Hydrochloric Acid → tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamate

HRID 579540Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 579540
O=[C:2]([CH2:14][CH2:15][CH:16]=[CH2:17])[CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10].[C:18]([O-:21])(=O)[CH3:19].[CH3:22][NH3+:23].[C:24]([N+:28]#[C-])([CH3:27])([CH3:26])[CH3:25].Cl.FC(F)(F)[CH2:33][OH:34]>C(OCC)(=O)C>[C:24]([NH:28][C:33]([C:2]([N:23]([CH3:22])[C:18](=[O:21])[CH3:19])([CH2:14][CH2:15][CH:16]=[CH2:17])[CH2:3][CH2:4][CH2:5][NH:6][C:7](=[O:13])[O:8][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:34])([CH3:25])([CH3:26])[CH3:27]

Komponenten

7

Edukt 5

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 23577Tert-Butyl isocyanideHCID 11564973Tert-butyl 4-oxooct-7-enylcarbamateHCID 14420923Methylammoniumacetat

Produkt 1

HCID 86663727tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamateAusbeute 26 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A solution of tert-butyl 4-oxooct-7-enylcarbamate (300 mg; 1.24 mmol), methylammonium acetate (680 mg, 7.46 mmol) in 2,2,2-trifluoroethanol (2 mL) was treated with tert-butyl isocyanide (0.56 mL, 5.0 mmol) and stirred at room temperature for 5 days. Ethyl acetate (5 mL) and 2 M aq HCl (2 mL) were added and the solution was vigorously stirred for 3 additional hrs. The phases were separated and the organic phase was washed successively with water and sat'd aq sodium chloride, dried over MgSO4, filtered and concentrated. The crude viscous yellow oil residue was purified by flash column chromatography (2% methanol in dichloromethane) to give tert-butyl 4-(tert-butylcarbamoyl)-4-(N-methylacetamido)oct-7-enylcarbamate (130 mg, 26%). 1H NMR (CDCl3, 500 MHz) δ 5.81-5.73 (m, 1H), 5.40 (s, 1H), 5.05-4.96 (m, 2H), 4.62 (bs, 1H), 3.15-3.09 (m, 2H), 3.01 (s, 3H) 2.17-2.12 (m, 2H), 2.10 (s, 3H) 2.04-1.94 (m, 2H), 1.77-1.71 (m, 2H), 1.43 (s, 9H), 1.38-1.34 (m, 2H), 1.32 (s, 9H). ESI MS found for C21H39N3O4 m/z [420.5 (M+Na+), 442.4 (M+HCOO−), 396.6 (M−1)].

Aufarbeitung

  1. stirringthe solution was vigorously stirred for 3 additional hrs
  2. customThe phases were separated
  3. washthe organic phase was washed successively with water
  4. dry with materialdried over MgSO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe crude viscous yellow oil residue was purified by flash column chromatography (2% methanol in dichloromethane)

Quellen und Nachweise

ORD-Eintrag
ord-a0e5572f1c124714b9d674d90a094608
Quelldatensatz
uspto-grants-2015_05
Patentnummer
US09040703B2

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