반응 #88148

반응 방정식

1-bromo-4-(perfluoroethoxy)benzene

THF

Ethyl chloroformate

→

ethyl 4-(perfluoroethoxy)benzoate

수율 50.2%

용매

EtOAc

반응 조건

후처리

1. 1
   기타To an oven-dried 500-mL round bottom flask equipped with a stirring bar
2. 2
   온도cooled in an ice bath for 10 min
3. 3
   workup.ADDITIONA solution of 1.3 M isopropylmagnesium chloride-lithium chloride complex (30 mL, 38.6 mmol) was added over 15 min
4. 4
   기타The ice bath was removed after 1 hour
5. 5
   온도The reaction was cooled in an ice bath
6. 6
   workup.ADDITION1.3 M isopropylmagnesium chloride-lithium chloride complex (5 mL) was added
7. 7
   기타The ice bath was removed after 20 min
8. 8
   workup.STIRRINGstirred at room temperature for 9 hours
9. 9
   온도The reaction was warmed slightly during the addition
10. 10
    workup.STIRRINGwas stirred at room temperature overnight
11. 11
    세척washed with saturated aqueous ammonium chloride
12. 12
    추출The aqueous layer was extracted three times with EtOAc
13. 13
    건조The organic layers were dried over anhydrous sodium sulfate
14. 14
    여과filtered
15. 15
    농축concentrated
16. 16
    기타to give a yellow liquid, which
17. 17
    기타was purified by flash chromatography (0-0, 0-4, 4-10% EtOAc/hexanes)

실험 절차

To an oven-dried 500-mL round bottom flask equipped with a stirring bar was added 1-bromo-4-(perfluoroethoxy)benzene (9.35 g, 32.1 mmol) and anhydrous THF (200 mL). The flask was placed under nitrogen and cooled in an ice bath for 10 min. A solution of 1.3 M isopropylmagnesium chloride-lithium chloride complex (30 mL, 38.6 mmol) was added over 15 min. The ice bath was removed after 1 hour, and the reaction was warmed to room temperature and stirred overnight. GC/MS showed the presence of starting material. The reaction was cooled in an ice bath and 1.3 M isopropylmagnesium chloride-lithium chloride complex (5 mL) was added. The ice bath was removed after 20 min and stirred at room temperature for 9 hours. Ethyl chloroformate (3.4 mL, 35.3 mmol) was added in a slow, steady stream. The reaction was warmed slightly during the addition and was stirred at room temperature overnight. The reaction was diluted with EtOAc and washed with saturated aqueous ammonium chloride. The aqueous layer was extracted three times with EtOAc. The organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated to give a yellow liquid, which was purified by flash chromatography (0-0, 0-4, 4-10% EtOAc/hexanes) to provide ethyl 4-(perfluoroethoxy)benzoate as a yellow liquid (4.58 g, 50%): 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J=8.8 Hz, 2H), 7.28 (d, J=8.7 Hz, 2H), 4.39 (q, J=7.1 Hz, 2H), 1.40 (t, J=7.1 Hz, 3H); 19F NMR (376 MHz, CDCl3) δ −86.05, −87.84; ESIMS m/z 284 ([M+11]+).

출처