Benzathine → Ethyl 1,4-dibenzyl-3-oxopiperazine-2-carboxylate

HRID 80506

反応式

HRID 80506 の反応式
[CH2:1]([NH:8][CH2:9][CH2:10][NH:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Br[CH:20]([C:26]([O:28]CC)=O)[C:21]([O:23][CH2:24][CH3:25])=[O:22]>C(#N)C.[OH-].[Na+]>[CH2:1]([N:8]1[CH2:9][CH2:10][N:11]([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[C:26](=[O:28])[CH:20]1[C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

参加物

5

反応物 2

HCID 8793BenzathineHCID 69637Diethyl bromomalonate

生成物 1

HCID 15645950Ethyl 1,4-dibenzyl-3-oxopiperazine-2-carboxylate

試薬・触媒・溶媒 2

HCID 6342Acetonitrile溶媒HCID 14798Sodium Hydroxide溶媒

反応条件

温度
90 °C

実験手順

To a solution of N,N′-dibenzylethylenediamine (14.12 mL, 60.2 mmol) in acetonitrile (100 mL) was added diethyl bromomalonate (5.14 mL, 30.1 mmol), and the mixture was heated with an oil bath at 90° C. (reflux) for 7 hours. The solvent was evaporated to provide a residue that was dissolved in 1M NaOH (aqueous), and the mixture was extracted with ethyl acetate twice, dried over Na2SO4, and the solvent was evaporated. The crude mixture was purified by silica gel chromatography (Analogix IntelliFlash 280, SF40-150) eluting with 15%-30% ethyl acetate/hexanes to afford the title compound. 1H NMR (500 MHz, DMSO-d6) δ ppm 7.38-7.20 (m, 100H), 4.54 (dd, J=15.0, 154.2, 2H), 4.20-4.10 (m, 2H), 4.03 (q, J=7.1, 1H), 3.96 (s, 1H), 3.61 (dd, J=13.5, 41.7, 2H), 3.27-3.14 (m, 2H), 3.05-2.95 (m, 1H), 2.60-2.52 (m, 1H), 1.23 (t, J=7.1, 3H); MS (ESI+) m/z 353.0 (M+H)+.

後処理

  1. temperature(reflux) for 7 hours
  2. customThe solvent was evaporated
  3. customto provide a residue that
  4. extractionthe mixture was extracted with ethyl acetate twice
  5. dry with materialdried over Na2SO4
  6. customthe solvent was evaporated
  7. customThe crude mixture was purified by silica gel chromatography (Analogix IntelliFlash 280, SF40-150)
  8. washeluting with 15%-30% ethyl acetate/hexanes

出典と根拠

ORDレコード
ord-db0d9fb1250f40c7b3788303d58a5c1a
出典データセット
uspto-grants-2014_09
特許番号
US08846663B2

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