Methanol → 4-Chloro-6-methyl-10,10-dioxo-2-[4-(2-piperazin-1-yl-ethyl)-piperazin-1-yl]-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid methyl ester

HRID 1927505Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1927505
[NH2:1][CH2:2][CH2:3][N:4]1[CH2:9][CH2:8][NH:7][CH2:6][CH2:5]1.Cl[CH2:11][CH2:12][N:13]([CH2:36][CH2:37]Cl)[C:14]1[CH:34]=[C:33]([Cl:35])[C:17]2[O:18][C:19]3[C:28]([CH3:29])=[CH:27][C:26]([C:30]([OH:32])=[O:31])=[CH:25][C:20]=3[S:21](=[O:24])(=[O:23])[CH2:22][C:16]=2[CH:15]=1.[CH3:39]O>>[CH3:39][O:32][C:30]([C:26]1[CH:27]=[C:28]([CH3:29])[C:19]2[O:18][C:17]3[C:33]([Cl:35])=[CH:34][C:14]([N:13]4[CH2:12][CH2:11][N:1]([CH2:2][CH2:3][N:4]5[CH2:9][CH2:8][NH:7][CH2:6][CH2:5]5)[CH2:37][CH2:36]4)=[CH:15][C:16]=3[CH2:22][S:21](=[O:23])(=[O:24])[C:20]=2[CH:25]=1)=[O:31]

Komponenten

4

Edukt 3

HCID 887MethanolHCID 8795AminoethylpiperazineHCID 1317284742-[Bis-(2-chloroethyl)amino]-4-chloro-6-methyl-10,10-dioxo-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]-cycloheptene-8-carboxylic acid

Produkt 1

HCID 1317284874-Chloro-6-methyl-10,10-dioxo-2-[4-(2-piperazin-1-yl-ethyl)-piperazin-1-yl]-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cycloheptene-8-carboxylic acid methyl ester

Reaktionsbedingungen

Temperatur
70 °C

Versuchsvorschrift

N-Aminoethyl piperazine (0.6 mL, 5.2 mmol) was added to a solution of Example 102j (0.5 g, 1.04 mmol) in methanol (5 mL), followed by the addition of n-tetrabutylammonium iodide (0.075 g, 0.20 mmol) in an atmosphere of nitrogen, in a pressure reactor vessel at 120° C. for 5 h. The reaction mixture was brought to room temperature, concentrated and treated with water. The solid that separated was washed with water, dried, treated with methanolic HCl solution, and refluxed at 70° C. for 2 h. The reaction mixture was concentrated, treated with aqueous sodium bicarbonate solution to neutral pH and extracted with n-butanol. The organic layer was washed with water, dried, concentrated and purified using flash chromatography (silica gel, 20% methanol/chloroform) to obtain the title compound. Yield: 0.075 g, (13%); 1H NMR (DMSO-d6): δ 2.50-2.60 (m, 4H, 2CH2), 2.70 (s, 3H, CH3), 3.00-3.40 (m, 14H, 7CH2), 3.70 (s, 1H, OH), 3.90 (s, 3H, OCH3), 5.20 (s, 2H, CH2), 7.10 (s, 1H, Ar), 7.20 (s, 1H, Ar), 8.10 (s, 1H, Ar), 8.20 (s, 1H, Ar); MS: m/e (EI+) 459 (M+1).

Aufarbeitung

  1. customwas brought to room temperature
  2. concentrationconcentrated
  3. additiontreated with water
  4. customThe solid that separated
  5. washwas washed with water
  6. customdried
  7. additiontreated with methanolic HCl solution
  8. concentrationThe reaction mixture was concentrated
  9. additiontreated with aqueous sodium bicarbonate solution to neutral pH
  10. extractionextracted with n-butanol
  11. washThe organic layer was washed with water
  12. customdried
  13. concentrationconcentrated
  14. custompurified

Quellen und Nachweise

ORD-Eintrag
ord-af506f6c69da4c09bc83d280d45c3073
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08183234B2

Notizen zur Reaktion

Wird geladen…