Phenyl Vinyl Sulfide → Dimethyl 3-(phenylthio)cyclobutane-1,2-dicarboxylate

To a solution of 1.06 g (7.34 mmol) of dimethyl fumarate in 20 mL of dry 1,2-dichloroethane under nitrogen atmosphere, was added with stirring, 7.34 mmol of a 1.0 M solution of ethylaluminum dichloride in hexane. The resultant yellow solution was heated to reflux and a solution of 1.0 g (7.34 mmol) of phenyl vinyl sulfide in 4 mL of dry 1,2-dichloroethane was added dropwise, via syringe, over a period of 20 minutes. The reaction mixture was allowed to stir at reflux for 3 h. After cooling to ambient temperature, the reaction was quenched carefully with 100 mL of 1.0 N hydrochloric acid solution and the reaction mixture was extracted with 3×50 mL of ethyl acetate. The organic extract was washed with 2×50 mL of water and 50 mL of brine, dried over anhydrous magnesium sulfate, filtered and concentrated to a viscous orange oil. The oil (1.56 g) was chromatographed on silica gel (25 g) eluted with 300 mL of 3% ethyl acetate in 1,2-dichloroethane. The resultant yellow oil was purified by bulb-to-bulb distillation to give the title compound as a yellow oil; b.p 120° C. (0.05 mm Hg); EI-MS, m/e (relative intensity): 280 (M+, 18), 136 (100), 91 (13); 1H NMR (CDCl3) δ2.20 (q, 1H), 2.61 (m, 1H), 3.22 (q, 1H), 3.34 (t, 1H), 3.66 (s, 3H), 3.67 (s, 3H), 3.87 (m, 1H), 7.30 (m, 5H).

1. temperatureThe resultant yellow solution was heated
2. temperatureto reflux
3. stirringto stir
4. temperatureat reflux for 3 h
5. customthe reaction was quenched carefully with 100 mL of 1.0 N hydrochloric acid solution
6. extractionthe reaction mixture was extracted with 3×50 mL of ethyl acetate
7. extractionThe organic extract
8. washwas washed with 2×50 mL of water and 50 mL of brine
9. dry with materialdried over anhydrous magnesium sulfate
10. filtrationfiltered
11. concentrationconcentrated to a viscous orange oil
12. customThe oil (1.56 g) was chromatographed on silica gel (25 g)
13. washeluted with 300 mL of 3% ethyl acetate in 1,2-dichloroethane
14. distillationThe resultant yellow oil was purified by bulb-to-bulb distillation

ORD record

ord-219ddea43bb2403b9dc232f4a67c5dcb

Source dataset

uspto-grants-1993_09

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05246931