Reacción #430062

Ecuación de reacción

4,7-dichloroquinoline

iodine

triethylamine

fluorine

fluorine

→

2-fluoro-4,7-dichloroquinoline

Rendimiento 88.0%

Disolventes

—

CF2ClCFCl2

sodium metabisulfite

Condiciones de reacción

Tratamiento posterior

1. 1
   Otrofitted with a drying tube
2. 2
   Extracciónextracted with dichloromethane
3. 3
   OtroThe organic extracts were dried
4. 4
   Otroevaporated to a brown oil (1.06 g)

Procedimiento

A solution containing 4,7-dichloroquinoline (1.0 g, 5 mmol), iodine (1.28 g, 5 mmol) and triethylamine (0.51 g, 5.1 mmol) in CF2ClCFCl2 (30 ml) was placed in a fluorination apparatus fitted with a drying tube filled with soda lime. Elemental fluorine (7 mmol) as a 10% mixture in dry nitrogen was then passed through the stirred solution using narrow bore PTFE tubing at ca. 15 ml/min. After the fluorine had been added, the solution was poured into 10% aqueous sodium metabisulfite solution (30 ml) and extracted with dichloromethane. The organic extracts were dried and evaporated to a brown oil (1.06 g). GC/MS analysis showed a 69% conversion of starting material. Column chromatography on silica gel with dichloromethane as eluant gave 2-fluoro-4,7-dichloroquinoline (0.66 g, 88%) as white crystals; m.p. 105°-106° C. (vacuum sublimation oil bath temp. 60° C./<1 mmHg); RF 0.72; (Found: C, 49.7; H, 1.7;N, 6.3. C9H4CI2FN requires: C, 50.0; H, 1.85; N, 6.5%); δH (400 MHz; CDCI3 ; Me4Si) 7.20 ppm (1H, d, JH3,F 2.4,H-3),7.58 (1H, d d, JH5,H6, 9.0 JH6,H8 2.2, H-6), 7.95 (1H, d, JH6,H8 2.0, H-8), 8.13 (1H, d, JH5,H6 9.2, H-5); δF (235MHz; CDCI3 ; Me4Si)-60.0ppm (s); δC (100 MHz, CDCI3, Me4Si)110.38 (d, 2J 45.8, C-3), 123.6 (d,4J 2.3, C-4a), 125.5 (s, C-6), 127.6 (d, 5J 1.2, C-5), 128.1 (d, 4J 2.6, C-8), 137.9 (s, C-7), 146.4 (d, 3J 24.6, C-4), 146.6 (d, 3J 18.5, C-8a), 160.9 (d, 1J 244.1, C-2); m/z (E1+) 215 (M+, 100%), 217 (61, M+ +2), 219 (11, M30 +4), 182(14), 180 (40), 145 (18).

Fuente