Hydrochloric Acid → ethyl 2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-2-(pent-4-enyl)hept-6-enoate

HRID 2045787Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2045787
C1(C(=[N:14][C:15]([CH2:26][CH2:27][CH2:28][CH:29]=[CH2:30])([CH2:21][CH2:22][CH2:23][CH:24]=[CH2:25])[C:16]([O:18][CH2:19][CH3:20])=[O:17])C2C=CC=CC=2)C=CC=CC=1.Cl.[CH:32]1[C:44]2[CH:43]([CH2:45]OC(ON3C(=O)CCC3=O)=O)[C:42]3[C:37](=[CH:38][CH:39]=[CH:40][CH:41]=3)[C:36]=2[CH:35]=[CH:34][CH:33]=1.[C:57](=[O:60])([O-:59])[O-].[Na+].[Na+]>C(OCC)C.CC(C)=O.O>[CH:41]1[C:42]2[CH:43]([CH2:45][O:59][C:57]([NH:14][C:15]([CH2:21][CH2:22][CH2:23][CH:24]=[CH2:25])([CH2:26][CH2:27][CH2:28][CH:29]=[CH2:30])[C:16]([O:18][CH2:19][CH3:20])=[O:17])=[O:60])[C:44]3[C:36](=[CH:35][CH:34]=[CH:33][CH:32]=3)[C:37]=2[CH:38]=[CH:39][CH:40]=1

Komponenten

8

Edukt 4

HCID 313Hydrochloric AcidHCID 10340Sodium CarbonateHCID 134122N-(9-Fluorenylmethoxycarbonyloxy)succinimideHCID 59409619Ethyl 2-(diphenylmethyleneamino)-2-(pent-4-enyl)hept-6-enoate

Produkt 1

HCID 68667175ethyl 2-(((9H-fluoren-9-yl)methoxy)carbonylamino)-2-(pent-4-enyl)hept-6-enoate

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 180AcetoneLösungsmittel2×HCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittel

Versuchsvorschrift

To a stirred solution of crude ethyl 2-(diphenylmethyleneamino)-2-(pent-4-enyl)hept-6-enoate 11 (18.2 g, 45.1 mmol) in ethyl ether (200 mL) was added a 6N solution of hydrochloric acid (45 mL) at 0° C. over 45 min and the resulting mixture was stirred for another 15 min. The organics were extracted in ethyl ether (2×100 mL), and the combined etherial layer was concentrated. The residue was dissolved in acetone (75 mL), to which a solution of N-(9-fluorenylmethoxycarbonyloxy)succinimide (16 g, 47.5 mmol, 1.05 equiv.) in acetone (75 mL) and a solution of sodium carbonate (19.1 g, 180.4 mmol, 4.0 equiv.) in water (150 mL) were consecutively added. The resulting mixture was stirred at room temperature for 16 h. The product was extracted with ethyl acetate (2×150 mL) and the combined organic layer was dried over MgSO4, filtered, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluting with 7% ethyl acetate in n-hexanes) to give 12 as a white solid: 1H-NMR (400 MHz, CDCl3) δ 7.77 (d, J=7.2 Hz, 2H), 7.62 (d, J=8.0 Hz, 2H), 7.40 (t, J=7.2 Hz, 2H), 7.32 (dt, J=7.2, 0.8 Hz, 2H), 5.90 (br s, 1H), 5.75 (m, 2H), 4.99 (d, J=17.6 Hz, 2H), 4.95 (d, J=11.2 Hz, 2H), 4.39 (d, J=6.8 Hz, 2H), 4.25 (m, 3H), 2.35 (dt, J=12.8, 4.0 Hz, 2H), 2.02 (m, 4H), 1.76 (dt, J=12.8, 4.0 Hz, 2H) 1.39 (m, 2H), 1.30 (t, J=7.2 Hz, 3H), 1.06 (m, 2H); 13C-NMR (100 MHz, CDCl3) δ 174.2, 154.0, 144.2, 141.6, 138.5, 127.9, 127.3, 125.3, 120.2, 115.1, 66.3, 64.2, 62.1, 47.6, 35.3, 33.6, 23.6, 14.5; HRMS (ESI) m/z for C29H36NO4 [M+H]+ calcd 462.2644. found 462.2637.

Aufarbeitung

  1. extractionThe organics were extracted in ethyl ether (2×100 mL)
  2. concentrationthe combined etherial layer was concentrated
  3. stirringThe resulting mixture was stirred at room temperature for 16 h
  4. extractionThe product was extracted with ethyl acetate (2×150 mL)
  5. dry with materialthe combined organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting residue was purified by silica gel column chromatography (eluting with 7% ethyl acetate in n-hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-1ce326df2831471c8ac0f2408e789975
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08592377B2

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