温控相分离催化剂的合成及催化分子间Stetter反应研究
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摘要
离子液体用于液/液两相催化是解决催化剂分离回收的一个新方法。本文基于温控相分离催化(TPSC)的概念,设计、合成出系列含有不同乙氧基链(n=11,16,42)和不同阴离子(Cl-、Br-、I-、BF4-、PF6-)的噻唑基和三唑基温控相分离离子液体催化剂,并用核磁(NMR)、红外(IR)对其结构进行了表征。考察不同温度下催化剂在不同有机溶剂中的溶解性,发现催化剂在甲苯/正庚烷混合溶剂中具有临界溶解温度(CST),表现出“高温均相反应,低温两相分离”的温控特性。
将首次设计、合成的具有温控效应的催化剂应用于催化丁醛与丙烯酸乙酯和呋喃甲醛与丙烯酸乙酯之间的stetter反应,考察了阴离子和乙氧基链的不同对反应的影响,发现当催化剂阴离子为溴负离子且乙氧基链为n=16的温控催化剂对stetter反应具有较好的催化活性和循环使用寿命。并且优化出较佳的工艺条件。
n=16的温控相分离噻唑溴催化剂在催化丁醛与丙烯酸乙酯反应的较佳工艺条件为：反应时间12 h,反应温度60℃,催化剂用量为反应原料的15%mol,转化率为99.0%,收率37.2%。催化剂循环使用6次,转化率在96.0%以上,收率高于34.0%；催化呋喃甲醛与丙烯酸乙酯反应的条件为：反应时间12 h,反应温度60℃,催化剂用量为反应原料的15%mol,转化率为99.0%,收率为42.3%。催化剂重复使用8次,转化率在95.0%以上,产率高于35.0%。
n=16的温控相分离三唑溴催化剂在催化丁醛与丙烯酸乙酯反应的较佳的工艺条件为：反应时间12h,反应温度70℃,催化剂用量为反应原料的15%mol,转化率为99.0%,产率为37.4%。催化剂重复使用5次,转化率在95.0%以上,产率高于34.0%；催化呋喃甲醛与丙烯酸乙酯的反应的较佳反应条件为：反应时间16 h,反应温度70℃,催化剂用量为反应原料的20%mol,转化率为99.0%,产率为41.8%。催化剂循环使用6次,转化率在95.0%以上,产率高于36.0%。循环实验结束后,催化剂质量损失约4.0%-5.0%。并用气-质联用(GC-MS)对stetter反应体系副产物进行分析,确定了副产物的结构和反应机理。
噻唑基、三唑基温控相分离催化剂催化stetter反应,反应体系具有“高温均相反应,低温两相分离”的特性,实现了反应-分离一体化,为有机反应中的绿色催化提供了一条新思路,也为液/液两相催化在其它有机反应中的应用做出了有效地借鉴。
Ionic liquids for liquid/liquid two-phase catalysis provides a new approach of resolving the catalyst separation and recovery. Based on the concept of thermoregulated phase-separable catalysis (TPSC), a series thiazolium and triazolium thermoregulated ionic liquid catalysts with different polyether-substituted chain (n=11,16,42) and different anion (Cl, Br-, I, BF4-, PF6-) were designed and synthesized. The structures of new compounds were characterized by NMR and IR. The solubility of catalysts in different temperatures and organic solvents were studied. The results showed that the catalysts possessed a critical solution temperature (CST) in toluene/n-heptane mixed solvent and exhibited the properties of "homogeneous reaction in high temperature and two-phase separation in low temperature".
The thermoregulated ionic liquid catalysts were used in Stetter reaction of ethyl acrylate with furfural and n-butanal. The effects of anion and ethoxy chain on reactions were investigated. The catalyst with bromine anion and ethoxy chain length n=16 showed good catalysis and recycle. The reaction conditions were also optimized.
In the stetter reaction of ethyl acrylate with n-butanal catalyzed by the thiazolium ionic liquid catalyst with Br- and n=16, the optimum reaction conditions were as follow:t=12 h, T=60℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of n-butanal and yield were 99.0% and 37.2%, respectively. After 6 recycles of the catalyst, the conversion and yield still could reach up to 96.0% and 34.0%, respectively. In the Stetter reaction of ethyl acrylate with furfural catalyzed by the thiazolium ionic liquid catalyst with Br-and n=16, the optimum reaction conditions were as follow:t=12 h, T=60℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of furfural and yield were 99.0% and 42.3%, respectively. After 8 recycles of the catalyst, the conversion and yield still were higher than 95.0% and 35.0%, respectively.
In the Stetter reaction of ethyl acrylate with n-butanal catalyzed by the triazolium ionic liquid catalyst with Br-and n=16, the optimum reaction conditions were as follow:t=16 h, T=70℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of n-butanal and yield were 99.0% and 37.4%, respectively. After 5 recycles of the catalyst, the conversion and yield still could reach up to 95.0% and 34.0%, respectively. In the Stetter reaction of ethyl acrylate with furfural catalyzed by the triazolium ionic liquid catalyst with Br- and n=16, the optimum reaction conditions were as follow:t=16 h, T=70℃, and the quantity of catalyst of 20 mol%. Under the optimum reaction conditions, the conversion of furfural and yield were 99.0% and 41.8%, respectively. After 6 recycles of the catalyst, the conversion and yield still were higher than 95.0% and 36.0%, respectively. The loss of the catalyst was about 4%-5% after 6 recycles. The byproducts of Stetter reactions were determined by GC-MS, and the reaction mechanism was discussed.
