CN106694045B - 3:1型Mg/Li双金属催化剂及其制备方法和应用 - Google Patents

3:1型Mg/Li双金属催化剂及其制备方法和应用 Download PDF

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CN106694045B
CN106694045B CN201611059463.0A CN201611059463A CN106694045B CN 106694045 B CN106694045 B CN 106694045B CN 201611059463 A CN201611059463 A CN 201611059463A CN 106694045 B CN106694045 B CN 106694045B
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魏学红
华宇鹏
郭志强
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Shanxi University
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Abstract

本发明提供了一种3:1型Li/Mg双金属催化剂及其制备方法和应用。催化剂制备方法：1)制备N,N,O‑三齿的胺基醇配体；2)在惰性气体保护和冰水浴下，将1.5倍量的正丁基锂逐滴滴加到胺基醇的乙醚溶液中，所得反应液中滴加0.5倍量的二丁基镁，然后滴入0.5倍量水的乙醚溶液，待反应完毕后过滤，真空浓缩滤液，析出无色透明晶体即可。该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、镁为催化活性金属，对不同类型的醛、酮化合物还原制备相应的一级和二级醇类化合物的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，有很好的工业应用前景。

Description

3:1型Mg/Li双金属催化剂及其制备方法和应用
技术领域
本发明涉及双金属催化剂，具体涉及一种3:1型N,N,O-三齿Mg/Li双金属及其制备方法和应用。
背景技术
一级和二级醇的选择性合成是有机合成、制药和食物香料工业等领域的一个重要转化过程。Meerwein-Ponndorf-Verley(MPV)反应被认为是由醛、酮制备一级和二级醇的重要反应之一，通常使用一个氢供体与强碱和催化剂的系统，而最主要的部分还是高效的催化剂。因此，开发新的和有效的催化反应系统仍然是科研工作者努力的重点。MPV反应通常使用主族金属、过渡金属、镧系和锕系等金属化合物作为催化剂，主要是单金属的醇盐，氧化物及其配合物等，而且催化剂存在结构复杂，不易制备，催化剂活性不够高，用量大，反应时间长等不足。双金属化合物因其含有两种金属原子显示出不同于其中任一单金属前体的催化性能，被认为是潜在的高效催化剂。金属锂和镁通常作为低毒的金属中心原子被广泛用于催化剂的合成与应用，而含Li/Mg的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
本发明的目的是提供一种3:1型Mg/Li双金属催化剂及其制备方法，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。
本发明提供的一种3:1型Mg/Li双金属催化剂，其结构式为：
式中：镁原子与两个氧原子和丁基的碳原子形成三配位模式，锂原子存在三配位和四配位两种成键模式，四配位的锂原子与配体中的氧原子和氮原子形成四配位结构，而且形成两个共用N-Li键的五元环；三配位的锂原子处于分子结构中心，并以Li-O配位键形成二聚体构型的分子结构。
本发明提供的一种3:1型Mg/Li双金属催化剂的制备方法，包括如下步骤：
(1)N,N,N′,N′-四甲基乙二胺(TMEDA)经正丁基锂锂化后与环己酮加成，在酸性条件下水解后，水相用氢氧化钠水溶液中和至弱碱性，再用无水乙醚萃取2-3次，有机相干燥后减压蒸馏，收集中间无色馏分得到N,N,O-三齿的胺基醇配体；反应式：
(2)在惰性气体保护下，首先将等1.5倍量的正丁基锂逐滴滴加到N,N,O-三齿胺基醇配体的乙醚溶液中，搅拌1-2小时，然后在冰水浴中缓慢滴入0.5倍当量的二丁基镁试剂，恢复室温搅拌2-4小时，然后滴入0.5倍量水的乙醚溶液，反应完毕后真空浓缩滤液，析出无色透明晶体，即为3:1型N,N,O-三齿Mg/Li双金属催化剂，产率84-86％。反应式：
该催化剂可在醛、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过程简单，原料易得，使用廉价、无毒的非过渡金属镁和锂为催化活性金属，反应条件温和，对醛、酮类化合物的MPV反应有较高选择性，能高效地合成相应的醇类化合物，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本发明3:1型N,N,O-三齿Mg/Li双金属催化剂的单晶X射线结构图
具体实施方式：
以下仅仅为详细说明本发明而给出的具体实施例，这些实施例并非用于限制本发明的保护范围。
