CN109092363A - 含氮氧离子型锂镁双金属催化剂及其制备方法和应用 - Google Patents

含氮氧离子型锂镁双金属催化剂及其制备方法和应用 Download PDF

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CN109092363A
CN109092363A CN201810966406.3A CN201810966406A CN109092363A CN 109092363 A CN109092363 A CN 109092363A CN 201810966406 A CN201810966406 A CN 201810966406A CN 109092363 A CN109092363 A CN 109092363A
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lithium magnesium
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nitrogenous cationic
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华宇鹏
上官灵芝
庞晶琳
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Ordos College Of Applied Technology
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Abstract

本发明涉及一种含氮氧离子型锂镁双金属催化剂及其制备方法和应用，属于双金属催化剂技术领域。本发明主要是解决现有MPV反应使用的催化剂都存在结构复杂，不易制备，催化剂活性不够高，用量大，反应时间长的技术问题。本发明的技术方案是：含氮氧离子型锂镁双金属催化剂的制备方法，其由下列步骤组成：1)制备N,N,O‑三齿胺基醇配体：按照现有技术制备；2)制备含氮氧离子型锂镁双金属催化剂：在氮气保护下，在0℃的乙醚溶液中用正丁基锂对N,N,O‑三齿胺基醇配体去氢，恢复室温后搅拌1‑2小时，然后在0℃下缓慢滴入0.5当量的二丁基镁，继续搅拌4‑6小时，反应完毕后过滤，真空浓缩滤液，析出无色透明晶体，即为含氮氧离子型锂镁双金属催化剂。

