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

HRID 1498046ノート

反応式

HRID 1498046 の反応式
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]

参加物

7

反応物 4

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

生成物 1

HCID 86669721methyl 2-[2-(5-bromo-1-methyl-1H-pyrazol-4-yl)-2-oxoethyl]-2-formylhydrazinecarboxylate収率 27.2%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6342Acetonitrile溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-a573d8e296bd47f899e95cf5682ff1c1
出典データセット
uspto-grants-2015_12
特許番号
US09200000B2

反応ノート

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