固体超强碱在羟醛缩合中的应用研究
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摘要
随着人们的生活水平不断提高，对化学品的需求不断增加和多样化，推动了化学工业的飞速发展。人们在享受化学工业繁荣带来的巨大财富和方便的同时，化学工业造成的环境污染也不断威胁着人们的健康乃至生存，造成严重的生态灾难。为保护地球——我们共同的家园，世界各国对化学工业发展带来的负面影响进行了沉痛反思。先发展后治理，随发展随治理的发展旧模式正被淘汰和摒弃，从源头上消除化学工业造成的污染，倡导可持续发展的新观念不断深入人心。随着环境保护意识的不断增强，对绿色化学研究的投入不断增加，化学工作者不断探索新的环境友好催化剂和环境友好合成工艺。因此，绿色化学研究得到了迅速的发展，开发对环境友好催化剂和合成新工艺成为当今化学领域研究的热点。
固体碱、固体超强碱催化剂便是重要的绿色催化剂之一，与Lewis和Brφnsted液体碱性催化剂相比，固体碱催化剂具有明显的优势，尤其是固体超强碱催化剂具有催化活性高、反应温度低、易与反应体系分离、产品后处理简单、不产生环境污染、可再生重复使用等优点，可发展成为新一代对环境友好的催化材料。目前固体碱催化已成为绿色化学研究的重要内容之一，开拓其应用领域，特别是探索在有机合成中的应用研究，已成为化学工作者的使命和研究热点。
怀着对新催化剂和催化性能探究的兴趣和愿望，笔者对固体超强碱催化剂的制备方法进行了研究，采用负载法把Na~+负载到γ-Al_2O_3载体的表面，合成了γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂，同时对γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂在羰基化合物缩合中的催化应用进行了探索性研究。
本文第一章，阐述了固体碱催化剂以及固体超强碱催化剂的研究进展。分别对固体碱催化剂的分类、固体超强碱的研究进展、固体超强碱的制备、表征以及在有机催化合成中的应用进行了介绍。总结了现有固体碱催化剂的优点和缺陷，针对现有碱催化剂存在的不足，提出本课题的研究方案。
第二章，以γ-Al_2O_3为载体，在较高的温度条件下先后与NaOH和Na反应，制备了γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂。并通过XRD、SEM、BET、红外光谱、碱强度和碱浓度测定等测试手段对γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂进行表征与分析。实验结果表明，该催化剂具有比较理想的孔道结构和比表面积，碱强度H-达37，属于固体超强碱的范畴。
第三章，以γ-Al_2O_2-O_(2-)2Na~+型固体超强碱为催化剂催化合成α,α′-二亚苄基环己酮、α,α′-二亚糠基环己酮、α,α′--二亚糠基丙酮、2,5-二(对甲氧基亚苄基)环己酮及2,5-二(对甲氧基亚苄基)环戊酮，并对产物进行了FT-IR和1H-NMR表征，考察了反应物的摩尔比、反应温度、反应时间以及催化剂用量对产物收率的影响，优化了合成条件。结果表明，该催化剂催化羟醛缩合反应，反应温度低，催化效率高，工艺较简单，并对环境友好，具有广阔的工业应用价值。
With the continuous improvement of living standards, the demand for chemicals is increasingand diversification, the chemical industries have developed rapidly. People get the wealth andconvenience in the development of the chemical industry. The pollution caused by the chemicalindustry is constantly threatening people's health and survival. The chemical pollution is causingserious ecological disaster. For the protection of the Earth-our common home, the worldresponded with bitter reflection. The old mode of production should be eliminated and discarded.We should eliminate the pollution of the chemical industry and implement the sustainabledevelopment. With the growing awareness of social environmental protection, the research ofgreen chemistry is increasing. Chemists continue to explore new environmentally friendlycatalysts and environmentally friendly synthesis process. Therefore, green chemistry has been arapid development. The development of environmentally friendly catalysts and the synthesis ofnew technology become a hot topic in the field of chemical.
