Dichloromethane → 9-Bromo-5-ethoxalylaminomethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione

HRID 52495

Reaktionsgleichung

Reaktionsgleichung von HRID 52495
Cl.[Br:2][C:3]1[CH:4]=[C:5]2[CH2:17][CH2:16][CH:15]([CH2:18][NH2:19])[N:7]3[C:8](=[O:14])[C:9](=[O:13])[NH:10][C:11]([CH:12]=1)=[C:6]23.ClCCl.C(N(CC)CC)C.[C:30](Cl)(=[O:36])[C:31]([O:33][CH2:34][CH3:35])=[O:32]>O.CN(C=O)C>[Br:2][C:3]1[CH:4]=[C:5]2[CH2:17][CH2:16][CH:15]([CH2:18][NH:19][C:30]([C:31]([O:33][CH2:34][CH3:35])=[O:32])=[O:36])[N:7]3[C:8](=[O:14])[C:9](=[O:13])[NH:10][C:11]([CH:12]=1)=[C:6]23

Komponenten

7

Edukt 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 20884Ethoxalyl chlorideHCID 678861339-bromo-5-aminomethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione hydrochloride

Produkt 1

HCID 678861209-Bromo-5-ethoxalylaminomethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dioneAusbeute 21,1 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 962WaterLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a solution of 9-bromo-5-aminomethyl-6,7-dihydro-1H, 5H-pyrido[1,2,3-de]quinoxaline-2,3-dione hydrochloride (300 mg, 0.866 mmol)in a 1:1 mixture of dichloromethane and DMF (10 mL)in the presence of triethylamine (0.3 mL, 2.16 mmol) was added ethyl chlorooxalate (0.102 mL, 0.909 mmol) at 0° C. The mixture was stirred for 15 min at 0° C. and for 10 h at room temperature and then water was added. The mixture was extracted with ethyl acetate. The aqueous layer was acidified with 1N hydrochloric acid to pH 1 and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over magnesium sulfate, and concentrated. The residual solid was recrystallized from ethanol-ether to give 75 mg of the title compound (21%): mp 214.5~220.5° C.; 1H NMR (270 MHz, DMSO-d6) δ12.01 (s, 1H), 9.11 and 9.04 (two triplet, 1H, J=6 Hz), 7.19 (s, 1H), 7.14 (s, 1H), 4.98~5.07 (m, 1H), 4.21 (q, 2H, J=7.5 Hz), 3.17~3.57 (m, 2H), 3.01 (ddd, 1H, J=17.1, 13.5, 4.5 Hz), 2.79, (dm, 1H, J=17.1 Hz), 2.10 (dm, 1H, 13.5 Hz), 1.70~1.85 (m, 1H), 1.26 (t, 3H, J=7.5 Hz).

Aufarbeitung

  1. extractionThe mixture was extracted with ethyl acetate
  2. extractionextracted with ethyl acetate
  3. washThe combined organic layers were washed with brine
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated
  6. customThe residual solid was recrystallized from ethanol-ether

Quellen und Nachweise

ORD-Eintrag
ord-b6fd3161a137452baeff9a05f959ac46
Quelldatensatz
uspto-grants-1997_04
Patentnummer
US05616586

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