1,3-Dichloro-5,5-dimethylhydantoin → 4-Amino-3-chloro-5-fluoro-6-propylpicolinaldehyde

HRID 508553

Reaktionsgleichung

Reaktionsgleichung von HRID 508553
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH2:10][CH3:11])[N:5]=[C:4]([CH:12]=[O:13])[CH:3]=1.[Cl:14]N1C(C)(C)C(=O)N(Cl)C1=O>>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH2:10][CH3:11])[N:5]=[C:4]([CH:12]=[O:13])[C:3]=1[Cl:14]

Komponenten

3

Edukt 2

HCID 83601,3-Dichloro-5,5-dimethylhydantoinHCID 867234014-Amino-5-fluoro-6-propylpicolinaldehyde

Produkt 1

HCID 867234004-Amino-3-chloro-5-fluoro-6-propylpicolinaldehydeAusbeute 59,3 %

Versuchsvorschrift

To a flask equipped with a stir bar and reflux condenser was added 4-amino-5-fluoro-6-propylpicolinaldehyde (0.250 g, 1.372 mmol) and 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione (0.149 g, 0.755 mmol). The flask was sealed, evacuated and backfilled with N2. Acetonitrile (13.72 mL) was added, and the reaction mixture was stirred at room temperature for ˜5 min, then heated to reflux (˜2 h). The reaction mixture color changed from yellow to orange then green over the course of 2 h. The reaction mixture was cooled to room temperature, diluted with EtOAc and washed with H2O. The layers were separated, and the organic layer was washed with dilute sodium bisulfite followed by saturated NaCl. The organic layer was dried (Na2SO4), filtered and concentrated onto silica. Purification via flash chromatography (silica; EtOAc, Hex) yielded 4-amino-3-chloro-5-fluoro-6-propylpicolinaldehyde (97 mg, 32.6%) as an off-white solid: mp 89-91° C.; 1H NMR (400 MHz, CDCl3) δ 10.09 (s, 1H), 4.81 (s, 2H), 2.81 (m, 2H), 1.76 (m, 2H), 0.99 (t, J=7.4 Hz, 3H); 19F NMR (376 MHz, CDCl3) δ −139.62; 13C NMR (101 MHz, CDCl3) δ 191.27, 152.80, 149.26, 146.64, 141.87, 139.82, 115.77, 37.04, 28.53.

Aufarbeitung

  1. customTo a flask equipped with a stir bar
  2. temperaturereflux condenser
  3. customThe flask was sealed
  4. customevacuated
  5. additionAcetonitrile (13.72 mL) was added
  6. temperatureheated
  7. temperatureto reflux (˜2 h)
  8. customgreen over the course of 2 h
  9. temperatureThe reaction mixture was cooled to room temperature
  10. additiondiluted with EtOAc
  11. washwashed with H2O
  12. customThe layers were separated
  13. washthe organic layer was washed with dilute sodium bisulfite
  14. dry with materialThe organic layer was dried (Na2SO4)
  15. filtrationfiltered
  16. concentrationconcentrated onto silica
  17. customPurification via flash chromatography (silica; EtOAc, Hex)

Quellen und Nachweise

ORD-Eintrag
ord-07cff94d198d4b1b9b96455e3152a400
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09096526B2

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