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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- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract description 2
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- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- 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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- 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
- B01J23/8926—Copper and noble metals
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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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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