CN108821996A - 用金属卟啉聚合物催化偶联芳香醇和乙腈制取酮腈 - Google Patents

用金属卟啉聚合物催化偶联芳香醇和乙腈制取酮腈 Download PDF

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CN108821996A
CN108821996A CN201810897800.6A CN201810897800A CN108821996A CN 108821996 A CN108821996 A CN 108821996A CN 201810897800 A CN201810897800 A CN 201810897800A CN 108821996 A CN108821996 A CN 108821996A
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aromatic alcohol
metalloporphyrin
acetonitrile
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阳卫军
柳恩情
高勇
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Hunan University
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Abstract

本发明公开了一种催化芳香醇和乙腈偶联制备酮腈化合物的方法。选用具有高孔状结构和比表面积、以含氮桥键连接而成的、含有2种配位金属离子的多孔聚合金属卟啉做催化剂，在温和条件下对芳香醇和乙腈进行催化氧化偶联，得到相对应的酮腈产物。催化剂用量小，催化效果好。这种催化剂在反应体系中不溶解不分解，可多次循环使用，反应转化率高，选择性好。

Description

用金属卟啉聚合物催化偶联芳香醇和乙腈制取酮腈
技术领域
本发明涉及在温和条件下催化氧化偶联芳香醇类化合物制备酮腈的方法。
背景技术
酮腈是一类非常有用的合成中间体。它们已被用作多种杂环结构的前体，包括氨基吡唑，氨基异恶唑，2-吡啶酮和咪唑。此外，它们已被用作合成多种药理活性化合物，例如抗HCV药物和抗NHE-1的抑制剂。用于制备β-酮腈的常用方法包括在强碱存在下烷基腈和酯的偶联或与α-溴代酮的氰化物置换反应。这些方法存在诸如需要强碱或高毒氰化物等缺点。例如专利US6822110、CN102020586A均采用了具有剧毒致命性的氢氰酸溶液。因此开发处一种低毒、高效的酮腈合成方法显得非常必要。
发明内容
本发明的目的是提供一种高选择性、高转化率和回收率，并避免使用强碱或高毒性氰化物盐来合成酮腈的方法，且反应显示高原子经济性，仅释放无害的H2O作为副产物。催化过程中聚合金属卟啉催化剂用量少，催化反应温度低，并且催化剂结构稳定可以回收重复利用。反应方程式如下：
本发明采用下述技术方案实现的：通入1-50atm的空气或氧气，加入碱添加剂，反应溶剂，控制反应温度10-100℃，选用通式(Ⅰ)结构金属卟啉聚合物作为催化剂。该聚合物结构中金属卟啉单元的四臂分别通过具有共轭效应的仲氨基和取代硝基相互偶联，聚合物分子中金属卟啉单体的重复数目为4-4000，该聚合物不溶于有机溶剂，分子中的电子流动性好，具有高度的热稳定性，孔隙度高，比表面积达100-2000m2/g，孔结构为介孔或微孔，孔径大于0.2nm。催化剂的用量为被氧化底物的0.001-0.5wt％。
共轭聚合金属卟啉催化剂(Ⅰ)单元结构
其中，结构式(Ⅰ)中金属原子M为过渡金属离子(如Co(Ⅱ),Cu(Ⅱ),Zn(Ⅱ))。由于共轭基团的偶联，使得金属卟啉单元的电子能够在大分子中流动，这大大加强了聚合物分子的催化活性。该催化剂对一级碳氧键氧化具有较好的选择催化作用，能催化氧化偶联芳香醇与乙腈，高选择性生成酮腈。所述的芳香醇其取代基R可位于苯环的邻位，间位和对位；取代基可以是-H,-CH3,-F,-Cl,-Br,-NO2等。
该聚合物催化剂的催化反应温度低且反应时间短，有效减小了副反应的生成。由于具有很好的化学稳定性，作为一种非均相催化剂，结构式(Ⅰ)所示的催化剂可以多次重复利用，如使用5次后仍保持很高的催化效率。
具体实施方式
下面结合实施例对本发明作进一步详细描述，但本发明的实施方式不限于此。
实施例1：
将10mg具有结构式(Ⅰ)结构的金属卟啉聚合物，M＝Cu(Ⅱ)，m＝382，比表面积面积730m2/g。苯甲醇(1mmol，0.108g)，乙腈(5mmol，0.206g)，KOH(3mmol，0.168g)，加入到10mL的N，N-二甲基甲酰胺中，通入50mL/min空气。在60℃下搅拌反应5小时，相应的酮腈收率93％，苯甲醇转化率92％。
实施例2：
将10mg具有结构式(Ⅰ)结构的金属卟啉聚合物，M＝Zn(Ⅱ)，m＝510，比表面积面积680m2/g。对硝基苯甲醇(1mmol，0.153g)，乙腈(10mmol，0.411g)，KOH(3mmol，0.168g)，加入到10mL的二甲基亚砜中，通入50mL/min空气。在80℃下搅拌反应3小时，相应的酮腈收率90％，对硝基苯甲醇转化率91％。
实施例3：
将10mg具有结构式(Ⅰ)结构的金属卟啉聚合物，M＝Co(Ⅱ)，m＝280，比表面积面积850m2/g。对甲基苯甲醇(1mmol，0.122g)，乙腈(10mmol，0.411g)，t-BuOK(3mmol，0.336g)，加入到10mL的1,3-二甲基-2-咪唑啉酮中，通入50mL/min空气。在50℃下搅拌反应8小时，相应的酮腈收率91％，对甲基苯甲醇转化率90％。
实施例4：
将实施例1中反应过后的催化剂金属卟啉聚合物(Ⅰ)离心过滤，并用丙酮洗涤，干燥。取该催化剂，加入苯甲醇(1mmol，0.108g)，乙腈(5mmol，0.206g)，KOH(3mmol，0.168g)，10mL的N，N-二甲基甲酰胺，通入50mL/min空气。在60℃下搅拌反应5小时，相应的酮腈收率92％,苯甲醇转化率91％。再经过4次循环反应后，相应的酮腈收率86％，苯甲醇转化率88％。

