离子液体在有机合成中的拓展研究
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摘要
目前,学术和工业界均致力于环境友好型技术的研发,以解决传统挥发性有机溶剂和腐蚀性催化剂所带来的污染问题。室温离子液体(RTIL,简称离子液体,IL)作为环境友好的“清洁”介质,具有蒸汽压低、不易挥发、稳定性和电导性好、液程宽、不可燃、无污染等优点。近年来,离子液体作为催化剂和溶剂在有机合成中得到了广泛应用,但其在阿司匹林合成反应、苯胺合成反应以及舒巴坦酸合成反应中的应用却未见相关报道。此三类合成反应的传统工艺过程由于使用了大量的有机溶剂和无机酸催化剂,不可避免会导致系列环境问题。采用离子液体替代传统有机溶剂和催化剂,可有效解决上述问题,基本实现反应过程的绿色化。因此,推广此三类反应进一步拓展离子液体在有机合成中的应用具有重要的创新意义和应用价值。
本论文主要包括以下三个方面内容：
1.离子液体在阿司匹林合成反应中的应用研究
传统的阿司匹林合成反应在浓硫酸催化下进行,存在副反应多、腐蚀设备和环境污染严重等缺点。本论文选择五种1,3-二烷基咪唑离子液体为催化剂应用于水杨酸和乙酸酐合成阿司匹林的反应中,考察反应时间、酸醇物质的量比等反应条件对该反应的影响。实验结果表明：离子液体1-丁基-3-甲基咪唑溴盐[bmim]Br对阿司匹林的合成有较好的催化效果,最佳反应条件为：n水杨酸：n乙酸酐=1：2,离子液体用量2 mL,反应温度80-85℃,反应时间3 h,产率最高可达81.6%。产物和离子液体不溶而分层,易于分离,离子液体重复使用5次后其催化活性无明显降低。
2.离子液体在苯胺合成反应中的应用研究
水合肼法制备芳胺的还原反应可在甲酸、乙酸、二氯乙烷等有机溶剂中进行,但存在反应时间长、水合肼用量大以及环境污染严重等缺点。本论文选择五种Brφnsted酸性离子液体作为反应溶剂,研究了以硝基苯为反应底物、Y.氧化铝作催化剂的水合肼还原硝基苯制苯胺的反应。通过考察还原过程中反应时间、温度、水合肼用量、催化剂用量等对产率的影响,确定了最佳反应条件为：n硝基苯：n水合肼=1：1.9,催化剂用量0.3 g,反应温度80℃,反应时间1 h,产率最高可达96.0%。这一反应体系有以下几个优点：1)反应时间短(约1 h),反应条件温和,产率较好；2)催化剂在离子液体中的分散性较好,催化活性增强；3)不必使用高浓度水合肼,可显著降低成本。
3.离子液体在舒巴坦酸合成反应中的应用研究
舒巴坦酸合成反应可在乙酸乙酯或二氯甲烷有机相中进行,并采用硫酸作氢源,存在产率低、设备腐蚀和污染严重等缺点。本论文选择了三种离子液体做为溶剂,探索了以水合肼作为氢源、铸铁铁粉作为电子转移剂的舒巴坦酸合成反应。通过考察还原过程中反应时间、温度、水合肼用量、铸铁铁粉用量等对产率的影响,确定了最佳反应条件为：n二溴青霉烷砜酸：n水合肼：n铸铁铁粉=1：10：4.5,反应温度25℃,反应时间4 h,产率最高可得87.0%。该方法具有反应条件温和、产率较高、不腐蚀设备等优点,为制备含卤素化合物脱卤合成目标产物提供了一种新的方法,同时也为治理芳香卤化物废水污染开辟了一条具有理论和应用价值的新途径。
Currently, a major drive is underway in academia and industry to substitute more environmentally friendly technologies for traditional ones in which damaging catalysts and volatile organic solvents are heavily used. Room temperature ionic liquid (RTIL, called IL for short) are considered as environmentally benign solvents, not only because of their low vapor pressures, but more importantly, also because of their ability to act as catalysts. Moreover, RTILs have several other attractive properties, including chemical and thermal stability, nonflammability, high ionic conductivity, and a wide electrochemical potential window. Recent years, ILs have been widely used as catalysts and solvents in organic synthesis, but those researches of application in the synthesis of aspirin, aromatic amines and sulbactam acid were hardly reported. On the other hand,the traditional technology for the three kind of syntheses, using organic reagent and inorganic acid as solvent or catalyst, which inevitably brought on serious environmental pollution and equipment corrosion,but instead,those problems can be solved by introducing ionic liquids as solvent or catalyst applied to the reaction. Therefore, further extended researches of ILs in organic synthesis have great significance and application values. This dissertation includes the three following aspects:
1. Research on the application of ILs in synthesis of Aspirin
Synthesis of Aspirin can be carried out in sulfuric acid, however, having some shortcomings, such as:the existence of many side reactions, corrosion of equipment and environmental pollution and etc. In this paper the synthesis of aspirin was investigated in 5 kinds of ionic liquids 1,3-dialkylimidazolium. The effects of reaction time and ratio of acid to alcohol on the reaction were examined. Experimental results showed that ionic liquid [bmim]Br could be used as a catalyst of aspirin. The optimized estefification conditions were:(n)salicylic acid:(n)acetic anhydride=1:2, catalyst 2 mL, reaction temperature 80-85℃, reaction time 3 h. The yield of esterification could reach 81.6%. The isolation of desired products could be achieved via simple decantation and the ILs can be reused five times without significant decrease of its catalytic activity.
