Some aspects of the chemistry of picrotoxinin and tutin

Abstract

Picrotoxin, first isolated by Boullay Boullay, B. Pharm., 1812, 4, 367 in 1812 is a typical member of the class of amaroids, or non-nitrogeneous bitter principles. Almost seventy years after its first isolation picrotoxin was shown L. Barth and M. Kretschy, Monatsch., 1884, 5, 65 Abstracts, 1884, 846 E. Paterno and A. Oglialoro, Gazetta, 1881, 10, 36 Abstracts, 1881, 440 to be composed of two substances, picrotoxinin, C15H16O6, the physiologically active constituent and picrotin C15H18O7, physiologically inactive, in equimolecular proportions. Picrotoxin can be readily separated into its two components by chemical means R. Meyer and P. Bruger, Ber., 1898, 31, 2958, P. Horrmann, Ber., 1912, 45, 2090 and is obtained from the fruit of the shrubs Anamirta Cocculus and Cocculus Indicus. Although originally used as a fish poison, it has recently found application in the treatment of barbiturate poisoning. Early work on picrotoxin was carried out by Barth (1863-64) and Paterno (1877-91) and was mainly concerned with the production of pure material and the establishment of the empirical formulae. Later workers, Meyer and Bruger, Angelico (1907-23) and Horrmann (1910-35) studied the chemistry of picrotoxin in more detail. Their work was complicated by the fact that both picrotoxinin and picrotin undergo intramolecular rearrangements and complex reactions with both acids and alkalies. These difficulties made some of their work unreliable and it was only from the work of Robertson and later, Conroy, that a reasonable formulation of the carbon skeleton of picrotoxinin and picrotin was put forward.