摘要：采用高锰酸钾氧化法制备4-（二苯基磷酰基）苯甲酸，选用二苯基对甲苯基膦为原料在碱性环境下进行反应。同时探究了制备4-（二苯基磷酰基）苯甲酸的最佳反应条件是在温度为96̊C，反应时间为12小时，而且对于后续的重结晶部分的实验操作进行了改进先2次无水乙醚萃取，后一次50%浓硫酸酸化，以达到提高产率的作用。为了进一步的酯化研究，也对4-（二苯基磷酰基）苯甲酸能否对酸和醇有催化酯化作用进行验证。为使反应为均相反应，因4-（二苯基磷酰基）苯甲酸较为难溶，也对反应溶剂进行了选择改良。还制备了固载型催化剂，选择无机物氨基化二氧化钛与其通过三苯氧膦链接，来探究催化酯化的作用效果及产率，同时探究酯化反应的最佳条件。由于氨基化二氧化钛颗粒体积较大所以催化效率不高，可以探究更合适的物质，但这是催化酯化合成的一种新思路。

关键词：4-（二苯基磷酰基）苯甲酸；草酰氯；固载型催化剂

Synthesis and Esterification of 4-diphenylphosphorylbenzoic Acid

Abstract: 4-diphenylphosphorylbenzoic acid was prepared by the oxidation of potassium permanganate, and the reaction was carried out in a basic environment using diphenylp-tolylphosphine as a raw material. At the same time, the optimal reaction conditions for the preparation of 4-diphenylphosphorylbenzoic acid were investigated. The temperature was 96°C, the reaction time was 12 hours, and the experimental operation of the subsequent recrystallization part was improved. Ether extraction followed by acidification of 50% concentrated sulfuric acid to achieve an increase in yield. For further esterification studies, it was also verified whether 4-diphenylphosphorylbenzoic acid can catalyze the esterification of acid and alcohol. In order to make the reaction a homogeneous reaction, 4-diphenylphosphorylbenzoic acid is hardly soluble, and the reaction solvent was also selectively modified. A solid-supported catalyst was also prepared, and the inorganic aminated titanium dioxide was selected to be linked with triphenylphosphine oxide to investigate the effect and yield of catalytic esterification, and the optimal conditions for the esterification reaction were also explored. Because of the large size of the amidated titanium dioxide particles, the catalytic efficiency is not high, and more appropriate substances can be explored, but this is a new idea for catalytic esterification synthesis.

Key Words: 4-diphenylphosphorylbenzoic acid；Oxalyl chloride；Fixed catalyst

目录

1 引言 1

1.1 4-（二苯基磷酰基）苯甲酸的简介、作用及开发 1

1.1.1 4-（二苯基磷酰基）苯甲酸的简介 1

1.1.2 三苯基膦衍生物的应用 2

1.2 反应文献综述 2

1.2.1 APPLE反应介绍 2

1.2.2 乙氧基硅烷与氧化物表面的反应 3

1.2.3 用1,3-二苯基二硅氧烷化学选择性还原氧化膦 4

1.2.4 钌-催化碳氢键-含烯烃的芳基磷氧化物的烷基化 4

1.2.5 固定化催化剂：在均相催化和多相催化之间的桥梁 5

1.2.6 载体材料的合成 5

1.2.7 用高锰酸钾方法合成苯甲酸工艺研究 6

1.3 合成酯类文献 6

1.3.1 三苯基膦催化形成酸酯 6

1.3.2 酰卤合成酯 6

1.3.3 酸酐法合成酯 7

1.3.4 杂多酸新型固体酸催化油酸酯化合成 7

1.3.5 苯甲酸酯类合成工艺 7

1.4 课题研究背景与选择意义 7

1.5 工艺路线的确定 8

1.5.1 4-（二苯基磷酰基）苯甲酸的合成 8

1.5.2 4-（二苯基膦酰基）苯甲酸的纯化 8

1.5.3 4-（二苯基膦酰基）苯甲酸的负载 9

1.5.4 负载型 4-（二苯基膦酰基）苯甲酸催化合成酯的路线确定 9

1.6 反应产物的分析方法确定 9

1.6.1 柱层析分离提纯验证 9

1.6.2 分析方法验证 9

2 实验部分 10