【作者】 肖鹏；

【导师】 陈雅丽；

【作者基本信息】 上海大学 ， 有机化学， 2019， 硕士

【摘要】 本论文主要研究了以苯并双（氧二硅茂）为苯炔前体,在温和条件下形成苯炔,与3-亚甲基吲哚-2-酮衍生物或3-亚甲基苯并呋喃-2-酮衍生物发生[4+2]环加成反应,继续脱氢芳构化,合成得到萘并吲哚酮或菲并呋喃酮衍生物;以氧二硅基萘为萘炔前体,在温和条件下形成萘炔,与3-亚甲基吲哚-2-酮衍生物反应,合成得到蒽并吲哚酮衍生物;研究了苯炔或萘炔分别与2-亚甲基苯并噻吩-3-酮衍生物发生[3+2]环加成反应及分子内β-消除反应,合成得到二苯并硫杂八环-5-酮或苯并萘并硫杂八环-5-酮衍生物。论文主要工作如下:第一部分:研究了以苯并双（氧二硅茂）为苯炔前体,在温和条件下形成苯炔,与3-亚甲基吲哚-2-酮衍生物或3-亚甲基苯并呋喃-2-酮衍生物发生[4+2]环加成反应,合成得到萘并吲哚酮或菲并呋喃酮衍生物;以氧二硅基萘为萘炔前体,在温和条件下形成萘炔,与3-亚甲基吲哚-2-酮衍生物反应,合成得到蒽并吲哚酮衍生物,并进一步探究其光电性能和热稳定性。该合成方法产率较高,操作简单,反应条件温和,符合原子经济性特点,为合成萘并吲哚酮、菲并呋喃酮和蒽并吲哚酮衍生物提供了有效途径。第二部分:研究了以苯并双（氧二硅茂）、邻（三甲基硅基）苯基三氟甲磺酸酯为苯炔前体,在温和条件下形成苯炔,分别与2-亚甲基苯并噻吩-3-酮衍生物发生[3+2]环加成反应,生成硫叶立德中间体,然后与水反应形成氢氧化巯盐,即刻发生分子内β-消除反应,合成得到二苯并硫杂八环-5-酮衍生物;以氧二硅基萘为萘炔前体,在温和条件下形成萘炔与2-亚甲基苯并噻吩-3-酮衍生物反应,合成得到苯并萘并硫杂八环-5-酮衍生物。利用芳炔与2-亚甲基苯并噻吩-3-酮衍生物反应一步构建芳并八元硫杂环化合物,具有合成方法创新性强,产率高,反应条件温和,操作简便,反应迅速,适用性好等优点,很好地提供了二苯并硫杂八环-5-酮和苯并萘并硫杂八环-5-酮衍生物的有效合成途径,丰富了有机含硫八元杂环化合物的合成方法。新的化合物结构经¹H NMR,¹³C NMR,IR,LRMS,HRMS,X-ray予以确定。更多还原

【Abstract】 This thesis mainly focused on the synthesis of naphthoxindoles or phenanthrofuranones by[4+2]cycloaddition reactions of 3-methyleneindolin-2-ones or 3-methylenebenzofuran-2-one with benzyne generated in situ from benzobis（oxadisilole）.The synthesis of anthraoxindoles by[4+2]cycloaddition reactions of 3-methyleneindolin-2-ones with naphthyne generated in situ from2,3-naphthoxadisilole.Studies on the synthesis of 5H-dibenzo[b,g]thiocin-5-ones or5H-benzo[b]naphtho[2,3-g]thiocin-5-one derivatives by[3+2]cycloaddition reactions andβ-elimination reactions of 2-methylenebenzothiophene-3-ones with arynes generated in situ from benzobis（oxadisilole）,2-（trimethylsilyl）phenyl trifluoromethanesulfonate or 2,3-naphthoxadisilole.The first part:Studied on the synthesis of naphthoxindoles or phenanthrofuranones by[4+2]cycloadditionreactionsof3-methyleneindolin-2-onesor3-methylenebenzofuran-2-one with benzyne generated in situ from benzobis（oxadisilole）.The synthesis of anthraoxindoles by[4+2]cycloaddition reactions of 3-methyleneindolin-2-ones with naphyne generated in situ from2,3-naphthoxadisilole.The photophysical,redox and thermal properties of naphthoxindoles and anthraoxindoles were characterized.The simplicity of these procedures and atomic economy should offer convenient way for the synthesis of heterocyclic compounds.The second part:Studied on the synthesis of the 5H-dibenzo[b,g]thiocin-5-ones or5H-benzo[b]naphtho[2,3-g]thiocin-5-one derivatives by[3+2]cycloaddition reactions andβ-elimination reactions of 2-methylenebenzothiophene-3-ones with arynes generated in situ from benzobis（oxadisilole）,2-（trimethylsilyl）phenyl trifluoromethanesulfonate or 2,3-naphthoxadisilole.One-step synthesis of8-membered sulfur heterocyclic compounds by the reaction of arynes with2-methylenebenzothiophene-3-one derivatives has many advantages,such as innovative synthesis method,high yield,mild reaction conditions,simple operation,rapid reaction and good applicability.The effective synthetic routes of dibenzo[b,g]thiocin-5-one and benzo[b]naphtho[2,3-g]thiocin-5-one derivatives are well provided,and the synthetic methods of organic sulfur-containing octacyclic compounds are enriched.The structures of these new compounds were confirmed by ¹H NMR,¹³C NMR,IR,LRMS,HRMS and X-ray spectroscopy.更多还原