苯并三氮唑及其衍生物的合成研究
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摘要
苯并三氮唑(BTA)是一类重要的有机合成中间体,主要应用于水质稳定剂,防腐剂,光稳定剂等领域中。其衍生物如三氟甲基苯并三氮唑等在生物化学、医药、农药等领域得到了广泛的应用。近年来,苯并三氮唑的需求量越来越大。而我国现有的苯并三氮唑的生产规模小,工艺落后,远不能满足社会需要。苯并三氮唑类衍生物由于具有多种生物活性,关于它们的合成以及活性研究受到越来越广泛的关注,因此,苯并三氮唑及其衍生物的研究与开发具有重要的意义。
本课题首先采用原料廉价易得的邻硝基氯苯法合成苯并三氮唑,对合成过程进行了研究。合成过程分两步,第一步,以邻硝基氯苯为原料,与水合肼反应得1-羟基苯并三氮唑(HBTA),实验采用溶剂法和相转移催化法两种合成方法,通过考察不同因素对产物收率的影响,得出最佳的工艺条件。在最佳工艺条件下,两种合成方法的产品收率都可达98%以上。但溶剂法存在溶剂价格高、沸点较高、回收困难、能耗大、成本高等缺点;而相转移催化法具有工艺原料摩尔比较小、反应时间较短、操作简便、能耗小等优点,同时,相转移催化剂PEG-800具有来源丰富、价格低、稳定性好、没有毒性、环境友好等特点,是具有工业前景的合成方法。因此选用相转移催化法合成1-羟基苯并三氮唑(HBTA),最佳工艺条件为:邻硝基氯苯、水合肼与PEG-800摩尔比为1:4:0.03,反应温度110℃、反应5h,搅拌速度500r/min,产品收率达98.1%,含量99.3%。第二步,以1-羟基苯并三氮唑为原料,在电解质存在下,与铁粉反应还原为苯并三氮唑(BTA),考察了不同的因素对还原产物收率的影响,得出了较佳的工艺条件为:HBTA与Fe粉摩尔比为1:2.5,还原温度85℃,反应时间4h,异辛醇为萃取剂,收率为88.7%,含量96.4%。
同时,本课题对HBTA和BTA建立了液相色谱分析方法。在一定质量浓度范围内,测定了方法的线性相关系数、回收率和精密度。HBTA回收率在98.0～103.0%之间,变异系数为0.25%,线性相关系数为0.9989。BTA的回收率在97.5～100.4%之间,变异系数为0.18%,线性相关系数为0.9992。该方法能快速有效对1-羟基苯并三氮唑和苯并三氮唑进行检测。
最后,本文由苯并三氮唑出发,采用微波辐射加热,干法合成了1-苄基苯并三唑和二(1-H-苯并三唑基)丙烷两种苯并三氮唑衍生物。分别试验了微波辐射功率,反应时间,物料配比,催化剂种类及用量对反应产率的影响,得出合成两种衍生物的较佳工艺条件,并对合成产物进行了IR、1HNMR分析。研究结果表明:微波辐射技术应用于有机反应显著缩短了反应时间,极大地提高了反应速率,操作简单,符合节能、清洁生产、绿色化学的当代化学化工发展趋势。
Benzotriazole (BTA) is an important organic synthesis intermediates,it is mainly used in the field of water stabilizers, preservatives, optical stabilizers and so on. Its derivatives such as trifluoromethyl benzotriazole are widely used in biochemistry, medicine, pesticides and other areas. In recent years, the need of benzotriazole is growing bigger and bigger. However, in China, the existing production of benzotriazole is small in scale, backward in technology, far from being able to meet the needs of the community. Due to a variety of biological activity, benzotriazole derivatives receive wider and wider spread attention about their synthesis as well as the activity research. Therefore, it is important that we must make efforts to explore the research and development of benzotriazole and its derivatives.
