CN105622646B - 一种锌配合物晶体 - Google Patents

一种锌配合物晶体 Download PDF

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CN105622646B
CN105622646B CN201511032335.2A CN201511032335A CN105622646B CN 105622646 B CN105622646 B CN 105622646B CN 201511032335 A CN201511032335 A CN 201511032335A CN 105622646 B CN105622646 B CN 105622646B
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罗梅
张志军
李学良
张竞成
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Hefei University of Technology
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Abstract

一种锌配合物晶体，其化学式如下：该锌配合物晶体(I)的合成方法，是称取1.2809g(0.002mol)四氰乙烯放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将1.2100g(0.001mol)二水合乙酸锌加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，滤液自然挥发，几天后有黄色晶体析出；该配合物在苯甲醛的亨利反应及腈硅化反应中显示了较好的催化性能，其转化率分别为87％及81％。

Description

一种锌配合物晶体
技术领域
本发明涉及一种新化合物及其制备方法，特别涉及一种锌配合物及其制备方法，确切地说是一种手性四氰乙烯锌配合物的制备及合成方法。
背景技术
随着有机化学的发展,金属有机化合物在有机合成中的应用愈来愈广,是现在有机化学中极为活跃的领域之一,已经广泛应用于有机合成反应中。20世纪60年代后期出现的使用手性配体与过渡金属络合物催化的不对称合成反应大大加速了手性药物的研究。化学催化不对称合成法的重要内容便是手性配体及含金属催化剂的设计,从而使反应具有高效和高对映选择性。近年来手性锌氮金属配合物在不对称催化领域取得了较好的催化效果。
参考文献：
1.Michaels,Heather A.；Murphy,Christopher S.；Clark,Ronald J.；Davidson,Michael W.；Zhu,Lei.Inorganic Chemistry(2010),49(9),4278-4287；
2..Mei,Luo；Ming,Tang Hai；Rong,Li Qian；Jie,Sun；Zhong,Yang Shan；Liang,Li Xue.Journal of Chemical Sciences(Bangalore,India)(2009),121(4),435-440；
3.Dong,Qingchen；Ma,Xiaping；Guo,Jianping；Wei,Xuehong；Zhou,Meisu；Liu,Diansheng.Inorganic Chemistry Communications(2008),11(6),608-611。
发明内容
本发明旨在提供一种Zn-N金属有机配合物以应用于催化领域，所要解决的技术问题遴选邻作为配体并合成手性锌氮配合物。
本发明所称的锌氮配合物是由四氰乙烯与二水合氯化锌制备的由以下化学式所示的配合物：
化学名称：多核四氰乙烯锌配合物,简称配合物(I)。该配合物在苯甲醛的亨利反应及腈硅化反应中显示了较好的催化性能，其转化率分别为87％及81％。
本合成方法包括合成和分离，所述的合成称取1.2809g(0.002mol)四氰乙烯放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将1.2100g(0.001mol)二水合乙酸锌加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，滤液自然挥发，几天后有黄色晶体析出。
合成反应如下：
本合成方法一步得到目标产物，工艺简单，操作方便。
该配合物形成的反应机理可推测为在大量路易斯酸二水合乙酸锌的作用下，四氰乙烯会脱去一个氰基，成为三氰基甲烷，其中一个氰基首先水解形成甲酸，或另一个氰基形成甲酰胺分子，在甲醇的作用下，分别与甲醇分子进行亲核加成反应，形成乙酸酯基及N,N,二甲酰基，并分别与金属锌原子配位。
附图说明
图1是多核四氰乙烯锌配合物的X-衍射分析图。
具体实施方式
1.多核四氰乙烯锌配合物的制备：称取1.2809g(0.002mol)四氰乙烯放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将1.2100g(0.001mol)二水合乙酸锌加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，滤液自然挥发，几天后有黄色晶体析出。
将黄色晶体用石油醚和正己烷冲洗3次，真空干燥30分钟，所得的目标产物的产率为33％，熔点为180-182℃。元素分析数据[Zn3(C29H43N11O14)]，理论值：C：36.06％；H：4.49％；N：15.95％；实测值：C：36.01％；H：4.64％；N：16.29％；红外光谱数据(KBr,cm-1)：467，552，686，755，805，959，1108，1136，1193，1193，1283，1381，1493，1650，2133，2207，2236，2413，2854，2955，3378，3616。
配合物的晶体数据：
经验式 C29H45N11O14Zn3
分子量 963.8660
温度 296.15 K
波长 0.71073 A
晶系，空间群 斜方晶系,Pnma
晶胞参数 α＝90°.
β＝90°.
γ＝90°.
体积
电荷密度 4,1.1580Mg/m^3
吸收校正参数 1.491 mm^-1
单胞内的电子数目 824
晶体大小 0.38x 0.33x 0.25mm
Theta角的范围 2.270to30.610
HKL的指标收集范围 -19<＝h<＝25-21<＝k<21,-9<＝l<＝8
收集/独立衍射数据 16177/2680[R(int)＝0.0311]
theta＝30.5的数据完整度 100.0％
吸收校正的方法 多层扫描
最大最小的透过率 0.7461and 0.6415
精修使用的方法 F^2的矩阵最小二乘法
数据数目/使用限制的数目/参数数目 2680/03/128
精修使用的方法 1.022
衍射点的一致性因子 R1＝0.0286，wR2＝0.0732
可观察衍射的吻合因子 R1＝0.0393,wR2＝0.0781
差值傅里叶图上的最大峰顶和峰谷 0.617and-0.625e.A^-3
晶体典型的键长数据：
晶体典型的键角数据
2.亨利反应应用
称取0.0604g(0.15mmol)四氰乙烯锌配合物(Ⅶ)，放置于25mL的小烧瓶中，加入2mL无水甲醇溶解，向溶液中加入0.1mL苯甲醛和0.5mL硝基甲烷，常温下搅拌反应24小时后，进行1HNMR检测，转化率：87％；
1H NMR(300MHz,CDCl3)7.28～7.32(m,5H,Ar-H),5.32～5.35(d,J＝9.18Hz,1H,-CH),4.38～4.56(m,2H,-CH2),3.89(br,1H,-OH)。
3.硅腈化反应应用
硅腈化反应也是一种常用的有机合成反应，是合成手性腈醇一种重要方法。在有机医药中间体方面也有广泛的应用；
其反应方程式：
称取0.0402g(0.15mmol)四氰乙烯锌配合物，放置于25mL小烧瓶中，加入2mL无水甲醇溶解，再向溶液中加入0.1mL苯甲醛和0.3mL三甲基硅腈，常温下搅拌72h，进行1HNMR检测,其催化转化率为81％。

Claims (3)

1.一种锌配合物，其化学式如下：
2.权利要求1所述的锌配合物晶体(I)，在293(2)K温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的MoKα射线以ω-θ扫描方式收集衍射数据，其特征在于晶体属斜方晶系，空间群Pnma，晶胞参数：α＝90°；β＝90°；γ＝90°。
3.权利要求1所述的锌配合物(I)的合成方法，包括合成和分离，所述的合成称取1.2809g四氰乙烯放入100mL圆底烧瓶中，加入40mL无水甲醇并搅拌使其溶解；将1.2100g二水合乙酸锌加入上述溶液，加热回流48h；反应结束后趁热过滤反应溶液，滤液自然挥发，几天后有黄色晶体析出。
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