实施例1 3:1型N,N,O-三齿Mg/Li双金属催化剂的制备
将正丁基锂(29.20mL，2.5M，正己烷溶液)在0℃缓慢滴入TMEDA(11.02g，73mmol)的乙醚溶液中，恢复室温后反应2小时，再将环己酮(7.54mL，73mmol)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-三齿的胺基醇配体，产率84％；
在惰性气体保护下，将N,N,O-三齿胺基醇配体(2.0mmol，0.43g)溶解在10mL乙醚溶剂中，然后逐滴滴加正丁基锂(1.20mL，2.5M，正己烷溶液)到搅拌上述溶液中，搅拌1小时，然后在冰水浴中缓慢滴入等当量的二丁基镁(1.0mL，1.0M，正戊烷溶液)，恢复室温搅拌2小时，然后滴入经脱气后的水(1.0mL,1.0M，乙醚溶液)，反应完毕后真空浓缩滤液，析出无色透明晶体，即为3:1型N,N,O-三齿Mg/Li双金属催化剂，产率86％，熔点为121-124℃。
晶体参数：化学式：C56H118Li6Mg2N8O6，单斜晶系(Monoclinic)，空间群P 21/c，晶胞参数α＝90.000°，β＝98.3980(10)°，γ＝90.000°，V＝3257.84(17)，Z＝2。单晶结构图见图1。部分键长Li(1)-O(1)1.934(5),Li(1)-O(2)1.925(5),Li(1)-N(1)2.191(5),Li(1)-N(2)2.076(5),Li(2)-O(1)1.927(5),Li(2)-O(2)1.976(5),Li(2)-N(3)2.188(5),Li(2)-N(4)2.032(5),Li(3)-O(1)1.867(5),Li(3)-O(3)1.947(5),Li(3)-O(3)′1.943(5),Mg(1)-O(2)2.008(2),Mg(1)-O(3)2.084(2)；键角(°)：O(3)-Li(3)-O(3)′98.9(2),Li(3)-O(3)-Li(3)′81.1(2),O(1)-Li(1)-O(2)98.0(2),O(1)-Li(1)-N(1)87.0(2),O(1)-Li(1)-N(2)129.8(3),O(2)-Li(1)-N(1)155.1(3),O(2)-Li(1)-N(2)106.8(2),N(1)-Li(1)-N(2)87.78(19),O(2)-Li(1)-O(3)80.97(18),O(1)-Li(1)-O(3)83.54(17),O(1)-Li(2)-O(2)96.6(2),O(1)-Li(2)-N(3)149.2(3),O(1)-Li(2)-N(4)118.2(3),O(2)-Li(2)-N(3)83.6(2),O(2)-Li(2)-N(4)114.9(2),N(3)-Li(2)-N(4)88.8(2),O(1)-Li(3)-O(3)109.8(2),O(1)-Li(3)-O(3)′148.4(3),O(3)-Li(3)-O(3)′98.9(2),O(2)-Mg(1)-O(3)96.04(8)。
实施例2
(1)催化剂的制备同实施例1
催化苯甲醛还原为苄醇(MPV)：常温氮气保护下，将苯甲醛(0.42g，4.0mmol)和异丙醇(0.37mL，4.8mmol)加入到氮气保护的3:1型N,N,O-三齿Mg/Li双金属催化剂(1.06g，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94％。1HNMR(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
(1)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(0.48g，4.0mmol)和异丙醇(0.37mL，4.8mmol)加入到氮气保护的3:1型N,N,O-三齿Mg/Li双金属催化剂(1.06g，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91％。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)。

Claims (3)

1.一种3:1型Li/Mg双金属催化剂，其特征在于，结构式为：
2.如权利要求1所述的一种3:1型Li/Mg双金属催化剂的制备方法，其特征在于，包括如下步骤：
1)N,N,N′,N′-四甲基乙二胺(TMEDA)经正丁基锂锂化后与环己酮加成，在酸性条件下水解后，水相用氢氧化钠水溶液中和至弱碱性，再用无水乙醚萃取2-3次，有机相干燥后减压蒸馏，收集中间无色馏分得到N,N,O-三齿的胺基醇配体；
2)在惰性气体保护下，首先将1.5倍摩尔量的正丁基锂逐滴滴加到N,N,O-三齿胺基醇配体的乙醚溶液中，搅拌1-2小时，然后在冰水浴中缓慢滴入0.5倍摩尔量的二丁基镁试剂，恢复室温搅拌2-4小时，然后滴入0.5倍摩尔量水的乙醚溶液，反应完毕后真空浓缩滤液，析出无色透明晶体即可。
3.如权利要求1所述的3:1型Mg/Li双金属催化剂在催化醛、酮类化合物的MPV反应中应用。
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