2. Research on the application of ILs in synthesis of aromatic amine
Synthesis of aromatic amine can be carried out in organic solvents, such as formic acid, acetic acid, dichloroethane and other organic solvents, which have some shortcomings:a long reaction time, a large amount of hydrazine hydrate, and serious environmental pollution and etc. In this paper, by employing 5 kinds of Brφnsted acidic ionic liquids as the reaction solvent, the reduction of nitrobenzene to aniline in the presence of hydrazine hydrate catalyzed by Y-alumina can be achieved.The effects of reaction time, temperature and amount of hydrazine hydrate and catalyst on the reaction were also examined. Experimental results showed that the optimized reduction conditions were:(n) nitrobenzene:(n) hydrazine hydrate=1:1.9, catalyst 0.3 g, reaction temperature 80℃. reaction time 1h. The yield of reduction could reach 96.0%. This study identified several advantages of the reaction carried out in ionic liquids, namely:1)shorter reaction time,milder conditions,satisfied yield; 2) higher catalyst distribution in the ionic liquids,exerted a strong influence on catalytic activity; 3)lower concentration of hydrazine hydrate, eased the cost.
3. Research on the application of ILs in synthesis of Sulbactam acid
Sulbactam acid synthesis can be carried out in organic phases of ethyl acetate or methylene chloride with using sulfuric acid as the catalyst and solvent, which have some shortcomings, such as:the existence of low yield, and serious corrosion and pollution. In this paper, by employing 3 kinds of Brφnsted acidic ionic liquids both as the reaction solvent and catalyst, hydrazine hydrate as the hydrogen source,cast iron as the electron transfer agent of the environment, the synthesis of Sulbactam acid can be achieved. The effects of reaction time, temperature and amount of hydrazine hydrate and cast iron powder on the reaction were also examined. Experimental results showed that the optimized reduction conditions were:The optimized conditions were:n(dibromo penicillin sulfoxide acid):n(hydrazine hydrate):n(cast iron powder)=1:10:4.5, reaction temperature 25℃, reaction time 4 h, the yield obtained 87.0% at most. The study identified several advantages, such as:milder conditions, satisfied yield, no serious corrosion and pollution. Therefore, it provided a new approach for the preparation of halogen-containing compounds synthesized through dehalogenation, and also for the management of wastewater pollution of aromatic halides, a theoretical and practical value of the new approach.
本论文主要包括以下三个方面内容：
1.离子液体在阿司匹林合成反应中的应用研究
传统的阿司匹林合成反应在浓硫酸催化下进行,存在副反应多、腐蚀设备和环境污染严重等缺点。本论文选择五种1,3-二烷基咪唑离子液体为催化剂应用于水杨酸和乙酸酐合成阿司匹林的反应中,考察反应时间、酸醇物质的量比等反应条件对该反应的影响。实验结果表明：离子液体1-丁基-3-甲基咪唑溴盐[bmim]Br对阿司匹林的合成有较好的催化效果,最佳反应条件为：n水杨酸：n乙酸酐=1：2,离子液体用量2 mL,反应温度80-85℃,反应时间3 h,产率最高可达81.6%。产物和离子液体不溶而分层,易于分离,离子液体重复使用5次后其催化活性无明显降低。
2.离子液体在苯胺合成反应中的应用研究
水合肼法制备芳胺的还原反应可在甲酸、乙酸、二氯乙烷等有机溶剂中进行,但存在反应时间长、水合肼用量大以及环境污染严重等缺点。本论文选择五种Brφnsted酸性离子液体作为反应溶剂,研究了以硝基苯为反应底物、Y.氧化铝作催化剂的水合肼还原硝基苯制苯胺的反应。通过考察还原过程中反应时间、温度、水合肼用量、催化剂用量等对产率的影响,确定了最佳反应条件为：n硝基苯：n水合肼=1：1.9,催化剂用量0.3 g,反应温度80℃,反应时间1 h,产率最高可达96.0%。这一反应体系有以下几个优点：1)反应时间短(约1 h),反应条件温和,产率较好；2)催化剂在离子液体中的分散性较好,催化活性增强；3)不必使用高浓度水合肼,可显著降低成本。
3.离子液体在舒巴坦酸合成反应中的应用研究
舒巴坦酸合成反应可在乙酸乙酯或二氯甲烷有机相中进行,并采用硫酸作氢源,存在产率低、设备腐蚀和污染严重等缺点。本论文选择了三种离子液体做为溶剂,探索了以水合肼作为氢源、铸铁铁粉作为电子转移剂的舒巴坦酸合成反应。通过考察还原过程中反应时间、温度、水合肼用量、铸铁铁粉用量等对产率的影响,确定了最佳反应条件为：n二溴青霉烷砜酸：n水合肼：n铸铁铁粉=1：10：4.5,反应温度25℃,反应时间4 h,产率最高可得87.0%。该方法具有反应条件温和、产率较高、不腐蚀设备等优点,为制备含卤素化合物脱卤合成目标产物提供了一种新的方法,同时也为治理芳香卤化物废水污染开辟了一条具有理论和应用价值的新途径。
Currently, a major drive is underway in academia and industry to substitute more environmentally friendly technologies for traditional ones in which damaging catalysts and volatile organic solvents are heavily used. Room temperature ionic liquid (RTIL, called IL for short) are considered as environmentally benign solvents, not only because of their low vapor pressures, but more importantly, also because of their ability to act as catalysts. Moreover, RTILs have several other attractive properties, including chemical and thermal stability, nonflammability, high ionic conductivity, and a wide electrochemical potential window. Recent years, ILs have been widely used as catalysts