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

HRID 1410904노트

반응식

HRID 1410904 반응식
[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]

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 887Methanol용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-456fe93080944365a757c9c782ff1d32
출처 데이터셋
uspto-grants-2014_12
특허 번호
US08921389B2

반응 노트

불러오는 중…