Ethyl Acetate → 1-(4-Methylbenzamido)-2-[2-(1,4-dioxa-8-azaspiro[4.5]dec-8-yl)acetylamino]-anthraquinone

HRID 1873718

反応式

HRID 1873718 の反応式
[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.[O:41]1[C:45]2([CH2:50][CH2:49][NH:48][CH2:47][CH2:46]2)[O:44][CH2:43][CH2:42]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:48]2[CH2:49][CH2:50][C:45]3([O:44][CH2:43][CH2:42][O:41]3)[CH2:46][CH2:47]2)=[O:7])=[CH:4][CH:3]=1

参加物

8

反応物 4

HCID 8857Ethyl AcetateHCID 674351,4-Dioxa-8-azaspiro(4.5)decaneHCID 81531DiisopropylethylamineHCID 533741991-(4-Methylbenzamido)-2-(chloroacetamido)-anthraquinone

生成物 1

HCID 533746861-(4-Methylbenzamido)-2-[2-(1,4-dioxa-8-azaspiro[4.5]dec-8-yl)acetylamino]-anthraquinone収率 55%

試薬・触媒・溶媒 3

HCID 702Ethanol溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

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 1,4-dioxa-8-azaspiro[4.5]decane (1.03 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 brown compound CC-40. Mol. Wt.: 539.5785 (C31H29N3O6); Rf: 0.34 (ethyl acetate:n-hexane=1:2); Yield: 55%; Mp.: 197-198° C. (EtOH); HRMS (EI) m/z: calcd [M]+, 539.2056 (C31H29N3O6+); found, 539.2051; 1H-NMR (300 MHz, DMSO-d6) δ (ppm): 1.39 (d, J=5.4 Hz, 8H, —CH2—), 2.43 (s, 3H, —CH3), 3.15 (s, 2H, —CH2N—), 3.77 (s, 4H, —CH2—), 7.41 (d, J=7.8 Hz, 1H, Ar—H), 7.88-7.91 (m, 2H, Ar—H), 8.06 (d, J=8.1 Hz, 2H, Ar—H), 8.10-8.19 (m, 2H, Ar—H), 8.26 (d, J=8.7 Hz, 1H, Ar—H), 8.70 (d, J=8.7 Hz, 1H, Ar—H), 10.03 (s, 1H, Ar—NH—), 10.60 (s, 1H, Ar—NH—); 13C-NMR (75 MHz, DMSO-d6) δ (ppm): 20.88, 33.68, 51.35, 61.29, 63.34, 63.52, 105.58, 125.90, 126.28, 126.32, 126.91, 127.75, 127.86, 128.18, 129.18, 129.40, 130.44, 132.29, 134.13, 134.38, 134.44, 140.32, 142.46, 166.29 (NCO), 169.31 (NCO), 181.44 (CO), 183.81 (CO).

後処理

  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 brown compound CC-40

出典と根拠

ORDレコード
ord-704a68aec88f42e09b53fd163673182d
出典データセット
uspto-grants-2012_11
特許番号
US08304415B2

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