In addition to hyoscine, the Australian, drug yielded three new alkaloids. Tigloidine, C13H21O2,N, a syrup, is tiglyl-ψ-tropëine and has been synthesised. Valeroidine, C 13H23O3N, m. p. 85°, [α] D20° -9.0°, is the isovaleryl ester of a dihydroxytropane, obtained by Wolfes and Hromatka (Merck's Jahresber., 1933, 47, 45) as a by-product in the manufacture of cocaine from Peruvian coca leaves. The third alkaloid, C12H21O2N, provisionally called base Z, is syrupy and yields a crystalline oxalate. The yields were respectively 0.1, 0.1, and 0.003% of the drug. The first base and the third are characterised by hydrobromides which are extracted as such from aqueous solution by chloroform. Dihydrotigloidine, dibromodihydrotigloidine, and tiglyltropëine have also been prepared. The hydrobromides of acetyltropëine and acetyl-ψ-tropëine are useful for characterising tropine and ψ-tropine respectively.