CN105859755A - 1,4-二甲基-2,5-二-1h-1,2,4-双三唑间苯二甲酸镉配合物单晶与应用 - Google Patents

1,4-二甲基-2,5-二-1h-1,2,4-双三唑间苯二甲酸镉配合物单晶与应用 Download PDF

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CN105859755A
CN105859755A CN201610255184.5A CN201610255184A CN105859755A CN 105859755 A CN105859755 A CN 105859755A CN 201610255184 A CN201610255184 A CN 201610255184A CN 105859755 A CN105859755 A CN 105859755A
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dimethyl
ipa
triazole
single crystal
phthalic acid
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王中良
王英
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Tianjin University
Tianjin Normal University
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Abstract

本发明公开了1,4‑二甲基‑2,5‑二‑1H‑1,2,4‑双三唑间苯二甲酸镉配合物单晶及其制备方法与应用，其结构：[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O，其中，L=1‑(2,5‑二甲基‑4‑(1H‑1,2,4‑三唑‑1‑基)苯基)‑1H‑1,2,4‑三唑；ipa=间苯二甲酸；NMP=1‑甲基‑2‑吡咯烷酮。同时还公开了单晶的制备方法。它是采用常温挥发法，即L、ipa和Cd(NO3)2·6H2O在水和NMP的混合溶剂中搅拌半小时后过滤，滤液常温挥发两周后得到适合X‑射线单晶衍射的无色块状晶体。其中L:ipa:Cd(NO3)2·6H2O的摩尔比为1:1:1。本发明进一步公开了1,4‑二甲基‑2,5‑二‑1H‑1,2,4‑双三唑间苯二甲酸镉配合物单晶专属性用于对氟苯硼酸生成4,4'‑二氟联苯的催化剂方面的应用。

Description

1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物 单晶与应用
本发明得到天津市教委创新团队(TD12-5037)的资助。
技术领域
本发明属于有机和无机合成技术领域，涉及1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}的制备方法及作为催化剂方面的应用，其中，L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；ipa = 间苯二甲酸；NMP = 1-甲基-2-吡咯烷酮。
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。
本发明即是采用常温挥发法，即L、ipa和Cd(NO3)2·6H2O在水和NMP的混合溶剂中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的无色块状晶体，结构为{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}，其中，L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；ipa = 间苯二甲酸；NMP = 1-甲基-2-吡咯烷酮。该配合物还可作为对氟苯硼酸生成4,4'-二氟联苯的催化剂得以应用。
发明内容
为此本发明人提供了如下的技术方案：
一种1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物的单晶，其特征在于该单晶结构采用APEX II CCD单晶衍射仪，使用经过石墨单色化的Mokα射线，λ = 0.71073Å为入射辐射，以ω-2θ扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值傅立叶电子密度图利用软件解出单晶数据：
其结构如下：
{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}，其中
L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；
ipa = 间苯二甲酸；
NMP = 1-甲基-2-吡咯烷酮。
本发明进一步公开了1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶的制备方法，其特征在于它是采用常温挥发法，将L、ipa和Cd(NO3)2·6H2O在水和NMP的混合溶剂中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的无色块状晶体；其中L:ipa:Cd(NO3)2·6H2O的摩尔比为1:1:1；
1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶的结构为{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}；其中L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；ipa = 间苯二甲酸；NMP = 1-甲基-2-吡咯烷酮；
L NMP。
本发明更进一步公开了1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂得以应用，实验结果显示：
(1) 实施例2中的配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂具有较好的催化效果，催化产率达到96%；
(2) 配合物单晶对3-甲氧基苯硼酸、1-萘苯硼酸、4-甲硫基苯硼酸、4-氯苯硼酸、4-吡啶苯硼酸催化效果一般甚至不反应。
本发明公开的一种1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶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1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶，生产成本低，方法简便，适合大规模生产。在催化对氟苯硼酸生成4,4'-二氟联苯方面具有良好的催化效果。
附图说明
图1：配合物单晶的晶体结构图；
图2：配合物单晶的二维结构图；
图3：4,4'-二氟联苯的1H NMR图。
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。所用原料均有市售。所有原料都是从国内外的化学试剂公司进行购买，例如1,4-二溴-2,5-二甲基苯等原料，没有经过继续提纯而是直接使用的。
实施例1
1,4-二溴-2,5-二甲基苯：1H-1,2,4-三唑：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50 mL三口圆底烧瓶内分别加入CuO (0.0398 mg,0.5 mmol)，碳酸钾 (2.0731 g, 15 mmol)，1H-1,2,4-三唑(0.345 mg, 5 mmol)，1,4-二溴-2,5-二甲基苯 (0.3360 g, 1 mmol)，20 mL NMP。开动搅拌在100 oC，反应24小时。反应结束后，将反应液降至室温，过滤，滤液加入100 mL水，析出大量沉淀，抽滤，收集滤饼，收率60%。元素分析(C12N6H12) 理论值(%)：C，59.99；H，5.03；N，34.98。实测值：C，60.02；H，5.05；N，35.05；
1,4-二溴-2,5-二甲基苯 1H-1,2,4-三唑。
本发明优选1,4-二溴-2,5-二甲基苯：1H-1,2,4-三唑：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。采用“一锅法”，将1,4-二溴-2,5-二甲基苯和1H-1,2,4-三唑在加热条件下制备该有机化合物，1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑(L)。
实施例2
1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑(L) (0.1 mmol)、间苯二甲酸(ipa) (0.1 mmol)和Cd(NO3)2·6H2O (0.1 mmol)在水 (10 mL)和NMP (2 mL)的混合溶剂中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的无色块状晶体。产率：40%。元素分析(C17H19N4O6Cd) 理论值(%)：C，46.33；H，4.35；N，12.71。实测值：C，46.36；H，4.25；N，12.62。
实施例3
晶体结构测定采用APEX II CCD单晶衍射仪，使用经过石墨单色化的Mokα射线，λ =0.71073 Å为入射辐射，以ω-2θ扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值傅立叶电子密度图利用软件解出晶体结构，并经洛仑兹和极化效应修正。所有的H原子由差值傅立叶合成并经理想位置计算确定。详细的晶体测定数据：
实施例4
专属性作为催化剂的实际例子
方法：将取代对氟苯硼酸(0.82 mmol)和碳酸铯(0.01 g)溶解在3 mL NMP中，加入5 mg催化剂，室温下搅拌5小时，CH2Cl2萃取，水洗，干燥，过滤，脱溶，粗产品经石油醚/乙酸乙酯混合液(v:v = 1:1)经硅胶层析柱洗脱得到产品。
结果：得到4,4'-二氟联苯0.0764 g，计算得到的催化产率为98%。
实施例5
结论：
(1) 1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物对于催化底物4-甲硫基苯硼酸不起任何催化作用。
(2) 1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物对于3-甲氧基苯硼酸、1-萘苯硼酸、4-氯苯硼酸、4-吡啶苯硼酸的催化效果一般，催化产率在2-11%之间。
(3) 1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物对于催化底物4-氟苯硼酸的催化效果最好，催化产率高达98%。
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 (3)

