臺灣博碩士論文加值系統

摘要
本研究使用含氮的萘醌衍生物1-3c 為起始物，和鈀金屬在開放系統下(空氣下)進行催化反應產生含氮的萘醌雜環化合物，4-6。首先，化合物1與環己甲胺進行催化反應，得到了產物4，其產率有20%左右，並且也經由X-光單晶繞射法得出其晶體結構。由產物結構得知，透過化合物1這種類型的起始物進行催化反應，並不會遵守陳思暐學長所推測的反應機制來達到我們所預期的螺旋環結構分子。
接著使用起始物2與三乙胺在氮氣條件下和鈀金屬進行催化反應，得到了2_a 與2_b 兩種不同胺化反應的產物，並且也養出2_a 的晶體，經由X-光單晶繞射法得出其晶體結構。然而嘗試了幾個不同的鹼仍然只回收到起始物，所以這個方法也無法得到我們所期待的螺旋環化合物的結果。
之後使用了起始物3a 與3b，分別與亞甲基環己烷在密閉條件下和鈀金屬進行催化反應，得到產物3a_a 和3b_a，也鑑定出了3a_a 與3b_a 的晶體結構，然而3a_a 與3b_a 這兩個分子的結構極為相似，並推測了其形成產物的反應機制後，便開始猜想若使用起始物3c或許就可以得到螺旋環結構分子的結果。
反應結果顯示，利用3c 和亞甲基環己烷與鈀金屬進行催化反應，並沒有得到預期的產物，反而產生了其他環化反應，得到了新型態產物5-7，其中產物5和產物6也都有得到晶體結構，但還有一個產物7並未養出晶體，所以無法確認其結構，在這反應中也產生了沒有環化反應的產物3c_a，產物3c_a 也得到了晶體結構，從結構來看這是一個Heck reaction 反應的產物。根據產物5、6和3c_a 的結構，我們藉以推測此反應的機制。

Abstract
In this study, several nitrogen-containing naphthoquinone heterocyclic compounds, 4-6, were prepared from naphthoquinone derivatives 1-3c. The reactions were carried out in an open air system and in the presence of Pd(OAc)2 as the catalyst.
Firstly, compound 4 was prepared from 1 with cyclohexylamine and in the yield of about 20%. Its crystal structure is resolved via single crystal X-ray determining methods. Obviously, a cyclization process took place during the reaction.
Next, two amination products 2_a and 2_b were produced through the reaction of 2 with triethylamine. The reaction was carried out under inert gas (N2) system and in the presence of Pd(OAc)2 as the catalyst. The crystal structure of 2_a was determined as well. In this reaction, the desired compound with expected spiro structure was not observed although several different bases had been attempted to achieve the goal.
Later, two amination products 3a_a and 3b_b were yielded through the reactions of cyclohexylamine with 3a and 3b, respectively, under inert gas (N2) system and in the presence of Pd(OAc)2 as the catalyst. The crystal structures of both 3a_a and 3b_a were determined as well. Rather similar structure features were shown for both compounds.
Finally, the reaction of cyclohexylamine with 3c under similar reaction condition produced several unexpected products, 5, 6 and 7. The crystal structures of 5 and 6 were determined except 7. The conformation of 7 remains unknown. There is one more product 3c_a was observed. Judging from its crystal structure, it is obviously a product of Heck reaction. A mechanism was proposed to accommodate the processes for the formations of all compounds.

目錄
摘要 i
Abstract iii
Scheme 目錄 vii
Figure 目錄 ix
Table 目錄 x
第一章　序論 1
第一節　Quinone簡介 2
第二節　C-H 鍵的活化反應簡介 5
第三節　1,4-萘醌(Naphthoquinone)上的C-H 鍵活化反應簡介 8
第四節　研究方向 12
第二章　實驗 15
第一節　儀器與設備 16
第二節　藥品 19
第三節　合成與鑑定 21
第三章　結果與討論 35
第一節　Amido-substituted naphthoquinone 與環己甲胺的反應 36
第二節　Amido-substituted naphthoquinone 與三乙胺的反應 39
第三節　Amine-substituted naphthoquinone 與亞甲基環己烷的反應 42
第四章　結論 55
第五章　參考文獻 56
第六章　附錄 59
第一節　光譜數據 60
第二節　晶體數據 91

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