Acetic Acid → HCID 59838016, compound

Temperature

130 °C

A mixture of 1-fluoro-3-iodo-5-nitrobenzene (1.145 g, 4.29 mmol), sodium acetate (0.430 g, 5.24 mmol), palladium(II) acetate (1.7 mg, 0.0076 mmol), methyl acrylate (0.425 mL, 4.71 mmol), and 1-methyl-2-pyrrolidinone (11 mL) under argon was degassed with three freeze/pump/thaw cycles. The reaction mixture was heated to 130° C. for 35 min and then at 100° C. for 14 h. The reaction mixture was diluted with water and saturated sodium bicarbonate solution and extracted three times with diethyl ether. The combined organic extracts were washed with saturated sodium bicarbonate solution, hydrochloric acid (1 N), and brine, dried (MgSO4), and concentrated under reduced pressure. The residue was suspended in a mixture of ethanol (12 mL), water (2.5 mL), and acetic acid (1.25 mmol) and heated to reflux. Iron powder (0.519 g, 9.28 mmol) was added portionwise over 30 min, and reflux was continued for an additional 30 min. The reaction mixture was concentrated under reduced pressure. The residue was partitioned between ethyl acetate and sodium bicarbonate solution and filtered through a glass fibre filter to remove a fine grey precipitate. The aqueous phase was extracted with ethyl acetate (3×) and the organic phase was dried (MgSO4) and concentrated under reduced pressure to give 19A (0.328 g, 74%) as a pale yellow solid. LC-MS m/z: 196.2 (M+H)+.

1. customwas degassed with three freeze/pump/thaw cycles
2. additionThe reaction mixture was diluted with water and saturated sodium bicarbonate solution
3. extractionextracted three times with diethyl ether
4. washThe combined organic extracts were washed with saturated sodium bicarbonate solution, hydrochloric acid (1 N), and brine
5. dry with materialdried (MgSO4)
6. concentrationconcentrated under reduced pressure
7. temperatureheated to reflux
8. temperaturereflux
9. waitwas continued for an additional 30 min
10. concentrationThe reaction mixture was concentrated under reduced pressure
11. customThe residue was partitioned between ethyl acetate and sodium bicarbonate solution
12. filtrationfiltered through a glass fibre
13. filtrationfilter
14. customto remove a fine grey precipitate
15. extractionThe aqueous phase was extracted with ethyl acetate (3×)
16. dry with materialthe organic phase was dried (MgSO4)
17. concentrationconcentrated under reduced pressure

ORD record

ord-f6321d1dd3c442b491a5cc49a15eeec6

Source dataset

uspto-grants-2009_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07592331B2