CN104230829B - 联苯双三唑化合物及其制备方法与应用 - Google Patents

联苯双三唑化合物及其制备方法与应用 Download PDF

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CN104230829B
CN104230829B CN201410498885.2A CN201410498885A CN104230829B CN 104230829 B CN104230829 B CN 104230829B CN 201410498885 A CN201410498885 A CN 201410498885A CN 104230829 B CN104230829 B CN 104230829B
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CN104230829A (zh
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王英
赵小军
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Tianjin Normal University
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Abstract

本发明公开了一种[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑的制备方法，及其应用。它是采用“一锅法”，即4,4’-二碘联苯，三唑，碳酸钾和氧化铜加热来制备该有机化合物。本发明的制备方法具有工艺操作简单，生产成本低，环境污染小的特点，适合大规模的工业化生产。本发明进一步公开了[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物在作为Mg2+荧光探针方面的应用。

Description

联苯双三唑化合物及其制备方法与应用
本发明由国家自然科学基金面上项目(21471113)、天津市教委项目和天津市高等学校创新团队培养计划资助(TD12-5038)。
技术领域
本发明属于有机合成技术领域，涉及[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物及其单制备方法与应用。
背景技术
1,2,4-三唑及其衍生物兼有吡唑和咪唑的配位特点，是配位能力较强的桥连配体，目前已合成并表征了大量的单核、多核和多维化合物。这些配体能够以1,2位上的氮原子与金属离子配位形成N1,N2-桥连模式，对于4位未取代的1,2,4-三唑衍生物能通过2,4位上的氮原子形成N2,N4-桥连模式，这种N2,N4-桥连模式同金属酶中咪唑的N1,N3-桥连模式类似。对于三唑类化合物的特殊用途还表现在分子器件化的设计上，合成具有不同维数的金属配合物乃是完成器件化至关重要的一步。
联苯双三唑是一类性能优良的光电材料。迄今为止，尚未查到[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑这个化合物，更未检索到有关[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑合成方法的文献报道。
发明内容
本发明的一个目的在于提供一种[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物及其制备方法。
本发明人在试验中惊奇地发现：以4,4’-二碘联苯，三唑，碳酸钾和氧化铜为主要原材料，反应中以二甲亚枫(DMSO)为溶剂，控制温度在80-200℃时，可以得到收率高的[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物。
本发明进一步公开了[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物在作为Mg2+荧光探针方面的应用。发现只有加入Mg2+荧光强度大幅度增强，实验的结果：说明[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物，是基于三唑衍生物配体的Mg2+荧光探针。
为实现上述目的，本发明人提供了如下的技术方案：
[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物具有如下的结构：
本发明所述[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑的制备方法,其特征在采用“一锅法”，在极性溶剂中，将4,4’-二碘联苯，三唑，碳酸钾和氧化铜在加热条件下制备该有机化合物；其中4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:10:30:1；
本发明优选4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:10:30:1；反应温度80-200℃，反应时间12-120小时。
本发明更加详细的制备方法如下：
一种[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑的制备方法其特征在于，在极性溶剂中，采用“一锅法”，将4,4’-二碘联苯，三唑，碳酸钾和氧化铜在加热条件下制备该有机化合物；
本发明所述的极性溶剂为二甲基亚砜。
其中4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:10-15:30:1；
本发明公开的[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物所具有的优点和特点在于：
(1)反应操作简便易行。
(2)反应收率高，所得产品的纯度高。
(3)本发明所制备的[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑生产成本低，利润空间大，更适合大规模的工业化生产。
附图说明
图1：[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑的核磁谱图；
图2：不同离子对[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑荧光强度的影响。
具体实施方式
下面结合实施例对本发明做进一步的说明，实施例仅为解释性的，决不意味着它以任何方式限制本发明的范围。所有的原料都是从国内外的化学试剂公司进行购买，没有经过继续提纯而是直接使用的。产物的熔点是在型号为X4Micro的熔点仪上进行测量的。
实施例1
4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:10:30:1
在装有磁子、回流冷凝器和温度计的50mL三口圆底烧瓶内分别加入CuO(0.0398mg,0.5mmol)，碳酸钾(2.0731g,15mmol)，三唑(0.345mg,5mmol)，4,4’-二碘联苯(0.4060g,1mmol)，20mLDMSO。开动搅拌在100oC，反应24小时。反应结束后，将反应液降至室温，过滤，滤液加入100mL水，析出大量沉淀，抽滤，收集滤饼，收率60%。
实施例2
其中4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:15:30:1；
我们还尝试过其他比例，比如4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:10:30:1，则反应产物有大量的原料剩余，无论反应进行的时间长短，反应都不完全。因此4,4’-二碘联苯：三唑：碳酸钾：氧化铜的摩尔比为2:15:30:1是最佳反应配比。
实施例3
该化合物配制浓度为10-3mol/L的DMSO溶液，采用荧光分析仪测得λem=550nm，当加入0-3倍浓度的Mg2+，Co2+，Ni2+和Ca2+，发现只有加入Mg2+荧光强度大幅度增强，说明该配合物是基于三唑衍生物配体的Mg2+荧光探针。
在详细说明的较佳实施例之后，熟悉该项技术人士可清楚地了解，在不脱离上述申请专利范围与精神下可进行各种变化与修改，凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均属于本发明技术方案的范围。且本发明亦不受说明书中所举实例实施方式的限制。

Claims (1)

1.[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物在增强Mg2+荧光强度方面的应用；所述的[4-(4-(1H-1,2,4-三氮唑-1-基)苯基)苯基]-1H-1,2,4-三氮唑化合物的结构如下：
。
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CN102485716A (zh) * 2010-12-03 2012-06-06 郑建鸿 间-三联苯衍生物及其在有机发光二极管的应用
CN103086988A (zh) * 2013-02-21 2013-05-08 天津师范大学 苯基双三唑化合物及其制备方法与应用

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JP4631259B2 (ja) * 2002-10-03 2011-02-16 コニカミノルタホールディングス株式会社 有機エレクトロルミネッセンス素子及び表示装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102485716A (zh) * 2010-12-03 2012-06-06 郑建鸿 间-三联苯衍生物及其在有机发光二极管的应用
CN103086988A (zh) * 2013-02-21 2013-05-08 天津师范大学 苯基双三唑化合物及其制备方法与应用

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