CN109678895A - 巯基吡啶间苯二酚杯[4]芳烃锌配合物及制备方法和应用 - Google Patents

巯基吡啶间苯二酚杯[4]芳烃锌配合物及制备方法和应用 Download PDF

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CN109678895A
CN109678895A CN201811471930.XA CN201811471930A CN109678895A CN 109678895 A CN109678895 A CN 109678895A CN 201811471930 A CN201811471930 A CN 201811471930A CN 109678895 A CN109678895 A CN 109678895A
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马继承
王丽
杨进
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Abstract

本发明公开了巯基吡啶间苯二酚杯[4]芳烃锌配合物，它的化学式为[Zn2(m‑bdc)2(L)]·8DMF·2CH3OH，所述的DMF为N,N‑二甲基甲酰胺；及其制备方法：将0.012g,0.04mmol的Zn(NO3)2·6H2O、0.007 g,0.04 mmol的间苯二甲酸和0.012g,0.10mmol的配体L，加入反应釜中，以5 mL的DMF和3 mL的甲醇做反应溶剂，在100℃下加热3天；此配合物具有层状结构，合成重复性强、产品性能稳定；作为异相催化剂，催化效率高；配合物可以选择性探测Cr2O7 2‑阴离子和Fe3+金属阳离子。

Description

巯基吡啶间苯二酚杯[4]芳烃锌配合物及制备方法和应用
技术领域
本发明属于化学技术领域，具体涉及巯基吡啶间苯二酚杯[4]芳烃锌配合物及其制备方法和应用。
背景技术
在传统杯芳烃中引入硫原子和活性有机配体合成硫杂杯芳烃衍生物，可以使大环结构具有更强的配位能力和更多的配位模式，进一步增强杯芳烃衍生物与金属离子配位合成配位聚合物的能力（A. S. Ovsyannikov, S. Ferlay, S. E. Solovieva, I. S.Antipin, A. I. Konovalov, N. Kyritsakas, M. W. Hosseini, CrystEngComm, 2018,20, 1130-1140）。作为一种新兴的晶态材料，一些功能化的配位聚合物已被发现可以作为多种有机反应的异相催化剂（C.-D. Wu, M. Zhao, Adv. Mater.,2017, 29, 1605446）。Knoevenagel缩合作为C-C键形成的重要反应，经常应用于药物合成和精细化学品制备（R.Saha, B. Joarder, A. S. Roy, Sk. M. Islam, S. Kumar, Chem. Eur. J., 2013, 19,16607 – 16614）。结合适当的不饱和金属位点和活性有机配体可以使配位聚合物成为非常有前景的Knoevenagel反应催化剂（W. Jiang, J. Yang, Y.-Y. Liu, S.-Y. Song, J.-F.Ma, Inorg. Chem., 2017, 56, 3036-3043）。研究还发现，使用具有荧光性质的配位聚合物可以进行离子检测，能够克服其它分析方法操作复杂、灵敏度低以及容易受其它物质干扰等因素的限制，具有反应时间短、操作简便和灵敏度高等特点（D. Zhao, Y. Cui, Y.Yang, G. Qian, CrystEngComm, 2016, 18, 3746–3759）。
发明内容
本发明目的是提供一种巯基吡啶间苯二酚杯[4]芳烃锌配合物及其制备方法和应用。
巯基吡啶间苯二酚杯[4]芳烃锌配合物，它的化学式为[Zn2(m-bdc)2(L)]·8DMF·2CH3OH，所述的DMF为N,N-二甲基甲酰胺；
所述的L为四[(4-巯基吡啶)甲基]间苯二酚杯[4]芳烃，结构式为：
。
巯基吡啶间苯二酚杯[4]芳烃锌配合物的制备方法，它包括：
将0.012g, 0.04mmol的Zn(NO3)2·6H2O、0.007 g, 0.04 mmol的间苯二甲酸和0.012g,0.10mmol的配体L，加入反应釜中，以5 mL的DMF和3 mL的甲醇做反应溶剂，在100℃下加热3天；
所述的配体L，是由下述方法制备的：
1）0.20mol 2,6-二羟基甲苯、50mL浓盐酸和200mL乙醇混合均匀后，搅拌下缓慢滴加0.20mol三聚乙醛， 70ºC下搅拌加热16h，冷却至室温，抽滤收集固体，用1:1乙醇-水洗涤，干燥后得中间产物A；
