双酚F合成工艺探究

以苯酚、甲醛溶液（质量分数为37%～40%）为原料,磷酸为催化剂,经缩合反应合成了双酚F。通过正交实验探讨了原料配比、催化剂用量、反应温度、反应时间等因素对反应的影响,并对纯化后的产品进行了电镜扫描、红外光谱和熔点测试等分析表征。实验结果表明,最优工艺条件为n（苯酚）∶n（甲醛）=2.2∶1.0,n（苯酚）∶n（磷酸）=2.2∶0.8,在温度为42℃时反应2h,再升温至65℃反应0.5h,最优条件下扩大实验所得的收率可稳定在90%左右。     

MnO2 Nanoparticles as Efficient Oxidant for Ultrasound-Assisted Synthesis of 2-substituted Benzimidazoles under Mild Conditions

In this article, a novel method for synthesis of 2-substituted benzimidazoles using MnO₂ nanoparticles as a convenient oxidant agent in ethanol-water (1:1) as solvent under ultrasound irradiation was demonstrated. In this protocol the desired products were purely obtained in high yields. The main advantages of this research are: mild procedure, simplicity of method, easily work-up, high yields, and short reaction times. The MnO₂ nanoparticles were synthesized through a solid-state reaction route using simple strarting materials. Furthermore, their structure was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR).     

芳香醛、苯乙酮和对硝基苯胺一锅法合成Mannich碱

在浓盐酸做催化剂的条件下,芳香醛、苯乙酮和对硝基苯胺能够发生Mannich反应,经过提纯得到相应的Mannich碱。用红外光谱对产物的结构进行表征,并研究浓盐酸的使用量、反应温度、反应时间等条件对产率的影响。实验发现在3滴浓盐酸催化下,控温在15~20℃,反应20 h,产率可达60%左右。     

连续反应技术在柑青醛生产中的应用研究

本文通过对多种不同类型连续反应装置的结构性能进行比较研究,探索连续反应装置结构类型及尺寸参数与反应产物选择性之间的关系,最终设计出一套理想的柑青醛连续生产工艺(反应装置),从而实现降低能耗50%、提高产物收率13%、质量达到国外产品同等水平、降低生产成本20%。     

Fe配合物催化的乙醛氢化反应机制的理论研究

利用Gaussian 03程序对Fe配合物催化的乙醛氢化反应机制进行了理论研究。此氢化反应包括两个过程:氢转移过程和氢活化过程。对于氢活化过程,本文根据是否需要乙醇的协助提出了两种反应路径:路径1是Fe的配合物单独与H2进行加成反应,路径2是Fe配合物在乙醇的协助下与H2进行加成反应。利用密度泛函理论对反应历程中所涉及到所有反应物、过渡态和产物的基态进行优化,并利用Gaussian 03程序中的NBO关键字对优化得到的反应物、过渡态和产物的构型进行了NPA电荷分析。通过比较反应能垒得到路径2是比较容易发生的反应,并得出在Fe配合物催化氢化乙醛的反应循环中,氢转移过程为决速步的结论。     

芳胺与芳醛希夫碱化合物的合成与表征

以3-硝基-4-羟基吡啶为原料,经过溴化、硝化、还原等反应,合成了5-溴-3,4-二氨基吡啶。然后分别以各种芳氨和芳醛为原料,以无水甲醇和离子液体为溶剂,合成了6种新型杂环希夫碱化合物6a～6f。所得化合物用IR和1 H NMR进行了确证,并考察了离子液体等对希夫碱收率的影响因素。     

乙醛氧化生成乙酸反应机理的分子模拟

采用基于密度泛函理论(DFT)的量子化学方法研究了乙醛氧化生成乙酸的反应过程。结果表明：无氧条件下链引发过程最难发生,反应能垒达到380.78 kJ/mol,但氧气可将此过程的反应能垒降至116.26 kJ/mol;乙酰基自由基生成过氧乙酸以及链终止反应的各步骤的反应能垒均较低,反应较快;过氧乙酸转化为乙酸的反应较难发生,为整体反应过程的速率控制环节。此过程有2个可能的反应路径,速率控制步骤分别为过氧乙酸均裂生成乙酸自由基和羟基自由基的过程和过氧乙酸和乙醛反应生成乙醛单过氧乙酸酯中间化合物的过程,反应能垒分别为147.18、137.21 kJ/mol。     

EO/EG装置生产过程中有机酸的生成原因分析

分析了环氧乙烷，乙二醇装置工艺系统中有机酸生成的原因．指出在银催化剂作用下，乙烯氧化过程有机酸生成主要成分是甲酸和乙酸，银催化剂不是影响氧化反应器出口醛含量的主要因素；杂质、温度等对反应器出口气中的醛含量有重要影响，也直接影响到装置前系统的有机酸含量；乙二醇后系统中有机酸的增加仅取决于两级吸收及解析工艺的稳定操作。     

Anionic synthesis and characterization of ω-formyl-functionalized polystyrenes

ω-Formyl-functionalized polystyrenes can be synthesized in quantitative yield by reacting poly(styryl)lithium (M _n = 2 × 10³?8 × 10³ g/mol) in benzene with a 0.1?0.4 molar excess of 4-morpholinecarboxaldehyde followed by methanol termination and precipitation into methanol. Narrow molecular weight distribution ω-formyl-functionalized polystyrenes were characterized by hydroxylamine end-group titration, thin layer chromatography and both ¹H and ¹³C NMR spectroscopy. The mechanism of the functionalization was studied by trapping the tetrahedral α-amino alkoxide intermediate with diphenylphosphinic chloride.     

Direct Synthesis of Hemiaminal Ethers via a Three‐Component Reaction of Aldehydes,Amines and Alcohols

The reaction of aldehydes, amines and alcohols usually leads to a series of equilibria from which isolation of one product is difficult to achieve. We have found that this three‐component reaction can be controlled and directed in an exclusive manner toward the formation of the hemiaminal ether. A series of 33 hemiaminal ethers has been obtained in high yields, from different aldehydes, amines and alcohols, under very mild conditions just with molecular sieves as promoter.