Studies on the Alkaloids of Menispermaceous Plants. LXXXVII

On the Structure of Biscoclaurine Alkaloids. (5). Cleavage Reaction of Diphenyl Ether and Diphenylene Dioxide Derivatives by Metallic Sodium in Liquid Ammonia

Abstract

The authors carried out the decomposition reactions of diphenylene dioxide, 3, 7-dimethyldiphenylene dioxide, phenoxthine, and several similar compounds by metallic sodium in liquid ammonia. As a result, the following new knowledge has been obtained:
1) When isotetrandrine, tetrandrine and cycleanine are reacted by metallic sodium in liquid ammonia, these are bisected into two coclaurine type molecules and when this mode of decomposition is compared with the fundamental experimental results obtained this time, both decomposition processes are found to proceed exactly in the same way.
2) Furthermore, diphenyl ether derivatives, having a phenolic hydroxyl group, show great resistance to cleavage reaction, and, if these substances are made to react forcibly, the cleavage products become resinous. Consequently, it was confirmed that berbamine and other phenolic bases cannot be bisected into two coclaurine type molecules by the cleavage of the two ethereal oxygen linkages in one step.