2）在烧瓶中加入0.030mol 的中间产物A、0.50mol CH2ClBr、0.60mol无水碳酸钾和300mL DMF，在70~80ºC下搅拌反应10~15h，氮气保护；冷却，过滤除去不溶物，旋蒸除去DMF，将上层液体用二氯甲烷萃取三次，萃取后下层液体，用饱和食盐水洗涤，有机相用无水硫酸钠干燥；干燥后的液体通过硅胶柱，并用二氯甲烷淋洗硅胶柱；合并收集到的有机相，加入45~55mL乙腈，旋蒸浓缩有机相，抽滤收集固体，干燥得到中间产物B；
3）在烧瓶中加入25mmol 中间产物B、101mmol N-溴代丁二酰亚胺、0.4g偶氮二异丁腈和400mL CCl4，在氮气下加热回流4~6h后，旋蒸除去CCl4，用乙醇超声振荡洗涤，抽滤收集固体，干燥，得到中间产物C；
4）取10.0mmol中间产物C、100.0mmol无水碳酸钾和50.0mmol 2-巯基吡啶，加入200mLDMF中，在85~95˚C下加热反应8~15小时，N2保护；冷却后抽滤，收集沉淀，洗涤，室温下干燥，用二氯甲烷进行索式提取，抽滤干燥，得到配体L；
步骤2）所述的在75ºC下搅拌反应12h；所述加入50mL乙腈；
步骤3）所述加热回流5h；
步骤4）所述在90˚C下加热反应10小时。
所述巯基吡啶间苯二酚杯[4]芳烃锌配合物在催化Knoevenagel缩合反应方面的应用。
所述巯基吡啶间苯二酚杯[4]芳烃锌配合物在检测金属阳离子和阴离子方面的应用；
所述的阳离子为Fe3+，阴离子为Cr2O7 2-。
本发明提供了巯基吡啶间苯二酚杯[4]芳烃锌配合物，它的化学式为[Zn2(m-bdc)2(L)]·8DMF·2CH3OH，所述的DMF为N,N-二甲基甲酰胺；及其制备方法：将0.012g,0.04mmol的Zn(NO3)2·6H2O、0.007 g, 0.04 mmol的间苯二甲酸和0.012g, 0.10mmol的配体L，加入反应釜中，以5 mL的DMF和3 mL的甲醇做反应溶剂，在100℃下加热3天；此配合物具有层状结构，合成重复性强、产品性能稳定；作为异相催化剂，催化效率高；配合物可以选择性探测Cr2O7 2-阴离子和Fe3+金属阳离子。
附图说明
图1 配体的合成路线图；
图2 配合物中锌离子的配位环境图；
图3 配合物的层状结构图；
图4 配合物的测试（上）与拟合（下）X-射线粉末衍射对比图；
图5 配合物在不同阴离子存在下的荧光光谱及识别Cr2O7 2-强度对比图；
图6 配合物在不同金属离子存在下的荧光光谱及识别Fe3+强度对比图。
具体实施方式
实施例1 配体L的制备
在500mL烧瓶中加入0.20mol 2,6-二羟基甲苯、50mL浓盐酸和200mL乙醇，混合均匀后，搅拌下缓慢滴加0.20mol三聚乙醛；混合物在70ºC搅拌加热16h后，冷却至室温，抽滤收集固体，用1:1乙醇-水洗涤，干燥后得中间产物A；在烧瓶中加入0.030mol A、0.50mol CH2ClBr、0.60mol无水碳酸钾和300mL DMF（N,N-二甲基甲酰胺），在氮气保护下75ºC搅拌反应12h；冷却后过滤除去不溶物；旋蒸滤液除去DMF，向滤液中加入500mL二氯甲烷和300mL水，充分搅拌震荡后转入分液漏斗中，静置分液；将上层液体先用二氯甲烷萃取三次，收集下层液体，用饱和食盐水洗涤三次后，有机相用无水硫酸钠干燥；干燥后的液体通过硅胶柱，并用二氯甲烷淋洗硅胶柱；合并收集到的有机相，加入50mL乙腈，旋蒸浓缩有机相至50mL；抽滤收集固体，干燥得到中间产品B。在烧瓶中加入25mmol B、101mmol N-溴代丁二酰亚胺（NBS）、0.4g偶氮二异丁腈（AIBN）和400mL CCl4，在氮气保护下加热回流5h后，旋蒸除去CCl4，加入200mL乙醇，超声振荡洗涤，抽滤收集固体，干燥得到中间产品C；取10.0mmol C、100.0mmol无水碳酸钾和50.0mmol 2-巯基吡啶，加入200mL DMF中，在90˚C N2保护下，加热反应10小时；冷却后抽滤，蒸馏水洗涤沉淀，室温干燥得粗产品；将粗产品用二氯甲烷进行索式提取，抽滤得到配体L，产率约85%（见图1）。
实施例2 锌配合物[Zn2(m-bdc)2(L)]·8DMF·2CH3OH的制备
将0.012g, 0.04mmol的Zn(NO3)2·6H2O、0.007 g, 0.04 mmol的间苯二甲酸和0.012g,0.10mmol的配体L，加入15mL特氟龙反应釜中，以5 mL的N,N-二甲基甲酰胺和3 mL的甲醇做反应溶剂，在100℃下加热3天，自然降温后得到黄色块状晶体，产率23%。
实施例3锌配合物[Zn2(m-bdc)2(L)]·8DMF·2CH3OH的红外光谱数据
1、红外吸收峰为：498.16(s), 555.69(s), 582.14(s), 661.56(s), 686.19(s),727.22(w), 814.97(s),928.79(m), 972.93(w), 1021.29(m), 1066.00(s), 1097.69(m), 1148.00(s), 1229.27(m), 1251.65(m), 1385.72(w), 1428.87(w), 1473.51(w),1601.4(w), 1665.27(w), 2936.72(m), 3390.40(m)。
