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A 250-mL flask was fitted with reflux condenser, nitrogen inlet, magnetic stirrer bar, and thermometer. Distilled [(2-chloroethyl)thio]benzene (17.3 g, 100 mmol), NaOH (8.00 g, 0.200 mmol) dissolved in water (50 mL), phase-transfer catalyst methyltricaprylammonium chloride (as Adogen 464, Aldrich Chemical Co.; 1.00 g, 2.26 mmol), and benzene (50 mL) were charged to the flask under nitrogen purge. The mixture was heated in an oil bath kept at 80—82 °C. After 24 h at reflux a GC sample showed 85.0% of (ethenylthio)benzene, 5.0% of an unknown substance and 10.1% of unreacted [(2-chloroethyl)thio]benzene. After an additional 6 h, GC showed no [(2-chloroethyl)thio]benzene, the layers were separated, and the yellow organic layer was rinsed with 1M HCl (10 mL) followed by water (10 mL, twice), and dried (CaCl2). Benzene was removed at the water pump through a 10-in. Vigreux column, with a variable take off, total reflux head, operated at a 10/1 reflux ratio. The column was then removed and (ethenylthio)benzene distilled as a clear, colorless liquid, bp 84—87 °C/14 mm, 11.5 g (bath at 88—96 °C), n25D 1.5836. GC: 95.2% of (ethenylthio)benzene, 3.96% of an unknown substance, and 0.84% of [(2-chloroethyl)thio]benzene. An additional 0.50 g of less pure (ethenylthio)benzene, bp 82—86 °C/14 mm (bath 116 °C, no reflux) was also obtained, giving a total yield of 87.8%. IR bands were identical with those reported. The residue was a dark liquid (2.72 g). A sample of (ethenylthio)benzene, kept cold and dark in a refrigerator, became only slightly colored during storage for 6 years, IR was unchanged, and GC gave [(2-chloroethyl)thio]benzene, 0.48%, (ethenylthio)benzene, 92.99%, 1,2-bis(phenylthio)ethane, 0.67%, and diphenyl disulfide, 0.47%, with unknowns of 2.24% and 1.65%.
A solution of 40 g. (0.26 mole) of ethyl phenyl sulfoxide in 40 ml. of methylene chloride was added to a heated solution of 34 g. (0.28 mole) of thionyl chloride in 40 ml. of methylene chloride during 2.5 hours. The solvent was distilled off, first at atmospheric pressure and finally with the aid of an aspirator. Distillation of the residue gave 11 g. (31%) yield of phenyl vinyl sulfide, b.p. 72—75° (6 mm.).
A solution of 0.15 mole of ethyl phenyl sulfoxide in 40 ml. of methylene chloride was added to a heated solution of 34 g. (0.28 mole) of thionyl chloride in 40 ml. of methylene chloride during 2.5 hours. The solvent was distilled off, first at atmospheric pressure and finally with the aid of an aspirator. The residue was heated with 75 ml. of pyridine at the reflux point for 30 minutes, diluted with 300 ml. of water and steam distilled. Extraction of the distillate with ether, drying the ether extract over potassium carbonate and distillation gave 13.3 g. (65%) of phenyl vinyl sulfide, b.p. 77—78° (12 mm.). Oxidation of a sample with hydrogen peroxide in acetic acid gave a 60% yield of phenyl vinyl sulfone, m.p. and mixed m.p. with an authentic sample, 66—67°. Phenyl vinyl sulfide became colored yellow within 24 hours and after one week turned to a black syrup.
© Collected Ruslan Anatolievich Kiper, burewestnik@mail.ru