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

  • George Barger
Date:
[1908]
Catalogue details

Licence: Attribution 4.0 International (CC BY 4.0)

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

Provider: This material has been provided by The Royal College of Surgeons of England. The original may be consulted at The Royal College of Surgeons of England.

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    identical with that obtained by oxidation of veratroin by ammoniaeal 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:c0h3-cho |kcn _h2c:o2:cch8-ch(oh)<;o-c0h8:o2:ch2 -> ii2c:o“:c(iH3-co-co-o6H3:o2:cH2 HCl SOC]2 A*/ y ^ y oc:o2:caH8-cci2-co-cflH8:o2:co (oh3-o)2c6h3-cho |h-C02h oc:o2:c0h3-co*co-cgh3:o2:co |h20 ' (OH3-O)2C6H3-CH(OH)-CO-C0Hs(O-CEr3)2 -^(HO)2O0H3-CO*CO-C6H3(OH)2 j (CH,-0)20flH3-C0*C0-06Hs(0-CH8)8 I * (CH3)3S04 Action of Tliionyl Chloride on Piperil. As might be expected, the same chloro-derivative is formed by thionyl chloride from piperil as from piperonyloin ; 047 gram piperil, heated to 180° with 2 c.c. of thionyl chloi’ide 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 Ilydropiperoin and isoHydropiperoin. By heating either of the above substances with thionyl chloride on the water-bath, the same substance is produced, namely, 3:4:3': 4'- dirnethylenedioxy-a/3-dichloro-s-diphenylethane, ch2:o2:c„h3-chci-chci-cgh8: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 •& crude mixture of hydropiperoin and its isomeride 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 recrystallised from benzene. The yield was only 0'51 gram : 01591 gave 0-2070 C02 and 0 0209 H20. 0 = 52-6 j H = 2 2. 0-1506 „ 0-1195 AgCl. 01 = 19-6. Cj8H806C12 requires C = 52-3 j H = 22 ; Cl = 19-3 per cent.