Pyridine → tert-Butyl (6-(chloromethyl)pyridin-2-yl)carbamate

HRID 1631212Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1631212
[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14]O)[N:9]=1)([CH3:4])([CH3:3])[CH3:2].N1C=CC=CC=1.O=S(Cl)[Cl:25]>C(Cl)Cl>[C:1]([O:5][C:6](=[O:16])[NH:7][C:8]1[CH:13]=[CH:12][CH:11]=[C:10]([CH2:14][Cl:25])[N:9]=1)([CH3:4])([CH3:3])[CH3:2]

Komponenten

5

Edukt 3

HCID 1049PyridineHCID 24386Thionyl ChlorideHCID 19349090Tert-butyl (6-(hydroxymethyl)pyridin-2-yl)carbamate

Produkt 1

HCID 21851761tert-Butyl (6-(chloromethyl)pyridin-2-yl)carbamateAusbeute 50 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

To a solution of ethyl 6-[(tert-butoxycarbonyl)amino]pyridine-2-carboxylate (456 mg, 1.71 mmol) in anhydrous ethanol (20 ml) was added pulverized CaCl2 (395 mg, 3.42 mmol). The suspension was stirred and cooled to 0° C. and NaBH4 (325 mg, 8.55 mmol) was added slowly. The reaction was stirred at 0° C. for 2 h, quenched with water, and extracted with CHCl3 (×3). The combined organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (30→50% ethyl acetate in hexane) to yield a colorless syrup (308 mg) as a mixture containing tert-butyl[6-(hydroxymethyl)pyridin-2-yl]carbamate as the major component (˜4:1 ratio). To a solution of the above mixture in CH2Cl2 (10 ml) was added pyridine (144 μl, 1.79 mmol) and SOCl2 (120 μl, 1.65 mmol). The reaction was stirred at room temperature for 4 h, quenched with water and saturated Na2CO3, and extracted with CHCl3. The combined organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel (10% ethyl acetate in hexane) to yield the title compound as a colorless syrup (208 mg, 50% over 2 steps).

Aufarbeitung

  1. customquenched with water and saturated Na2CO3
  2. extractionextracted with CHCl3
  3. dry with materialThe combined organic layer was dried over Na2SO4
  4. concentrationconcentrated
  5. customThe residue was purified by column chromatography on silica gel (10% ethyl acetate in hexane)

Quellen und Nachweise

ORD-Eintrag
ord-41c2e52386d34070bc71579f3bf85b93
Quelldatensatz
uspto-grants-2014_07
Patentnummer
US08791161B2

Notizen zur Reaktion

Wird geladen…