ethyl N-ethoxycarbonyliminocarbamate → tert-butyl 3-(3-methoxy-4-nitro-1H-pyrazol-1-yl)azetidine-1-carboxylate

HRID 928212Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 928212
[CH3:1][O:2][C:3]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][NH:5][N:4]=1.[C:11]([O:15][C:16]([N:18]1[CH2:22][CH2:21][CH:20](O)C1)=[O:17])([CH3:14])([CH3:13])[CH3:12].N(C(OCC)=O)=NC(OCC)=O>C1COCC1.CCOC(C)=O>[CH3:1][O:2][C:3]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]([CH:21]2[CH2:22][N:18]([C:16]([O:15][C:11]([CH3:12])([CH3:13])[CH3:14])=[O:17])[CH2:20]2)[N:4]=1

Komponenten

6

Edukt 3

HCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 44169391-Boc-3-pyrrolidinolHCID 178494320HCID 178494320, Verbindung

Produkt 1

HCID 118073710tert-butyl 3-(3-methoxy-4-nitro-1H-pyrazol-1-yl)azetidine-1-carboxylateAusbeute 72,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a cooled (0° C.) suspension of 3-methoxy-4-nitro-1H-pyrazole (1.00 g, 6.99 mmol, 1.00 eq), tert-butyl-3-hydroxypyrrolidine-1-carboxylate (2.12 g, 12.2 mmol, 1.75 eq), and polystyrene bound triphenylphosphine (4.06 g, 12.2 mmol, 1.75 eq, 3 mmol/gram) in THF (45 mL) was added diethyl azodicarboxylate (2.42 mL, 13.0 mmol, 1.90 eq) in a drop-wise manner over 3 min. The reaction mixture was allowed to warm to ambient temperature and stirred for 15 hr. The reaction mixture was then diluted with EtOAc (60 mL), filtered and the filtrate concentrated. The crude reaction mixture was purified via flash chromatography on silica gel eluting with a gradient of 0-60% EtOAc in heptane to give the title compound (1.52 g, 72.9% yield) as a white solid. 1H NMR (400 MHz, CDCl3) δ ppm 8.12 (s, 1H) 4.87 (tt, J=5.6, 7.5 Hz, 1H) 4.40-4.28 (m, 4H) 4.09 (s, 3H) 1.48 (s, 9H). m/z (APCI+) for C7H11N4O3 198.9 (M−Boc+H)+.

Aufarbeitung

  1. temperatureTo a cooled
  2. filtrationfiltered
  3. concentrationthe filtrate concentrated
  4. customThe crude reaction mixture
  5. customwas purified via flash chromatography on silica gel eluting with a gradient of 0-60% EtOAc in heptane

Quellen und Nachweise

ORD-Eintrag
ord-f37ea0bb011c4c07a11b3e80201942a0
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09290496B2

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