多取代5,14-二氮代五并苯衍生物之合成

Synthesis of Multi-Substituted 5,14-Diazapentacene Derivatives

黃靖凱(JING-KAI HUANG)

指導教授 ： 曾瑞昌

朝陽科技大學/理工學院/應用化學系/碩士(2016年)

摘要

利用5,5-二甲氧基-1,2,3,4-四氯環戊二烯 (39) 為起始物，經四個步驟合成出一系列喹嵌入氯化五并苯醌酯類75a、75b、75c及多取代5,14-二氮代五并苯類化合物81a、81b、83b、94b。
合成策略包含以5,5-二甲氧基-1,2,3,4-四氯環戊二烯 (39) 與1,4-萘醌 (40b) 進行狄爾斯–亞德環化加成反應，得到相對應之狄爾斯–亞德加成物41b。利用狄爾斯–亞德加成物41b進行釕金屬催化氧化反應，將環加成物的二氯乙烯架橋轉換為含有二酮結構之化合物。所得之二酮結構再與各式鄰-苯二胺在醋酸下進行縮合反應。最後進行醋酸條件下一鍋化或三氟醋酸促化之開環裂解反應，其開環裂解反應之機制會隨酸鹼條件而有所不同。最後利用紫外-可見光吸收光譜及螢光放光譜來測量並探討這些化合物在氯仿溶液中的光物理性質。

關鍵字

二氮代五并苯

並列摘要

A series of quinoxaline-embedded chlorinated pentacenoquinone esters 75a, 75b, 75c and multi-substituted 5,14-diazapentacenes 81a, 81b, 83b, 94b, synthesized from 5,5-dimethoxy-1,2,3,4-tetrachlorocyclopentadiene (39) has been achieved in four steps.
The synthetic strategy started with the Diels–Alder reaction of 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene (39) and 1,4-naphthoquinone (40b) which produces the adduct 41b. Then the Diels–Alde adduct 41b was converted into -diketone 76 by the catalytic ruthenium-promoted oxidation and the resulting -diketone 76 then was under went condensation reactions with various arene-1,2-diamines. The successine one-pot acetic acid-promoted or trifluoroacetic acid-promoted Grob-type fragmentation–aromatization process generated the corvesponding aromatic heterocycles The proposed reaction mechanism of the ring-opening fragmentation was different depending on acid- or basic- conditions. In addition, the photophysical properties of these aromatic compounds were investigated by using UV-vis absorption spectra and fluorescence spectroscopy.

並列關鍵字

diazapentacene

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