Cesium carbonate → HCID 117974517, compound

Temperature

70 °C

To a mixture of Cs2CO3 (29.5 g, 91 mmol) in DMF (150 mL) at 0° C. was added 2-ethoxyacetic acid (18.0 mL, 191 mmol), and the resulting mixture was heated at 70° C. for 30 min. The reaction was cooled to 0° C., chloromethyl phenylsulfide (10.56 mL, 79 mmol) was added, and the reaction was heated at 70° C. for 90 min. The mixture was cooled to room temperature, and then 0° C., before diluting with H2O (200 mL; an exotherm was observed). The reaction mixture was divided into two equal portions and one portion was further diluted with water (400 mL) and extracted with Et2O (200 mL×2, 100 mL×1). The combined organic extracts were diluted with hexane (100 mL) and washed successively with 1.0 M aqueous NaOH (100 mL) and brine (2×200 mL), dried over anhydrous MgSO4, filtered, and concentrated. The second portion of the reaction mixture from above was processed in an identical fashion and the two lots were combined and concentrated in vacuo to afford the title compound as a yellow oil (12.28 g, 97%): 1H NMR (400 MHz, CDCl3) δ 7.48-7.41 (m, 2H), 7.31 (ddd, J=12.6, 7.9, 6.3 Hz, 3H), 5.51 (s, 2H), 4.11 (s, 2H), 3.59 (q, J=7.0 Hz, 2H), 1.24 (t, J=7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 170.00, 134.35, 130.53, 129.16, 127.55, 68.46, 68.10, 67.32, 14.99; ESIMS: m/z 226 ([M]+).

1. temperatureThe reaction was cooled to 0° C.
2. temperaturethe reaction was heated at 70° C. for 90 min
3. temperatureThe mixture was cooled to room temperature
4. extractionextracted with Et2O (200 mL×2, 100 mL×1)
5. additionThe combined organic extracts were diluted with hexane (100 mL)
6. washwashed successively with 1.0 M aqueous NaOH (100 mL) and brine (2×200 mL)
7. dry with materialdried over anhydrous MgSO4
8. filtrationfiltered
9. concentrationconcentrated
10. concentrationconcentrated in vacuo

ORD record

ord-4b641e1147da403282eaf0f44875cabc

Source dataset

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09265253B2