Claims (5)

1.一种基于化学结构式如(Ⅰ)所示的共轭聚合金属卟啉催化剂，作为催化剂催化偶联芳香醇和乙腈，以制备相应的酮腈化合物；反应条件为：通入1-50atm的空气或氧气，加入碱添加剂和反应溶剂，反应温度10-100℃，芳香醇与乙腈的配比为摩尔比1:(1-20)，金属卟啉聚合物(Ⅰ)的用量为反应物芳香醇质量的0.001-0.5wt％，
共轭聚合金属卟啉催化剂(Ⅰ)单元结构
催化反应方程式如下：
2.根据权利要求1所述化学结构式如(Ⅰ)所示的聚合金属卟啉，其特征在于：金属卟啉单体的四臂分别通过具有共轭效应的仲氨基和取代硝基相互偶联，桥联处的N上进一步配合了金属离子，聚合物分子中金属卟啉单体的重复数目为4-4000，该聚合物不溶于有机溶剂，分子中的电子流动性好，具有高度的热稳定性，孔隙度高，比表面积达100-2000m2/g，结构为介孔或微孔，孔径大于0.2nm；其中，结构式(Ⅰ)中金属离子M为过渡金属原子Co(Ⅱ),Cu(Ⅱ),Zn(Ⅱ)。
3.根据权利要求1所述催化空气氧化偶联芳香醇和乙腈的方法，其特征在于通入1-50atm的空气或氧气，反应时间4小时,加入的碱添加剂为氢氧化钾、叔丁醇钾、氢化钠；反应溶剂为N，N-二甲基甲酰胺，二甲基亚砜，1,3-二甲基-2-咪唑啉酮；反应底物的转化率可达到90％以上。
4.根据权利要求1所述催化氧化偶联芳香醇和乙腈的方法，其特征在于所述的芳香醇其取代基可位于苯环的邻位，间位或对位；取代基可以是-H,-CH3,-F,-Cl,-Br,-NO2；反应产物为相应的β-酮腈，其选择性90％以上。
5.根据权利要求1所述催化氧化偶联芳香醇和乙腈的方法，催化剂可以多次重复回收利用，催化剂循环使用5次时，同样反应条件下，反应底物的转化率及选择性均达到85％以上。
CN201810897800.6A 2018-08-08 2018-08-08 用金属卟啉聚合物催化偶联芳香醇和乙腈制取酮腈 Pending CN108821996A (zh)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311387A (zh) * 2014-09-12 2015-01-28 湖南大学 用共轭聚合金属卟啉催化氧化甲苯和取代甲苯成醛和醇方法
CN104909971A (zh) * 2015-06-18 2015-09-16 湖南大学 用含-n-桥键的共轭金属卟啉聚合物催化氧化醇类化合物的方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104311387A (zh) * 2014-09-12 2015-01-28 湖南大学 用共轭聚合金属卟啉催化氧化甲苯和取代甲苯成醛和醇方法
CN104909971A (zh) * 2015-06-18 2015-09-16 湖南大学 用含-n-桥键的共轭金属卟啉聚合物催化氧化醇类化合物的方法

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Application publication date: 20181116