反应详情

To a solution of 2-TMS-thiazole (2.25 mL, 14.1 mmol) in DCM (5 mL) at 0° C. was slowly added a solution of phosgene in toluene (20%, 7.45 mL, 14.1 mmol) over 15 Min. After stirring for 2 h at RT, the resulting solution was slowly added via syringe to a solution of N—BOC-1,4-phenylenediamine (4.42 g, 21.2 mmol) and pyridine (2.3 mL, 28.2 mmol) in DCM (100 mL) at 0° C. After stirring for 20 h at RT, the reaction mixture was quenched by addition of sat. NaHCO3 (100 mL), EtOAc (150 mL) was added, and the phases were separated. The aqueous phase was extracted with EtOAc (2×75 mL), and the combined organic extracts were dried over MgSO4 and concentrated in vacuo. Purification by column chromatography (10-50% EtOAc in hexanes) afforded the product as an orange solid (452 mg, 10%). 1H-NMR (400 MHz, DMSO-d6) δ 10.66 (s, 1H), 9.34 (s, 1H), 8.12 (d, J=3.1 Hz, 1H), 8.09 (d, J=3.1 Hz, 1H), 7.72 (d, J=7.0 Hz, 2H), 7.42 (d, J=8.9 Hz, 2H), 1.48 (s, 9H). LC/MS (10-99%) M/Z: M+1 obs=320.3; tR=2.90 min.

1. stirringAfter stirring for 20 h at RT
2. customthe reaction mixture was quenched by addition of sat. NaHCO3 (100 mL), EtOAc (150 mL)
3. additionwas added
4. customthe phases were separated
5. extractionThe aqueous phase was extracted with EtOAc (2×75 mL)
6. dry with materialthe combined organic extracts were dried over MgSO4
7. concentrationconcentrated in vacuo
8. customPurification by column chromatography (10-50% EtOAc in hexanes)