Hydrochloric Acid → 2-Iodo-4-(trifluoromethyl)benzaldehyde

温度

0 °C

A 1.0 M solution of diisobutylaluminum hydride in toluene (13 mL, 13 mmol) was added slowly drop-wise to a 0° C. solution of 2-iodo-4-trifluoromethyl-benzonitrile (3.58 g, 12 mmol) in toluene (11 mL). The reaction mixture was stirred at 0° C. for 30 minutes. The reaction mixture was warmed to room temperature, then stirred at room temperature for 24 hours. The reaction mixture was cooled to 0° C., then ethyl acetate (5 mL), and ethanol (5 mL) were added dropwise to the cold reaction mixture. After stirring at 0° C. for 10 minutes, the reaction mixture was concentrated to give a yellow, oily liquid. The residue was cooled to 0° C. Methylene chloride (10 mL) was added. Water (10 mL) was added slowly drop-wise, then 1.0 N aqueous HCl was added slowly drop-wise. After stirring at 0° C. for 10 minutes, concentrated HCl (1 mL) was added followed by additional methylene chloride (60 mL). The mixture was stirred at 0° C. for 10 minutes, then warmed to room temperature. Stirring at room temperature continued for 105 minutes. The mixture was poured into a separatory funnel, and the organic phase was separated, dried over Na2SO4, filtered, and concentrated to an oily, yellow solid. The crude product was purified using flash chromatography (RediSep® Flash column, 230-400 mesh, 0-3% ethyl acetate in hexanes) to give 1.44 g (40%) of 2-iodo-4-trifluoromethyl-benzaldehyde as a slightly yellow solid. 1H NMR (300 MHz, CDCl3) δ ppm 10.11 (s, 1 H), 8.20 (s, 1 H), 7.97 (d, J=8.2 Hz, 1 H), 7.73 (d, J=8.2 Hz, 1 H).

1. temperatureThe reaction mixture was warmed to room temperature
2. stirringstirred at room temperature for 24 hours
3. temperatureThe reaction mixture was cooled to 0° C.
4. stirringAfter stirring at 0° C. for 10 minutes
5. concentrationthe reaction mixture was concentrated
6. customto give a yellow, oily liquid
7. temperatureThe residue was cooled to 0° C
8. stirringAfter stirring at 0° C. for 10 minutes
9. stirringThe mixture was stirred at 0° C. for 10 minutes
10. temperaturewarmed to room temperature
11. stirringStirring at room temperature
12. waitcontinued for 105 minutes
13. additionThe mixture was poured into a separatory funnel
14. customthe organic phase was separated
15. dry with materialdried over Na2SO4
16. filtrationfiltered
17. concentrationconcentrated to an oily, yellow solid
18. customThe crude product was purified

ORDレコード

ord-5a053ab31a10427bad3cafe620295adb

出典データセット

uspto-grants-2012_02

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08124629B2