Dimethylformamide → Tert-butyl 4-formyl-2-methylbenzoate

A solution of 4-bromo-2-methyl-benzoic acid tert-butyl ester (Example I16) (75 g) in dry tetrahydrofuran (750 ml) was cooled to −100° C. A solution of n-butyl lithium (1.6 M in hexane) (163 ml) was added dropwise at −100° C. The reaction mixture was stirred at −95° C. for 20 minutes. N,N-Dimethylformamide (43 ml) was added dropwise. The reaction mixture was stirred at −95° C. for 45 minutes. The reaction was quenched by addition of aqueous ammonium chloride (saturated) (8 ml) at −90° C. The mixture was stirred for 10 minutes at −90° C., warmed to 0° and poured on a mixture of ice and water. The mixture was allowed to warm to ambient temperature and then extracted twice with ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate, and concentrated to give 4-formyl-2-methyl-benzoic acid tert-butyl ester (60.3 g) as yellow oil. 1H-NMR (CDCl3, 400 MHz): 10.03 (s, 1H), 7.93 (d, 1H), 7.75 (m, 2H), 2.65 (s, 3H), 1.65 (s, 9H).

1. customwas cooled to −100° C
2. stirringThe reaction mixture was stirred at −95° C. for 45 minutes
3. customThe reaction was quenched by addition of aqueous ammonium chloride (saturated) (8 ml) at −90° C
4. stirringThe mixture was stirred for 10 minutes at −90° C.
5. temperaturewarmed to 0°
6. additionpoured on a mixture of ice and water
7. temperatureto warm to ambient temperature
8. extractionextracted twice with ethyl acetate
9. washThe combined organic phases were washed with water
10. dry with materialdried over sodium sulfate
11. concentrationconcentrated

ORD-Eintrag

ord-02508503fcb34245800548cddde74605

Quelldatensatz

uspto-grants-2014_01

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US08623896B2