Diisopropylethylamine → tert-butyl 3-(1-methyl-4-nitro-1H-pyrazol-5-ylamino)propylcarbamate

HRID 1915732Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1915732
Cl[C:2]1[N:6]([CH3:7])[N:5]=[CH:4][C:3]=1[N+:8]([O-:10])=[O:9].[NH2:11][CH2:12][CH2:13][CH2:14][NH:15][C:16](=[O:22])[O:17][C:18]([CH3:21])([CH3:20])[CH3:19].CCN(C(C)C)C(C)C>CCO>[CH3:7][N:6]1[C:2]([NH:11][CH2:12][CH2:13][CH2:14][NH:15][C:16](=[O:22])[O:17][C:18]([CH3:20])([CH3:19])[CH3:21])=[C:3]([N+:8]([O-:10])=[O:9])[CH:4]=[N:5]1

Komponenten

5

Edukt 3

HCID 81531DiisopropylethylamineHCID 2735700tert-Butyl (3-aminopropyl)carbamateHCID 123448365-chloro-1-methyl-4-nitro-1H-pyrazole

Produkt 1

HCID 67436676tert-butyl 3-(1-methyl-4-nitro-1H-pyrazol-5-ylamino)propylcarbamateAusbeute 86,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 702EthanolLösungsmittel

Reaktionsbedingungen

Temperatur
130 °C

Versuchsvorschrift

A mixture of 5-chloro-1-methyl-4-nitro-1H-pyrazole from Example 1 (0.81 g, 5 mmol), tert-butyl 3-aminopropylcarbamate (0.85 g, 4.88 mmol) and DIPEA (1.8 mL, 10.5 mmol) in EtOH (5 mL) was heated at 130° C. in the microwave for 90 min. On cooling the reaction mixture was concentrated under reduced pressure and the residue purified via silica gel column chromatography (0-100% EtOAc/isohexane) to afford tert-butyl 3-(1-methyl-4-nitro-1H-pyrazol-5-ylamino)propylcarbamate as a yellow gum (1.27 g, 85%). A mixture of this gum (0.3 g, 1 mmol), K2CO3 (0.41 g, 3 mmol) and methyl iodide (0.1 mL, 1.58 mmol) in DMF (5 mL) was stirred at 60° C. for 18 hr. More methyl iodide (0.1 mL, 1.58 mmol) was added and stirring at 60° C. was continued for 24 hr. The reaction mixture was cooled and concentrated under reduced pressure. The residue was triturated in DCM (100 mL), filtered and the filtrate concentrated under reduced pressure. Purification via silica gel column chromatography (0-100% EtOAc/isohexane) gave tert-butyl 3-(methyl(1-methyl-4-nitro-1H-pyrazol-5-yl)amino)propylcarbamate as a pale yellow gum (0.122 g, 38%). 1H-NMR (400 MHz, CDCl3) δ 8.03 (s, 1H), 4.60 (s, 1H), 3.77 (s, 3H), 3.20-3.14 (m, 4H), 2.86 (s, 3H), 1.72-1.61 (m, 2H), 1.42 (s, 9H).

Aufarbeitung

  1. temperatureOn cooling the reaction mixture
  2. concentrationwas concentrated under reduced pressure
  3. customthe residue purified via silica gel column chromatography (0-100% EtOAc/isohexane)

Quellen und Nachweise

ORD-Eintrag
ord-f1650ff8d8e549ea818dedbd9067f57c
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08614206B2

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