Carbon Dioxide → 1-tert-Butyl-1H-pyrazole-4-carboxylic acid

HRID 599312

Reaktionsgleichung

Br[C:2]1[CH:3]=[N:4][N:5]([C:7]([CH3:10])([CH3:9])[CH3:8])[CH:6]=1.[Li]CCCC.[C:16](=[O:18])=[O:17]>C1COCC1>[C:7]([N:5]1[CH:6]=[C:2]([C:16]([OH:18])=[O:17])[CH:3]=[N:4]1)([CH3:10])([CH3:9])[CH3:8]

Komponenten

Reaktionsbedingungen

Temperatur: -78 °C

Versuchsvorschrift

To a −78° C. solution of 4-bromo-1-t-butyl-1H-pyrazole (15 g, 74.3 mmol) in anhydrous THF (100 mL) was added n-BuLi (2.5 M in hexane, 53 mL, 132 mmol) under N2, and the resulting mixture was stirred at −78° C. for 30 min. Excess dry ice was added at −78° C., and the mixture was warmed slowly to RT and stirred overnight. The reaction was concentrated in vacuo, water was added and the pH was adjusted to pH 3 by the addition of 2N aq HCl. The aqueous solution was extracted with EtOAc. The extracts were washed with brine, dried (MgSO4) and concentrated in vacuo. The residue was recrystallized (EtOAc-pet. ether) to give 1-t-butyl-1H-pyrazole-4-carboxylic acid (8.0 g, 67% yield). 1H NMR (300 MHz, CDCl3): δ 8.10 (s, 1 H), 8.03 (s, 1 H), 1.64 (s, 9 H); MS (ESI) m/z: 168.9 [M+H]+.

Aufarbeitung

temperaturethe mixture was warmed slowly to RT
stirringstirred overnight
concentrationThe reaction was concentrated in vacuo, water
additionwas added
additionthe pH was adjusted to pH 3 by the addition of 2N aq HCl
extractionThe aqueous solution was extracted with EtOAc
washThe extracts were washed with brine
dry with materialdried (MgSO4)
concentrationconcentrated in vacuo
customThe residue was recrystallized (EtOAc-pet. ether)

Quellen und Nachweise

ORD-Eintrag: ord-37b8b203c16841d38f21c12262051204
Quelldatensatz: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US07897762B2

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