2、锌配合物的相关表征
（1）配合物的晶体结构测定
[Zn2(m-bdc)2(L)]·8DMF·2CH3OH配合物的衍射数据是在Oxford DiffractionGemini R Ultra衍射仪上收集，Cu Kα射线(λ = 1.5418 Å)，293 K。使用技术扫描进行校正。晶体结构通过SHELEXL-97程序以直接法解出，用全矩阵最小二乘法使用SHELEXL-97进行精修。非氢原子的温度因子用各向异性进行修正。详细的晶体测定数据见表2；重要的键长和键角数据见表3；晶体结构见图2-图3。
[Zn2(m-bdc)2(L)]·8DMF·2CH3OH配合物晶体属于三斜晶系，空间群为P-1，晶胞参数为a = 11.1567(8) Å，b = 21.5856(9) Å，c = 23.5414(13) Å，α = 110.239(4)°，β =91.864(5)°，γ = 93.666(5)°，V = 5299.4(5) Å3。不对称单元中含有两个Zn2+离子、两个m-bdc2-阴离子，一个巯基吡啶间苯二酚杯[4]芳烃配体L，八个游离的DMF分子和两个游离的水分子。Zn1和Zn2都是四面体的配位方式，与来自不同m-bdc阴离子的两个羧基氧原子和两个L配体的氮原子配位。m-bdc阴离子的两个羧基采取单齿配位模式将Zn2+离子连接为四元环，L 配体为四齿配位模式，将 [Zn4(m-bdc)4]环连接为层状结构。由于配体L具备独特的碗状空腔，结构的孔隙率很大。去掉所有的溶剂分子后，利用 PLATON 计算得到配合物的空体积占结构总体积的46.8% (总体积5299.4 Å3)。
（2）配合物的PXRD相纯度表征（Rigaku Dmax 2000 X-射线衍射器）
通过粉末X-射线衍射检测了配合物晶体的相纯度（见图4）。
实施例4 锌配合物[Zn2(m-bdc)2(L)]·8DMF·2CH3OH的Knoevenagel缩合催化反应实验
将配合物晶体浸没于甲醇中12小时，然后置于80°C真空干燥箱中12小时，制备活化配合物；将醛 (1 mmol)、丙二腈(2 mmol)和活化的配合物(0.006 mmol，10 mg)置于15 mL圆底烧瓶中，60℃搅拌1小时，催化Knoevenagel缩合反应，产率通过GC计算，产物通过1H NMR确定；如表1所示，使用配合物作为催化剂时，苯甲醛与丙二腈反应1小时后，得到产物苄烯丙二腈的产率是98%；我们进一步进行了此配合物催化其它的醛的实验，其催化临-氯苯甲醛，对-氰基苯甲醛、对-硝基苯甲醛、对-甲基苯甲醛和萘基苯甲醛与丙二腈的缩合反应都具有优异的产率(95-99%)；对临-羟基苯甲醛和己醛与丙二腈缩合催化反应的产率较高（81%和92%）；上述实验所用仪器为：WondaCAP 17气相色谱仪，Shimadzu FID 探测器；Varian 500 MHz核磁共振波谱仪。
实施例5 锌配合物[Zn2(m-bdc)2(L)]·8DMF·2CH3OH的荧光识别实验
由于锌配合物在水溶液中具有很好的稳定性，所以我们尝试利用这个配合物来检测金属阳离子和阴离子；实验方法为4 mg样品分别放入装有4mL 0.01 M K2SO4、KI、K2CO3、KBr-、KCl、K2Cr2O7等不同阴离子或MnCl2、AgNO3、NiCl2、CdCl2、CaCl2、NaCl、FeCl3等不同金属阳离子的水溶液中，超声得到悬浮液，用Edinburgh FLSP920荧光光谱仪进行荧光测试；如图5和图6所示，当加入不同的阴离子和不同金属阳离子时产生的荧光强度有所不同，以水为参照，配合物在K2Cr2O7和FeCl3的溶液中的荧光强度乎完全淬灭；这个结果说明配合物可以选择性探测Cr2O7 2-阴离子和Fe3+金属阳离子。
实施例5 锌配合物[Zn2(m-bdc)2(L)]·8DMF·2CH3OH的荧光识别实验
由于锌配合物在水溶液中具有很好的稳定性，所以我们尝试利用这个配合物来检测金属阳离子和阴离子；实验方法为4 mg样品分别放入装有4mL 0.01 M K2SO4、KI、K2CO3、KBr-、KCl、K2Cr2O7等不同阴离子或MnCl2、AgNO3、NiCl2、CdCl2、CaCl2、NaCl、FeCl3等不同金属阳离子的水溶液中，超声得到悬浮液，用Edinburgh FLSP920荧光光谱仪进行荧光测试；如图5和图6所示，当加入不同的阴离子和不同金属阳离子时产生的荧光强度有所不同，以水为参照，配合物在K2Cr2O7和FeCl3的溶液中的荧光强度乎完全淬灭；这个结果说明配合物可以选择性探测Cr2O7 2-阴离子和Fe3+金属阳离子。
。

