Honey, picrotoxanes

Isolation from Toxic Honey and Quantitative Analysis of its Main Picrotoxanes... 

Via a plant hopper and honeybees, partly metabolized picrotoxanes from Coriaria spp. growing in New Zealand are found in toxic honey. The rather difficult isolation of picrotoxanes from honey has been described several times 2,3,10,99,100) and even now the procedure seems not entirely satisfactory (700). Originally, the isolation of picrotoxanes was achieved by extraction of honey with acetone. Later, ethyl acetate was the preferred solvent. In the late 1960s, the two main picrotoxanes were identified as tutin (11) and hyenanchin (15). Originally, the detection was governed by the physical properties of crystals obtained, color reactions, and bromoether formation. Palmer—Jones then developed a method... 

Two new sesquiterpenoids of the picrotoxane group are amotin (208) and amoenin (209). In the course of an investigation of the toxic substances of the honeydew honey excreted by a sap-sucking insect which feeds on Coriaria arborea Lindsey, the two dihydro-derivatives of tutin (210) and hyenanchin (211) have been identified.Included in this paper are the n.m.r. spectral assignments of a number of compounds belonging to the picrotoxane series. Another milestone in sesquiterpenoid chemistry has been passed by the successful synthesis of (-)-picrotoxinin (212) starting from (-)-carvone (Scheme 33).One of the crucial steps in this fairly long synthesis was the double lactonization towards the end of the route. 

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