CN111939982A - 基于聚离子液体的双金属催化剂的制备方法及其应用 - Google Patents
基于聚离子液体的双金属催化剂的制备方法及其应用 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 37
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 30
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
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- 238000000034 method Methods 0.000 claims description 20
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- 238000005580 one pot reaction Methods 0.000 claims description 5
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- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 3
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- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 8
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 description 7
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
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- JZJWCDQGIPQBAO-UHFFFAOYSA-N 1-(4-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=C(I)C=C1 JZJWCDQGIPQBAO-UHFFFAOYSA-N 0.000 description 4
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- 150000002739 metals Chemical class 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 2
- IWLHOUBDKCKJJQ-UHFFFAOYSA-N 1-(3-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(I)=C1 IWLHOUBDKCKJJQ-UHFFFAOYSA-N 0.000 description 2
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种基于聚离子液体的双金属催化剂的制备方法，首先将聚离子液体和手性钌无规共聚物通过络合作用制备表面含有PIL结构的钌纳米催化剂颗粒，再将金属Pd负载在钌纳米催化剂颗粒表面的PIL上制得具有核壳结构的双功能Ru‑Pd催化剂，该双功能Ru‑Pd催化剂用于在水相中进行一锅两步的选择性催化Suzuki偶联和不对称转移氢化反应，其中基于聚粒子液体的双金属催化剂离心回收后重复循环使用，不仅提高了有机反应的转化率和对映选择性，具有多功能多相催化剂的优越性，同时克服了多相催化剂活性低的局限性。
Description
技术领域
本发明属于双金属催化剂的制备及应用技术领域，具体涉及一种基于聚离子液体的双金属催化剂的制备方法及其应用。
背景技术
受生物***协同效应的启发，用于多步串联有机反应的多功能负载型催化剂的开发吸引了许多不对称催化研究者的关注，由于受两个主要发展限制，首先是将两种有机金属化合物负载在同一载体上不可避免地会导致两种物质之间的“交叉干扰”。其次，多相催化剂的手性结构对催化体系微环境的变化也非常敏感从而影响反应。因此，如果要获得串联反应的高对映选择性，既要克服固有的“交叉干扰”又要保留原始均相手性催化体系的微环境，这仍然是一个具有挑战性的问题。
