四甲基萘并二呋喃的合成和DNA嵌入性能及其结构的分子模拟研究

Syntheses,DNA Intercalation Activities and Molecular Modelling on Structures of Tatramethyldifuronaphthalenes

将２，７－二羰烷氧基萘（２）在三氯氧磷中环化成７３％不对称及２７％对称的四甲基萘并二呋喃（４和５）。在盐酸作用下２环化成３，随后在乙酰乙酸乙酯／二氯甲烷中及三溴化硼作用下生成区域选择性环化产物（５）。采用荧光强度测定法发现４对小牛胸腺ＤＮＡ有嵌入作用。分子模拟方法指出４与５在ＤＮＡ嵌入性能上的差别主要是由它们分子平面性不同所致。

Dialkoxynaphthalene(2) formed from the condensation of 2, 7-dihydroxynaphthalene(1) with 3-chloro-2-butanone, refluxed in POCl3/CCl4 to give cyclized products of 73% asymmerical 4 and symmetrical tetramethyldifuronaphthalene 5. In the presence of hydrochloride,2 was partly cyclized to give 3,followed by cyclization at room temperature in acetylacetate/methylenechloride under the action of BBr3 to give only symmetrical product 5.The structures of all products was fully characterized using IR,UV,FL,￣1H NMR,(13)CNMR, MS and elementary analysis,It was found that 4 can intercalate into Calf Thymus DNA,but 5 couldn't, and the apparrent intercalation constant for 4 was recorded. Using molecular modelling study,not only the bond lengths and angles of 5 were calculated well, but also it is indicated that the difference in DNA intercalation activity between 4 and 5 mainly depends on that in their molecular planarity.