【作者】 刘彤；

【导师】 李亚明；

【作者基本信息】 大连理工大学 ， 精细化工， 2020， 硕士

【摘要】 本文主要研究了光诱导N-芳基丙炔酰胺环加成反应合成卤代氮杂螺[4,5]三烯酮的方法。第一部分研究了光诱导条件下高价碘试剂PhI（OCOCF₃）₂作用的N-芳基丙炔酰胺合成卤代氮杂螺[4,5]三烯酮的方法。首先以高价碘试剂PhI（OCOCF₃）₂作为碘化试剂,对试剂用量、溶剂和反应时间等条件进行筛选,确定最佳反应条件为PhI（OCOCF₃）₂的用量为2倍量、无机碱NaOAc的用量为2倍量、乙腈作为溶剂,在氙灯照射下进行反应,氧气氛围室温搅拌18 h。随后,加入KBr/KCl,通过PhI（OCOCF₃）₂与KBr/KCl共同作用作为卤化试剂,对试剂的用量、溶剂和反应时间等条件进行筛选,确定最佳反应条件为PhI（OCOCF₃）₂的用量为1.5倍量、KBr/KCl的用量为2倍量、无机碱NaOAc的用量为2倍量、乙腈作为溶剂,蓝灯照射室温反应2 h。在得到最佳反应条件后探索了该方法的底物适应性范围。该部分实现了卤代氮杂螺[4,5]三烯酮的合成,该方法反应条件温和,避免了使用过渡金属催化剂,且底物适应性范围良好。第二部分研究了1,3-二卤-5,5-二甲基海因作为卤化试剂的N-芳基丙炔酰胺合成卤代氮杂螺[4,5]三烯酮的方法。首先以N-芳基丙炔酰胺为底物,1,3-二溴-5,5-二甲基海因（DBDMH）为溴化试剂,乙腈作为溶剂进行了条件筛选。确定最佳反应条件为1,3-二溴-5,5-二甲基海因（DBDMH）为0.6倍量、无机碱NaOAc的用量为2倍量、乙腈作为溶剂,在蓝灯照射下进行反应,室温搅拌12 h。随后以1,3-二氯-5,5-二甲基海因（DCDMH）为氯化试剂合成氯代氮杂螺[4,5]三烯酮的产物。确定最佳反应条件为1,3-二氯-5,5-二甲基海因（DCDMH）为1.2倍量,1 mol%曙红B作为光敏剂,过氧化叔丁醇（TBHP）为3.5倍量,无机碱NaOAc为2倍量、乙腈作为溶剂,在蓝灯照射下进行反应,室温搅拌18 h。在最佳条件下考察该方法的底物适应性范围,烷基、芳基取代的丙炔酰胺都能进行反应并取得中等以上收率,此外芳基丙炔酸酯也能够进行反应。该部分实现了N-芳基丙炔酰胺的一种廉价、高效、温和的卤代螺环化反应,避免了使用金属光敏剂。更多还原

【Abstract】 Photo-induced cycloaddition synthesis of halogenated spiro[4,5]trienones of N-aryl alkynamides have been investigated.In section one,the photo-induced synthesis halogenated spiro[4,5]trienones from N-aryl alkynamides with hypervalent iodine reagent PhI（OCOCF₃）₂ was developed.Firstly,the hypervalent iodine reagent PhI（OCOCF₃）₂ was used as the iodination reagent,and the reaction parameters were screened.The optimal reaction conditions were determined as 2.0equiv PhI（OCOCF₃）₂,2.0 equiv NaOAc in acetonitrile,irradiation of the xenon lamp at room temperature under an oxygen atmosphere for 18 h.Subsequently,we investigated a photo-induced brominated spirocyclization and chlorinated spirocyclization with PIFA and KBr/KCl as sources of halogen radical.The reagent amount,solvent,and reaction time were screened to determine the optimal reaction conditions:1.5 equiv PhI（OCOCF₃）₂,2.0 equiv KBr/KCl,2.0 equiv NaOAc in acetonitrile,irradiation of the blue LED at room temperature for 2 h.Having identified the optimal reaction conditions for halogenated spirocyclization of N-aryl alkynamides,we investigated the substrate scope.Therefore,this method has the advantages of mild reacting condition without using transition metals photosensitizer and good tolerance of functional groups.Section two focuses on the photo-induced synthesis halogenated spiro[4,5]trienones from N-aryl alkynamides of 1,3-dihalo-5,5-dimethylhydantoin as a halogenation reagent.Firstly,the brominated spirocyclization of N-aryl alkynamides with DBDMH was selected as a model to screen the reaction parameters.It was determined that the optimal reaction conditions:0.6equiv DBDMH,2.0 equiv NaOAc in acetonitrile and irradiation of the blue LED at room temperature for 12 h.Chlorinated spirocyclization of N-aryl alkynamides used DCDMH as chlorinating reagent.The optimal reaction conditions were determined as 1.2 equiv DCDMH,1 mol%Eosin B as the photosensitizer,3.5 equiv tert-butyl hydroperoxide,2.0 equiv NaOAc in acetonitrile and irradiation of the blue LED at room temperature for 18 h.Under the optimal conditions,the substrate scope was examined.The N-aryl alkynamides substituted with alkyl and aryl,and phenyl 3-phenylpropiolate,proceed smoothly.Therefore,a cheap,efficient,and mild reaction was achieved without using transition metals photosensitizer.更多还原