CN106699575B - 一种含氮氧三齿化合物及其制备方法和应用 - Google Patents

一种含氮氧三齿化合物及其制备方法和应用 Download PDF

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CN106699575B
CN106699575B CN201611057427.0A CN201611057427A CN106699575B CN 106699575 B CN106699575 B CN 106699575B CN 201611057427 A CN201611057427 A CN 201611057427A CN 106699575 B CN106699575 B CN 106699575B
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华宇鹏
魏学红
郭志强
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Shanxi University
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
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    • B01J2531/11—Lithium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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    • B01J2531/31—Aluminium

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Abstract

本发明提供了一种含氮氧三齿化合物的制备方法和应用，该化合物可用于金属配合物的制备，尤其是用于双金属配合物的合成。制备方法：冰水浴氮气保护下，在N,N,N′,N′‑四甲基乙二胺(TMEDA)和N,N‑二甲基苯胺(1:1)的乙醚混合溶液中，用等当量的正丁基锂对TMEDA的甲基氢原子选择性锂化后与酮加成，反应混合液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，收集中间无色馏分即可。该化合物制备方法简单，反应条件温和，成本较低，制得的含氮氧三齿化合物容易生成稳定的Mg/Li和Al/Li双金属配合物；这类双金属配合物在Meerwein‑Ponndorf‑Verley(MPV)反应中表现出较高催化活性。

