Hydrochloric Acid → 2-(5-Methyl-3-nitro-pyridin-2-yl)-malonic acid diethyl ester

HRID 1838302ノート

反応式

HRID 1838302 の反応式
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].Cl[C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][C:18]([CH3:24])=[CH:17][N:16]=1.Cl>COCCOC>[CH2:10]([O:9][C:1](=[O:8])[CH:2]([C:15]1[C:20]([N+:21]([O-:23])=[O:22])=[CH:19][C:18]([CH3:24])=[CH:17][N:16]=1)[C:3]([O:5][CH2:6][CH3:7])=[O:4])[CH3:11]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 7761Diethyl MalonateHCID 24758Sodium hydrideHCID 8183002-Chloro-5-methyl-3-nitropyridine

生成物 1

HCID 600601582-(5-Methyl-3-nitro-pyridin-2-yl)-malonic acid diethyl ester

試薬・触媒・溶媒 1

HCID 80711,2-Dimethoxyethane溶媒3 回

実験手順

A solution of diethyl malonate (72 g, 0.436 mol) in DME (200 mL) is added dropwise to a magnetically stirred suspension of NaH (23 g, 0.58 mol) in dry 1,2-dimethoxyethane (DME, 350 mL). The mixture is stirred at room temperature for 1 hour and then a solution of 2-chloro-5-methyl-3-nitro-pyridine (50 g, 0.290 mol) in DME (100 mL) is added to give a dark red solution. After stirring for 18 hours, the reaction mixture is poured into ice-cold water and acidified to pH 3 with 6N HCl solution. The mixture is extracted with ethyl acetate. The organic phase is washed with water, brine, dried over Na2SO4, and concentrated. The excess diethymalonate is removed at 50° C. under high vacuum to give 2-(5-Methyl-3-nitro-pyridin-2-yl)-malonic acid diethyl ester i as a dark red-colored thick residue; 1H NMR (300 MHz, CDCl3) δ 1.28 (t, J=9 Hz, 6H), 4.26 (q, J=9 Hz, 4H), 8.27 (s, 1H), 8.63 (s, 1H).

後処理

  1. customto give a dark red solution
  2. stirringAfter stirring for 18 hours
  3. additionthe reaction mixture is poured into ice-cold water
  4. extractionThe mixture is extracted with ethyl acetate
  5. washThe organic phase is washed with water, brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated
  8. customThe excess diethymalonate is removed at 50° C. under high vacuum

出典と根拠

ORDレコード
ord-3c1db0c2ddf84dc89146cc6969e4ea06
出典データセット
uspto-grants-2004_01
特許番号
US06673811B1

反応ノート

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