CN106397345B - 一种3-羧基-1，2，4-三氮唑类钴配合物及其原位合成方法 - Google Patents

一种3-羧基-1，2，4-三氮唑类钴配合物及其原位合成方法 Download PDF

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CN106397345B
CN106397345B CN201610816851.2A CN201610816851A CN106397345B CN 106397345 B CN106397345 B CN 106397345B CN 201610816851 A CN201610816851 A CN 201610816851A CN 106397345 B CN106397345 B CN 106397345B
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triazole
carboxyl
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CN106397345A (zh
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蒋毅民
张晓强
黄富平
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Guangxi Normal University
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    • C07—ORGANIC CHEMISTRY
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明公开了一种3‑羧基‑1，2，4‑三氮唑钴配合物及其原位合成方法，该钴配合物化学式为[Co2(L3)2(H2O)2](HL3=3‑羧基‑1，2，4‑三氮唑）。其原位合成方法，包括下述步骤：分别称取0.04‑0.05 g二(5‑硫酮‑1,2,4‑三氮唑)甲烷（L1）和0.10‑0.15g CoCl2·6H2O于7‑8mL水中混合，再加入1‑1.5mL DMF，常温搅拌30‑35min；将上述溶液移入到25 mL聚四氟乙烯反应釜中，置于130‑140℃的恒温烘箱中60‑80小时后，以每小时5℃降温至室温，过滤，用无水甲醇洗涤，得到红棕色单晶级块状晶体。本发明配合物的原位合成，克服了溶剂法的缺点，具有原料易得、成本低廉、工艺简单等优点。

