반응 #2176484

반응 방정식

potassium iodide

sulfuric acid

4-cyclopropyl-2-fluoroaniline

sodium nitrite

→

4-cyclopropyl-2-fluoro-1-iodobenzene

수율 71.3%

용매

DCM

water

water

water

반응 조건

후처리

1. 1
   기타constant at 0° C
2. 2
   기타This resulting reaction mixture
3. 3
   workup.STIRRINGthe reaction mixture was stirred at 60° C. for 3 h
4. 4
   기타The biphasic layers were separated
5. 5
   추출the aqueous layer was extracted with DCM (2×150 mL)
6. 6
   세척The combined organic layers were washed with saturated aqueous Na2S2O4, water, and brine
7. 7
   건조dried over Na2SO4
8. 8
   여과filtered
9. 9
   농축concentrated under reduced pressure
10. 10
    기타The crude residue was purified via flash column chromatography
11. 11
    세척eluted with 100% heptane

실험 절차

To a stirred mixture of 4-cyclopropyl-2-fluoroaniline (1.63 g, 10.78 mmol) in water (20 mL) at 0° C. was added concentrated sulfuric acid (8.6 mL, 15.0 eq.) dropwise, while keeping the temperature constant at 0° C. A solution of sodium nitrite (781.0 mg, 11.32 mmol, 1.05 eq.) in water (2.7 mL) was added and stirred for 5 minutes. This resulting reaction mixture was then added to a solution of potassium iodide (3.76 g, 22.64 mmol, 2.1 eq.) in water (9.7 mL), and the reaction mixture was stirred at 60° C. for 3 h. DCM (400 mL) was added to the cooled reaction. The biphasic layers were separated, and the aqueous layer was extracted with DCM (2×150 mL). The combined organic layers were washed with saturated aqueous Na2S2O4, water, and brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude residue was purified via flash column chromatography eluted with 100% heptane to give 2.01 g (71.28%) of 4-cyclopropyl-2-fluoro-1-iodobenzene as a clear oil. 1H NMR (400 MHz, CDCl3) δ 7.57 (dd, J=8.0, 6.9 Hz, 1H), 6.76 (dd, J=9.4, 1.9 Hz, 1H), 6.64 (dd, J=8.2, 1.9 Hz, 1H), 1.94-1.77 (m, 1H), 1.09-0.95 (m, 2H), 0.79-0.56 (m, 2H).

출처