Nitrogen → HCID 54681487, compound

A solution of methyl-[4-(1-oxoethyl)phenoxy]-acetate (2.50 g, 10.86 mmol) in CH2Cl2 (25.0 mL) was cooled to 0° C. (N2 atmosphere) and treated with triethylamine (3.03 mL, 21.7 mmol) followed by trimethylsilyltriflate (2.52 mL, 13.0 mmol). The solution was then warmed to ambient temperature, allowed to stir for 15 min., and subsequently quenched into a mixture of diethyl ether (50 mL) and saturated aqueous NaHCO3 (20 mL). The layers were separated and the organic layer washed with a 1:1 mixture of brine: saturated NaHCO3 (20 mL). The ethereal solution was then dried with Na2SO4 and the solvent removed in vacuo. The resulting silyl enol ether was then transferred to a flask containing diethyl 2-(thiophenyl)propane-1,3-dioate (0.97 g, 3.6 mmol). The mixture was then heated to 140° C. for 16 h. and allowed to cool to room temperature where it was submitted to chromatography (SiO2 --230 to 400 mesh, 100% CH2Cl2 to 2.0% MeOH/CH2Cl2) to provide an impure solid which was diluted with diethyl ether (20 mL) and extracted with saturated Na2CO3 (3×20 mL). The combined aqueous extracts were washed with diethyl ether (3×100 mL) and then acidifed with conc. HCl to pH 0. The mixture was then extracted with ethyl acetate (3×100 mL), the organic layers combined, dried with Na2SO4 and the solvent removed in vacuo. to provide the title compound (0.695 g, m.p. 186°-188° C.). 1H NMR (300 MHz, DMSO-d6) δ 13.175 (bs, 1 H), 12.425 (bs, 1 H), 7.809 (d, 2 H, J=9 Hz), 7.298-7.247 (m, 2 H), 7.149-7.004 (m, 5 H), 6.785 (s, 1 H), 4.804 (s, 2 H).

1. customsubsequently quenched into a mixture of diethyl ether (50 mL) and saturated aqueous NaHCO3 (20 mL)
2. customThe layers were separated
3. washthe organic layer washed with a 1:1 mixture of brine
4. dry with materialThe ethereal solution was then dried with Na2SO4
5. customthe solvent removed in vacuo
6. customThe resulting silyl enol ether was then transferred to a flask
7. temperatureThe mixture was then heated to 140° C. for 16 h.
8. temperatureto cool to room temperature where it
9. customto provide an impure solid which
10. extractionextracted with saturated Na2CO3 (3×20 mL)
11. washThe combined aqueous extracts were washed with diethyl ether (3×100 mL)
12. extractionThe mixture was then extracted with ethyl acetate (3×100 mL)
13. dry with materialdried with Na2SO4
14. customthe solvent removed in vacuo

ORD record

ord-e990b10573e34973a4e9e47907de7deb

Source dataset

uspto-grants-1998_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05808062