Claims (9)

1.巯基吡啶间苯二酚杯[4]芳烃锌配合物，它的化学式为[Zn2(m-bdc)2(L)]·8DMF·2CH3OH，所述的DMF为N,N-二甲基甲酰胺。
2.根据权利要求1所述的巯基吡啶间苯二酚杯[4]芳烃锌配合物，其特征在于：所述的L为四[(4-巯基吡啶)甲基]间苯二酚杯[4]芳烃，结构式为：
。
3.巯基吡啶间苯二酚杯[4]芳烃锌配合物的制备方法，它包括：
将0.012g, 0.04mmol的Zn(NO3)2·6H2O、0.007 g, 0.04 mmol的间苯二甲酸和0.012g,0.10mmol的配体L，加入反应釜中，以5 mL的DMF和3 mL的甲醇做反应溶剂，在100℃下加热3天；
所述的配体L，是由下述方法制备的：
1）0.20mol 2,6-二羟基甲苯、50mL浓盐酸和200mL乙醇混合均匀后，搅拌下缓慢滴加0.20mol三聚乙醛， 70ºC下搅拌加热16h，冷却至室温，抽滤收集固体，用1:1乙醇-水洗涤，干燥后得中间产物A；
2）在烧瓶中加入0.030mol 的中间产物A、0.50mol CH2ClBr、0.60mol无水碳酸钾和300mL DMF，在70~80ºC下搅拌反应10~15h，氮气保护；冷却，过滤除去不溶物，旋蒸除去DMF，将上层液体用二氯甲烷萃取三次，萃取后下层液体，用饱和食盐水洗涤，有机相用无水硫酸钠干燥；干燥后的液体通过硅胶柱，并用二氯甲烷淋洗硅胶柱；合并收集到的有机相，加入45~55mL乙腈，旋蒸浓缩有机相，抽滤收集固体，干燥得到中间产物B；
3）在烧瓶中加入25mmol 中间产物B、101mmol N-溴代丁二酰亚胺、0.4g偶氮二异丁腈和400mL CCl4，在氮气下加热回流4~6h后，旋蒸除去CCl4，用乙醇超声振荡洗涤，抽滤收集固体，干燥，得到中间产物C；
4）取10.0mmol中间产物C、100.0mmol无水碳酸钾和50.0mmol 2-巯基吡啶，加入200mLDMF中，在85~95˚C下加热反应8~15小时，N2保护；冷却后抽滤，收集沉淀，洗涤，室温下干燥，用二氯甲烷进行索式提取，抽滤干燥，得到配体L。
4.根据权利要求3所述的巯基吡啶间苯二酚杯[4]芳烃锌配合物的制备方法，其特征在于：步骤2）所述的在75ºC下搅拌反应12h；所述加入50mL乙腈。
5.根据权利要求4所述的巯基吡啶间苯二酚杯[4]芳烃锌配合物的制备方法，其特征在于：步骤3）所述加热回流5h。
6.根据权利要求3、4或5所述的巯基吡啶间苯二酚杯[4]芳烃锌配合物的制备方法，其特征在于：步骤4）所述在90˚C下加热反应10小时。
7.权利要求1所述巯基吡啶间苯二酚杯[4]芳烃锌配合物在催化Knoevenagel缩合反应方面的应用。
8.权利要求1所述巯基吡啶间苯二酚杯[4]芳烃锌配合物在检测金属阳离子或阴离子方面的应用。
9.根据权利要求8所述的应用，其特征在于：所述的阳离子为Fe3+，阴离子为Cr2O7 2-。
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