert-butyl-1-(2-methylpyridine-5-yl)pyrazoleYield 71%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 5-hydrazinyl-2-methylpyridine hydrochloride from Example B27 (5.0 g, 31.4 mmol) and 4,4-dimethyl-3-oxopentanenitrile (8.3 g, 66.3 mmol) in EtOH (50 mL) was heated at reflux overnight. The reaction was concentrated and the residue was dissolved in EtOAc and neutralized with saturated Na2CO3 solution. The organic layer was dried (Na2SO4), concentrated in vacuo and purified by column chromatography to yield 3-tert-butyl-1-(6-methylpyridin-3-yl)-1H-pyrazol-5-amine (5.2 g, 71% yield). 1HNMR (400 MHz, CDCl3) δ 8.72 (s, 1 H), 7.81 (dd, J=8.0, 2.4 Hz, 1 H), 7.23 (d, J=8.4 Hz, 1 H), 5.54 (s, 1 H), 3.71 (br s, 1 H), 2.58 (s, 3 H), 1.29 (s, 9 H); MS (ESI) m/z: 231.2 (M+H+).

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. concentrationThe reaction was concentrated
  4. dissolutionthe residue was dissolved in EtOAc and neutralized with saturated Na2CO3 solution
  5. dry with materialThe organic layer was dried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. custompurified by column chromatography

Sources & evidence

ORD record
ord-52ba7c88256d4dd3a9ea135427487c12
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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