CN110357907B - 一种4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法及用途 - Google Patents
一种4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法及用途 Download PDFInfo
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- -1 4, 6-di (pyridine-2-yl) pyrimidine-2-amine copper Chemical compound 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 115
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- YNGPSRSYQLVKAD-UHFFFAOYSA-N 4,6-dipyridin-2-ylpyrimidin-2-amine Chemical compound N=1C(N)=NC(C=2N=CC=CC=2)=CC=1C1=CC=CC=N1 YNGPSRSYQLVKAD-UHFFFAOYSA-N 0.000 claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000006683 Mannich reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
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- 229940125904 compound 1 Drugs 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
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- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 description 1
- ZNTJVJSUNSUMPP-UHFFFAOYSA-N 1-ethyl-4-ethynylbenzene Chemical group CCC1=CC=C(C#C)C=C1 ZNTJVJSUNSUMPP-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- UVFFOABHOIMLNB-UHFFFAOYSA-N 1-ethynyl-4-propylbenzene Chemical group CCCC1=CC=C(C#C)C=C1 UVFFOABHOIMLNB-UHFFFAOYSA-N 0.000 description 1
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 1
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- 230000005291 magnetic effect Effects 0.000 description 1
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Abstract
本发明公开了一个4,6‑二(吡啶‑2‑基)嘧啶‑2‑胺铜配合物制备方法，该种方法将氯化铜、4,6‑二(吡啶‑2‑基)嘧啶‑2‑胺、二甲基亚砜置于烧杯中反应，反应完毕后，过滤、滤液静置缓慢挥发，得到铜配合物催化剂。本发明方法具有反应速度快、反应过程简单，得到的产品纯度高，后处理简单等特点。并且在催化取代苯乙炔、甲醛与六氢吡啶的Mannich反应中，转化率较高，选择性高达100%。
Description
技术领域
本发明属于催化剂材料制备技术领域，其中涉及到4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物制备方法及用途。
技术背景
金属铜盐及其配合物由于其具有较好的氧化还原性、廉价易得以及结构的多样性等优点在无机配位化学、有机合成催化反应、材料化学等领域而备受关注。近年来铜配位化合物的超分子结构研究发展迅速，这不仅因其呈现的千变万化的结构类型，更重要的这类物质在光、电、磁化学和分离、吸附、催化等领域具有潜在的应用前景。
Mannich反应在有机合成及工业生产中占有十分重要的地位，所得的产物Mannich碱它不仅在药物、农药、染料、调料、涂料、炸药等方面有着广泛的用途，而且也是有机化学中合成天然生物活性分子的重要中间体。在Mannich反应中传统的催化剂是在弱酸、碱或者过渡金属盐的催化下进行的，存在着催化剂不能回收利用，对环境污染严重，不能在室温下反应等问题(Green Chem.,2010,12,949-952；RSCAdv.,2015,5,99095-99098；RSCAdv.,2016,6,79180-79184)，因此寻找一种经济、高效、反应条件温和、对环境友好且易于回收利用的催化剂仍然是目前十分重要的课题。
通过检索，尚未发现与本发明申请相关的公开专利文献。
发明内容
本项发明的目的是解决在弱酸、碱或者过渡金属盐的催化Mannich反应中催化剂无法循环利用且不能在室温条件下反应等问题。提供了一种合成4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物制备的方法，以期在室温条件下对Mannich反应起到较好的催化作用。
这类催化剂的晶体结构信息通过如下方法获得的：
通过常规的溶液反应合成得到4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的晶体，具体的描述实验方法如下：
在一个洁净的烧杯中依次加入4,6-二(吡啶-2-基)嘧啶-2-胺(0.1～0.3mmol)、70～210mmol二甲基亚砜(缩写为DMSO)，在室温下电磁搅拌20～50min，CuCl2·2H2O(0.2～0.4mmol)，电磁搅拌2.0～5.0小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约40～60％。
产品通过单晶X衍射，粉末X射线衍射进行表征，得到关于晶体结构的准确信息。具体的结果如下：
晶体的分子式为[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO,其中阳离子部分为Cu2+阳离子，阴离子为Cl-离子。
本发明主要是合成了4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物，已经将其应用于Mannich反应中。此催化剂可以在较室温条件下实现催化取代苯乙炔、甲醛与六氢吡啶的反应，转化率较高，选择性高达100％。
本发明的目的是通过如下技术方案实现的：
其分子结构为：
分子式分别为：
化合物1[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO
上述炔烃为苯乙炔、对甲基苯乙炔、对乙基苯乙炔、对丙基基苯乙炔、对氯苯乙炔、对甲氧基苯乙炔等，溶剂选用乙腈等，转化率，选择性通过气相色谱检测。
