【作者】 刘俊；

【导师】 曲红梅；

【作者基本信息】 天津大学 ， 制药工程， 2010， 硕士

【摘要】 研究苯衍生物的合成在合成化学和实际应用中都有非常重要的意义,关键问题是选择性比较差,目前没有关于3,6位取代基相同并且4,5位取代基相同的六取代苯的合成报道。本文首次提出了合成该类新型化合物的新方法。首先对3,6-二三甲基硅基邻二甲酸二甲酯进行本位碘脱硅基作用,得到3,6-二碘邻二甲酸二甲酯,然后与亲电试剂发生取代反应,对3,6位的碘进行取代得到目标化合物。当亲电试剂为碘代烷烃时,对3,6-二碘邻二甲酸二甲酯进行锂化,再用亲电试剂淬灭得到了3,6-二烷基邻二甲酸二甲酯;亲电试剂为碘代噻吩和碘代芳烃时用锂化方法不能得到目标产物。3,6-二碘邻二甲酸二甲酯与有机锌试剂进行Negishi偶联反应制得了3,6-二噻吩邻二甲酸二甲酯; 3,6-二碘邻二甲酸二甲酯与有机硼试剂进行Suzuki偶联反应制得了3,6-二芳基邻二甲酸二甲酯。三种方法都高选择性高收率的得到了3,6位取代基相同并且4,5位取代基相同的六取代苯。喹啉类化合物在医药、分子生物学、染料工业等各领域都有着重要的应用,因此喹啉化合物的合成在方法学和实际应用中都有重要意义。本文首次采用氮杂锆杂环戊二烯与二碘苯进行偶联反应,合成了一系列喹啉衍生物,其中氮杂锆杂环戊二烯由二茂锆与一分子炔烃和一分子腈制得。并且研究了氮杂锆杂环戊二烯的取代基和二碘苯的取代基对反应的影响。更多还原

【Abstract】 Studies on synthesis of benzene derivatives are very important in the synthetic chemistry and practical application. The key issue is the relatively poor selectivity. To the present there is no report for preparation hexasubstituted benzenes which have the same substituent in the 3 and 6 positions, and the same substituent in 4 and 5 positions. The new method on systhesis of these new kind of compounds is reported first in this dissertation. In the dissertation, 3,6-diiodo-phthalic acid dimethyl esters are prepared by bis ipso iododesilylation of 3,6-bis-trimethylsilanyl-phthalic acid dimethyl esters. Then 3,6-diiodo-phthalic acid dimethyl esters occur substitution reaction with electrophiles and we can get the target compounds. When the electrophile is alkyl iodide, lithiation on 3,6-diiodo-phthalic acid dimethyl ester and then quenching with excess electrophile give the 3,6-dialkyl-phthalic acid dimethyl ester. When the electrophile is thienyl iodide and aryl iodide, we can’t prepare the target compounds using lithiation. We prepare 3,6-dithienyl- phthalic acid dimethyl ester using Negishi coupling and 3,6-diaryl- phthalic acid dimethyl ester using Suzuki coupling. The three methods all get hexasubstituted benzenes which have the same substituent in the 3 and 6 positions, and the same substituent in 4 and 5 positions with excellent selectivity in high yields.Quinoline derivatives have important areas of applications in pharmaceutical, molecular biology and dyestuff insudtry, so the systhesis of quinoline derivatives have important significance both in methodology and practical application. In this dissertation, we carry out the coupling reaction of azazirconacyclopentadienes, which are conveniently prepared from zirconocene with one internal alkyne and one nitrile,with substituted diiodobenzenes at the first time,and get a series of quinoline derivatives. We also study the effects of azazirconacyclopentadiene substituents and diiodobenzene substituents on the coupling reaction.更多还原