Description

一种含氮氧三齿化合物及其制备方法和应用
技术领域
本发明涉及双金属催化剂，具体涉及含氮氧三齿化合物及其制备方法和应用。
背景技术
C-H键的去质子化通常需要使用强碱性的有机碱化合物。毫无疑问，商用的正丁基锂正己烷溶液是最常用的烷基化试剂，但是对于一些特殊的C-H键很难用正丁基锂去质子化。除了增加反应温度和烷基化试剂的浓度，有效的方法是使用极性溶剂(比如四氢呋喃)或者金属络合助溶剂N,N,N′,N′-四甲基乙二胺(TMEDA)来增强其去质子化活性。正丁基锂在溶剂中是四聚体，或者六聚体，用TMEDA有助于解聚，同时也可以形成螯合物以帮助活化孤电子对给予体邻位的氢。通常条件下TMEDA甲基上的C-H键是不会被正丁基锂活化，它们以稳定的[(n-BuLi)2(TMEDA)2]二聚体结构存在。只有使用更强的碱或者正丁基锂和强碱的混合物时TMEDA才会发生化学反应。例如：Frank曾报道叔丁基锂锂化TMEDA的主要位置是的甲基，正丁基锂和叔丁醇钠的混合物锂化TMEDA的位置是亚甲基。2009年Mulvey报道LiTMP(TMP＝2,2,6,6-四甲基哌啶)和三叔丁基铝的混合物可以使TMEDA的甲基去质子化。因此，由于TMEDA化学性质的稳定性，使其在化学反应中多数是作为溶剂或金属的配位试剂，很少用作有机合成的反应物。我们的研究显示，TMEDA在N,N-二甲基苯胺存在时，正丁基锂可以选择性锂化TMEDA的甲基，并合成含氮氧三齿化合物。这类含氮氧三齿化合物容易生成稳定的Mg/Li和Al/Li双金属配合物，而双金属配合物在Meerwein-Ponndorf-Verl ey(MPV)反应中表现出较高催化活性。该类含氮氧三齿化合物制备方法简单，反应条件温和，成本较低，其制备方法可作为一种新的合成思路应用于有机合成化学。
发明内容
本发明的目的是提供一种含氮氧三齿化合物及其制备方法，该化合物可进一步合成稳定的Mg/Li和Al/Li双金属配合物，并在MPV反应中表现出较高的催化活性。
本发明提供的一种含氮氧三齿化合物，其结构式为：
本发明提供的一种含氮氧三齿化合物的制备方法，包括如下步骤：
冰水浴氮气保护下，在TMEDA和N,N-二甲基苯胺(1:1)的乙醚混合溶液中，用等当量的正丁基锂对TMEDA的甲基氢原子选择性锂化后与环己酮或苯乙酮加成，反应混合液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，收集中间无色馏分即可；反应式：
该化合物可用于合成稳定的Mg/Li和Al/Li双金属配合物，且这类双金属配合物在MPV反应中表现出较高催化活性。
与现有技术相比本发明的优点和效果：本发明在温和的条件下，用正丁基锂对TMEDA的甲基选择性锂化合成含氮氧三齿化合物的制备过程简单，原料易得，可进一步合成高稳定性的Mg/Li和Al/Li双金属配合物，该类化合物作为三齿配体在催化剂合成中有很好的应用前景。
附图说明
图1为实施例1的核磁氢谱图
图2为实施例2的核磁氢谱图
图3为实施例3的晶体结构图
图4为实施例4的晶体结构图
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1一种含氮氧三齿化合物的制备
在氮气保护下，将N,N-二甲基苯胺(3.63g,30mmol)和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℃无色馏分得含氮氧三齿的化合物，产率84％，1H NMR(CDCl3,δ/ppm):1.26-1.33(m,3H,C5H10),1.43-1.44(m,2H,C5H10),1.54-1.55(m,3H,C5H10),1.64-1.69(m,2H,C5H10),2.25(s,6H,NC2H6),2.36(s,4H,NC2H4N),2.40(s,3H,NCH3),2.55-2.57(t,2H,C5H10CH2),5.25(br,1H,C5H10OH)，具体见图1。
实施例2另一种含氮氧三齿化合物的制备
在氮气保护下，将N,N-二甲基苯胺(3.63g,30mmol)和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，再将苯乙酮(3.51mL，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110℃无色馏分得含氮氧三齿的化合物，产率78％，1H NMR(CDCl3,δ/ppm):1.49(s,3H,CH3),2.07(s,3H,NCH3),2.29(s,6H,NC2H6),2.31-2.34(m,1H,NC2H4N),2.37-2.41(s,1H,NC2H4N),2.45-2.52(m,2H,NC2H4N),2.64-2.73(m,2H,C6H5CCH2),6.67(br,1H,C6H5COH)，7.20-7.23(t,2H,C6H5),7.32-7.34(t,2H,C6H5),7.49(d,J＝7.2Hz,2H,C6H5),具体见图2。
实施例3含氮氧三齿Mg/Li双金属配合物的制备
(1)含氮氧三齿化合物的制备同实施例1
(2)在惰性气体保护下，将含氮氧三齿化合物(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，即为含氮氧三齿Mg/Li双金属催化剂，产率86％，熔点为121-124℃。晶体图见图3。
实施例4含氮氧三齿Al/Li双金属配合物的制备
(1)含氮氧三齿化合物的制备同实施例1
(2)在惰性气体保护下，将含氮氧三齿化合物(2.2mmol，0.46g)溶解在10mL乙醚溶剂中，然后逐滴滴加三甲基铝(1.10mL，2.0M，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正丁基锂(0.88mL，2.5M，正戊烷溶液)，恢复室温搅拌2小时，反应完毕后真空浓缩滤液，析出无色透明晶体，即为含氮氧三齿Al/Li双金属催化剂，产率92％，熔点为154-157℃。晶体图见图4。
实施例5
(1)催化剂的制备同实施例3
(2)催化苯甲醛还原为苄醇(MPV)：常温氮气保护下，将苯甲醛(0.42g，4.00mmol)和异丙醇(0.37mL，4.80mmol)加入到氮气保护的含氮氧三齿Mg/Li双金属催化剂(1.06g，0.20mmol)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96％。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6
(1)催化剂的制备同实施例4
(2)催化苯甲醛还原为苄醇(MPV)：常温氮气保护下，将苯甲醛(0.42g，4.00mmol)和异丙醇(0.37mL，4.80mmol)加入到氮气保护的含氮氧三齿Al/Li双金属催化剂(0.66g，0.20mmol)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93％。1H NMR(300MHz,CDCl3):δ(ppm)3.62(s,1H,OH),4.55(s,2H,CH2),6.86-7.39(m,5H,C6H5)。

Claims (2)

1.一种含氮氧三齿化合物的制备方法，其特征在于包括如下步骤：冰水浴氮气保护下，在摩尔比为1:1的N,N,N′,N′-四甲基乙二胺(TMEDA)和N,N-二甲基苯胺的乙醚混合溶液中，用等摩尔量的正丁基锂对TMEDA的甲基选择性锂化后与环己酮或苯乙酮加成，反应混合液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，收集中间无色馏分即可；
所述含氮氧三齿化合物，结构式为：
2.如权利要求1所述方法制备的含氮氧三齿化合物在合成双金属催化剂中的应用。
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