HOSHINO Masamatsu Saitama University, Department of Chemistry, Faculty of Science, Professor, 理学部, 教授 (20008808)
ISHII Akihiko Saitama University, Department of Chemistry, Faculty of Science, Assistant, 理学部, 助手 (90193242)
|Budget Amount *help
¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1991: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1990: ¥1,600,000 (Direct Cost: ¥1,600,000)
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.