The synthesis of thionaphthen derivatives from styrenes and thionyl chloride / by George Barger and Arthur James Ewins.

  • Barger, George, 1878-1939
Date:
[1908?]
Catalogue details

Licence: Public Domain Mark

Credit: The synthesis of thionaphthen derivatives from styrenes and thionyl chloride / by George Barger and Arthur James Ewins. Source: Wellcome Collection.

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    could be obtained, nor was any obtainable from phenylmethylcarbinol, even after heating to 240° for twenty hours. The distillate in the latter case gave a brilliant red coloration with isatin and sulphuric acid, and, after distillation with zinc dust, the same reagents produced a green coloration. c5 Trichloro-5-methoxythionaphthen, MeO I 01 || ||C1. \/\/ci s By heating 1*5 grams of y>-methoxyphenylmethylcarbinol (from anisaldehyde) with 12 grams of thionyl chloride for three hours to 200°, and distilling under diminished pressure, a viscid liquid was obtained (b. p. 195—215°/12 mm.), which yielded a small quantity of a substance crystallising from light petroleum in white needles and melting at 153° : 0*0747 gave 01152 AgCl and 0*0649 BaS04. Cl = 38*2; S = 12*l. C0Hr>OCl3S requires Cl = 39'8; S = 12*0 per cent. Tetrachloro-5-methoxythionaphthen, MeO a i| ||C1. \/\/Cl s By heating 1-5 grams of y>-methoxyphenylmethylcarbinol with 12 grams of thionyl chloride to 180° for eight hours, and removal of the excess of thionyl chloride on the water-bath, 3 6 grams of a distillate were collected, b. p. 200—225°/12 mm. On dissolving in hot light petroleum (b. p. 70—100°) and cooling, 0'35 gram of silky, white needles, m. p. 109—1110, separated. The melting point was unchanged by recrystallisation : 01536 gave 0-2966 AgCl and 0*1265 BaS04. Cl = 47*7; S= 11*3. C9H40C14S requires 01 = 46*8 ; S= 10*6 per cent. As the analyses show, neither this nor the previous substance was obtained quite pure ; they are formed simultaneously, and the small quantities at our disposal did not enable us to effect a complete separation. In either case the methoxy-group must be in position 5 ; that of the chlorine atoms in the benzene ring is doubtful. Action of Thionyl Chloride on isoSafrole Dibromide. isoSafrole dibromide reacts less readily with thionyl chloride than its lower homologue (a/3-dibromomethylenedioxystyrene), but, neverthe¬ less, yielded a small quantity of a thionaphthen derivative. From ^sosafrole dichloride, however, this derivative could not be obtained ]