The action of thionyl chloride on the methylene ethers of catechol derivatives. Pt. 2, Piperonyloin, piperil and hydropiperoin / by George Barger and Arthur James Ewins.

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

Licence: Public Domain Mark

Credit: The action of thionyl chloride on the methylene ethers of catechol derivatives. Pt. 2, Piperonyloin, piperil and hydropiperoin / by George Barger and Arthur James Ewins. Source: Wellcome Collection.

    7/12 (page 739)
    identical with that obtained by oxidation of veratroin by aramoniacal cupric oxide, already described by Fritsch (Annalen, 1903, 329, 37). The transformation of the substances referred to above may be represented as follows : h2c:o2:c6h3-cho h2c:o2:cgh3-c HC1 KCN i(oh)-co*c6h3:o2:ch0 ' if,o:o2:c0ii3-co-co<v,H3:o2:CH2 SOCl, 6*/ V cP\ oc:o2:c6H3-cci2*co-c6na:o2:co (CH3*0)2C6H3-CH0 * H’COoH oc:o2:cgh3-co*co-cgh3:o2:co v |h20 (CH3-0)2C6H3-CH(0H)-C0-C6H3(0-CH3)2 ->(HO)2C6H3-CO-CO-C6H3(OH).2 1 (UH3-O)2C0H3-CO-CO-CsH3(O-CH3)2 * (CH8)sS04 Action of Thionyl Chloride on Piperil. As might be expected, the same chloro-derivative is formed by thionyl chloride from piperil as from piperonyloin ; 0'47 gram piperil, heated to 180° with 2 c.c. of thionyl chloride for six hours, gave 0‘3 gram of a substance melting at 190°, and identical with 3:4:3': 4,-dicarbonyldioxy-aa-dichlorodeoxybenzoin obtained from piperonyloin. The mixture of both specimens melted at 191°. Action of Thionyl Chloride on Hydropiperoin and isoIlydropiperoin. By heating either of the above substances with thionyl chloride on the water-bath, the same substance is produced, namely, 3:4:3': 4'- dimethylenedioxy-a/3-dichloro-s-diphenylethane, ch2:o2:c6h3-chci-chci*c6h3:o2:ch2, already obtained by Fittig and Remsen (Annalen, 1871, 159, 144) by the action of acetyl chloride. At a much higher temperature, the methylene groups are also attacked. Five grams of-a crude mixture of hydropiperoin and its isomeride I were heated with 20 c.c. of thionyl chloride to 180° for five hours. The contents of the tube were cooled in a freezing mixture, and deposited crystals, which were rocrystallised from benzene. The yield was only 0’51 gram : 0T591 gave 0-2070 C02 and 0 0209 H20. C = 52-6; H = 2 2. 0*1506 „ 0*1195 AgCl. 01 = 19*6. C18H8OgC12 requires G1 = 52*3 ; IT = 2*2 ; Cl = 19*3 per cent.