Solid base and solid super base is the important one of the green catalyst. Compared with theLewis and Brφnsted catalyst, solid base have some obvious advantages. Because solid base andsolid super base have high catalytic activity, low reaction temperature, and easy to be separatedfrom the reaction, gain the products easily, no pollution to environment. Solid base and solidsuper base can be used as a new generation of environmentally friendly catalytic materials.
Solid super base has become an important part of green chemistry research. Developingthe applications of solid super base, especially exploring the application of research in organicsynthesis has become a mission and research to chemists.
With Interesting in new catalysts and catalytic properties, the preparation method of solidsuper base catalyst was studied. With γ-Al_2O_3sieve as the carrier, Na+was loaded in the carriersurface. A solid super base γ-Al_2O_2-O_(2-)2Na~+was prepared successfully. The applications of thesolid super base catalyst in organic synthesis were studied preliminary.
In the first chapter of this paper, the research of solid base catalyst and solid super basecatalyst was summarized. Such as the classification, preparation of the solid super base catalysts,methods of superficial syndrome and the application in the organic synthesis and so on. Theadvantages and disadvantages of the solid base catalyst were summarized. And the topic researchplan was proposed.
In the second chapter of this paper, based on the existing research of our laboratory, the catalyst γ-Al_2O_2-O_(2-)2Na~+was improved. The structure and surface properties of the obtainedmaterials were character by XRD, FT-IR, SEM, BET and the base strength of determination. Theresults showed that the catalyst had ideal structure. The base strength was H-≥37, and theγ-Al_2O_2-O_(2-)2Na~+is solid super base catalyst.
In the third chapter of this paper, the solid super base catalyst γ-Al_2O_2-O_(2-)2Na~+was used inpreparation of α,α'-bis(benzylidene)cyclohexanones, α,α'-bis(furfuryl)cyclohexanones, α,α'-Difurf urylacetones,2,5-di(p-methoxy)cyclohexanones,2,5-di(p-methoxy)cyclopentanones. TheFT-IR and1H-NMR were characterized. The dosage of the solvent, reaction temperature,reaction time and the modification of the dosage of the super base catalyst were assessed. Theresults showed that the catalyst used in aldol reaction, the reaction temperature is low, highcatalytic efficiency, simple in the process, and environmentally friendly. The γ-Al_2O_2-O_(2-)2Na~+solid super base catalyst has a broad industrial application.
固体碱、固体超强碱催化剂便是重要的绿色催化剂之一，与Lewis和Brφnsted液体碱性催化剂相比，固体碱催化剂具有明显的优势，尤其是固体超强碱催化剂具有催化活性高、反应温度低、易与反应体系分离、产品后处理简单、不产生环境污染、可再生重复使用等优点，可发展成为新一代对环境友好的催化材料。目前固体碱催化已成为绿色化学研究的重要内容之一，开拓其应用领域，特别是探索在有机合成中的应用研究，已成为化学工作者的使命和研究热点。
怀着对新催化剂和催化性能探究的兴趣和愿望，笔者对固体超强碱催化剂的制备方法进行了研究，采用负载法把Na~+负载到γ-Al_2O_3载体的表面，合成了γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂，同时对γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂在羰基化合物缩合中的催化应用进行了探索性研究。
本文第一章，阐述了固体碱催化剂以及固体超强碱催化剂的研究进展。分别对固体碱催化剂的分类、固体超强碱的研究进展、固体超强碱的制备、表征以及在有机催化合成中的应用进行了介绍。总结了现有固体碱催化剂的优点和缺陷，针对现有碱催化剂存在的不足，提出本课题的研究方案。
第二章，以γ-Al_2O_3为载体，在较高的温度条件下先后与NaOH和Na反应，制备了γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂。并通过XRD、SEM、BET、红外光谱、碱强度和碱浓度测定等测试手段对γ-Al_2O_2-O_(2-)2Na~+型固体超强碱催化剂进行表征与分析。实验结果表明，该催化剂具有比较理想的孔道结构和比表面积，碱强度H-达37，属于固体超强碱的范畴。
第三章，以γ-Al_2O_2-O_(2-)2Na~+型固体超强碱为催化剂催化合成α,α′-二亚苄基环己酮、α,α′-二亚糠基环己酮、α,α′--二亚糠基丙酮、2,5-二(对甲氧基亚苄基)环己酮及2,5-二(对甲氧基亚苄基)环戊酮，并对产物进行了FT-IR和1H-NMR表征，考察了反应物的摩尔比、反应温度、反应时间以及催化剂用量对产物收率的影响，优化了合成条件。结果表明，该催化剂催化羟醛缩合反应，反应温度低，催化效率高，工艺较简单，并对环境友好，具有广阔的工业应用价值。