Description

含氮氧离子型锂镁双金属催化剂及其制备方法和应用
技术领域
本发明涉及一种含氮氧离子型锂镁双金属催化剂及其制备方法和应用，属于双金属催化剂技术领域。
背景技术
Meerwein-Ponndorf-Verley(MPV)反应是一种高选择性、高效率制备一级和二级醇的还原反应。该反应通常使用的催化剂都存在结构复杂，不易制备，催化剂活性不够高，用量大，反应时间长等不足。因此开发新型高效的催化剂仍然是研究该反应的重点。目前文献报道的都是以单一金属为中心的醇盐，氧化物及其配合物等。双金属化合物因其含有两种不同金属中心，在催化过程中能显示出不同于其中任一单金属中心的协同性能，被认为是潜在的高效催化剂。含金属锂或金属镁的化合物由于其毒性低、催化性能好被广泛用于催化剂的合成与应用，而含氮氧离子型锂镁双金属化合物用于催化MPV反应有望成为具有高活性、低毒性和可再生利用的新型催化剂，旨在为今后的工业应用开发新技术。
发明内容
本发明的目的是解决现有MPV反应使用的催化剂都存在结构复杂，不易制备，催化剂活性不够高，用量大，反应时间长的技术问题，提供一种含氮氧离子型锂镁双金属催化剂及其制备方法和应用，该催化剂合成简便，反应条件温和，对选择性合成一级和二级醇具有较高的催化活性。
为解决上述技术问题，本发明采用的技术方案是：一种含氮氧离子型锂镁双金属催化剂，其结构式为：
式中：三个锂原子分别与配体中的氧原子和两个氮原子及另一配体的氧原子形成四配位模式，且形成两个共用N-Li键的五元环，另一个锂原子分别于三个配体中的氧原子形成三配位模式；其中三个配体与四个锂原子形成正一价离子，镁原子与三个正丁基形成负一价离子。
一种含氮氧离子型锂镁双金属催化剂的制备方法，其由下列步骤组成：
1)制备N,N,O-三齿胺基醇配体：按照现有技术制备(Y.P.Hua,Z.Q.Guo,H.F.Han,X.H.Wei,N,N,O-Tridentate Mixed Lithium-Magnesium and Lithium-AluminumComplexes:Synthesis,Characterization and Catalytic Activities,Organometallics,2017,36(4):877-883.)反应式如下：
2)制备含氮氧离子型锂镁双金属催化剂：在氮气保护下，在0℃的乙醚溶液中用正丁基锂对N,N,O-三齿胺基醇配体去氢，恢复室温后搅拌1-2小时，然后在0℃下缓慢滴入0.5当量的二丁基镁，继续搅拌4-6小时，反应完毕后过滤，真空浓缩滤液，析出无色透明晶体，即为含氮氧离子型锂镁双金属催化剂，产率90-94％；反应式：
所述含氮氧离子型锂镁双金属催化剂在醛、酮化合物还原制备相应的一级、二级醇类化合物中的应用。
与现有技术相比本发明的优点和效果：本发明合成的催化剂制备方法简便，条件要求低，使用廉价、低毒性的非过渡金属锂和镁为催化活性金属，成本较低，对不同类型的醛、酮化合物的Meerwein-Ponndorf-Verley(MPV)反应具有较高选择性和催化活性，该催化反应时间短，产率高，有很好的应用前景。
附图说明
图1是本发明含氮氧离子型锂镁双金属催化剂的单晶X射线结构图。
具体实施方式
下面结合实施例对本发明做进一步的详细描述。
实施例1
本实施例中的含氮氧离子型锂镁双金属催化剂，其结构式为：
式中：三个锂原子分别与配体中的氧原子和两个氮原子及另一配体的氧原子形成四配位模式，且形成两个共用N-Li键的五元环，另一个锂原子分别于三个配体中的氧原子形成三配位模式；其中三个配体与四个锂原子形成正一价离子，镁原子与三个正丁基形成负一价离子。
上述含氮氧离子型锂镁双金属催化剂的制备方法，其由下列步骤组成：
1)制备N,N,O-三齿胺基醇配体：在氮气保护下，将N,N-二甲基苯胺(3.63g,30mmol)和N,N,N′,N′-四甲基乙二胺(TMEDA 3.49g，30mmol)加入到盛有20mL乙醚的反应瓶中，缓慢滴入正丁基锂(12.00mL，2.5M，正己烷溶液)并继续搅拌，恢复室温后反应2小时，再将环己酮(3.10mL，30mmol)滴入上述反应液中继续反应2小时，然后在酸性条件下水解，分液后所得水相用5％的氢氧化钠水溶液中和至弱碱性，再用无水乙醚萃取三次，有机相用无水硫酸镁干燥后减压蒸馏，收集78℃无色馏分得N,N,O-三齿胺基醇化合物，产率84％；
2)制备含氮氧离子型锂镁双金属催化剂：在氮气保护下，将N,N,O-三齿胺基醇配体(2.2mmol，0.47g)溶解在10mL乙醚溶剂中，在0℃时滴加正丁基锂(1.06mL，2.5M，正己烷溶液)至上述溶液中，恢复室温后搅拌2小时，然后在0℃时缓慢滴入二丁基镁(1.1mL，1.0M，正戊烷溶液)，继续搅拌5小时，反应完毕后过滤，真空浓缩滤液，析出无色透明晶体，即为含氮氧离子型锂镁双金属催化剂，产率94％。
晶体参数：化学式：C48H102Li4MgN6O3，单斜晶系(Monoclinic)，空间群P6(3)，晶胞参数α＝90.00°，β＝90.00°，γ＝120.00°，V＝3441.0(5)，Z＝1。单晶结构图见图1。
部分键长Li(1)-O(1)1.963(13)，Li(2)-O(1)1.891(10)，O(1)-Li(1)″1.973(13)，N(2)-Li(1)″2.100(14)，N(1)-Li(1)″2.137(17)，Li(1)-O(1)′1.973(13)，Li(1)-N(2)′2.100(14)，Li(1)-N(1)′2.136(17)，Li(2)-O(1)″1.891(10)，Li(2)-O(1)′1.891(10)；键角(°)：Li(2)-O(1)-Li(1)″79.6(5)，Li(1)-O(1)-Li(1)″120.9(7)，O(1)-Li(1)-O(1)′96.9(6)，O(1)-Li(1)-N(2)′131.0(7)，O(1)′-Li(1)-N(2)′88.7(6)，O(1)-Li(1)-N(1)′128.0(8)，O(1)′-Li(1)-N(1)′124.0(7)，N(2)′-Li(1)-N(1)′84.8(8)，O(1)-Li(1)-Li(1)′83.1(3)，O(1)’-Li(1)-Li(1)′29.5(3)，N(2)′-Li(1)-Li(1)′117.2(6)，N(1)′-Li(1)-Li(1)′116.1(5)，O(1)″-Li(2)-O(1)102.3(7)，O(1)″-Li(2)-O(1)′102.3(7)，O(1)-Li(2)-O(1)′,102.3(7)。
实施例2
所述含氮氧离子型锂镁双金属催化剂在醛化合物还原制备中的应用。
1)含氮氧离子型锂镁双金属催化剂的制备同实施例1。
2)催化苯甲醛还原为苄醇(MPV)：常温氮气保护下，将苯甲醛(4.0mmol)和异丙醇(4.8mmol)加入到氮气保护的含氮氧离子型锂镁双金属催化剂(0.2mmol)中，回流搅拌反应1小时后，然后用水终止反应，用乙醚萃取，干燥，旋蒸后，用柱层析法分离(流动相为7:3的正己烷和乙酸乙酯混合溶剂)，浓缩后即为苯甲醇。产率97％。1H NMR(300MHz，CDCl3):δ(ppm)3.62(s，1H，OH)，4.55(s，2H，CH2)，6.86-7.39(m，5H，C6H5)。
实施例3
所述含氮氧离子型锂镁双金属催化剂在酮化合物还原制备中的应用。
1)含氮氧离子型锂镁双金属催化剂的制备同实施例1。
2)催化苯乙酮还原为1-苯乙醇(MPV)：常温氮气保护下，将苯乙酮(4.0mmol)和异丙醇(4.8mmol)加入到氮气保护的含氮氧离子型锂镁双金属(0.2mmol)中，回流搅拌反应1小时后，然后用水终止反应，用乙醚萃取，干燥，旋蒸后，用柱层析法分离(流动相为7:3的正己烷和乙酸乙酯混合溶剂)，浓缩后即为1-苯乙醇，产率94％。1H NMR(300MHz,CDCl3):δ(ppm)1.48(d,3H,CH3)，3.62(s,1H,OH)，4.65(s,H,CH),7.13-7.45(m,5H,C6H5)。
以上所述，仅是本发明的较佳实施例，并非对本发明作任何限制，凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变化，均仍属于本发明技术方案的保护范围内。

