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

1985年，我们开发了一种新的噻吩合成方法，该方法涉及容易获得的二酮硫化物的分子内还原偶联。一种新方法是非常通用的，并且允许制备各种各样的噻吩，包括3，4-二叔丁基-和3，4-二-L-金刚烷基噻吩（1和2）。以1和2为起始原料，成功地合成了一系列相邻位置上带有两个叔丁基和I-金刚烷基的芳香族化合物和烯烃，并对其性质进行了研究。以I为起始原料合成了1，2，3，4，5，6，7，8，10，12，14，15，16，17，18，19以3，4-二叔丁基锂1，1-二氧化物为原料，通过Diels-Alder反应合成了顺式取向的丁基化合物2，3-二叔丁基双环[2.2.2]辛烯; 3）4，5-二叔丁基-3，6-二甲基邻苯二甲酸二甲酯，4，5-二-1-金刚烷基-3，6-二甲基邻苯二甲酸二甲酯，合成了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动态核磁共振氢谱、碳谱对其结构进行了表征<13>。4）发展了一种利用噻吩I，I-二氧化物与N-苯基三唑啉-3，5-二酮的Dieals-Alder反应合成哒嗪的新方法。发现在3-和4-位上带有大取代基的I -二氧化物作为起始产物得到相应的环氧化物，该环氧化物经过新的重排得到相应的硫杂环丁烷1，1 -二氧化物。

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.