With the continuous improvement of living standards, the demand for chemicals is increasingand diversification, the chemical industries have developed rapidly. People get the wealth andconvenience in the development of the chemical industry. The pollution caused by the chemicalindustry is constantly threatening people's health and survival. The chemical pollution is causingserious ecological disaster. For the protection of the Earth-our common home, the worldresponded with bitter reflection. The old mode of production should be eliminated and discarded.We should eliminate the pollution of the chemical industry and implement the sustainabledevelopment. With the growing awareness of social environmental protection, the research ofgreen chemistry is increasing. Chemists continue to explore new environmentally friendlycatalysts and environmentally friendly synthesis process. Therefore, green chemistry has been arapid development. The development of environmentally friendly catalysts and the synthesis ofnew technology become a hot topic in the field of chemical.
Solid base and solid super base is the important one of the green catalyst. Compared with theLewis and Brφnsted catalyst, solid base have some obvious advantages. Because solid base andsolid super base have high catalytic activity, low reaction temperature, and easy to be separatedfrom the reaction, gain the products easily, no pollution to environment. Solid base and solidsuper base can be used as a new generation of environmentally friendly catalytic materials.
Solid super base has become an important part of green chemistry research. Developingthe applications of solid super base, especially exploring the application of research in organicsynthesis has become a mission and research to chemists.
With Interesting in new catalysts and catalytic properties, the preparation method of solidsuper base catalyst was studied. With γ-Al_2O_3sieve as the carrier, Na+was loaded in the carriersurface. A solid super base γ-Al_2O_2-O_(2-)2Na~+was prepared successfully. The applications of thesolid super base catalyst in organic synthesis were studied preliminary.
In the first chapter of this paper, the research of solid base catalyst and solid super basecatalyst was summarized. Such as the classification, preparation of the solid super base catalysts,methods of superficial syndrome and the application in the organic synthesis and so on. Theadvantages and disadvantages of the solid base catalyst were summarized. And the topic researchplan was proposed.
In the second chapter of this paper, based on the existing research of our laboratory, the catalyst γ-Al_2O_2-O_(2-)2Na~+was improved. The structure and surface properties of the obtainedmaterials were character by XRD, FT-IR, SEM, BET and the base strength of determination. Theresults showed that the catalyst had ideal structure. The base strength was H-≥37, and theγ-Al_2O_2-O_(2-)2Na~+is solid super base catalyst.
In the third chapter of this paper, the solid super base catalyst γ-Al_2O_2-O_(2-)2Na~+was used inpreparation of α,α'-bis(benzylidene)cyclohexanones, α,α'-bis(furfuryl)cyclohexanones, α,α'-Difurf urylacetones,2,5-di(p-methoxy)cyclohexanones,2,5-di(p-methoxy)cyclopentanones. TheFT-IR and1H-NMR were characterized. The dosage of the solvent, reaction temperature,reaction time and the modification of the dosage of the super base catalyst were assessed. Theresults showed that the catalyst used in aldol reaction, the reaction temperature is low, highcatalytic efficiency, simple in the process, and environmentally friendly. The γ-Al_2O_2-O_(2-)2Na~+solid super base catalyst has a broad industrial application.
引文
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