Sodium Carbonate → methyl 2-[2-(5-bromo-1-methyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-formylhydrazinecarboxylate

HRID 1907213Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1907213
COC1C=CC(CN[CH:9]=[N:10][NH:11][C:12]([O:14][CH3:15])=[O:13])=CC=1.Br[CH2:19][C:20]([C:22]1[CH:23]=[N:24][N:25]([CH3:28])[C:26]=1[Br:27])=[O:21].C(=O)([O-])[O-:30].[Na+].[Na+].C(N(CC)C(C)C)(C)C>C(#N)C.O>[Br:27][C:26]1[N:25]([CH3:28])[N:24]=[CH:23][C:22]=1[C:20](=[O:21])[CH2:19][N:10]([CH:9]=[O:30])[NH:11][C:12]([O:14][CH3:15])=[O:13]

Komponenten

7

Edukt 4

HCID 10340Sodium CarbonateHCID 81531DiisopropylethylamineHCID 866697172-bromo-1-(5-bromo-1-methyl-1H-pyrazol-4-yl)ethanoneHCID 178502533HCID 178502533, Verbindung

Produkt 1

HCID 86669721methyl 2-[2-(5-bromo-1-methyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-formylhydrazinecarboxylateAusbeute 27,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

Methyl 2-{[(4-methoxybenzyl)amino]methylene}hydrazinecarboxylate (3.28 g, 13.8 mmol), 2-bromo-1-(5-bromo-1-methyl-1H-pyrazol-4-yl)ethanone (3.90 g, 13.8 mmol) and sodium carbonate (1.16 g, 13.8 mmol) were combined in a mixture of N,N-diisopropylethylamine (99.5%, 2.30 mL, 13.8 mmol) and acetonitrile (30 mL). The reaction was heated at 80° C. for 18 hours, at which time water was added, and heated was continued for 10 minutes. After removal of solvent in vacuo, the aqueous residue was partitioned between water and ethyl acetate (100 mL). The aqueous layer was extracted with ethyl acetate (4×100 mL), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification using silica gel chromatography (Gradient: 0% to 100% ethyl acetate in heptane) provided the product (1.20 g), contaminated with some impurities. This material was taken directly to the following step. LCMS m/z 319.0 (M+1). 1H NMR (400 MHz, CD3OD) δ, product peaks: 3.74 (s, 3H), 3.92 (s, 3H), 4.82 (br s, 2H), 8.14 (s, 1H), 8.24 (s, 1H).

Aufarbeitung

  1. additionwas added
  2. temperatureheated
  3. customAfter removal of solvent in vacuo
  4. customthe aqueous residue was partitioned between water and ethyl acetate (100 mL)
  5. extractionThe aqueous layer was extracted with ethyl acetate (4×100 mL)
  6. dry with materialthe combined organic layers were dried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customPurification

Quellen und Nachweise

ORD-Eintrag
ord-d30d833e49df4e8c8823dac5d7b871a4
Quelldatensatz
uspto-grants-2013_12
Patentnummer
US08598155B2

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