4-Pentenal → HCID 86713815, Verbindung

Temperatur

-40 °C

A solution of 1-methyl-4-nitro-1H-pyrazole (9.7 g, 76.7 mmol) and 4-pentenal (10 g, 84.4 mmol) in dry THF (250 mL) was cooled to −78° C. and stirred under nitrogen. A solution of LiHMDS (1 M in THF, 192 mL, 191.7 mmol) was added dropwise over a period of 3 hr. The reaction mixture was allowed to warm and to −40° C. and stirred for 2 hr, quenched by dropwise addition of saturated ammonium chloride solution (100 mL), warmed to room temperature and diluted with EtOAc (200 mL). The organic layer was washed with saturated ammonium chloride solution (50 mL), separated, dried over MgSO4 and the solvent removed under reduced pressure. Purification via silica gel chromatography (0-100% EtOAc/DCM) followed by silica gel chromatography (0-100% EtOAc/isohexane) to gave 1-(1-methyl-4-nitro-1H-pyrazol-5-yl)pent-4-en-1-ol as a pale yellow oil (5.75 g, 36%). 1H NMR (400 MHz, CDCl3) δ 8.06 (s, 1H), 5.85-5.78 (m, 1H), 5.32-5.26 (m, 1H), 5.12-5.04 (m, 2H), 3.98 (s, 3H), 3.45 (d, J=8.7 Hz, 1H), 2.92-2.09 (m, 3H), 1.90-1.86 (m, 1H).

1. stirringstirred for 2 hr
2. customquenched by dropwise addition of saturated ammonium chloride solution (100 mL)
3. temperaturewarmed to room temperature
4. additiondiluted with EtOAc (200 mL)
5. washThe organic layer was washed with saturated ammonium chloride solution (50 mL)
6. customseparated
7. dry with materialdried over MgSO4
8. customthe solvent removed under reduced pressure
9. customPurification via silica gel chromatography (0-100% EtOAc/DCM)

ORD-Eintrag

ord-a751eb78b67e49309b996ebe2882add8

Quelldatensatz

uspto-grants-2016_05

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US09328106B2