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.

    4/12 (page 2087)
    Experimental. 1 : 2-Dichloro-i : 5(or 5 : 6)-carbonyldioxy thionaphthen, or 2*2 Grams of 3 : 4-methylenedioxyphen}4methylcarbiriol were heated with 13 grams of thionyl chloride for five hours in a sealed tube at 170°. On opening the tube there was found to be a great pressure ; the contents were a reddish-brown liquid and a crystalline solid (the thionaphthen). The latter was collected and recrystallised from benzene ; the yield was 45 per cent, of the theoretical. One gram of a/3-dibromo-3 : 4-methylenedioxystyrene, heated with 5 grams of thionyl chloride to 250—260° for seven hours, yielded 0*6 gram of the same substance or 70 per cent, of the theoretical. After repeated crystallisation from benzene, the substance from either source formed white prisms melting at 198° : 0-1668 gave 0*2514 C02 and 0 0124 II20. C-4M ;H = 0*8. 0-1151 „ 0-1251 AgCl. 01 = 26-9. 0-2472 „ 0-2150 BaS04. S=li*9. 0*3798, in 11-74 naphthalene, gave A= -0*87°. M. SV. = 257. C0H3O8C]2S requires 0 = 41-4; H = 0’8; 01=27*2; S=122 percent. M.W. = 261. In addition to the secondary alcohol and the dibromo-derivative already mentioned, the following substances also yielded this thio¬ naphthen derivative on heating with thionyl chloride: the ether, [CH2:02:06H3-CHMe]20; the dichloride, 0H2:02:C6H3*CHC1*CH201, and the corresponding chloro- and bromo-hydrins. Since the side- chain in all these cases is readily chlorinated, the chlorine atoms in the resulting thionaphthen derivative are in all probability iu positions 1 and 2. The para-hydroxyl group must be in position 5, and the meta-hydroxyl in either 4 or 6 ; that the substance is a cyclic carbonate is proved below. 1 : 2-Dichloro-i : 5(or 5 ; 6)-dihydroxy thionaphthen, ho/\—nCi A,'—ncl HOl^l^Cl or HCh^y^CT S HO S The previously-described substance, C9H203C12S, was hydrolysed by gently warming it in an atmosphere of hydrogen with 50 per cent, aqueous pyridine ; carbon dioxide was evolved. The yellow solution co< o/\