In this paper, firstly, synthesizing technology of benzotriazole was studied, using cheap and simple O-nitrochlorobenzene as material, the process contains two steps: the first step was that 1-hydroxy benzotriazole (HBTA) was obtained by O-nitrochlorobenzene reacted with hydrazine hydrate. Solvent method and phase-transfer catalysis method have been used, the synthesis conditions on the yield were studied by experiments, under the best conditions, the yield of products exceeded 98%, but the solvent method has some shortcomings: high price of solvent, high boiling point, difficult recovery, energy consumption, high cost and so on; the phase-transfer catalysis process has some advantages: the small mole ratio of raw materials, the reaction time is shorter, easy to operate, low energy consumption, and the phase transfer catalyst PEG-800 is abundant, low price, good stability, none toxicity and environmentally friendly. So phase-transfer catalysis process is the prospect industrial synthetic method of HBTA. The optimum reaction conditions of HBTA were as follows: the molar of O-chloronitrobenzene to hydrazine hydrate to PEG-800 was 1:4:0.03, the reaction time、the reaction temperature、the yield and the purity was 5h、110℃、98.1% and 99.3%.The second step of the process is HBTA reverted to benzotriazole, in the presence of electrolytes, HBTA as raw material, iron reduction is used in this step,The different factors affecting the reaction were investigated,the optimum reaction conditions of BTA were as follows: the molar of HBTA to Fe was 1:2.5, isooctyl alcohol as extracting agent, the reaction time、the reaction temperature、the yield and the purity was 4 h、85℃、88.7% and 96.4%.
At the same time, the liquid chromatography analysis method of HBTA and BTA are established. In a certain concentration range, the linear correlation coefficient、the recovery and the accuracy of the method are measured: HBTA, the recovery was 98.0~103.0%,the coefficient of variation was 0.25%,the linear correlation coefficient was 0.9989. The corresponding coefficient of BTA were:98.0～100.4%,0.18%,0.9992. This method can rapidly and effectively detect HBTA and BTA.
Finally, N-1-benzylbenzotriazole and bis(benzotriazol-1-yl)-a-w-propane are synthesized by dry method of microwave radiation from benzotriazole . Microwave radiation power, reaction time, ratio of raw materials, the type and amount of catalyst on the reaction yield were tested in the paper, the optimum conditions were obtained, their structures were determined by IR and 1HNMR.The results showed: microwave radiation technology for organic reactions significantly shorten the reaction time and greatly improve the reaction rate. It conforms to the energy conservation, the clean production, the green chemistry development tendency.
本课题首先采用原料廉价易得的邻硝基氯苯法合成苯并三氮唑,对合成过程进行了研究。合成过程分两步,第一步,以邻硝基氯苯为原料,与水合肼反应得1-羟基苯并三氮唑(HBTA),实验采用溶剂法和相转移催化法两种合成方法,通过考察不同因素对产物收率的影响,得出最佳的工艺条件。在最佳工艺条件下,两种合成方法的产品收率都可达98%以上。但溶剂法存在溶剂价格高、沸点较高、回收困难、能耗大、成本高等缺点;而相转移催化法具有工艺原料摩尔比较小、反应时间较短、操作简便、能耗小等优点,同时,相转移催化剂PEG-800具有来源丰富、价格低、稳定性好、没有毒性、环境友好等特点,是具有工业前景的合成方法。因此选用相转移催化法合成1-羟基苯并三氮唑(HBTA),最佳工艺条件为:邻硝基氯苯、水合肼与PEG-800摩尔比为1:4:0.03,反应温度110℃、反应5h,搅拌速度500r/min,产品收率达98.1%,含量99.3%。第二步,以1-羟基苯并三氮唑为原料,在电解质存在下,与铁粉反应还原为苯并三氮唑(BTA),考察了不同的因素对还原产物收率的影响,得出了较佳的工艺条件为:HBTA与Fe粉摩尔比为1:2.5,还原温度85℃,反应时间4h,异辛醇为萃取剂,收率为88.7%,含量96.4%。
同时,本课题对HBTA和BTA建立了液相色谱分析方法。在一定质量浓度范围内,测定了方法的线性相关系数、回收率和精密度。HBTA回收率在98.0～103.0%之间,变异系数为0.25%,线性相关系数为0.9989。BTA的回收率在97.5～100.4%之间,变异系数为0.18%,线性相关系数为0.9992。该方法能快速有效对1-羟基苯并三氮唑和苯并三氮唑进行检测。
最后,本文由苯并三氮唑出发,采用微波辐射加热,干法合成了1-苄基苯并三唑和二(1-H-苯并三唑基)丙烷两种苯并三氮唑衍生物。分别试验了微波辐射功率,反应时间,物料配比,催化剂种类及用量对反应产率的影响,得出合成两种衍生物的较佳工艺条件,并对合成产物进行了IR、1HNMR分析。研究结果表明:微波辐射技术应用于有机反应显著缩短了反应时间,极大地提高了反应速率,操作简单,符合节能、清洁生产、绿色化学的当代化学化工发展趋势。