为了克服这些困难本课题组开发了通过聚离子液体(PIL)来制备具有双金属的Ru-Pd催化剂，基于PIL的优越性，通过调控聚离子液体本身的结构来调控催化反应的催化微环境使其具有更高的反应活性，两种金属又同时存在催化剂上形成一种具有手性核壳结构的催化剂，使其能够在一锅反应中进行Suzuki偶联和不对称氢转移两步反应，提高了有机反应的的转化率和对映选择性。具有多功能多相催化剂的优越性，同时克服了多相催化剂活性低的局限性。
发明内容
本发明解决的技术问题是提供了一种新型基于聚离子液体的双金属催化剂的制备方法，该方法首先将聚离子液体和手性钌无规共聚物通过络合作用制备表面含有PIL结构的钌纳米催化剂颗粒，再将金属Pd负载在钌纳米催化剂颗粒表面的PIL上制得具有核壳结构的双功能Ru-Pd催化剂。由于催化剂上含有Ru-Pd两种金属，其能够在水相中进行一锅两步的选择性催化Suzuki偶联和不对称转移氢化反应。
本发明为解决上述技术问题采用如下技术方案，基于聚离子液体的双金属催化剂的制备方法，其特征在于具体过程为：首先将聚离子液体和手性钌无规共聚物通过络合作用制备表面含有PIL结构的钌纳米催化剂颗粒，再将金属Pd负载在钌纳米催化剂颗粒表面的PIL上制得具有核壳结构的双功能Ru-Pd催化剂，该双功能Ru-Pd催化剂的结构模型为：
进一步限定，所述基于聚离子液体的双金属催化剂的制备方法，其特征在于具体步骤为：将手性钌无规共聚物和聚离子液体在二甲基亚砜溶液中混合，在超声条件下将混合液滴加到含0.5wt％氨水的乙醇溶液中，产生大量的沉淀复合物，再经超声处理，采用沉淀法、乙醇洗涤法和真空干燥法制得纯的表面含有PIL结构的钌纳米催化剂颗粒；将表面含有PIL结构的钌纳米催化剂颗粒分散于二甲基亚砜溶剂中，再逐滴加入醋酸钯的二甲基亚砜溶液，然后在充氮气条件下进行反应，反应结束后在***中沉淀，粗品用二氯甲烷洗涤以去除未反应的原料，最终制得具有核壳结构的双功能Ru-Pd催化剂；上述制备过程中的具体合成路线为：
进一步限定，所述聚离子液体的具体制备过程为：将0.50mmol聚环氧氯丙烷(PECH)加入到单颈圆底烧瓶中，脱气30min后用注射器加入0.28mmol甲基咪唑，搅拌至完全溶解后将单颈圆底烧瓶密封并浸入80℃的油浴中反应10h，然后用***沉淀收集聚离子液体粗品，再用***洗涤数次直至无小分子杂质，并于60℃真空干燥48h得到聚离子液体。
进一步限定，所述表面含有PIL结构的钌纳米催化剂颗粒的具体制备过程为：将0.247mL氨水注入50mL乙醇溶液中制得含0.5wt％氨水的乙醇溶液即复合溶剂，将数控超声波清洗机的声波振幅设为40％，将复合溶剂加入到超声波清洗机中30min，将0.9mmol手性钌无规共聚物与1.8mmol所制得的聚离子液体在3mL二甲基亚砜溶液中混合，再在超声条件下通过滴管加入到复合溶剂中，大量的聚离子液体复合物快速沉淀，经超声处理30min，过滤掉，采用沉淀法、乙醇洗涤法和真空干燥法，于40℃干燥24h，去除杂质制得表面含有PIL结构的钌纳米催化剂颗粒。
进一步限定，所述双功能Ru-Pd催化剂的具体制备过程为：将62.4mg表面含有PIL结构的钌纳米催化剂颗粒用schlenk烧瓶分散于1mL二甲基亚砜中，再逐滴加入含有8.4mg醋酸钯的二甲基亚砜溶液，在氮气条件下进行反应12h，反应结束后在***中沉淀，粗品在***中沉淀，用二氯乙烷洗涤去除未反应原料，最终制得具有核壳结构的双功能Ru-Pd催化剂。
本发明所述的基于聚离子液体的双金属催化剂用于在水相中进行一锅两步的选择性催化Suzuki偶联和不对称转移氢化反应，其中基于聚离子液体的双金属催化剂离心回收后重复循环使用。
本发明与现有技术相比具有以下优点：基于聚离子液体制备得到具有双功能Ru-Pd的催化剂，它克服了多相催化剂活性低的局限性，基于PIL的优越性，通过调控聚离子液体本身的结构来调控催化反应的催化微环境使其具有更高的反应活性，两种金属又同时存在催化剂上，形成一种具有手性核壳结构的催化剂，能够在水体系中进行一锅两步的Suzuki偶联和不对称转移氢化反应，提高了有机反应的转化率和对映选择性，具有多功能多相催化剂的优越性。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
聚离子液体的制备
将0.50mmol聚环氧氯丙烷(PECH)加入到单颈圆底烧瓶中，脱气30min后用注射器加入0.28mmol甲基咪唑，搅拌至完全溶解后将单颈圆底烧瓶密封并浸入80℃的油浴中反应10h，然后用***沉淀收集聚离子液体粗品，再用***洗涤数次直至无小分子杂质，并于60℃真空干燥48h得到聚离子液体(PIL)，收率为94％。
表面含有PIL结构的钌纳米催化剂颗粒的制备
将0.247mL氨水注入50mL乙醇溶液中制得含0.5wt％氨水的乙醇溶液即复合溶剂，将数控超声波清洗机的声波振幅设为40％，将复合溶剂加入到超声波清洗机中30min，将0.9mmol手性钌无规共聚物与1.8mmol所制得的聚离子液体在3mL二甲基亚砜溶液中混合，再在超声条件下通过滴管加入到复合溶剂中，大量的聚离子液体复合物快速沉淀，经超声处理30min，过滤掉，采用沉淀法、乙醇洗涤法和真空干燥法，于40℃干燥24h，去除杂质制得表面含有PIL结构的钌纳米催化剂颗粒，收率为73％。
所述双功能Ru-Pd催化剂的制备
将62.4mg表面含有PIL结构的钌纳米催化剂颗粒用schlenk烧瓶分散于1mL二甲基亚砜中，再逐滴加入含有8.4mg醋酸钯的二甲基亚砜溶液，在氮气条件下进行反应12h，反应结束后在***中沉淀，粗品在***中沉淀，用二氯乙烷洗涤去除未反应原料，最终制得双功能Ru-Pd催化剂，收率为80％。
实施例2
将实施例1制得的双功能Ru-Pd催化剂应用于催化对碘苯乙酮和苯硼酸的偶联及不对称氢转移反应
将实施例1制得的双功能Ru-Pd催化剂(0.1mmol％Ru，0.1mmol％Pd)、1mmol碘化苯乙酮、1.1mmol苯硼酸、1.0mmol HCOO2Na、3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收。反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物4'-乙醇联苯产率为95％，ee值为94％。
实施例3
将实施例1制得的双功能Ru-Pd催化剂应用于催化对碘苯乙酮和4-氟苯硼酸偶联及不对称氢转移反应
将实施例所1制得的双功能Ru-Pd催化剂(0.1mmol％Ru，0.1mmol％Pd)、1mmol碘化苯乙酮、1.1mmol 4-氟苯硼酸、1.0mmol HCOO2Na、3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物4-氟-4'-乙醇联苯产率为89％，ee值为95％。
实施例4
将实施例1制得的双功能Ru-Pd催化剂应用于催化对碘苯乙酮和4-甲苯硼酸偶联及不对称氢转移反应
将实施例1制得的双功能Ru-Pd催化剂(0.1mmol％Ru，0.1mmol％Pd)、1mmol对碘苯乙酮、1.1mmol 4-甲苯硼酸、1.0mmol HCOO2Na、0.3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物4-甲基-4'-乙醇联苯产率为96％，ee值为94％。
实施例5
将实施例1制得的双功能Ru-Pd催化剂应用于催化3-碘苯乙酮和苯硼酸偶联及不对称氢转移反应
将实施例1制得的双功能Ru-Pd催化剂(0.1mmol％Ru，0.1mmol％Pd)、1mmol 3-碘苯乙酮、1.1mmol苯硼酸、1.0mmol HCOO2Na、0.3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物3-甲基-4'-乙醇联苯产率为93％，ee值为91％。
实施例6
将实施例1制得的双功能Ru-Pd催化剂应用于催化3-碘乙酮和2,4二甲基苯硼酸偶联及不对称氢转移反应
将实施例1制得的双功能Ru-Pd催化剂(0.1mmol％Ru，0.1mmol％Pd)、1mmol 3-碘乙酮、1.1mmol 2,4二甲基苯硼酸、1.0mmol HCOO2Na、0.3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，于30℃真空中干燥24h，得到产物2,4二甲基-4'-乙醇联苯产率为93％，ee值为97％。
实施例7
将实施例2回收的双功能Ru-Pd催化剂应用于催化对碘苯乙酮和苯硼酸的偶联及不对称氢转移反应
将实施例2回收的双功能Ru-Pd催化剂重复使用(0.1mmol％Ru，0.1mmol％Pd)、1mmol碘化苯乙酮、1.1mmol苯硼酸、1.0mmol HCOO2Na、3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物4'-乙醇联苯产率为95％，ee值为94％。
实施例8
将实施例7回收的双功能Ru-Pd催化剂应用于催化对碘苯乙酮和苯硼酸的偶联及不对称氢转移反应
