Ammonia → 4-Chloro-6-methyl-10,10-dioxo-2-piperazin-1-yl-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cyclo heptene-8-carboxylic acid methyl ester

HRID 1172505Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1172505
[NH3:1].Cl[CH2:3][CH2:4][N:5]([CH2:28][CH2:29]Cl)[C:6]1[CH:26]=[C:25]([Cl:27])[C:9]2[O:10][C:11]3[C:20]([CH3:21])=[CH:19][C:18]([C:22]([OH:24])=[O:23])=[CH:17][C:12]=3[S:13](=[O:16])(=[O:15])[CH2:14][C:8]=2[CH:7]=1.[CH3:31]O>>[CH3:31][O:24][C:22]([C:18]1[CH:19]=[C:20]([CH3:21])[C:11]2[O:10][C:9]3[C:25]([Cl:27])=[CH:26][C:6]([N:5]4[CH2:4][CH2:3][NH:1][CH2:29][CH2:28]4)=[CH:7][C:8]=3[CH2:14][S:13](=[O:15])(=[O:16])[C:12]=2[CH:17]=1)=[O:23]

Komponenten

4

Edukt 3

HCID 222AmmoniaHCID 887MethanolHCID 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 115410724-Chloro-6-methyl-10,10-dioxo-2-piperazin-1-yl-10,11-dihydro-5-oxa-10lambda*6*-thia-dibenzo[a,d]cyclo heptene-8-carboxylic acid methyl ester

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

Aqueous ammonia solution (30%, 4 mL) was added to a solution of Example 102j (0.5 g, 1.04 mmol) in methanol (1 mL), in an atmosphere of nitrogen, sealed in a pressure reactor vessel and heated at 110° C. for 6 h. The reaction mixture was brought to room temperature, concentrated, treated with chilled water and dilute HCl to neutral pH. The solid that precipitated was filtered, washed with water and dried. It was treated with methanolic HCl solution and stirred at 70° C. for 2.5 h. The reaction mixture was cooled and the solid that separated was filtered, washed with methanol, dried and purified using flash chromatography (silica gel, MeOH/CHCl3) to obtain the title compound as an off white solid. Yield: 0.220 g (48.24%); 1H NMR (DMSO-d6): δ 2.30 (m, 4H, 2CH2), 2.70 (s, 3H, CH3), 3.10 (m, 4H, 2CH2), 3.95 (s, 3H, OCH3), 5.10 (s, 2H, CH2), 7.10 (s, 1H, Ar), 7.20 (s, 1H, Ar), 8.05 (s, 1H, Ar) 8.20 (s, 1H, Ar): MS: m/e (ES+) 422 (M+1).

Aufarbeitung

  1. customsealed in a pressure reactor vessel
  2. customwas brought to room temperature
  3. concentrationconcentrated
  4. additiontreated with chilled water and dilute HCl to neutral pH
  5. customThe solid that precipitated
  6. filtrationwas filtered
  7. washwashed with water
  8. customdried
  9. additionIt was treated with methanolic HCl solution
  10. temperatureThe reaction mixture was cooled
  11. customthe solid that separated
  12. filtrationwas filtered
  13. washwashed with methanol
  14. customdried
  15. custompurified

Quellen und Nachweise

ORD-Eintrag
ord-a99dbbbcf49947198f28e46d00d97592
Quelldatensatz
uspto-grants-2010_11
Patentnummer
US07834001B2

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