Hydrochloric Acid → tert-Butyl {3-[(3-aminobenzyl)thio]phenyl}carbamate

Temperature

60 °C

A mixture of iron (0.62 g, 11 mmol) in ethanol (22 mL) was treated with 1 M HCl in water (1.1 mL) and heated at 60° C. for 2 h. The reaction mixture was cooled to 55-60° C. and treated with 5 M ammonium chloride in water (1.9 mL). The reaction mixture was then treated with a solution of tert-butyl {3-[(3-nitrobenzyl)thio]phenyl}carbamate (0.80 g, 2.2 mmol) in ethanol (2.5 mL) while the temperature was kept at 60° C. The resulting suspension was stirred at 60-65° C. for 30 min. The reaction mixture was cooled to 40° C., diluted with ethanol, treated with celite, filtered over a pad of celite, and washed with ethanol. The filtrate was concentrated to a tan solid that was diluted with ethyl acetate (50 mL) and saturated sodium bicarbonate (50 mL). The organic layer was separated and washed with brine (25 mL), dried over anhydrous sodium sulfate, filtered, and evaporated to give a crude tan oil. This material was purified by flash column chromatography to give the desired product (0.63 g, 85%). LCMS for C18H23N2O2S (M+H)+: m/z=331.1.

1. temperatureThe reaction mixture was cooled to 55-60° C.
2. customwas kept at 60° C
3. temperatureThe reaction mixture was cooled to 40° C.
4. additiontreated with celite
5. filtrationfiltered over a pad of celite
6. washwashed with ethanol
7. concentrationThe filtrate was concentrated to a tan solid
8. additionthat was diluted with ethyl acetate (50 mL) and saturated sodium bicarbonate (50 mL)
9. customThe organic layer was separated
10. washwashed with brine (25 mL)
11. dry with materialdried over anhydrous sodium sulfate
12. filtrationfiltered
13. customevaporated
14. customto give a crude tan oil
15. customThis material was purified by flash column chromatography

ORD record

ord-c3d57fe86e4b4044b12f56bd8d54d406

Source dataset

uspto-grants-2014_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08871753B2