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Synthesis, Structure, and Reactivity of Aromatic compounds and Alkenes Carrying Two Bulky substituents on Adjacent Positions

相邻位置带有两个大取代基的芳香族化合物和烯烃的合成、结构和反应性

基本信息

批准号：
02640383
负责人：
NAKAYAMA Juzo
金额：
$ 1.28万
依托单位：
Saitama University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1990
资助国家：
日本
起止时间：
1990 至 1991
项目状态：
已结题

项目摘要

In 1985 we developed a new thiophene synthesis which involves intramolecular reductive coupling of readily obtainable diketo sulfides. 'ne new method is very versatile and allows the preparation of a wide variety of thiophenes including 3, 4-di-t-buty-and3, 4-di-l-adamantylthiophenes(land2). By using 1 and 2 as the starting materials, a series of aromatic compounds and alkenes carrying two t-butyl and I-adamantyl groups on adjacent positions were satisfactorily synthesized and their properties were studied as summarized below.1)New compounds, 3, 4-di-t-butylfuran, selenophene, and pyrrole were synthesized starring from I and their properites were studied by using NMR and MMP2 calculations.2)A sterically hindered cycloalkene carrying two t-butyls in cis orientation, 2, 3-di-t-butylbicyclo[2.2.2]octene, was synthesized by Diels-Alder reaction of 3, 4-di-t-butyltliiophene 1, 1-dioxide ; which is readily obtainable from 1, and its structure and chemical reactivities were studied in detail.3)Dismethyl 4, 5-di-t-butyl-3, 6-dimethylphthalate, dimethyl 4, 5-di-l-adamantyl-3, 6-dimethylphathalate, dimethyl 4-adamantyl-3-t-butyl-3, 6-dimethylphathale were synthesized and their structures were investigated by X-ray single crystal structure analyses and dynamic ^1H and ^<13>C NMR.4)A new pyridazine synthesis which utilizes the Dieals-Alder reaction of thiopliene I, I-dioxides with N-phenyltriazoline-3, 5-dione was developed.5)Oxidation of thiophetie 1, I -dioxides carrying bulky substituents on 3- and 4-positions was found to give the corresponding epoxides as the initial products which undergo a new rearrangement leading to the corresponding thietes 1, 1 -dioxides.

1985年，我们开发了一种新的噻吩类化合物的合成方法，它涉及到容易得到的二酮硫化物的分子内还原偶联反应。一种新的方法非常通用，可以制备各种各样的噻吩类化合物，包括3，4-二叔丁基-和3，4-二L-金刚基噻吩类化合物(LAND2)。以1和2为起始原料，合成了一系列邻位含2个叔丁基和1-金刚烷基的芳香族化合物和烯烃，并研究了它们的性质：1)以1为原料合成了3，4-二叔丁基呋喃、硒和吡咯等新化合物，并用核磁共振和MMP2方法研究了它们的性质；2)以3，4-二叔丁基对苯二环[2.2.2]辛烯为原料，通过Diels-Alder反应合成了空间位阻环烯1-二氧化物；3)合成了4，5-二叔丁基-3，6-二甲基邻苯二甲酸二甲酯、4，5-二L-金刚烷基-3，6-二甲基邻苯二甲酸二甲酯、4-金刚烷基-3-叔丁基-3，6-二甲基邻苯二甲酸二甲酯，并通过X-射线单晶结构分析和~1H和~(13)GT；5)硫杂环丁烯1，I-氧化物与N-苯基三唑啉-3，5-二酮的Dieals-Alder反应。5)3-和4-位上带有大体积取代基的硫杂硫杂环己烷的氧化反应，得到相应的环氧化物作为起始产物，发生新的重排反应生成相应的硫化物1，1-二氧化硫。