반응 #86459

반응 방정식

2-chloro-6-fluoro-3,5-dimethoxybenzoic acid

triethyl amine

TFA

Diphenyl phosphoryl azide

→

title compound

수율 60.0%

2-chloro-6-fluoro-3,5-dimethoxyaniline

수율 60.0%

용매

tert-BuOH

dichloromethane

반응 조건

후처리

1. 1
   workup.ADDITIONwas added
2. 2
   workup.WAITkept at this temperature for overnight
3. 3
   농축The reaction mixture was then concentrated in vacuo
4. 4
   기타to obtain a crude residue
5. 5
   온도cooled to 0° C
6. 6
   기타the resultant reaction mixture
7. 7
   workup.STIRRINGwas then stirred at room temperature for 2 h
8. 8
   기타The solvents were removed under vacuum
9. 9
   workup.ADDITIONthe crude residue was diluted with ethyl acetate and saturated sodium carbonate solution
10. 10
    기타The aqueous layer was separated
11. 11
    추출extracted with ethyl acetate (3×30 mL)
12. 12
    세척The organic phase was washed with brine
13. 13
    건조dried over Na2SO4
14. 14
    여과filtered
15. 15
    농축concentrated
16. 16
    기타The residue was purified by silica gel column chromatography

실험 절차

A suspension of 2-chloro-6-fluoro-3,5-dimethoxybenzoic acid (10.8 g, 0.0077 mol) and triethyl amine (0.934 g, 0.0092 mol) in tert-BuOH (50 mL) was stirred for 5 min. To the resulting reaction mixture, Diphenyl phosphoryl azide (2.53 g, 0.0092 mol) was added and heated up to 82° C. and kept at this temperature for overnight. The reaction mixture was then concentrated in vacuo to obtain a crude residue. The crude residue was dissolved in dichloromethane (20 mL) and cooled to 0° C. TFA (4 mL) was added to the reaction mixture and the resultant reaction mixture was then stirred at room temperature for 2 h. The solvents were removed under vacuum and the crude residue was diluted with ethyl acetate and saturated sodium carbonate solution. The aqueous layer was separated and extracted with ethyl acetate (3×30 mL). The organic phase was washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by silica gel column chromatography using the eluent (gradient hexane to hexane-ether (65:35)) to afford the title compound (0.95 g, yield: 60%) as solid. MS (ESI): 205.7 [M+H]+.

출처