本发明提供铜配合物催化剂具有以下特点：
1.制备方法简单、并且催化剂都具有明确的分子结构，利于研究反应机理。
2.催化剂便于容易分离，经处理后可以多次使用，并且仍能保持良好的催化活性，有利于工业化生产。
附图说明
图1.化合物1[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的晶体结构(为了结构清晰两个溶剂分子及氢原子已经省去)；
图2.化合物1[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的粉末衍射(简写为RXRD)表征。
具体实施方式
实施例1：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.1mmol)、70mmol DMSO，在室温下电磁搅拌30min，CuCl2·2H2O(0.2mmol)，电磁搅拌5小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约57％。
实施例2：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、140mmol DMSO，在室温下电磁搅拌30min，CuCl2·2H2O(0.3mmol)，电磁搅拌4小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约50％。
实施例3：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.3mmol)、200mmol DMSO，在室温下电磁搅拌20min，CuCl2·2H2O(0.2mmol)，电磁搅拌3小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约40％。
实施例4：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、150mmol DMSO，在室温下电磁搅拌30min，CuCl2·2H2O(0.2mmol)，电磁搅拌5小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约48％。
实施例5：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.2mmol)、200mmol DMSO，在室温下电磁搅拌30min，CuCl2·2H2O(0.3mmol)，电磁搅拌3小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约52％。
实施例6：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.1mmol)、200mmol DMSO，在室温下电磁搅拌40min，CuCl2·2H2O(0.4mmol)，电磁搅拌4小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约55％。
实施例7化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.3mmol)、80mmol DMSO，在室温下电磁搅拌50min，CuCl2·2H2O(0.4mmol)，电磁搅拌5小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约58％。
实施例8：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.1mmol)、200mmol DMSO，在室温下电磁搅拌20min，CuCl2·2H2O(0.2mmol)，电磁搅拌2小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约41％。
实施例9：化合物[(CuCl2)2(C14H11N5)(DMSO)2]·2DMSO的制备
在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺(0.1mmol)、100mmol DMSO，在室温下电磁搅拌40min，CuCl2·2H2O(0.3mmol)，电磁搅拌3小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周左右得到块状晶体。产率约47％。
表1.化合物1的晶体学数据
具体试验例：催化取代苯乙炔、甲醛与六氢吡啶的反应
取0.25～0.40mmol取代苯乙炔、0.7～1.0mmol六氢吡啶、1.4～2.0mmol甲醛水溶液，加入2～5ml乙腈溶剂，并加入催化剂5～10mg,保持室温搅拌，反应8～12h后，用气相色谱检测，具体化数据见表2。
表2化合物对取代苯乙炔、甲醛、六氢吡啶催化的结果
由表2可知此4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物催化剂，对于不同取代的芳乙炔与甲醛与六氢吡啶反应均具有良好的非均相催化效果，转化率均达到80％以上，实现了常温条件下Mannich反应，并且此催化剂可以循环利用，解决了催化剂难以回收的问题。
Claims (7)
1.一种4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法，其特征在于：其合成步骤为：在一个洁净的烧杯中依次加入有机配体4,6-二(吡啶-2-基)嘧啶-2-胺、 二甲基亚砜，在室温下电磁搅拌20~50min，再加入CuCl2·2H2O，电磁搅拌2.0~5.0小时，反应完毕后，过滤，滤液在室温下静置缓慢蒸发，一周后得到块状晶体；其结构式如下：
2.根据权利要求1所述的4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法，其特征在于：4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物1的分子式：[(CuCl2)2(C14H11N5)(DMSO)2] 。
3.根据权利要求1所述的4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法，其特征在于：所述的4,6-二(吡啶-2-基)嘧啶-2-胺：CuCl2·2H2O 的物质的量0.1~0.3：0.1~0.3。
4.根据权利要求1所述的4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法，其特征在于：所用溶剂为二甲基亚砜，4,6-二(吡啶-2-基)嘧啶-2-胺：CuCl2·2H2O：二甲基亚砜的物质的量0.1~0.3：0.1~0.3：70~210。
5.根据权利要求1所述的4,6-二(吡啶-2-基)嘧啶-2-胺铜配合物的制备方法，其特征在于：反应时间为2~5h。
6.一种权利要求1-5任一项所述制备方法制备得到的铜配合物。
7.权利要求1-5任一项所述制备方法制得的铜配合物在取代芳乙炔、甲醛与六氢吡啶参与的Mannich反应中的催化应用。
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