Claims (3)

1.一种含氮氧离子型锂镁双金属催化剂，其特征在于，结构式为：
2.如权利要求1所述的含氮氧离子型锂镁双金属催化剂的制备方法，其特征在于：它由下列步骤组成：
1)制备N,N,O-三齿胺基醇配体：按照现有技术制备；
2)制备含氮氧离子型锂镁双金属催化剂：在氮气保护下，在0℃的乙醚溶液中用正丁基锂对N,N,O-三齿胺基醇配体去氢，恢复室温后搅拌1-2小时，然后在0℃下缓慢滴入0.5当量的二丁基镁，继续搅拌4-6小时，反应完毕后过滤，真空浓缩滤液，析出无色透明晶体即可。
3.如权利要求1所述的含氮氧离子型锂镁双金属催化剂，其特征在于：所述含氮氧离子型锂镁双金属催化剂在醛、酮化合物还原制备相应的一级、二级醇类化合物中的应用。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113173938A (zh) * 2021-04-08 2021-07-27 鄂尔多斯应用技术学院 一种磁性车轮六核铽簇合物催化剂及其制备方法和应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1801130A1 (en) * 2005-12-22 2007-06-27 DSMIP Assets B.V. Zwitterionic catalyst comprising a monoanionic bidentate imine ligand
CN106694045A (zh) * 2016-11-25 2017-05-24 山西大学 3:1型Mg/Li双金属催化剂及其制备方法和应用
CN106699575A (zh) * 2016-11-25 2017-05-24 山西大学 一种含氮氧三齿化合物及其制备方法和应用
CN106749430A (zh) * 2016-11-25 2017-05-31 山西大学 N,N,O‑三齿Mg/Li双金属催化剂及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1801130A1 (en) * 2005-12-22 2007-06-27 DSMIP Assets B.V. Zwitterionic catalyst comprising a monoanionic bidentate imine ligand
CN106694045A (zh) * 2016-11-25 2017-05-24 山西大学 3:1型Mg/Li双金属催化剂及其制备方法和应用
CN106699575A (zh) * 2016-11-25 2017-05-24 山西大学 一种含氮氧三齿化合物及其制备方法和应用
CN106749430A (zh) * 2016-11-25 2017-05-31 山西大学 N,N,O‑三齿Mg/Li双金属催化剂及其制备方法和应用

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YONG HUANG ET AL.: "Potassium, zinc, and magnesium complexes of a bulky OOO-tridentate bis(phenolate) ligand: synthesis,structures, and studies of cyclic ester polymerisation", 《DALTON TRANSACTIONS》 *
华宇鹏: "含氮氧金属化合物的合成、结构与反应性研究", 《中国博士学位论文全文数据库 工程科技I辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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