Methyl iodide → Tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate

HRID 2036730Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2036730
[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[C:8]2[NH:7][C:6]3[CH2:12][CH:13]4[NH:17][CH:16]([C:5]=3[C:4]=2[C:3]=1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15][CH2:14]4.[H-].[Na+].I[CH3:28]>CN(C=O)C.C(OCC)(=O)C>[Br:1][C:2]1[CH:10]=[C:9]([CH3:11])[C:8]2[N:7]([CH3:28])[C:6]3[CH2:12][CH:13]4[NH:17][CH:16]([C:5]=3[C:4]=2[C:3]=1[C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:15][CH2:14]4

Komponenten

6

Edukt 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 67085300Tert-butyl 2-bromo-4-methyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate

Produkt 1

HCID 67085249Tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylateAusbeute 80 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a solution of the product of step B (410 mg, 1.05 mmol) in DMF (3.5 ml) at 0° C., under nitrogen was added sodium hydride (60% dispersion in mineral oil, 51 mg, 2.09 mmol). The mixture was stirred for 45 min at 0-5° C. before iodomethane (0.13 mL, 2.09 mmol) was added. The mixture was stirred for a further 90 min then quenched with ice water. The mixture was diluted with ethyl acetate, washed with water, brine and dried over anhydrous sodium sulfate. Concentration in vacuo afforded a viscous oil which was dissolved in a minimal amount of ethyl acetate and precipitated by addition of hexanes. The separated solid was filtered and dried in vacuo to give tert-butyl 2-bromo-4,5-dimethyl-5,6,7,8,9,10-hexahydro-7,10-epiminocyclohepta[b]indole-carboxylate (340 mg, 80%) as an off-white solid. 1H NMR (CDCl3, 300 MHz): δ 7.43 (d, J=1.2 Hz, 1H), 6.94 (d, J=1.2 Hz, 1H), 5.05-5.30 (m, 1H), 4.52-4.70 (m, 1H), 3.80 (s, 3H), 3.15-3.47 (m, 1H), 2.69 (s, 3H), 2.43 (dd, J=15.9, 0.9 Hz, 1H), 2.23-2.30 (m, 1H), 2.08-2.22 (m, 1H), 1.85-1.95 (m, 1H), 1.58-1.64 (m, 1H), 1.39 (br s, 9H).

Aufarbeitung

  1. additionwas added
  2. customthen quenched with ice water
  3. additionThe mixture was diluted with ethyl acetate
  4. washwashed with water, brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationConcentration in vacuo
  7. customafforded a viscous oil which
  8. customprecipitated by addition of hexanes
  9. filtrationThe separated solid was filtered
  10. customdried in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-7ecf305bf32c4c7aaa9cd25e7ff4c381
Quelldatensatz
uspto-grants-2013_11
Patentnummer
US08575186B2

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