【作者】 蒋欢妹；

【导师】 蒋佑清； 何农跃；

【作者基本信息】 湖南工业大学 ， 材料学， 2007， 硕士

【摘要】 取代基苯硼酸(substituent phenylboronic acids)是有芳香气味的硼酸,其种类繁多,发展非常快,被广泛应用于电子、化学、医药、生物等领域,特别是在糖类传感器方面。本文首先介绍了各种取代基苯硼酸的合成与应用研究,展望了其发展趋势,然后对对位取代基苯硼酸的制备及工艺改进进行了研究,重点研究和改进了对叔丁基、对异丙基苯硼酸和对氯苯硼酸的制备工艺,从而确定了各自的优化合成条件。应用正交设计实验和灰色关联度分析法对影响对叔丁基苯硼酸产率的诸因素如反应时间、反应温度和反应物的物质的量比进行了分析,确定影响对叔丁基苯硼酸产率的因素中,影响最大的为反应温度,其余依次为反应时间和反应物的物质的量比,结合正交实验确定优化合成条件为:亲核取代温度为-20℃,反应物质对溴叔丁基苯与硼酸三甲酯的物质的量之比为1/1.4,反应时间为160 min,总产率高达69.5%;对影响对异丙基苯硼酸产率的诸因素如反应温度和反应物的物质的量的比也进行了分析,确定优化合成条件为:反应物配比对异丙基溴苯与硼酸三丁酯的摩尔比为1/1.5,反应温度为-10℃,酸性水解后总产率56.6%;对影响对氯苯硼酸产率的诸因素如反应时间、反应温度和反应物的物质的量的比也进行了分析,确定优化合成条件为:对氯溴苯与硼酸三丁酯的摩尔比为1/2,反应温度为-40℃,反应时间为160 min,最终产率高达87.77%。此外我们还对对溴苯硼酸的合成条件进行了初步研究。应用质谱、核磁共振光谱、红外光谱和高效液相色谱对上述每个产品进行了分析表征,结果表明所得产物与目标产物结构一致。更多还原

【Abstract】 There are various kinds of substituent phenylboronic acids which smell sweet, are being developed rapidly and have been widely used in the fields of electronics, chemistry, medicine and biology, especially in glucose sensors. In this thesis, the synthesis, the application and the prospect of substituent phenylboronic acids were summarized, and the synthesises of 4-tert-Butylphenylboronic acid, 4-iso-propylphenyl boronic acid and 4-chlorophenylboronic acid and their improvement were studied in detail. The influencing factors such as temperature, reaction time, reactants molar ratio were analyzed with the orthogonal experiment and the Grey Correlation Degree method, an optimized process for the preparation of 4-tert-Butylphenylboronic acid was thus obtained as follows: the reactant molar ratio of 1-bromo-4-tert-butylbenzene to the trimethyl borate was 1/1.4, the temperature was -20℃, and the reaction time was 160 min. The final yield was 69.5%. An optimized process was obtained by investigating the influence of the temperature, reactant proportion on the yield of 4-iso-propylphenyl boronic acid: The molar ratio of reactants is n(C8H9Br): n(B(OC4H9)3)=1/1.5, the temperature is -10℃,and the isolated total yield is 56.6%. An optimized process for the synthesis of 4-chlorophenylboronic acid was also obtained as follows: the reactant molar ratio of p-chlorobromobenzene to the tributylborate was 1/2, the temperature was -40℃, and the reaction time was 160 min. The final yield was 87.77%. Meanwhile, the preliminary synthesis of 4-bromophenylboronic acid was investigated too. Each of the above products was identified by mass spectrum, 1HNMR, IR and HPLC.更多还原