Studies on the chemical-regulation of marine sessile organisms using phloroglucinol compounds from Eucalyptus sp

在本研究中，我们得到了以下两个结果。1)葛根素的合成：采用交替改进的方法，经三步反应制得桂皮酚，收率为13%。以1，3，5-三甲氧基苯为起始原料合成了延胡索酮衍生物。N-异戊基很容易通过与异戊酰氯反应而引入。异戊基三甲氧基苯用LAH还原，然后在CHCl_3中辐射脱水，得到了苯乙烯化合物。此外，在氢气气氛下用Pt2O处理苯乙烯化合物生成烷基苯。经芳香族溴化、加ClCO2Me、消除、还原、氧化等9步反应，总收率13%。在成功制备了所需化合物后，对其进行了Diels-Alder环加成反应。给出了产率为14%的目标产物和产率为18%的区域异构体。最后，用BBr3S(Me)2对目标产物的羟基进行脱保护反应，完成了大黄素的首次合成。2)间苯三酚类化合物的构效关系。在分子力学计算的基础上，讨论了间苯三酚类化合物的构效关系。当这些化合物相互叠加并以最强的缓蚀剂为模板时，其他化合物的排斥能与对数附着抑制活性成正比。结果表明，在铁氧基A的两个间苯三酚环中，C环更为重要，那些在立体化学和静电上与模板分子相似的化合物活性更高。

In this research we had the following two results. 1) The synthesis of grandinal : We prepared grandinol by an alternate and improved procedurein three steps in 13% yield. Synthesis of the jensenone derivative was started 1,3,5-trimethoxybenzene. n isovaleryl group was readily introduced by a reaction with isovaleryl chloride. Reduction of the isovaleryl trimethoxybenzene with LAH and subsequent dehydration by irradiation in CHCl_3 gave the styrene compound. Further, the styrene compound was reduced by treatment with Pt2O under H2 atmosphere to yield the alkylbenzene. By aromatic bromination, adding ClCO_2Me, elimination, reduction and oxidation, the jensenone derivative was synthesized in nine steps in 13% overall yiels. Having successfull prepared the desired compounds, the jensenone derivative was subjected to Diels-Alder cycloaddition. The desired product in 14% yield and the regio isomer in 18% yield were given. Finally, the desired product was subjected to deprotection of the hydroxy groups with BBr_3S(Me)_2. We accomplished the first synthesis of grandinal. 2) Structure-activity relationship of phloroglucinol compounds. We discuss the structure-activity relationship of phloroglucinol compounds on the basis of molecular mechanics caluculations. When these compounds were superimposed on each other and the strongest inhibitor was applied as a template, the repulsion energy of the other compounds was proportional to the logarithmic attachment-inhibiting activity. It is concluded that, of the two phloroglucinol rings in sideroxylonal A, ring C is more important, and those compounds that stereo-chemically and electrostationally resemple the template molecule are more active.