Acetic Acid → Dimethyl 3-(cyanomethylidene)pentanedioate

HRID 552323ノート

反応式

HRID 552323 の反応式
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5](=O)[CH2:6][C:7]([O:9][CH3:10])=[O:8].[C:13]([CH2:15]C(O)=O)#[N:14].C(O)(=O)C>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5](=[CH:15][C:13]#[N:14])[CH2:6][C:7]([O:9][CH3:10])=[O:8]

参加物

5

反応物 3

HCID 176Acetic AcidHCID 9740Cyanoacetic acidHCID 74591Dimethyl 3-oxoglutarate

生成物 1

HCID 254955Dimethyl 3-(cyanomethylidene)pentanedioate収率 68.1%

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

実験手順

To a solution of 3-oxo-pentanedioic acid dimethyl ester (523 g) in toluene (750 mL), cyanoacetic acid (511 g), NH4OAc (46.3 g) and acetic acid (90.1 g) were added and heated at reflux with dehydrating by Dean-Stark apparatus for 8 h. After cooling to room temperature, the reaction mixture was washed with water, saturated aqueous NaHCO3 solution and brine. The organic phase was dried over MgSO4, filtered, and concentrated under reduced pressure to give crude 3-cyanomethylene-pentanedioic acid dimethyl ester (403 g) as an oil. 1H NMR (200 MHz, CDCl3) δ ppm 3.39 (d, J=0.88 Hz, 2 H), 3.62 (s, 2 H), 3.72 (s, 3 H), 3.74 (s, 3 H), 5.51 (s, 1 H).

後処理

  1. temperatureheated
  2. temperatureat reflux with dehydrating by Dean-Stark apparatus for 8 h
  3. washthe reaction mixture was washed with water, saturated aqueous NaHCO3 solution and brine
  4. dry with materialThe organic phase was dried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure

出典と根拠

ORDレコード
ord-8707aa4769d24718a1ef1f2b54279d00
出典データセット
uspto-grants-2011_05
特許番号
US07951811B2

反応ノート

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