掩飾鄰苯醌雙聚合物之照光重排反應之研究

Photo-Induced Rearrangement of Dimerization Products of Masked o-Benzoquinones

許秀弼(Hsiu-Pi Hsu)

指導教授 ： 莊敬

中原大學/理學院/化學研究所/碩士(2017年)

https://doi.org/10.6840/cycu201700632

摘要

本研究主題為以掩飾鄰苯醌雙聚合物作為起始物的光化學研究，其中一個主題為掩飾鄰苯醌雙聚物的研究，研究發現掩飾鄰苯醌雙聚物41a-d在306 nm紫外光照射下會進行分子內[2+2]環加成反應，得到產物42a-d及一個未知物。
另一個主題為掩飾鄰苯醌雙聚物經α-β還原後產物之研究，還原產物43a-d利用306 nm紫外光進行照光反應，研究發現若是以丙酮作為溶劑，容易進行氧-雙--甲烷重排 (oxa-di--methane rearrangement)反應得到產物44a；若溶劑為乙腈時，則趨向於直接進行1,3-醯基位移 (1,3-acyl migration)得到產物46a，當照光時間愈長則愈傾向於進行光誘導脫基羰基1,3-位移 (photoinduced decarbonylative 1,3-migration)反應。

關鍵字

掩飾鄰苯醌雙聚合物 ； 照光重排反應

並列摘要

The topic of this research was based on the photochemistry of dimers of masked o-benzoquinones. We studied the photolysis of the dimer of MOBs and found not only the reaction yielded [2+2] products, but an unknown product was also found during the separation.
We had also applied an α-β reduction on MOBs dimers, and the photolysis of this reduced compound generated different types of rearranged products in different solvents. In acetone, oxa-di--methane rearrangement was found to be the major pathway, along with minor product resulted from photoinduced decarbonylative 1,3-migration. And when acetonitrile was used as solvent, photoinduced decarbonylative 1,3-migration was found to be the only pathway.

並列關鍵字

Masked o-Benzoquinones；Dimer ； Photo-Induced Rearrangement

參考文獻

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