5-AMINO-1-(T-BUTYL)PYRAZOLE-4-CARBONITRILE

To a suspension of fe/ -butylhydrazine hydrochloride (15.0 g, 120.4 mmol) in ethanol (600 ml_) was added triethylamine (16.8 ml_, 120.4 mmol). The mixture was stirred for 60 min until the hydrazine had dissolved. Ethoxymethylenemalononitrile (14.7 g, 120.4 mmol) was added in portions and the reaction mixture was heated to 80 °C and stirred at this temperature overnight. The reaction mixture was concentrated to dryness and the obtained residue was taken up in EtOAc. The organic layer was washed with water, dried over Na2S04, filtered and concentrated under reduced pressure. The solid was then recrystallized in DCM to afford 5-amino-1 -fe/?-butyl-pyrazole-4-carbonitrile (18.6 g, 1 13.4 mmol, 94percent yield) as a light yellow solid. LC-MS (ESIn tert-butylhydrazine hydrochloride (8.67 g, 69.6 mmol)Was added triethylamine (9.7 mL, 69.6 mmol)After adding anhydrous ethanol (460 mL), the mixture was stirred and dissolved at room temperature, Ethoxymethylenemalononitrile (8.5 g, 69.6 mmol) was added in small portions.After heating the solution to reflux for 3 hours, After cooling, the solvent was evaporated to give an orange solid.And extracted with ethyl acetate (0.5 L) and water (0.25 L)After drying by adding magnesium sulfate, The organic layer was evaporated to give an orange-yellow solid.The resulting solid was continuously washed with a 10percent ethyl acetate in cyclohexane solution to give a crystalline solid5-amino-1-tert-butyl hydrogen - pyrazol-4-cyano 9.54g(Yield: 83percent).A mixture of t-butylhydrazine hydrochloride (4.67 g, 53 mmol) and triethylamine (5.35 g, 53 mmol) in anhydrous ethanol (250 ml) was stirred and ethoxymethylene malononitrile (6.47 g, 53 mmol) was slowly added in portions. The mixture was heated at reflux for 3 hr. The solvent was removed in vacuo and the product was crystallized from ethyl acetate -hexane followed by ether to afford the title compound as light pale brown crystals (5.6 g, 64.4 percent); LC/MS, API-ES, Neg, (M-H)To a mixture of t-butylhydrazine (1.0 g, 8.2 mmol) and triethylamine (1.1 ml, 8.2 mmol) in anhydrous ethanol (20 ml) was added ethoxymethylene malononitrile (7, 1.0 g, 8.2 mmol) slowly in portions. The mixture was heated in a microwave at 100 °C for 30 min. and then concentrated via evaporation of the solvent under a reduced pressure. The residue was washed with ether then dried under a reduced pressure. The product was isolated as a yellow solid in 83 percent yield (1.1 g, 6.7 mmol). (a)

Molecular Weight:164.21
XLogP3:1
Hydrogen Bond Donor Count:1
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:164.106196400
Monoisotopic Mass:164.106196400
Topological Polar Surface Area:67.6
Heavy Atom Count:12
Complexity:209
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes