CN106111132B - 一种用于制备芳香族氰基化合物的Pd-Zn双金属催化剂 - Google Patents
一种用于制备芳香族氰基化合物的Pd-Zn双金属催化剂 Download PDFInfo
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- B01J23/60—Platinum group metals with zinc, cadmium or mercury
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
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Abstract
本发明公开了一种用于制备芳香族氰基化合物的Pd‑Zn双金属催化剂，所述催化剂通过如下步骤制备：将醋酸钯与锌盐在DMF中搅拌均匀，并加入一定量的PVP作为稳定剂，搅拌至溶液澄清透明，加入还原剂KBH4搅拌反应，得到Pd‑Zn双金属催化剂。本发明使用Pd‑Zn双金属纳米颗粒作为催化剂，反应过程中不需要再加入配体，催化剂为纳米级别，催化活性位点与反应底物的接触几率更大，催化活性更高，并且催化剂中Pd与Zn形成合金结构，能有效的防止金属Pd被毒化，延长催化寿命。
Description
技术领域
本发明属于有机合成领域，具体涉及一种芳香族氰基化合物的制备方法。
背景技术
氰基化产物的通式为RCN，官能团为氰基（-CN）。芳香族氰基化产物是一个非常重要的有机合成中间体。在农药，染料，医药等方面有重要意义。并且可以作为中间体合成许多重要化合物比如水解制备酸和酰胺，还原制备胺。也是生物学，制药学，农药化学以及天然产品中重要的原料。因此氰基化反应不仅在理论上，在实际应用上也有重要作用。
目前氰基化化合物的制备主要使用取代法来制备，其中卤素取代法相对较为简单，是目前应用较为广泛的氰基化合物的合成方法。常用用的氰基化试剂主要有CuCN、NaCN、KCN、Zn(CN)2、Me3SiCN、(n-C4H9)3SnCN、(CH3)2C(OH)CN、K4[Fe(CN)6]等，其中NaCN和KCN剧毒；Zn(CN)2和CuCN会造成严重金属污染；TMSCN容易吸潮，处理不方便；(CH3)2C(OH)CN会在反应过程中放出剧毒的HCN气体，造成环境严重污染。K4[Fe(CN)6]具有六个氰根但是却没有氰化物的毒性，而且廉价易得，此外，K4[Fe(CN)6]作为氰基化试剂无需经过复杂的预处理，其六个氰根均可与卤素交换，是一种非常有前景的氰基化试剂。
最简单的以K4[Fe(CN)6]为氰基化试剂的催化体系还是均相的无配体Pd(OAc)2催化体系，但是反应过程中发现金属Pd在反应过程中容易生成金属氰化物，导致催化剂活性降低。近年来，化学家研究合成了一系列配体，这些配体加入反应体系中可以与金属Pd形成络合物以此来稳定催化剂，使其保持高活性。但是，这些均相金属催化剂分离困难，多数无法回收套用，而且在较高温度下均相催化剂Pd络合物不稳定，易形成低活性或无活性的Pd黑。
由于均相催化剂的成本太高，限制了在工业上的应用，因此，研究开发非均相催化体系，以克服均相催化体系的这些弊端，成为近年来研究的热点。Seki小组报道了Pd／C为催化剂，PPh3为配体，并加入了Zn粉和ZnBr2作为添加剂，对卤代芳烃进行氰基化反应，但是，Pd／C为催化剂反应活性较低，仍需加入膦配体PPh3来促进反应进行，同时，Pd／C为催化剂在氰基化反应中容易被毒化，需加入锌粉促使高价的金属原子还原到低价状态，保持金属催化剂的稳定性。
发明内容
本发明的目的在于提供一种用于制备芳香族氰基化合物的Pd-Zn双金属催化剂。
本发明的目的是这样实现的：一种用于制备芳香族氰基化合物的Pd-Zn双金属催化剂，所述催化剂通过如下步骤制备：
将醋酸钯与锌盐在DMF中搅拌均匀，并加入一定量的PVP作为稳定剂，搅拌至溶液澄清透明，加入还原剂KBH4搅拌反应，得到Pd-Zn双金属催化剂。
进一步，醋酸钯与醋酸锌的摩尔比为1:1。
进一步，PVP在DMF中的质量浓度不低于100mg/ml。
进一步，KBH4与醋酸锌的摩尔比为6:1。
与现有技术相比，本发明的优点有：
使用Pd-Zn双金属纳米颗粒作为催化剂，反应过程中不需要再加入配体，催化剂为纳米级别，催化活性位点与反应底物的接触几率更大，催化活性更高。并且催化剂中Pd与Zn形成合金结构，能有效的防止金属Pd被毒化，延长催化寿命。
具体实施方式
将本发明制备的双金属催化剂运用到溴苯的氰基化反应中，反应使用K4[Fe(CN)6]作为氰基化试剂。反应过程如下：在双金属催化剂中加入溴苯及碳酸钠，边加边搅拌，加入完毕后搅拌10min，随后缓慢加入K4[Fe(CN)6]，加热反应24h。
具体反应式如下:
。
实施例1
室温条件下将醋酸钯 (0.025 mmol) 醋酸锌 (0.025 mmol)与PVP (100 mg)混溶于1.5 mL DMF，搅拌至澄清透明得金属前体溶液。随后缓慢将还原剂硼氢化钾 (0.15mmol)加入到金属前体溶液中，加入硼氢化钾的过程中伴随剧烈搅拌。加入完毕后搅拌10分钟制得Pd-Zn双金属催化剂。分别将碳酸钠 (0.5mmol)，溴苯 (0.5mmol)加入至上述所制备的双金属催化剂中,随后缓慢加入亚铁氰化钾 (0.1mmol)。加入完毕后，充入氮气保护，在120OC条件下反应24h。反应结束后，降至室温，加入水和乙酸乙酯。有机相旋蒸去除溶剂后，得到产物，之后水相离心沉淀分离出催化剂。所得对硝基苯甲腈收率为91.4%。
实施例2
反应步骤与实施例1完全相同，不同之处在于：
反应底物为0.5mmol硝基溴苯，对硝基苯甲腈收率为95%。
实施例3
反应步骤与实施例1完全相同，不同之处在于：
醋酸锌的使用量为0.012mmol,苯甲腈收率为91.0%。
实施例4
反应步骤与实施例1完全相同，不同之处在于：
金属前体为0.025mmol醋酸钯, 0.025 mmol醋酸铜,苯甲腈收率为51.1%。
实施例5
反应步骤与实施例1完全相同，不同之处在于：
金属前体为0.025mmol醋酸钯, 0.025 mmol醋酸亚铁,苯甲腈收率为62.4%。
实施例6
反应步骤与实施例1完全相同，不同之处在于：
金属前体为0.025mmol醋酸钯, 0.025 mmol醋酸镍,苯甲腈收率为36.2%。
实施例7
反应步骤与实施例1完全相同，不同之处在于：
醋酸锌的使用量为0.05mmol,苯甲腈收率为69.3%。
实施例8
反应步骤与实施例1完全相同，不同之处在于：
反应温度为130 OC,苯甲腈收率为88.7%。
实施例9
反应步骤与实施例1完全相同，不同之处在于：
反应温度为110 OC,苯甲腈收率为82.8%。
实施例10
反应步骤与实施例1完全相同，不同之处在于：
反应溶剂为1.5 mL DMAC,苯甲腈收率为75.3%。
实施例11
反应步骤与实施例1完全相同，不同之处在于：
反应溶剂为1.5 mL DMAC,苯甲腈收率为75.3%
实施例12
所使用的催化剂为实施例1中水相中分离回收的催化剂，回收的催化剂重新分散在1.5 mL PVP的DMF溶液。随后操作步骤与实施例1完全相同，苯甲腈收率为90%。
Claims (3)
1.一种双金属催化剂在溴苯的氰基化反应中的应用，所述催化剂通过如下步骤制备：将醋酸钯与醋酸锌在DMF中搅拌均匀，并加入一定量的PVP作为稳定剂，搅拌至溶液澄清透明，加入还原剂KBH4搅拌反应，得到Pd-Zn双金属催化剂，其中，醋酸钯与醋酸锌的摩尔比为1:1。
2.如权利要求1所述的应用，其特征在于，PVP在DMF中的质量浓度不低于100mg/ml。
3.如权利要求1所述的应用，其特征在于，KBH4与醋酸锌的摩尔比为6:1。
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| CN103086917A (zh) * | 2013-01-15 | 2013-05-08 | 湖北兴发化工集团股份有限公司 | 一种芳香族有机氰化物的合成方法 |
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