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，它涉及到容易得到的二酮硫化物的分子内还原偶联。这种新方法用途广泛，可以制备多种噻吩，包括3,4 -二-t-丁基和3,4 -二- 1 -金刚烷基噻吩（land2）。以1和2为起始原料，令人满意地合成了一系列相邻位置携带两个t-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。1)以I为主要原料合成了3,4 -二叔丁基呋喃、硒烯和吡咯等新化合物，并通过NMR和MMP2计算研究了它们的性质。2)以3,4 -二-丁基噻吩1,1 -二氧化物为原料，采用Diels-Alder反应合成了一种空间位阻环烯烃，该环烯烃携带两个顺式t-丁基2,3 -二-丁基双环[2.2.2]辛烯；对其结构和化学反应性进行了详细的研究。3)合成了二甲基4,5 -二叔丁基- 3,6 -二甲基邻苯二甲酸二甲酯、二甲基4,5 -二叔丁基- 3,6 -二甲基邻苯二甲酸二甲酯、二甲基4-叔丁基-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力学^1H和^<13>C nmr对其结构进行了研究。4)利用噻吩I， I-二氧化物与n -苯基三唑啉- 3,5 -二酮的dials - alder反应合成了一种新的吡啶嘧啶。5)在3位和4位上携带大量取代基的噻吩1,1 -二氧化物氧化得到相应的环氧化物作为初始产物，这些环氧化物经过新的重排生成相应的噻吩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.