N-difluoroMenthyl-4-nitropyrazole Chemical Properties

Boiling point:

87-90℃ (20 Torr)

Density 

1.71±0.1 g/cm3(Predicted)

storage temp. 

2-8°C

pka

-5.19±0.19(Predicted)

Appearance

Light yellow to yellow Liquid

InChI

InChI=1S/C4H3F2N3O2/c5-4(6)8-2-3(1-7-8)9(10)11/h1-2,4H

InChIKey

VCURCUIEDUUUEA-UHFFFAOYSA-N

SMILES

N1(C(F)F)C=C([N+]([O-])=O)C=N1

N-difluoroMenthyl-4-nitropyrazole Usage And Synthesis

Application

1-Difluoromethyl-4-nitropyrazole is an organic intermediate that can be prepared in one step from 4-nitro-1H-pyrazole and sodium 2-chloro-2,2-difluoroacetate, or from the nitration of 1-difluoromethylpyrazole.

Synthesis

General procedure for the synthesis of 1-(difluoromethyl)-4-nitro-1H-pyrazole from 4-nitropyrazole and sodium difluorochloroacetate: 4-nitro-1H-pyrazole (5.00 g, 44.2 mmol) was added by suspending cesium carbonate (Cs2CO3, 14.41 g, 44.2 mmol) in N,N-dimethylformamide (DMF, 40 mL). The mixture was heated to 120 °C and held for 5 min, followed by addition of solid sodium 2-chloro-2,2-difluoroacetate (13.48 g, 88 mmol) in 10 portions over 20 min. Heating was continued for 10 min and the reaction was completed. The reaction mixture was transferred to a partition funnel containing 100 mL of water and extracted with ether (Et2O, 2 x 50 mL). The organic layers were combined and concentrated. The crude product was purified by normal-phase chromatography using a gradient elution with hexane/ethyl acetate (EtOAc) to afford 1-(difluoromethyl)-4-nitro-1H-pyrazole (6.99 g, 42.9 mmol, 97% yield) as a clear, colorless oil.1H NMR (500 MHz, CDCl3) δ 8.58 (s, 1H), 8.22 (s, 1H) 7.39-7.05 (t, J = 60 Hz, 1H).

References

[1] Patent: WO2015/116886, 2015, A1. Location in patent: Page/Page column 200
[2] Patent: WO2015/116882, 2015, A1. Location in patent: Page/Page column 84; 88
[3] Patent: WO2016/51193, 2016, A1. Location in patent: Paragraph 00558; 00559; 00560
[4] Patent: WO2017/74832, 2017, A1. Location in patent: Page/Page column 202

N-difluoroMenthyl-4-nitropyrazole(956477-64-8)Related Product Information

• 1-(difluoromethyl)-1h-pyrazol-4-amine
• 4-BROMO-1-(DIFLUOROMETHYL)-1H-PYRAZOLE
• (1-(Difluoromethyl)-1H-pyrazol-4-yl)boronic acid
• 1-(difluoromethyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole
• 1-(difluoromethyl)-1H-pyrazole
• 1-(difluoroMethyl)-4-iodo-1H-pyrazole