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1、广东药学院 硕士学位论文 二苯甲酰甲烷及其衍生物的合成新方法与性能研究 姓名：魏丹 申请学位级别：硕士 专业：药物化学 指导教师：李敏谊 20090501 广东药学院硕士研究生学位论文 I 中 文 摘 要 魏 丹药物化学 指导老师李敏谊副教授 紫外线是一种高能电磁波长时间暴露在紫外线下人体皮肤会发生病变严 重时甚至引发皮肤癌随着工业的迅速发展臭氧层遭到的破坏日益严重以致到达 地面的紫外线辐射量逐渐增加对人们的危害也越来越大因此研制能抵制紫外线 并能应用于人们的日常生活中的紫外线吸收剂具有重要意义二苯甲酰甲烷类是目 前公认的安全性较高的紫外线吸收剂 目前绿色化学越来越受到人们的重视原子利用率高且
2、对环境友好的合成方法 成为化学工作者研究的热点微波辐射由于其独特的作用机理使有机合成化学反应 可以在短时间内高产率地完成且操作简单因此是一种理想的加热方式本文以绿 色化学为指导原则采用微波辐射对二苯甲酰甲烷类紫外线吸收剂的合成进行研究 具体如下 1 以对叔丁基甲苯为起始原料在微波辐射的照射下相转移催化环境友好 地氧化合成了对叔丁基苯甲酸系统考察了各因素对反应的影响实验结果表明以 苄基三乙基氯化铵BTEAC为相转移催化剂对叔丁基甲苯与高锰酸钾的摩尔配比 为11.5反应功率为660W反应时间为50min所得产率为82.6%产物的结构用IR 1HNMR进行了表征 2 在微波辐射下以浓H2SO4为催化
3、剂对叔丁基苯甲酸无水甲醇为酯化 原料合成了对叔丁基苯甲酸甲酯其中采用单因素考察了对叔丁基苯甲酸甲酯合成 的因素影响实验证明在微波辐射下以浓H2SO4为催化剂时酯化反应较传统方 法产率更高产物更纯产物结构用IR 1HNMR进行了表征 3 芳香酮与芳香酯在强碱作用下发生Claisen缩合合成了5个二苯甲酰甲 烷结构的化合物并正交设计法系统考察了主要产物4-叔丁基-4? -甲氧基二苯甲酰 甲烷合成的影响因素通过IR 1HNMR MS对这些产品的结构进行了表征 4 按国家标准对这5个目标产物的紫外-可见光谱进行了测定 并且按它们在 紫外光区吸收的波段不同进行复配测定复配物的紫外线吸收性能 结果表明相较
4、于传统加热方法微波辐射进行充分的内部加热反应物不易碳 广东药学院硕士研究生学位论文 II 化提高原子利用率使反应速率大大加快极大地缩短反应时间提高了反应效率 是一种绿色高效的合成方法合成所得的5个化合物的分别在紫外线A B波段有较 好的吸收相互组合复配得到的复合物能吸收包括UV-A和UV-B在内的紫外线是一 种良好的紫外线全波段吸收剂 关键词二苯甲酰甲烷及其衍生物 Claisen缩合 微波辐射 紫外线防护 广东药学院硕士研究生学位论文 i A new method of synthesising of dibenzoylmethane and its derivatives and resea
5、rch of their capability Wei Dan(Medicinal Chemistry) Supervisor:Li MinyiAssociate Professor AbstractSkin will be damged when exposed to high-energy ultraviolet ray for a long time, even it would result in skin cancer if skin is radiated seriously.With the rapid development of industry, the ozone lay
6、er was badly destroyed, so that more and more ultraviolet ray could cross through the aerosphere and arrived in the ground, and this has a bad influence on the human. Based on this, it is of great significance to develop an ultraviolet ray absorber which is anti-ultraviolet ray and could be applied
7、to daily life. It is accepted that the kind of dibenzoylmethane ultraviolet ray absorber is proved to be safety. Recently, the concept of green chemistry is gradually accepted by many people. The sythesis methods that are enviromentally benign and show high atom efficiency has become a hot spot. Wit
8、h its special mechanism, microwave irradiation become an ideal heating method by accomplishing chemical reaction with high yield in short time and its easy handling. Under the guidance of green chemistry, the sythesis of the kind of dibenzoylmethane ultraviolet ray absorber was studied by using micr
9、owave radiation. (1) with p-tert-butyl toluene as feedstock, under microwave irradiation and using phase transfer catatysis, the sythesis of p-t-butylbenzoic acid was accomplished environment-friendly. Through a series of experiments, factors influencing oxidation were discussed. The optimum conditi
10、ons were determined as followsthe yield of p-t-butylbenzoic acid was 82.6% when using BTEAC as phase transfer catatysis, the molar ratio of p-tert-butyl toluene and KMnO4 was 1:1.5, microwave irradiation power was 660W, the reaction time was 50min. The structure of product was confirmed by IR and 1H
11、NMR. (2) using microwave irradiation, the preparation of p-tert-butylbenzoic-acid- methyl 广东药学院硕士研究生学位论文 ii ester by the reaction of p-butyl-benzoic acid with methanol,by using H2SO4 as a catalyst. The single-factor test were used to optimize esterfication conditions.It is indicate that when using H
12、2SO4 as a catalyst, under microwave irradidtion,the esterfication conditions get higher yield and purer product than unedr traditional heating method.The structure of product was confirmed by IR and 1HNMR. (3) five dibenzoylmethane compounds were synthesised from aromatic ketone and ester by classic
13、al Claisen condensation usingstrong alkali as catalyst. The sythesis of compound(4-tert-butyl-4-methoxy-dibenzoylmethane) were mainly studied .The factors of condensation were investigated by orthogonal test. The structure of products were confirmed by IR and 1HNMR. (4) according to national standar
14、ds, five products UV - visible spectrum was determined. In accordance with their areas in UV absorption band, we mixed these compounds. Then we measure these mixtures UV - visible spectrum. It was proved that, compared with traditional heating method, microwave irradiation could heat reactants compl
15、etely, and the carbonization of reactants is not simple. This improved the efficience of atoms, greatly increased reaction rate, shotened reaction time and raised reaction efficiency. It is a green and highly efficient method.The results show that their absorptions in ultraviolet A and B were good,
16、and the mixture absorb all kinds of ultraviolet rays including ultraviolet A and B. The kind of dibenzoylmethane ultraviolet ray absorber was fine. Key wordsDibenzoylmethane and its derivatives Claissen condensation Microwave-assisted Ultraviolet protction 广东药学院学位论文原创性声明 本人郑重声明本人所呈交的学位论文系我个人在导师指导 下进行研究工作所得到的成果 除文中已特别加以标注和致谢的地方 外不包含其它个人或机构已经发表或撰写过的研究成果 对本研究 做出贡献的其它个人和集体 均已在文中明确说明和致谢 本人充分 意识到本声明的法律结果完全由本人承担 学位论文作者签名 日期 年 月 日 学位论文使用授权的声明 本人完全了解广东药学院有关保留和使用学位论文的规定 学校 有权保留和
