4-Bromobenzoic acid → HCID 89543238, compound

Temperature

-78 °C

n-BuLi (13.59 mL of 2.5 M, 33.97 mmol) was added dropwise to a solution of 4-bromobenzoic acid (3.41 g, 16.98 mmol) in tetrahydrofuran (31 mL) held at −78° C. The resulting mixture was stirred for 0.5 hours at −78° C. and 2-[(S)-tert-butylsulfanylsulfinyl]-2-methyl-propane (3.00 g, 15.4 mmol) in tetrahydrofuran (31 mL) was added slowly to the mixture. The mixture was allowed to stir for 0.5 hours at −78° C., before the reaction was allowed to warm up to room temperature. The reaction was quenched with water (50 mL) and the mixture was washed with ethyl acetate (3×30 mL). The aqueous layer was acidified with hydrochloric acid and the aqueous layer was extracted with ethyl acetate (3×50 mL). The combined organic layers were dried over sodium sulfate, filtered and the solvent was evaporated under reduced pressure. The residue was dissolved in dichloromethane, filtered and the filtrate was purified by silica gel chromatography utilizing a gradient of 0-100% ethyl acetate in hexane to yield to yield (S)-4-(tert-Butylsulfinyl)benzoic acid (770 mg, 22%) as a white solid. 1H NMR (400 MHz, DMSO) δ 13.30 (s, 1H), 8.10 (d, J=8.4 Hz, 2H), 7.72 (d, J=8.4 Hz, 2H), 1.09 (s, 9H). ESI-MS m/z calc. 226.1, found 227.3 (M+1)+; Retention time: 1.07 minutes (3 min run).

1. customheld at −78° C
2. stirringto stir for 0.5 hours at −78° C., before the reaction
3. temperatureto warm up to room temperature
4. customThe reaction was quenched with water (50 mL)
5. washthe mixture was washed with ethyl acetate (3×30 mL)
6. extractionthe aqueous layer was extracted with ethyl acetate (3×50 mL)
7. dry with materialThe combined organic layers were dried over sodium sulfate
8. filtrationfiltered
9. customthe solvent was evaporated under reduced pressure
10. dissolutionThe residue was dissolved in dichloromethane
11. filtrationfiltered
12. customthe filtrate was purified by silica gel chromatography
13. customto yield

ORD record

ord-9b45487816894728adb9e2330d05d64f

Source dataset

uspto-grants-2016_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09365588B2