Iodine → (4-Iodo-5-methyl-pyridin-3-yl)-carbamic acid tert-butyl ester

HRID 2216062

Reaktionsgleichung

Reaktionsgleichung von HRID 2216062
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:9]=[N:10][CH:11]=[C:12]([CH3:14])[CH:13]=1)([CH3:4])([CH3:3])[CH3:2].CNCCN(C)C.C([Li])CCC.[I:28]I>C1COCC1>[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[CH:9]=[N:10][CH:11]=[C:12]([CH3:14])[C:13]=1[I:28])([CH3:4])([CH3:3])[CH3:2]

Komponenten

6

Edukt 4

HCID 807IodineHCID 673381,2-Ethanediamine, N1,N1,N2-trimethyl-HCID 21300389HCID 21300389, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 60026355(4-Iodo-5-methyl-pyridin-3-yl)-carbamic acid tert-butyl esterAusbeute 14 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

(5-Methyl-pyridin-3-yl)-carbamic acid tert-butyl ester (255 mg, 1.2 mmol, Example 139: step a) and trimethylethylenediamine (905 μL, 6.0 mmol) were dissolved into THF (4 mL) and cooled to −78° C. To this was added n-Butyllithium (2.5M, 2.4 mL, 6.0 mmol). The reaction was stirred at −78° C. for 30 minutes and then warmed to RT for 30 minutes. Iodine (1.5 g, 6.0 mmol) was dissolved into THF (4 mL) and added to the reaction mixture at −78° C. slowly. The reaction was warmed to RT for 1 hour and the solvents were removed in vacuo. The residue was dissolved into EtOAc and washed with brine and water. The combined organic layers were dried (MgSO4) and solvents were removed in vacuo followed by purification by flash column chromatography (SiO2) (50% EtOAc in hexanes) that yielded the title compound as a yellow solid (55 mg, 14%). 1H-NMR (CDCl3): δ 8.91 (s, 1H), 8.07 (s, 1H), 6.81 (br s, 1H), 2.44 (s, 3H), 1.56 (s, 9H). ESI-MS (m/z): Calcd. for C11H15IN2O2: 335.0 (M+1); found: 334.9.

Aufarbeitung

  1. temperaturewarmed to RT for 30 minutes
  2. additionadded to the reaction mixture at −78° C. slowly
  3. temperatureThe reaction was warmed to RT for 1 hour
  4. customthe solvents were removed in vacuo
  5. dissolutionThe residue was dissolved into EtOAc
  6. washwashed with brine and water
  7. dry with materialThe combined organic layers were dried (MgSO4) and solvents
  8. customwere removed in vacuo
  9. customfollowed by purification by flash column chromatography (SiO2) (50% EtOAc in hexanes)

Quellen und Nachweise

ORD-Eintrag
ord-a9fb5039e9944f5ea5e3f040f9088009
Quelldatensatz
uspto-grants-2006_09
Patentnummer
US07109354B2

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