4-Fluoroiodobenzene → HCID 178476783, compound

To a degassed mixture of 4-fluoro-1-iodo-benzene (25.0 g, 112.6 mmol), anilinium hypophosphite (21.5 g, 135.1 mmol) and 3-aminopropyl triethoxysilane (24.9 g, 135.1 mmol) in anhydrous acetonitrile (750 mL) were added palladium acetate (560 mg, 2.48 mmol) and 1,3-bis(diphenylphosphino)propane (1.02 g, 2.48 mmol). The mixture was refluxed overnight. After cooling down to room temperature, the reaction mixture was concentrated in vacuo. The residue was diluted with ethyl acetate and hydrochloric acid (1M) and partitioned. The aqueous layer was further extracted with ethyl acetate and the combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine. The volatiles were removed in vacuo, and then the residue was purified by column chromatography using 50 to 100% ethyl acetate in petroleum ether, affording compound AZ2 (10.1 g) as a dark orange oil in 48% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.84 (t, J=7.1 Hz, 3H), 4.08-4.24 (m, 2H), 7.20 (td, J=8.7 and 2.5 Hz, 2H), 7.58 (d, J=566.6 Hz, 1H), 7.74-7.85 (m, 2H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 23.62 (J=566.8 Hz).

1. temperatureThe mixture was refluxed overnight
2. concentrationthe reaction mixture was concentrated in vacuo
3. additionThe residue was diluted with ethyl acetate and hydrochloric acid (1M)
4. custompartitioned
5. extractionThe aqueous layer was further extracted with ethyl acetate
6. washthe combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
7. customThe volatiles were removed in vacuo
8. customthe residue was purified by column chromatography
9. customaffording compound AZ2 (10.1 g) as a dark orange oil in 48% yield

ORD record

ord-6ae82ebfa1114e719dc329a8d8869490

Source dataset

uspto-grants-2013_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08481748B2