CN104447518A - 柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法 - Google Patents

柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法 Download PDF

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CN104447518A
CN104447518A CN201410732189.3A CN201410732189A CN104447518A CN 104447518 A CN104447518 A CN 104447518A CN 201410732189 A CN201410732189 A CN 201410732189A CN 104447518 A CN104447518 A CN 104447518A
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flexible
pyridine
synthetic method
ethyl acetate
bromo
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石靖
胡博文
龚大伟
崔文
陈大发
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Harbin Institute of Technology
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/61—Halogen atoms or nitro radicals

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Abstract

一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，在N2保护下，向三口瓶中加入40mol2-甲基吡啶，加入80ml四氢呋喃作为溶剂，-80℃滴加16ml正丁基锂，低温搅拌60min；慢慢升温至-20℃，加入20mol2,6-二溴吡啶，回流反应4h；加水淬灭反应，分液，水层用乙酸乙酯或二氯甲烷萃取二～四次；合并有机层，有机层干燥1～3小时后，将有机溶剂旋干，过一段氧化铝的柱子，以石油醚和乙酸乙酯为洗脱液，得到红色油状液体。该方法合成了一种不对称的柔性联吡啶配体，并在吡啶2-号位引入了卤素原子，方便官能团之间的转换，以便合成带有不同取代基团的联吡啶类衍生物，从而构筑具有不同空间构型的晶态网络配合物。

Description

柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法
技术领域
本发明涉及一种联吡啶类衍生物的合成方法，具体涉及一种新型柔性联吡啶化合物6-溴-2-吡啶亚甲基吡啶联吡啶类衍生物的合成方法。
背景技术
联吡啶类衍生物是合成功能型材料的主要原料之一，其中2,2’-联吡啶是应用最广泛的金属络合物的配位体，这主要是由于联吡啶的两个氮原子表现出较强的σ电子给予能力，而π共轭的联吡啶体系又具有电子接受能力，因而其过度金属和稀土离子配合物都具有光、电、磁等方面的性质。如果在两个芳香氮原子之间通过一定长度碳链连接将会增强联吡啶的柔性，与刚性联吡啶配体相比较，柔性联吡啶配体不仅具有配位指向性较好的N原子，还拥有更好的变形能力，可以通过配位环境的不同采取多种配位构型，同时配位点间距离、夹角及连接基团的形状都能进行调整以适应配位环境的改变，从而为构筑具有新颖拓扑结构的金属有机配合物体系提供了丰富多彩的识别和组装方式。此外，在联吡啶配体中卤素原子的引入使得光能团之间的转换成为了可能，使合成含有不同取代基团的联吡啶配体变得更加简单易得。
目前，人们对柔性联吡啶金属有机络合物的研究日渐增多，主要是以对称柔性的联吡啶金属配合物为主，非对称柔性联吡啶金属有机配合物的发展相对较为缓慢，因此能够合成结构新颖的非对称柔性联吡啶配体将有助于构筑更为独特的晶态网络结构。
2002年G. Ciani等人用对称柔性联吡啶配体1,3-(4-吡啶基)丙烷与不同阴离子的AgNO3、AgBF4、AgClO4、AgPF6配体得到了四个配合物的晶态网络结构，呈现出不同的拓扑结构。
2007年，Amitava Das 等人用非对称柔性联吡啶配体N-(3-pyridyl) nicotinamide (L1)和N-(3-pyridyl) isonicotinamide (L2)与金属离子锌、镉配位，得到了结构新颖的晶态网络配合物。  
发明内容
本发明的目的是提供一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法。该方法合成了一种不对称的柔性联吡啶配体，并在吡啶2-号位引入了卤素原子，方便官能团之间的转换，以便合成带有不同取代基团的联吡啶类衍生物，从而构筑具有不同空间构型的晶态网络配合物。
本发明的目的是通过以下技术方案实现的：
一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，具体合成步骤如下：
在N2保护下，向三口瓶中加入40mol 2-甲基吡啶，加入80ml四氢呋喃作为溶剂，-80℃滴加16ml、 2.5mol/L正丁基锂，低温搅拌60min，体系溶液由淡黄色色渐变橙黄色；慢慢升温至 -20℃，加入20mol 2,6-二溴吡啶，回流反应 4 h；加水淬灭反应，分液，水层用乙酸乙酯或二氯甲烷萃取二～四次；合并有机层，有机层无水硫酸钠或氯化钙干燥1～3小时后，将有机溶剂旋干，过一段氧化铝的柱子，以石油醚：乙酸乙酯=10～20:1（v/v）为洗脱液，得到红色油状液体。
本发明具有如下优点：
（1）反应操作简单，一步即可得到一种新型的、未见报道的不对称柔性联吡啶化合物。
（2）化合物中卤素基团的引入增强了官能团之间的转化。
（3）柔性基团（亚甲基）的引入为构筑具有不同空间构型的金属有机化合垫定了坚实的基础。
附图说明
图1为实施例1合成的6-溴-2-吡啶亚甲基吡啶的核磁氢谱共振图谱。
具体实施方式
下面结合附图对本发明的技术方案作进一步的说明，但并不局限于此，凡是对本发明技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，均应涵盖在本发明的保护范围中。
实施例1：
本实施例提供了一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，具体合成步骤如下：
在N2保护下，向三口瓶中加入2-甲基吡啶3.7g（40mol），加入四氢呋喃80ml作为溶剂，-78℃滴加正丁基锂16ml（M=2.5mol/L）。低温搅拌45min，体系溶液由淡黄色色渐变橙黄色，慢慢升温-20℃，加入2,6-二溴吡啶4.7g（20mol），回流反应4h，加水淬灭反应，分液，水层用乙酸乙酯萃取三次，有机层无水硫酸钠干燥2小时后，将有机溶剂旋干，过一段氧化铝的柱子，以石油醚：乙酸乙酯=20:1（v/v）为洗脱液，得到红色油状液体（1.86g，36%）。如图1所示，1H NMR (400 Hz, CDCl3)δ8.55 (brs, 1H), δ7.63 (t, J = 8 Hz, 1H), δ7.45 (t, J = 8Hz, 1H), δ7.34 (d, J = 8Hz, 1H), δ7.30 (d, J = 8Hz, 1H), δ7.22 (d, J = 8Hz, 1H), δ7.15 (t, J = 8Hz,1H), δ4.32 (s, 2H)。反应方程式如下：
实施例2：
本实施例提供了一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，具体合成步骤如下：
在N2保护下，向三口瓶中加入2-甲基吡啶3.7g（40mol），加入四氢呋喃80ml作为溶剂，-78℃滴加正丁基锂16ml（M=2.5mol/L）。低温搅拌45min，体系溶液由淡黄色色渐变橙黄色，慢慢升温-20℃，加入2,6-二溴吡啶4.7g（20mol），回流反应4h，加水淬灭反应，分液，水层用二氯甲烷萃取三次，有机层氯化钙干燥2小时后，将有机溶剂旋干，过一段氧化铝的柱子，以石油醚：乙酸乙酯=10:1（v/v）为洗脱液，得到红色油状液体（1.86g，36%）。

