Hydrochloric Acid → 3-Methoxyimino-1H-1,5-benzodiazepine-2,4(3H,5H)-dione

HRID 131364

反応式

HRID 131364 の反応式
CC[O-].[Na+].[C:5]1([NH2:12])[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[NH2:11].C([O:15][C:16](=O)[C:17](=[N:23][O:24][CH3:25])[C:18](OCC)=[O:19])C.Cl>C(O)C.C(#N)C>[CH3:25][O:24][N:23]=[C:17]1[C:18](=[O:19])[NH:12][C:5]2[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=2[NH:11][C:16]1=[O:15]

参加物

7

反応物 4

HCID 313Hydrochloric AcidHCID 7243O-PhenylenediamineHCID 533643Diethyl 2-(methoxyimino)malonateHCID 2723922Sodium ethoxide

生成物 1

HCID 190708143-Methoxyimino-1H-1,5-benzodiazepine-2,4(3H,5H)-dione収率 76%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒2 回HCID 6342Acetonitrile溶媒

反応条件

温度
70 °C

実験手順

Dissolve 21 wt % NaOEt in EtOH solution (164 g, 0.507 mol) in 2B-3 ethanol (331 mL) and add 1,2-phenylenediamine (27.4 g, 0.253 mol). Stir the resulting mixture allow to stir at ambient temperature for approximately 30 minutes during which time all the solid material dissolves producing a dark amber solution. Add 2-methoxyimino-malonic acid diethyl ester (51.5 g, 0.253 mol). Heat the resulting mixture to 70° C. and stir under nitrogen for approximately 4 hours monitoring by HPLC analysis (Zorbax RX C18, 55% ACN/45% 0.1% TFA, 1 mL/min, 233 nm). Allow the reaction mixture to cool to ambient temperature. Lower the pH of the reaction mixture from 11.6 to 1.2 by the addition of 700 mL of aqueous 1N HCl solution. Concentrate the reaction mixture in vacuo to remove the ethanol. Filter the resulting amber slurry through a glass frit. Collect the solid and rinse with aqueous 1N HCl and dry under vacuum at 50° C. to afford 42 g (76% yield) of the title compound as a yellow solid; 1H NMR (300 MHz, CDCl3) δ 11.1 (s, 1H), 10.9 (s, 1H), 7.22 (s, 4H), 3.86 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 161.7; 159.4, 148.1, 128.5, 127.8, 125.8, 125.7, 122.8, 122.7, 63.1; IR (CHCl3) 3062, 2970, 2902, 1704, 1656, 1606, 1505, 1414, 1058, 1043, 754 cm−1; UV (EtOH) λmax 278 nm (ε 4623), 276 nm (ε 4618), 216 nm (ε 41495); HRMS (ES+) exact mass calc'd for C10H9N3O3 242.0542, Found 242.0553; Anal. calc'd for C10H9N3O3: C, 54.79; H, 4.14; N, 19.17. Found: C, 54.60; H, 4.15; N, 18.94.

後処理

  1. stirringto stir at ambient temperature for approximately 30 minutes during which time all the solid material
  2. dissolutiondissolves
  3. customproducing a dark amber solution
  4. stirringstir under nitrogen for approximately 4 hours
  5. temperatureto cool to ambient temperature
  6. concentrationConcentrate the reaction mixture in vacuo
  7. customto remove the ethanol
  8. filtrationFilter the resulting amber slurry through a glass frit
  9. customCollect the solid
  10. washrinse with aqueous 1N HCl
  11. customdry under vacuum at 50° C.

出典と根拠

ORDレコード
ord-80a4a8bfe9554057b960a8b7538ea671
出典データセット
uspto-grants-2008_06
特許番号
US07384934B2

関連ノート

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