Methyl acetoacetate → 4-[1-(4-Cyano-benzylamino)-ethylidene]-pent-2-enedioic acid dimethyl ester

HRID 919898ノート

反応式

HRID 919898 の反応式
[C:1]([C:3]1[CH:10]=[CH:9][C:6]([CH2:7][NH2:8])=[CH:5][CH:4]=1)#[N:2].[CH3:11][O:12][C:13](=[O:18])[CH2:14][C:15](=O)[CH3:16].[CH3:19][O:20][C:21](=[O:24])[C:22]#[CH:23]>CO>[CH3:19][O:20][C:21](=[O:24])[CH:22]=[CH:23][C:14](=[C:15]([NH:2][CH2:1][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[CH:5][CH:4]=1)[CH3:16])[C:13]([O:12][CH3:11])=[O:18]

参加物

5

反応物 3

HCID 7757Methyl acetoacetateHCID 13536Methyl propiolateHCID 826084-(Aminomethyl)benzonitrile

生成物 1

HCID 867141454-[1-(4-Cyano-benzylamino)-ethylidene]-pent-2-enedioic acid dimethyl ester収率 46.9%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

A mixture of 4-cyanobenzyl amine (3 g, 22.7 mmol) and 3-oxo-butyric acid methyl ester (2.94 mL, 27.2 mmol) in MeOH (80 mL) was refluxed for 2 h. Propynoic acid methyl ester (3.03 mL, 34 mmol) was added, and the resulting mixture was refluxed for 48 h. After cooling to r.t., the solvent was evaporated, and the crude residue was recrystallized from MeOH to give 3.35 g of the title compound as a light yellow solid. 1H NMR (CDCl3, 200 MHz): δ=10.97 (br s, 1H), 7.72 (d, 1H, J=15.4 Hz), 7.67 (d, 2H, J=8.8 Hz), 7.37 (d, 2H, J=8.4 Hz), 6.11 (d, 1H, J=15.8 Hz), 4.63 (d, 2H, J=6.0 Hz), 3.79 (s, 3H), 3.73 (s, 3H), 2.21 (s, 3H).

後処理

  1. temperaturewas refluxed for 2 h
  2. temperaturethe resulting mixture was refluxed for 48 h
  3. customthe solvent was evaporated
  4. customthe crude residue was recrystallized from MeOH

出典と根拠

ORDレコード
ord-d53a74e172514f908207c5e9443a778b
出典データセット
uspto-grants-2016_03
特許番号
US09271970B2

反応ノート

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