将实施例7回收的双功能Ru-Pd催化剂重复使用(0.1mmol％Ru，0.1mmol％Pd)、1mmol碘化苯乙酮、1.1mmol苯硼酸、1.0mmol HCOO2Na、3mmol Cs2CO3和4mL H2O/iPrOH混合溶剂加入试管中。反应在60℃下进行6min，生成了二苯乙酮，然后冷却至25℃并持续10h(使用薄层色谱法监测反应直至反应结束)。反应结束后将催化剂离心回收，反应液经乙酸乙酯萃取，柱层析分离得到纯品，旋蒸，在30℃真空中干燥24h，得到产物4'-乙醇联苯产率为96％，ee值为94％。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (6)
1.基于聚离子液体的双金属催化剂的制备方法，其特征在于具体过程为：首先将聚离子液体和手性钌无规共聚物通过络合作用制备表面含有PIL结构的钌纳米催化剂颗粒，再将金属Pd负载在钌纳米催化剂颗粒表面的PIL上制得具有核壳结构的双功能Ru-Pd催化剂，该双功能Ru-Pd催化剂的结构模型为：
2.根据权利要求1所述的基于聚离子液体的双金属催化剂的制备方法，其特征在于具体步骤为：将手性钌无规共聚物和聚离子液体在二甲基亚砜溶液中混合，在超声条件下将混合液滴加到含0.5wt％氨水的乙醇溶液中，产生大量的沉淀复合物，再经超声处理，采用沉淀法、乙醇洗涤法和真空干燥法制得纯的表面含有PIL结构的钌纳米催化剂颗粒；将表面含有PIL结构的钌纳米催化剂颗粒分散于二甲基亚砜溶剂中，再逐滴加入醋酸钯的二甲基亚砜溶液，然后在充氮气条件下进行反应，反应结束后在***中沉淀，粗品用二氯甲烷洗涤以去除未反应的原料，最终制得具有核壳结构的双功能Ru-Pd催化剂；上述制备过程中的具体合成路线为：
3.根据权利要求1所述的基于聚离子液体的双金属催化剂的制备方法，其特征在于：所述聚离子液体的具体制备过程为：将0.50mmol聚环氧氯丙烷(PECH)加入到单颈圆底烧瓶中，脱气30min后用注射器加入0.28mmol甲基咪唑，搅拌至完全溶解后将单颈圆底烧瓶密封并浸入80℃的油浴中反应10h，然后用***沉淀收集聚离子液体粗品，再用***洗涤数次直至无小分子杂质，并于60℃真空干燥48h得到聚离子液体。
4.根据权利要求1所述的基于聚离子液体的双金属催化剂的制备方法，其特征在于：所述表面含有PIL结构的钌纳米催化剂颗粒的具体制备过程为：将0.247mL氨水注入50mL乙醇溶液中制得含0.5wt％氨水的乙醇溶液即复合溶剂，将数控超声波清洗机的声波振幅设为40％，将复合溶剂加入到超声波清洗机中30min，将0.9mmol手性钌无规共聚物与1.8mmol所制得的聚离子液体在3mL二甲基亚砜溶液中混合，再在超声条件下通过滴管加入到复合溶剂中，大量的聚离子液体复合物快速沉淀，经超声处理30min，过滤掉，采用沉淀法、乙醇洗涤法和真空干燥法，于40℃干燥24h，去除杂质制得表面含有PIL结构的钌纳米催化剂颗粒。
5.根据权利要求1所述的基于聚离子液体的双金属催化剂的制备方法，其特征在于：所述双功能Ru-Pd催化剂的具体制备过程为：将62.4mg表面含有PIL结构的钌纳米催化剂颗粒用schlenk烧瓶分散于1mL二甲基亚砜中，再逐滴加入含有8.4mg醋酸钯的二甲基亚砜溶液，在氮气条件下进行反应12h，反应结束后在***中沉淀，粗品在***中沉淀，用二氯乙烷洗涤去除未反应原料，最终制得具有核壳结构的双功能Ru-Pd催化剂。
6.根据权利要求1-5中任意一项所述的方法制得的基于聚离子液体的双金属催化剂用于在水相中进行一锅两步的选择性催化Suzuki偶联和不对称转移氢化反应，其中基于聚离子液体的双金属催化剂离心回收后重复循环使用。
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| CN114870818A (zh) * | 2022-05-13 | 2022-08-09 | 长春黄金研究院有限公司 | 一种利用聚离子液体凝胶吸附剂吸附分离金、铂、钯的方法 |
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| CN114870818B (zh) * | 2022-05-13 | 2024-02-27 | 长春黄金研究院有限公司 | 一种利用聚离子液体凝胶吸附剂吸附分离金、铂、钯的方法 |
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