Description

一种3-羧基-1，2，4-三氮唑类钴配合物及其原位合成方法
技术领域
本发明涉及钴配合物及其原位合成方法，具体是一种3-羧基-1，2，4-三氮唑钴配合物及其原位合成方法。
背景技术
近年来出现的原位合成技术，广泛应用于化学、化工、材料等领域。原位合成是指在一定条件下，通过化学反应，在反应体系内原位生成一种或几种新型的化合物。通过原位合成，可以获得其他合成方法难以获得的化合物。目前虽有不少文献报道了原位配体反应，但未见有二(5-硫酮-1,2,4-三氮唑)甲烷被氧化成羧酸的报导。产物3-羧基-1，2，4-三氮唑作为中间体广泛应用于医药、农药等领域，其与金属离子形成配合物具有较好的抗菌与抗癌活性，具有重要的潜在用途。
发明内容
为了获得新的3-羧基-1，2，4-三氮唑类配体配位聚合物，本发明一方面在于提供一种3-羧基-1，2，4-三氮唑钴配合物，另一方面还提供以二(5-硫酮-1,2,4-三氮唑)甲烷（L1）为原料的该配合物的原位合成方法。
本发明一种3-羧基-1，2，4-三氮唑类钴配合物，化学式为[Co2(L3)2(H2O)2] (HL3=3-羧基-1，2，4-三氮唑），其晶体属于单斜晶系，P21/c空间群，晶胞参数为：a =9.0021(11)Å，b = 8.7698(12)Å ，c =6.879(3)Å，α= 90.00º，β= 93.979 (16)º，γ= 90.00º，V =541.7 (2) Å3。
本发明所述的配合物的原位合成方法，包括下述步骤：
（1）分别称取0.04-0.05 g二(5-硫酮-1,2,4-三氮唑)甲烷（L1）和0.10-0.15 gCoCl2·6H2O于7-8 mL水中混合，再加入1-1.5 mL DMF，常温搅拌30-35 min；
（2）将上述溶液移入到25 mL聚四氟乙烯反应釜中，置于130-140 ℃的恒温烘箱中60-80小时后，以每小时5℃降温至室温，过滤，用无水甲醇洗涤，得到红棕色单晶级块状晶体。
在本发明配合物的原位反应过程中，原母体配体二(5-硫酮-1,2,4-三氮唑)甲烷（L 1）在反应过程中发生原位反应，脱去一个 5-硫酮-1,2,4-三氮唑后，剩余分子片上5位的S也脱去，同时，3位上的亚甲基被氧化成羧基，生成3-羧基-1,2,4-三氮唑新配体，进而与金属钴离子配位。
本发明所述配合物中仅有一个晶体学上独立的Co(Ⅱ)离子，其中心钴离子分别与来自两个三氮唑上的N原子和两个羧基上的O原子及两个水分子的O原子配位。
本发明配合物经弱键作用构成二维网面结构，相邻的共平面二维结构又通过层层之间的π···π相互作拓展为三维层状的超分子结构。
本发明配合物的原位合成，克服了溶剂法的缺点，具有原料易得、成本低廉、工艺简单等优点。
附图说明
图1为本发明配合物的原位合成实施图；
图2为本发明配合物的分子结构图；
图3为本发明配合物的三维堆积图。
具体实施方式
下面结合实施例对本发明内容作进一步的说明，但不是对本发明的限定。
实施例
参见图1，一种3-羧基-1，2，4-三氮唑钴配位聚合物的原位合成：分别称取0.0428g二(5-硫酮-1,2,4-三氮唑)甲烷（L1）和0.1068 g CoCl2·6H2O，加入1 mL DMF和7 mL H2O，室温下搅拌30 min后，再移入到带聚四氟乙烯衬底的容积为25 mL的反应釜中，置于
140 ℃的恒温烘箱中72小时，然后以每小时5℃冷却至室温。过滤，用无水甲醇洗涤，得到红棕色单晶级块状晶体。
从图1可以看出，原母体配体二(5-硫酮-1,2,4-三氮唑)甲烷（L 1）在反应过程中发生原位反应，脱去一个 5-硫酮-1,2,4-三氮唑后，剩余分子片上5位的S也脱去，同时，3位上的亚甲基被氧化成羧基，生成3-羧基-1,2,4-三氮唑新配体，进而与金属钴离子配位。
参见图2，从图中可以看出，该配合物中仅有一个晶体学上独立的Co(Ⅱ)离子，中心钴离子分别与来自两个三氮唑上的N原子和两个羧基上的O原子及两个水分子的O原子配位。
参见图3，从图中可以看出，该配合物经弱键作用构成二维网面结构，相邻的共平面二维结构又通过层层之间的π···π相互作拓展为三维层状的超分子结构。

Claims (1)

1.一种3-羧基-1，2，4-三氮唑类钴配合物的原位合成方法，其特征是包括下述步骤：
（1）分别称取0.04-0.05 g二(5-硫酮-1,2,4-三氮唑)甲烷L1和0.10-0.15 g CoCl2·6H2O于7-8 mL水中混合，再加入1-1.5 mL DMF，常温搅拌30 min；
（2）将上述溶液移入到25 mL聚四氟乙烯反应釜中，置于130-140 ℃的恒温烘箱中60-80小时后，以每小时5℃降温至室温，过滤，用无水甲醇洗涤，得到红棕色单晶级块状晶体；
该配合物化学式为[Co(L3)2(H2O)2] ，HL3=3-羧基-1，2，4-三氮唑，其晶体属于单斜晶系，P21/c空间群，晶胞参数为：a =9.0021(11) Å，b = 8.7698(12)Å ，c =6.879(3)Å，α=90.00º，β= 93.979 (16)º，γ=90.00º，V = 541.7 (2) Å3。
CN201610816851.2A 2016-09-12 2016-09-12 一种3-羧基-1，2，4-三氮唑类钴配合物及其原位合成方法 Expired - Fee Related CN106397345B (zh)

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CN109867689B (zh) * 2019-04-22 2021-05-14 广西师范大学 一种含硫-硫键的双核Cd(Ⅱ)配合物及其原位合成方法

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