Chlorotrimethylsilane → HCID 89657401, Verbindung

HRID 521417

Reaktionsgleichung

Reaktionsgleichung von HRID 521417
[CH2:1]([N:8]1[CH2:13][CH2:12][CH:11]([C:14]([O:16]CC)=O)[C:10](=O)[CH2:9]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH2:20][C:21]1[CH:22]=[C:23]([CH:28]=[CH:29][C:30]=1[Br:31])[C:24]([O:26][CH3:27])=[O:25].O1CCOCC1.C[Si](Cl)(C)C>CO>[CH2:1]([N:8]1[CH2:9][C:10]2[NH:20][C:21]3[C:30]([Br:31])=[CH:29][CH:28]=[C:23]([C:24]([O:26][CH3:27])=[O:25])[C:22]=3[C:14](=[O:16])[C:11]=2[CH2:12][CH2:13]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Komponenten

6

Edukt 4

HCID 6397ChlorotrimethylsilaneHCID 312751,4-DioxaneHCID 419705Ethyl 3-oxo-1-(phenylmethyl)-4-piperidinecarboxylateHCID 3928639Methyl 3-amino-4-bromobenzoate

Produkt 1

HCID 89657401HCID 89657401, VerbindungAusbeute 25,4 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

A mixture of ethyl 1-benzyl-3-oxopiperidine-4-carboxylate (16.1 g, 70 mmol), methyl 3-amino-4-bromobenzoate (21.9 g, 84 mmol), polyphosphoric acid (120 g) and dioxane (120 mL) was heated at 110° C. for 4 hours. After cooling to room temperature, the mixture was poured into ice water, filtered and the filtrate was extracted with EtOAc (500 mL×3). The combined organic layers were dried, and concentrated to give crude residue, which was chromatographed on silica gel using gradient eluant of 20% to 50% ethyl acetate in petroleum ether to give the crude product. Then the crude product was dissolved in MeOH (1 L), TMSCl (150 mL) was added, and the mixture was stirred at reflux for 12 h. After cooling to room temperature, the solvent was evaporated and the residue was recrystallized from MeOH to afford methyl 2-benzyl-9-bromo-5-oxo-1,2,3,4,5,10-hexahydrobenzo[b][1,7]naphthyridine-6-carboxylate (7.6 g). 1H NMR (CDC3-d1) δ 10.9 (s, 1H), 8.06 (d, 1H, J=7.8 Hz), 7.51-7.74 (m, 5H), 7.20 (d, 1H, J=7.8 Hz), 4.36-4.62 (m, 4H), 3.82 (s, 3H), 3.67-3.72 (m, 2H), and 2.82-2.83 (m, 2H). MS (ESI) m/e [M+1]+427.0.

Aufarbeitung

  1. temperatureAfter cooling to room temperature
  2. filtrationfiltered
  3. extractionthe filtrate was extracted with EtOAc (500 mL×3)
  4. customThe combined organic layers were dried
  5. concentrationconcentrated
  6. customto give crude residue, which
  7. customwas chromatographed on silica gel using gradient eluant of 20% to 50% ethyl acetate in petroleum ether
  8. customto give the crude product
  9. temperatureat reflux for 12 h
  10. temperatureAfter cooling to room temperature
  11. customthe solvent was evaporated
  12. customthe residue was recrystallized from MeOH

Quellen und Nachweise

ORD-Eintrag
ord-f233bcec8dfa4089bfc002bb786c69cb
Quelldatensatz
uspto-grants-2016_05
Patentnummer
US09328111B2

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