自由基反應在現今受到重視並且被廣泛地利用於有機合成中，其中利用自由基與不飽和鍵作用並進一步做環化反應的合成方法十分常見。在本篇論文中將使用催化劑量硝酸銀(I)搭配過硫酸鉀水溶液來氧化對甲苯亞磺酸鈉鹽生成碸基自由基，並與2-[(2’-乙炔基)苯胺基]-1,4-萘醌類化合物上的不飽和鍵作用，接著進行分子內環合反應生成吖啶類化合物。在反應中意外發現苯并吖庚因類化合物的生成，故而又將反應拆分為兩個步驟，藉此來合成苯并吖庚因類化合物，根據合成之化合物的不同，將此篇論文分為兩個部分：

SUMMARY
The methods which use free radicals for cyclization reaction can be found in many literatures. Herein we used sulfonyl radical with the compounds that contain triple bond in the presence of silver(I) nitrate and potassium persulfate via the oxidative free radical cyclization reaction to synthesis benzo[b]acridine derivatives. Surprisingly, we found that azepine derivatives were produced as the by-products under certain conditions. So we divided the reaction into two steps to synthesis benzo[b]naphtho[2,3-f]azepine derivatives alone.
Keywords: silver(I) nitrate; sulfonyl radical; acridine; benzazepine.

INTRODUCTION
The skeleton of acridine has been vary attention because it has a good biological activity and pharmacological activity. Acridines can often be found in the drugs as antibacterial, anticorrosion and anticancer, since they have a planar structure and the nitrogen atom is able to interact with base pairs in DNA or RNA readily. Dibenzazepine is a fused tricycles structure, and it is an intermediate for the synthesis of anticonvulsants and antidepressants. In many tricyclic antidepressants (TCAs) we can found the skeleton of acridine as the core.
Free radical reaction is an important synthetic method. Due to the radical intermediates have high activity and the reaction has regio- and stereo-selectivity, the literatures which use free radicals to do the cyclization reaction have been published in a large number. Our laboratory had also published the researches that use silver(II), copper(II), manganese(III) or cerium(IV) to generate oxidative radicals to do the free radical reactions. Silver(II) ion is unstable and expensive, so it is usually generated by catalytic amount of silver(I) nitrate and potassium persulfate. With the rise of environmental awareness, reducing the solvent and catalyst is the direction of efforts, so the use of catalytic amount of silver reagent will be better than the other metal ions.
In this thesis, we divided the content into two parts according to the product of the synthesis. The first part is mediated by sulfonyl radical to do the oxidative radical cyclization reaction to synthesis benzo[b]acridine derivatives. The second part is the synthesis of benzo[b]naphtho[2,3-f]azepine derivatives by electroplic reaction and radical addition reaction.

RESULTS AND DISCUSSION
In the first part, we used catalytic amount of silver(I) nitrate with potassium persulfate aqueous solution to oxidize p-toluenesulfinate sodium salt (TsNa) to generate the sulfonyl radical. The sulfonyl radical interacts with the unsaturated triple bond on 2-(2-ethynylphenylamino)naphthalene-1,4-diones and undergo an intramolecular cyclization reaction to form benzo[b]acridine derivatives. We used the optimized reaction condition to synthesis the methyl substited or halogen substited compounds and achieved good yields. The other hand, we got the unexpected by-product, benzo[b]naphtho[2,3-f]azepine derivatives, in the specific condition.

In the second part, we divided the reaction of the first part into two steps to get 12,13-ditosyl-12,13-dihydro-5H-benzo[b]naphtho[2,3-f]azepine-6,11-diones. Initially, we only added silver(I) nitrate to catalyze the electrophilic cyclization reaction to form 5H-benzo[b]naphtho[2,3-f]azepine-6,11-diones. In this step, methyl substited or halogen substited compounds had high yields, but the electron-withdrawing group would decrease the yields. In the second step, TsNa and potassium persulfate were added to carry out free radical addition reaction to obtain 12,13-disubstituted benzo[b]naphtho[2,3-f]azepine compounds, and in this reaction no matter the electron-donating group, the electron-withdrawing group or halogen didn't affect the yields of the reaction.


CONCLUSION
The synthesis of benzo[b]acridine derivatives and benzo[b]naphtho[2,3-f]azepine derivatives can have good results in this research. The catalytic amount of silver(I) nitrate is used to oxidize TsNa to generate sulfonyl radicals in the first part and catalyze the electrophilic cyclization reaction in the second part. The rate of ionic reaction is significantly slower than the free radical reaction, so the reaction conditions must be divided into two steps to obtain benzo[b]naphtho[2,3-f]azepine derivatives, and compared with the previous examples of the laboratory, the use of silver(I) nitrate catalyst can get better results than Au(III) or Ce(IV).

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