1.一种1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物的单晶，其特征在于该单晶结构采用APEX II CCD单晶衍射仪，使用经过石墨单色化的Mokα射线，λ =0.71073 Å为入射辐射，以ω-2θ扫描方式收集衍射点，经过最小二乘法修正得到晶胞参数，从差值傅立叶电子密度图利用软件解出单晶数据：
其结构如下：
{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}，其中
L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；
ipa = 间苯二甲酸；
NMP = 1-甲基-2-吡咯烷酮。
2.权利要求1所述1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶的制备方法，其特征在于它是采用常温挥发法，即L、ipa和Cd(NO3)2·6H2O在水和NMP的混合溶剂中搅拌半小时后过滤，滤液常温挥发两周后得到适合X-射线单晶衍射的无色块状晶体，其中L:ipa:Cd(NO3)2·6H2O的摩尔比为1:1:1；
1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶的结构为{[Cd(L)(ipa)(H2O)]·1.5NMP·2.25H2O}；其中L = 1-(2,5-二甲基-4-(1H-1,2,4-三唑-1-基)苯基)-1H-1,2,4-三唑；ipa = 间苯二甲酸；NMP = 1-甲基-2-吡咯烷酮；
L NMP。
3.权利要求1所述1,4-二甲基-2,5-二-1H-1,2,4-双三唑间苯二甲酸镉配合物单晶专属性对氟苯硼酸生成4,4'-二氟联苯的催化剂方面的应用。
CN201610255184.5A 2016-04-25 2016-04-25 1,4-二甲基-2,5-二-1h-1,2,4-双三唑间苯二甲酸镉配合物单晶与应用 Pending CN105859755A (zh)

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CN110577474A (zh) * 2018-06-11 2019-12-17 天津师范大学 三维多孔结构的Cd(II)配合物的合成方法和应用

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CN104497018A (zh) * 2014-12-15 2015-04-08 天津师范大学 具有催化对氟苯硼酸的三唑-高氯酸铜配合物及其制备方法

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CN104497018A (zh) * 2014-12-15 2015-04-08 天津师范大学 具有催化对氟苯硼酸的三唑-高氯酸铜配合物及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577474A (zh) * 2018-06-11 2019-12-17 天津师范大学 三维多孔结构的Cd(II)配合物的合成方法和应用
CN110577474B (zh) * 2018-06-11 2022-05-31 天津师范大学 三维多孔结构的Cd(II)配合物的合成方法和应用

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