Vinylidene chloride → 3,3-Dichloro-1-(2,6-dichloro-5-fluoro-3-pyridinyl)-2-propen-1-one

Temperature

0 °C

A solution of the 2,6-dichloro-5-fluoronicotinoyl chloride from the previous reaction in CH2Cl2 (25 mL) was added slowly to a cooled (0° C.) and stirred slurry solution of AlCl3 (7.9 g, 59.5 mmol) in CH2Cl2 (25 mL). After 15 min, vinylidene chloride (4.75 mL, 59.5 mmol) was added to the mixture dropwise. The reaction was allowed to warm to room temperature and was stirred overnight. The mixture was poured over ice and partitioned with CH2Cl2. The organic layer was collected and cooled to 0° C. before TEA (8.3 mL, 59.5 mmol) was added. After 15 min, the ice bath was removed and the reaction was allowed to warm to room temperature and stirred for an additional 30 min. The solution was washed with 1N HCl, NaHCO3, and water. The organic layer was passed through a pad of silica gel and concentrated in vacuo to afford 3,3-dichloro-1-(2,6-dichloro-5-fluoro-3-pyridinyl)-2-propen-1-one: (6.1 g, 90%) as a brown oil: 1H-NMR (d6-DMSO, 300 MHz)δ8.43 (d, 1H, J=8.4 Hz), 7.56 (s, 1H), Rf=0.76 (3:1 Hex:EtOAc).

1. additionwas added slowly to
2. temperatureto warm to room temperature
3. additionThe mixture was poured over ice
4. custompartitioned with CH2Cl2
5. customThe organic layer was collected
6. additionwas added
7. waitAfter 15 min
8. customthe ice bath was removed
9. temperatureto warm to room temperature
10. stirringstirred for an additional 30 min
11. washThe solution was washed with 1N HCl, NaHCO3, and water
12. concentrationconcentrated in vacuo

ORD record

ord-0890fdd35ba24de789d458a82f3c84fa

Source dataset

uspto-grants-2005_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06964971B2