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Ethyl Acetate → 1-(4-Methylbenzamido)-2-[2-[(1,3-dioxolan-2-ylmethyl)(methyl)amino]acetylamino]-anthraquinone

HRID 40773
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 40773
[CH3:1][C:2]1[CH:31]=[CH:30][C:5]([C:6]([NH:8][C:9]2[C:22]3[C:21](=[O:23])[C:20]4[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=4)[C:14](=[O:24])[C:13]=3[CH:12]=[CH:11][C:10]=2[NH:25][C:26](=[O:29])[CH2:27]Cl)=[O:7])=[CH:4][CH:3]=1.CCN(C(C)C)C(C)C.[CH3:41][NH:42][CH2:43][CH:44]1[O:48][CH2:47][CH2:46][O:45]1.C(OCC)(=O)C>O1CCCC1.CCO.CCCCCC>[CH3:1][C:2]1[CH:31]=[CH:30][C:5]([C:6]([NH:8][C:9]2[C:22]3[C:21](=[O:23])[C:20]4[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=4)[C:14](=[O:24])[C:13]=3[CH:12]=[CH:11][C:10]=2[NH:25][C:26](=[O:29])[CH2:27][N:42]([CH2:43][CH:44]2[O:48][CH2:47][CH2:46][O:45]2)[CH3:41])=[O:7])=[CH:4][CH:3]=1
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

8

Edukt 4

HCID 8857Ethyl AcetateHCID 81531DiisopropylethylamineHCID 5417541,3-Dioxolane-2-methanamine, N-methyl-HCID 533741991-(4-Methylbenzamido)-2-(chloroacetamido)-anthraquinone

Produkt 1

HCID 533745861-(4-Methylbenzamido)-2-[2-[(1,3-dioxolan-2-ylmethyl)(methyl)amino]acetylamino]-anthraquinoneAusbeute 43 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittelHCID 8058HexaneLösungsmittel

Versuchsvorschrift

Compound CC-12 (0.86 g, 2 mmole) was dissolved in anhydrous tetrahydrofuran (30 ml), and to the solution was added successively with DIPEA (1 ml, 6 mmole) and 2-methylaminomethyl-1,3 dioxolane (0.91 ml, 8 mmole) under stirring for 5 to 10 minutes. This mixture was heated under reflux for 16 hours. After the completion of the reaction, the mixture was filtered, and the filtrate was concentrated by reduced pressure concentrator (such as Vacuum Evaporator). The residue was extracted with ethyl acetate for several times. The extract was dried on magnesium sulfate, and concentrated under reduced pressure. The crude product was washed with ethyl acetate/hexane. Finally, the crude product was recrystallized in hot ethanol to obtain a kelly green compound CC-36. Mol. Wt.: 513.5412 (C29H27N3O6); Rf: 0.31 (ethyl acetate: n-hexane=1:2); Yield: 43%; Mp.: 156-157° C. (EtOH); HRMS (EI) m/z: calcd [M]+, 513.1900 (C29H27N3O6+). Found, 513.1902. 1H-NMR (300 MHz, DMSO-d6) δ (ppm): 2.18 (s, 3H, —CH3), 2.44 (s, 3H, —CH3), 2.54 (d, J=8.7 Hz, 2H, —NCH2—), 3.26 (s, 2H, —CH2N—), 3.52-3.55 (m, 2H, —OCH2—), 3.72-3.77 (m, 2H, —OCH2—), 4.58 (t, J=4.5 Hz, 1H, —OCHO—), 7.43 (d, J=7.8 Hz, 2H, Ar—H), 7.88-7.92 (m, 2H, Ar—H), 8.04 (d, J=8.1 Hz, 2H, Ar—H), 8.10-8.19 (m, 2H, Ar—H), 8.27 (d, J=8.4 Hz, 1H, Ar—H), 8.70 (d, J=8.7 Hz, 1H, Ar—H), 10.15 (s, 1H, Ar—NH—), 10.53 (s, 1H, Ar—NH—); 13C-NMR (75 MHz, DMSO-d6) δ (ppm): 20.87, 43.49, 59.43, 61.73, 63.91, 102.61, 125.50, 126.31, 126.48, 126.90, 127.89, 128.06, 129.06, 129.31, 130.75, 132.33, 134.16, 134.38, 134.45, 140.42, 142.29, 166.25 (NCO), 169.59 (NCO), 181.46 (CO), 183.70 (CO).

Aufarbeitung

  1. temperatureThis mixture was heated
  2. temperatureunder reflux for 16 hours
  3. customAfter the completion of the reaction
  4. filtrationthe mixture was filtered
  5. concentrationthe filtrate was concentrated by reduced pressure concentrator (such as Vacuum Evaporator)
  6. extractionThe residue was extracted with ethyl acetate for several times
  7. customThe extract was dried on magnesium sulfate
  8. concentrationconcentrated under reduced pressure
  9. washThe crude product was washed with ethyl acetate/hexane
  10. customFinally, the crude product was recrystallized in hot ethanol
  11. customto obtain a kelly green compound CC-36

Quellen und Nachweise

ORD-Eintrag
ord-d35826ad94ef4ebe87ea18c01de95dde
Quelldatensatz
uspto-grants-2013_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08530465B2

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