Benzotriazole (BTA) is an important organic synthesis intermediates,it is mainly used in the field of water stabilizers, preservatives, optical stabilizers and so on. Its derivatives such as trifluoromethyl benzotriazole are widely used in biochemistry, medicine, pesticides and other areas. In recent years, the need of benzotriazole is growing bigger and bigger. However, in China, the existing production of benzotriazole is small in scale, backward in technology, far from being able to meet the needs of the community. Due to a variety of biological activity, benzotriazole derivatives receive wider and wider spread attention about their synthesis as well as the activity research. Therefore, it is important that we must make efforts to explore the research and development of benzotriazole and its derivatives.
In this paper, firstly, synthesizing technology of benzotriazole was studied, using cheap and simple O-nitrochlorobenzene as material, the process contains two steps: the first step was that 1-hydroxy benzotriazole (HBTA) was obtained by O-nitrochlorobenzene reacted with hydrazine hydrate. Solvent method and phase-transfer catalysis method have been used, the synthesis conditions on the yield were studied by experiments, under the best conditions, the yield of products exceeded 98%, but the solvent method has some shortcomings: high price of solvent, high boiling point, difficult recovery, energy consumption, high cost and so on; the phase-transfer catalysis process has some advantages: the small mole ratio of raw materials, the reaction time is shorter, easy to operate, low energy consumption, and the phase transfer catalyst PEG-800 is abundant, low price, good stability, none toxicity and environmentally friendly. So phase-transfer catalysis process is the prospect industrial synthetic method of HBTA. The optimum reaction conditions of HBTA were as follows: the molar of O-chloronitrobenzene to hydrazine hydrate to PEG-800 was 1:4:0.03, the reaction time、the reaction temperature、the yield and the purity was 5h、110℃、98.1% and 99.3%.The second step of the process is HBTA reverted to benzotriazole, in the presence of electrolytes, HBTA as raw material, iron reduction is used in this step,The different factors affecting the reaction were investigated,the optimum reaction conditions of BTA were as follows: the molar of HBTA to Fe was 1:2.5, isooctyl alcohol as extracting agent, the reaction time、the reaction temperature、the yield and the purity was 4 h、85℃、88.7% and 96.4%.
At the same time, the liquid chromatography analysis method of HBTA and BTA are established. In a certain concentration range, the linear correlation coefficient、the recovery and the accuracy of the method are measured: HBTA, the recovery was 98.0~103.0%,the coefficient of variation was 0.25%,the linear correlation coefficient was 0.9989. The corresponding coefficient of BTA were:98.0～100.4%,0.18%,0.9992. This method can rapidly and effectively detect HBTA and BTA.
Finally, N-1-benzylbenzotriazole and bis(benzotriazol-1-yl)-a-w-propane are synthesized by dry method of microwave radiation from benzotriazole . Microwave radiation power, reaction time, ratio of raw materials, the type and amount of catalyst on the reaction yield were tested in the paper, the optimum conditions were obtained, their structures were determined by IR and 1HNMR.The results showed: microwave radiation technology for organic reactions significantly shorten the reaction time and greatly improve the reaction rate. It conforms to the energy conservation, the clean production, the green chemistry development tendency.
引文
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[3] 丁著明,王玲.苯并三唑类光稳定剂的研究进展[J].化工文摘,2004,(6):34-36.
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