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研究生: 林書玉
Shu-Yu Lin
論文名稱: 探討利用唑啶酮與鹵素芳香醚類進行擴環反應以合成七員環之雜環化合物
Ring Expansion Strategy on the Synthesis of 7-Membered Hetercycles from Azolidinone and haloaryl Ethers
指導教授: 胡紀如
Reuben Jih-Ru Hwu
口試委員:
學位類別: 碩士
Master
系所名稱: 理學院 - 化學系
Department of Chemistry
論文出版年: 2005
畢業學年度: 93
語文別: 英文
中文關鍵詞: 雜環環化反應鹵素烷基芳香醚四氫化1,4苯二氮平酮
外文關鍵詞: benzyne, sodium bis(trimethylsilyl)amide, hetercycles
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  • 利用鹵素烷基芳香醚類和1.3-dimethyl-2-imidazolidinone與NaN(SiMe3)2在加熱迴流的條件下,生成「對應四氫化1,4苯二氮平酮」,其產率為76-82%。在鹵素芳香醚類上具有立體障礙之烷基時,會得到較低產率之「1,4苯二氮平酮」。當利用「異丁基二甲基矽鹵素芳香醚」取代鹵素烷基芳香醚類亦能進行相同之環化反應。然而有部份之起始物在反應中進行脫去矽保護基,而產生帶有醇基之苯二氮平酮。
    當利用oxazolidinone、 thiazolidinone、pyrrlidinone取代imidazolidinone欲進行雜環環化反應時,並無得到相對應之7員雜環化合物。利用X-ray 晶體鑑定得知以間位苯氧基烷與oxazolidinone反應時,會生成1-(3-methoxyphenyl)-3-methyl-2-imidazolidine,其產率為25%。在一系列不同的鹼包含lithium 2,2,6,6-tetramethylpiperidide、sodium bis(trimethylsiyl)amide、sodium tert-butoxide、sodium hydride中以利用sodium bis(trimethylsiyl)amide 為最適合進行一步之環化反應之鹼。


    Tetrahydro-1,4-benzodiazepin-5-ones with an alkoxy group at the C-6 position were synthesized in 76–82% yields from alkyl haloaryl ethers and 1.3-dimethyl-2-imidazolidinone in the presence of sodium bis(trimethylsilyl)amide at reflux. A bigger alkyl group in haloaryl ethers gave a lower yields of the correspondng benzodiazepinone. The same annellation was also accomplished by use of the t-butyldimethylsilyl haloaryl ether to replace an alkyl haloaryl ether. Nevertheless, partial desilylation took place to lead to the desired benzodiazepinone bearing an –OH group.
    Although the heterocycle fromation was accomplished by use of 1,3-dimethyl-2-imidazolidinone as the starting materials, its replacement with 3-methyl-2-oxazolidinone, 3-methyl-2-thiazolidinone, or 1-methyl-2-pyrrolidinone did not give the corresponding 7-membered heterocycles. Furthermore, ours results indicate that reaction of meta-iodoanisole with 3-methyl-2-oxazolidinone generated 1-(3-methoxyphenyl)-3-methyl-2-imidazolidinone in 25% yield, of which the structure was confirm by X-ray crystallography. Among various bases including lithium 2,2,6,6-tetramethylpiperidide, sodium bis(trimethylsilyl)amide, sodium tert-butoxide, and sodium hydride, choice of sodium bis(trimethylsilyl)amide was essential for the "one-flask" annellation to proceed.

    Contents English Abstract i Chinese Abstract ii Acknowlegements iii Contents iv Introduction 1 Results 4 Discussion 12 Conclusion 17 Experimental Section 18 Reference 25 Spectra 27

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