Tetrahydrofuran → 1,1-Dimethylethyl N-(2-formyl-4-(trifluoromethoxy)phenyl)carbamate

온도

-78 °C

A magnetically stirred solution of tert-butyl 4-(trifluoromethoxy)phenylcarbamate (19.95 g, 72 mmol) and TMEDA (16.7 g, 144 mmol) in THF (300 mL) at −78° C. was treated with the dropwise addition of a 1.4M solution of sec-butyllithium in cyclohexane (170 mL, 237 mmol), at a rate which maintained the internal temperature below −60° C. The mixture was stirred for 1 h at −78° C., then allowed to warm to −50° C. and stirred an additional 30 min. The solution was returned to −78° C., treated with the dropwise addition of N,N-dimethylformamide, at a rate which maintained the internal temperature below −60° C. The reaction was stirred at −78° C. for 30 min, allowed to warm to −20° C., then quenched with the addition of saturated ammonium chloride solution (200 mL). The mixture was transferred to a 1 L seperatory funnel, diluted with diethyl ether (400 mL), and the layers were separated. The organic phase was washed successively with saturated ammonium chloride solution (100 mL), water (100 mL), and brine (100 mL), dried over sodium sulfate, and concentrated in-vacuo to a yellow solid. The solid was purified over silica gel, eluting with 5% ethyl acetate/hexanes, to yield 18.36 g of a colorless solid as product. 1H NMR (400 MHz, CDCl3) δ ppm 1.55 (m, 9 H) 7.26 (s, 4 H) 7.43 (dd, J=9.23, 2.64 Hz, 6 H) 7.48 (s, 1 H) 8.54 (d, J=9.23 Hz, 1 H) 9.88 (s, 1 H) 10.33 (s, 1 H).

1. temperaturemaintained the internal temperature below −60° C
2. temperatureto warm to −50° C.
3. stirringstirred an additional 30 min
4. customwas returned to −78° C.
5. temperaturemaintained the internal temperature below −60° C
6. stirringThe reaction was stirred at −78° C. for 30 min
7. temperatureto warm to −20° C.
8. customquenched with the addition of saturated ammonium chloride solution (200 mL)
9. customThe mixture was transferred to a 1 L seperatory funnel
10. additiondiluted with diethyl ether (400 mL)
11. customthe layers were separated
12. washThe organic phase was washed successively with saturated ammonium chloride solution (100 mL), water (100 mL), and brine (100 mL)
13. dry with materialdried over sodium sulfate
14. concentrationconcentrated in-vacuo to a yellow solid
15. customThe solid was purified over silica gel
16. washeluting with 5% ethyl acetate/hexanes

ORD 기록

ord-f192e989e3d84e9486afead813b582ad

출처 데이터셋

uspto-grants-2007_11

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US07291615B2