반응 #531837

반응 방정식

5-Bromo-2-chloropyridine

n-Butyllithium

formylpiperidine

→

2-chloro-5-formylpyridine

수율 63.5%

용매

diethyl ether

Diethyl ether

반응 조건

후처리

1. 1
   온도After the reaction vessel had been cooled to −70° C.
2. 2
   workup.WAITthe stirring was continued for another 60 minutes while the mixture
3. 3
   기타to return to room temperature
4. 4
   기타The resulting reaction mixture
5. 5
   workup.ADDITIONmixed with it
6. 6
   기타to separate organic
7. 7
   추출aqueous phases, and extraction
8. 8
   세척The combined organic phase was washed with water
9. 9
   건조dried over anhydrous magnesium sulfate
10. 10
    농축The resulting solution was concentrated under reduced pressure
11. 11
    기타the residue was purified with a fractional operation by means of column chromatography (silica gel; toluene)
12. 12
    기타The product was further purified by recrystallization from heptane
13. 13
    workup.DISTILLATIONThe solvent was distilled off
14. 14
    기타the product was dried

실험 절차

5-Bromo-2-chloropyridine (T-9) (15.0 g) and diethyl ether (450 ml) were put in a reaction vessel and cooled to −50° C. under an atmosphere of nitrogen. n-Butyllithium (1.57 M in n-hexane; 54.6 ml) was added dropwise in the temperature range of −50° C. to −45° C., and the stirring was continued for another 90 minutes. After the reaction vessel had been cooled to −70° C., formylpiperidine (9.70 g) was added dropwise in the temperature range of −70° C. to −65° C., and the stirring was continued for another 60 minutes while the mixture was allowed to return to room temperature. The resulting reaction mixture was poured into ice-water (500 ml) and mixed with it. Diethyl ether (200 ml) was added to the solution to separate organic and aqueous phases, and extraction was carried out. The combined organic phase was washed with water and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure and the residue was purified with a fractional operation by means of column chromatography (silica gel; toluene). The product was further purified by recrystallization from heptane. The solvent was distilled off and the product was dried, giving 2-chloro-5-formylpyridine (T-10) (7.01 g). The yield based on the compound (T-9) was 68%.

출처