Synthesis of New Highly-strained Cyclophanes Bridged by Cyclobutane Rings and Use of Their Properties

环丁烷环桥连的新型高应变环烷的合成及其性能的利用

• 批准号: 01470093
• 负责人: NISHIMURA Jun
• 金额: $ 3.71万
• 依托单位: Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470093/
• 关键词: Cyclophanes; Cyclobutane Ring; Styrene Derivatives; Photocycloaddition; Photochromism; Naphthaleneophanes; Phenanthrenophanes; Transannular Reaction; ビフェニロファン; 光環化付加反応; パドラン; 高歪分子

A novel synthesis of cyclophanes using intramolecular [2 + 2] photocycloaddition of styrene derivatives was developed in our laboratories. So we were prompted to study its mechanism, its scope and limitation as a synthetic method, further reactions of cyclophanes obtained, and the use of properties of unique cyclophanes. Results obtained in the two year period of this project are listed below ; (1) Many vinylarenes, including 1, 3-bis (6-viny-1-1-phenanthryl) propance and cis-1, 2-bis (-vinyphenyl) cyclobutane, were prepared and irradiated. The corresponding phanes like a phenanthrenphane and [2.2] metacyclophane bridged by two cyclobutane rings were obtained. These results suggest the wide applicability of the reaction for cycrophane synthesis. (2) As one of mechanistic investigations, the effects of substituents attaching at the vinyl groups of vinylnaphthalene derivatives was studied. The reaction courses were affected greatly by the position and sort of substituents. (3) In order t … More o shorten the linkage by making a small ring, 1, 2-ethano [2.3] paracyclophane was brominated at the trimethylene chain, followed by the treatment with n-butyllithium, to afford the desired [2.2]paracyclophane linked by a cyclobutane ring and cyclopropane ring in a reasonable yield. This compound gathers much attention as one of the unique paddlaes. (4) cis-1, 2-Ethano-syn-[2.3] (1, 4) -naphthalenophane produced a highly strained cubane-type compound by photoirradiation. The product showed an interesting thermal cycloreversion, whose late was determined. (5) Small cyclophanes obtained by the reaction underwent the ring opening reaction. The rates of the reaction depended on the strain energies of the cyclophanes. (6) Cyclophanes obtained showed several intriguing properties like photochromism mentioned above, but there were no compounds which could be applied to any advanced materials. We would like to stress, however, that several crown ethers possessing cyclophane structures were prepared in surprisingly high yields and that did exhibit quite high Li^+ selectivity at the transport experiments. Less

利用苯乙烯衍生物的分子内[2 + 2]光环加成合成了一种新的环番化合物。因此，我们需要研究它的作用机理，它作为一种合成方法的范围和局限性，得到进一步的环番反应，并利用独特的环番性质。本项目两年期间取得的成果如下：(1)制备了包括1,3 -二（6-乙烯-1-1-苯基）丙烷和顺- 1,2 -二（-乙烯-苯基）环丁烷在内的多种乙烯基芳烃，并进行了辐照处理。得到了两环丁烷桥接的吩吩和[2.2]元环吩。这些结果表明该反应在环己烷合成中具有广泛的适用性。(2)作为机理研究之一，研究了取代基在乙烯基萘衍生物上的吸附作用。取代基的位置和种类对反应过程有很大影响。(3)为了进一步缩短环链，在三亚甲基链上溴化1,2 -乙醇[2.3]对环己烷，然后用正丁基锂处理，以合理的产率得到由环丁烷环和环丙烷环连接的所需[2.2]对环己烷。这种化合物作为一种独特的桨叶而备受关注。(4)顺式- 1,2 -乙醇-syn-[2.3](1,4) -萘芬通过光照射制备了高应变的立方烷型化合物。产物表现出有趣的热循环还原，并确定了其后期。(5)反应得到的小环番发生开环反应。反应速率取决于环烷的应变能。(6)所得到的环烷化合物表现出如上所述的一些有趣的性质，如光致变色，但没有可以应用于任何先进材料的化合物。然而，我们想强调的是，几种具有环烷结构的冠醚以惊人的高收率制备，并且在输运实验中确实表现出相当高的Li^+选择性。少

项目成果

Y.Okada,S.Mabuchi,M.Kurahayashi,J.Nishimura: "Synthesis and Structural Analysis of Dimethoxy[2.n]metacyclophanes" Chem.Letters.

Y.Okada，S.Mabuchi，M.Kurahayashi，J.Nishimura：“二甲氧基[2.n]偏环芬的合成和结构分析”Chem.Letters。

Y.Okada,K.Sugiyama,M.Kurahayashi,J.Nishimura: "Synthesis of ThreeーBridged Cyclophanes via Metaーand Orthoーcyclophane" Tetrahedron Letters.

Y. Okada、K. Sugiyama、M. Kurahayashi、J. Nishimura：“通过间位和邻位环芳烷合成三桥环芳烷”四面体字母。

S. Inokuma, T. Yamamoto, and J. Nishimura,: "Efficient Intramolecular [2 + 2] Photocycloaddition of Styrene derivatives toward New Crown Ethers" Tetrahedron Lett.,. 31. 97-100 (1990)

S. Inokuma、T. Yamamoto 和 J. Nishimura，“苯乙烯衍生物对新冠醚的高效分子内 [2 2] 光环加成”Tetrahedron Lett.，。

J.Nishimura,Y.Horikoshi Y.Wada,H.Takahashi,M.Sato: "Intramolecular[2+2]photocycloaddition.10.Conformationally Stable synー[2+2]Metacyclophane" J.Am.Chem.Soc.

J. Nishimura、Y. Horikoshi Y. Wada、H. Takahashi、M. Sato：“分子内[2+2]photocycloaddition.10.构象稳定的 syn-[2+2]Metacyclophane”J.Am.Chem.Soc。

S.Inokuma,T.Yamamoto,J.Nishimura: "Efficient Intramolecular〔2+2〕Photocycloaddition of styrene Derivatives Toward New Crown Ethers" Tetrahedron Letters. 31. 97-100 (1990)

S.Inokuma、T.Yamamoto、J.Nishimura：“苯乙烯衍生物对新冠醚的有效分子内〔2+2〕光环加成”四面体快报 31. 97-100 (1990)。