The thiazolium and triazolium thermoregulated phase-separable catalysis with the characteristic of "homogeneous reaction in high temperature, two-phase separation in low temperature" can achieve the integration of reaction-separation. It not only provides a new idea of green catalysis in Stetter reaction but also makes a very effectively way for liquid/liquid two-phase catalysis in other organic reactions.
将首次设计、合成的具有温控效应的催化剂应用于催化丁醛与丙烯酸乙酯和呋喃甲醛与丙烯酸乙酯之间的stetter反应,考察了阴离子和乙氧基链的不同对反应的影响,发现当催化剂阴离子为溴负离子且乙氧基链为n=16的温控催化剂对stetter反应具有较好的催化活性和循环使用寿命。并且优化出较佳的工艺条件。
n=16的温控相分离噻唑溴催化剂在催化丁醛与丙烯酸乙酯反应的较佳工艺条件为：反应时间12 h,反应温度60℃,催化剂用量为反应原料的15%mol,转化率为99.0%,收率37.2%。催化剂循环使用6次,转化率在96.0%以上,收率高于34.0%；催化呋喃甲醛与丙烯酸乙酯反应的条件为：反应时间12 h,反应温度60℃,催化剂用量为反应原料的15%mol,转化率为99.0%,收率为42.3%。催化剂重复使用8次,转化率在95.0%以上,产率高于35.0%。
n=16的温控相分离三唑溴催化剂在催化丁醛与丙烯酸乙酯反应的较佳的工艺条件为：反应时间12h,反应温度70℃,催化剂用量为反应原料的15%mol,转化率为99.0%,产率为37.4%。催化剂重复使用5次,转化率在95.0%以上,产率高于34.0%；催化呋喃甲醛与丙烯酸乙酯的反应的较佳反应条件为：反应时间16 h,反应温度70℃,催化剂用量为反应原料的20%mol,转化率为99.0%,产率为41.8%。催化剂循环使用6次,转化率在95.0%以上,产率高于36.0%。循环实验结束后,催化剂质量损失约4.0%-5.0%。并用气-质联用(GC-MS)对stetter反应体系副产物进行分析,确定了副产物的结构和反应机理。
噻唑基、三唑基温控相分离催化剂催化stetter反应,反应体系具有“高温均相反应,低温两相分离”的特性,实现了反应-分离一体化,为有机反应中的绿色催化提供了一条新思路,也为液/液两相催化在其它有机反应中的应用做出了有效地借鉴。
Ionic liquids for liquid/liquid two-phase catalysis provides a new approach of resolving the catalyst separation and recovery. Based on the concept of thermoregulated phase-separable catalysis (TPSC), a series thiazolium and triazolium thermoregulated ionic liquid catalysts with different polyether-substituted chain (n=11,16,42) and different anion (Cl, Br-, I, BF4-, PF6-) were designed and synthesized. The structures of new compounds were characterized by NMR and IR. The solubility of catalysts in different temperatures and organic solvents were studied. The results showed that the catalysts possessed a critical solution temperature (CST) in toluene/n-heptane mixed solvent and exhibited the properties of "homogeneous reaction in high temperature and two-phase separation in low temperature".
The thermoregulated ionic liquid catalysts were used in Stetter reaction of ethyl acrylate with furfural and n-butanal. The effects of anion and ethoxy chain on reactions were investigated. The catalyst with bromine anion and ethoxy chain length n=16 showed good catalysis and recycle. The reaction conditions were also optimized.
In the stetter reaction of ethyl acrylate with n-butanal catalyzed by the thiazolium ionic liquid catalyst with Br- and n=16, the optimum reaction conditions were as follow:t=12 h, T=60℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of n-butanal and yield were 99.0% and 37.2%, respectively. After 6 recycles of the catalyst, the conversion and yield still could reach up to 96.0% and 34.0%, respectively. In the Stetter reaction of ethyl acrylate with furfural catalyzed by the thiazolium ionic liquid catalyst with Br-and n=16, the optimum reaction conditions were as follow:t=12 h, T=60℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of furfural and yield were 99.0% and 42.3%, respectively. After 8 recycles of the catalyst, the conversion and yield still were higher than 95.0% and 35.0%, respectively.
In the Stetter reaction of ethyl acrylate with n-butanal catalyzed by the triazolium ionic liquid catalyst with Br-and n=16, the optimum reaction conditions were as follow:t=16 h, T=70℃, and the quantity of catalyst of 15 mol%. Under the optimum reaction conditions, the conversion of n-butanal and yield were 99.0% and 37.4%, respectively. After 5 recycles of the catalyst, the conversion and yield still could reach up to 95.0% and 34.0%, respectively. In the Stetter reaction of ethyl acrylate with furfural catalyzed by the triazolium ionic liquid catalyst with Br- and n=16, the optimum reaction conditions were as follow:t=16 h, T=70℃, and the quantity of catalyst of 20 mol%. Under the optimum reaction conditions, the conversion of furfural and yield were 99.0% and 41.8%, respectively. After 6 recycles of the catalyst, the conversion and yield still were higher than 95.0% and 36.0%, respectively. The loss of the catalyst was about 4%-5% after 6 recycles. The byproducts of Stetter reactions were determined by GC-MS, and the reaction mechanism was discussed.
The thiazolium and triazolium thermoregulated phase-separable catalysis with the characteristic of "homogeneous reaction in high temperature, two-phase separation in low temperature" can achieve the integration of reaction-separation. It not only provides a new idea of green catalysis in Stetter reaction but also makes a very effectively way for liquid/liquid two-phase catalysis in other organic reactions.
引文
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