Triethylamine → 3-methyl-1-(oxan-4-yl)-1H-pyrazol-5-amine

HRID 1522424Notizen

Reaktionsgleichung

N/[C:2](/[CH3:6])=[CH:3]\[C:4]#[N:5].[O:7]1[CH2:12][CH2:11][CH:10]([NH:13][NH2:14])[CH2:9][CH2:8]1.C(N(CC)CC)C>C(O)C>[CH3:6][C:2]1[CH:3]=[C:4]([NH2:5])[N:13]([CH:10]2[CH2:11][CH2:12][O:7][CH2:8][CH2:9]2)[N:14]=1

Komponenten

Reaktionsbedingungen

Temperatur: 75 °C

Versuchsvorschrift

(2Z)-3-Amino-2-butenenitrile (0.538 g, 6.55 mmol), tetrahydro-2H-pyran-4-ylhydrazine (1 g, 6.55 mmol) and triethylamine (0.913 mL, 6.55 mmol) were added to ethanol (300 mL), and the reaction mixture was stirred at 75° C. for 16 hours. The solvent was removed in vacuo, and the crude material suspended in EtOAc. The organic phase was washed with water and then brine. The organic layer was then dried over MgSO4, filtered, and concentrated in vacuo. Half of the crude material was purified by reverse HPLC (mobile phase: 0-30% ACN/H2O, 0.1% TFA) to afford 380 mg of the desired product. The other half of the crude material was purified via silica gel chromatography (eluent: 0% to 100% EtOAc:Hex then 0% to 20% MeOH:DCM). An additional 300 mg of the desired product was obtained (overall yield: 57%). LCMS E-S (M+H)=182.0. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.78 (dd, 2 H), 1.94 (qd, J=12.13, 4.55 Hz, 2 H), 2.19 (s, 3 H), 3.30-3.46 (m, 2 H), 3.99 (dd, J=11.49, 4.17 Hz, 2 H), 4.49 (m, J=11.65, 11.65, 4.11, 3.92 Hz, 1 H), 5.53 (s, 1 H).

Aufarbeitung

customThe solvent was removed in vacuo
washThe organic phase was washed with water
dry with materialThe organic layer was then dried over MgSO4
filtrationfiltered
concentrationconcentrated in vacuo
customHalf of the crude material was purified by reverse HPLC (mobile phase: 0-30% ACN/H2O, 0.1% TFA)

Quellen und Nachweise

ORD-Eintrag: ord-deb75d8d5caf4682b3d9e069995b22cf
Quelldatensatz: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US09073924B2

Notizen zur Reaktion

Wird geladen…