Claims (4)

1.一种柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，其特征在于所述合成方法步骤如下：
在N2保护下，向三口瓶中加入40mol 2-甲基吡啶，加入80ml四氢呋喃作为溶剂，-80℃滴加16ml正丁基锂，低温搅拌60min，体系溶液由淡黄色色渐变橙黄色；慢慢升温至-20℃，加入20mol 2,6-二溴吡啶，回流反应4h；加水淬灭反应，分液，水层用乙酸乙酯或二氯甲烷萃取二～四次；合并有机层，有机层干燥1～3小时后，将有机溶剂旋干，过一段氧化铝的柱子，以石油醚和乙酸乙酯为洗脱液，得到红色油状液体。
2.根据权利要求1所述的柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，其特征在于所述正丁基锂的浓度为2.5mol/L。
3.根据权利要求1所述的柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，其特征在于所述石油醚和乙酸乙酯的体积比为10～20:1。
4.根据权利要求1所述的柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法，其特征在于所述有机层用无水硫酸钠干燥或氯化钙。
CN201410732189.3A 2014-12-06 2014-12-06 柔性联吡啶衍生物6-溴-2-吡啶亚甲基吡啶的合成方法 Pending CN104447518A (zh)

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US20070059552A1 (en) * 2005-09-09 2007-03-15 Fuji Photo Film Co., Ltd. Organic electroluminescent device and complex compound
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN114569612A (zh) * 2022-03-15 2022-06-03 江苏科技大学 联吡啶在家蚕蝇蛆病防治中的应用
CN114569612B (zh) * 2022-03-15 2024-02-27 江苏科技大学 联吡啶在家蚕蝇蛆病防治中的应用

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