and solvents in organic synthesis, but those researches of application in the synthesis of aspirin, aromatic amines and sulbactam acid were hardly reported. On the other hand,the traditional technology for the three kind of syntheses, using organic reagent and inorganic acid as solvent or catalyst, which inevitably brought on serious environmental pollution and equipment corrosion,but instead,those problems can be solved by introducing ionic liquids as solvent or catalyst applied to the reaction. Therefore, further extended researches of ILs in organic synthesis have great significance and application values. This dissertation includes the three following aspects:
1. Research on the application of ILs in synthesis of Aspirin
Synthesis of Aspirin can be carried out in sulfuric acid, however, having some shortcomings, such as:the existence of many side reactions, corrosion of equipment and environmental pollution and etc. In this paper the synthesis of aspirin was investigated in 5 kinds of ionic liquids 1,3-dialkylimidazolium. The effects of reaction time and ratio of acid to alcohol on the reaction were examined. Experimental results showed that ionic liquid [bmim]Br could be used as a catalyst of aspirin. The optimized estefification conditions were:(n)salicylic acid:(n)acetic anhydride=1:2, catalyst 2 mL, reaction temperature 80-85℃, reaction time 3 h. The yield of esterification could reach 81.6%. The isolation of desired products could be achieved via simple decantation and the ILs can be reused five times without significant decrease of its catalytic activity.
2. Research on the application of ILs in synthesis of aromatic amine
Synthesis of aromatic amine can be carried out in organic solvents, such as formic acid, acetic acid, dichloroethane and other organic solvents, which have some shortcomings:a long reaction time, a large amount of hydrazine hydrate, and serious environmental pollution and etc. In this paper, by employing 5 kinds of Brφnsted acidic ionic liquids as the reaction solvent, the reduction of nitrobenzene to aniline in the presence of hydrazine hydrate catalyzed by Y-alumina can be achieved.The effects of reaction time, temperature and amount of hydrazine hydrate and catalyst on the reaction were also examined. Experimental results showed that the optimized reduction conditions were:(n) nitrobenzene:(n) hydrazine hydrate=1:1.9, catalyst 0.3 g, reaction temperature 80℃. reaction time 1h. The yield of reduction could reach 96.0%. This study identified several advantages of the reaction carried out in ionic liquids, namely:1)shorter reaction time,milder conditions,satisfied yield; 2) higher catalyst distribution in the ionic liquids,exerted a strong influence on catalytic activity; 3)lower concentration of hydrazine hydrate, eased the cost.
3. Research on the application of ILs in synthesis of Sulbactam acid
Sulbactam acid synthesis can be carried out in organic phases of ethyl acetate or methylene chloride with using sulfuric acid as the catalyst and solvent, which have some shortcomings, such as:the existence of low yield, and serious corrosion and pollution. In this paper, by employing 3 kinds of Brφnsted acidic ionic liquids both as the reaction solvent and catalyst, hydrazine hydrate as the hydrogen source,cast iron as the electron transfer agent of the environment, the synthesis of Sulbactam acid can be achieved. The effects of reaction time, temperature and amount of hydrazine hydrate and cast iron powder on the reaction were also examined. Experimental results showed that the optimized reduction conditions were:The optimized conditions were:n(dibromo penicillin sulfoxide acid):n(hydrazine hydrate):n(cast iron powder)=1:10:4.5, reaction temperature 25℃, reaction time 4 h, the yield obtained 87.0% at most. The study identified several advantages, such as:milder conditions, satisfied yield, no serious corrosion and pollution. Therefore, it provided a new approach for the preparation of halogen-containing compounds synthesized through dehalogenation, and also for the management of wastewater pollution of aromatic halides, a theoretical and practical value of the new approach.
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