CN106986817A - 一种2,2’-联吡啶的合成方法 - Google Patents

一种2,2’-联吡啶的合成方法 Download PDF

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CN106986817A
CN106986817A CN201610052642.5A CN201610052642A CN106986817A CN 106986817 A CN106986817 A CN 106986817A CN 201610052642 A CN201610052642 A CN 201610052642A CN 106986817 A CN106986817 A CN 106986817A
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cyclo
bipyridyl
octadiene
cobalt
reaction
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Pyridine Compounds (AREA)

Abstract

本发明属于化学工业合成领域，具体涉及一种2，2’-联吡啶的合成方法。本发明方法包括如下顺序的步骤：(1)环辛二烯在氨基钠(或金属钠)的催化下和无水氯化钴反应，生成环辛二烯基茂钴，是一种活性较高的催化剂(2)2-氰基吡啶在环辛二烯基茂钴的催化下和乙炔气体反应，生成2，2’-联吡啶。

Description

一种2，2’-联吡啶的合成方法
技术领域
本发明属于化学合成领域，具体涉及一种2，2’-联吡啶的合成方法。
背景技术
2，2’-联吡啶是联吡啶异构体之一，是一种重要的有机合成中间体，主要用于医药中间体、有机合成等，同时它也是一种应用广泛的螯合剂、涂料添加剂，广泛应用于染料生产，农药生产及香料等方面。
2，2’-联吡啶，分子式：C10H8N2，分子量：156.2，CAS NO：366-18-7，英文名称：2，2’-Dipyridyl，外观为白色或浅红色结晶性粉末。
目前国内采用的方法：①无水吡啶和无水氯化铁混合加热反应，生成2，2’-联吡啶；②2-氯吡啶在催化剂的催化下偶联反应，生成2，2，-联吡啶。它们的副反应多，处理过程复杂，生产成本高。本发明的合成方法副反应少，操作简单，生产成本低，产品的质量好，并且环境污染少，是一种比较理想的合成工艺。
发明内容
本发明方法包括如下顺序的步骤：
1.环辛二烯基茂钴的制备
在四氢呋喃溶剂中加入氨基钠(或金属钠)，搅拌状态下，滴加环辛二烯，滴加完毕后，回流反应2小时，降至常温，然后，缓慢滴加至四氢呋喃的无水氯化钴溶液中，滴加完毕后，回流反应6小时，反应结束后，回收溶剂，回收完全后，加入2-氰基吡啶，液封保存。
本发明的特征在于，在四氢呋喃溶剂中，环辛二烯在氨基钠(或金属钠)的参与下和无水氯化钴反应，生成环辛二烯基茂钴，作为催化剂。
2.2，2’-联吡啶的制备
在高压反应釜中加入2-氰基吡啶和环辛二烯基茂钴(或二茂钴)混合液，抽真空，升温至140℃，通入经处理的乙炔气体，温度上升，温度维持在140～180℃通入乙炔气体，压力保持在≤2.0MPa，通气结束后，在150～180℃高压反应2h，反应结束后，减压蒸馏，得2，2，-联吡啶。
本发明的特征在于，2-氰基吡啶在催化剂环辛二烯基茂钴(或二茂钴)的催化下，在高压釜内和乙炔气体反应，生产2，2’-联吡啶。
具体实施方法
下面结合具体实验实例对本发明作进一步详细的描述。
实施例1：2，2’-联吡啶的制备
(1)环辛二烯基茂钴的制备
在250ml的三口瓶中，加入100ml四氢呋喃和8g氨基钠，在搅拌状态下滴加环辛二烯20g，温度上升，滴加完毕后，升温回流2小时，反应结束后，降至常温，备用；在500ml的三口瓶中，加入无水100ml四氢呋喃和24g无水氯化钴，搅拌升温，当温度升至50℃时，缓慢滴加上述制备溶液，滴加完毕后，回流反应5h，反应完毕后，回收四氢呋喃，当四氢呋喃流量减少时，减压回收四氢呋喃，回收完全后，加入2-氰基吡啶50g，降至常温，密闭各用。
(2)对氯苄基吡啶的制备
在500ml高压釜中加入2-氰基吡啶200g和催化剂环辛二烯基茂钴20g，抽真空，升温至140℃，通入经处理的乙炔气体，温度上升，温度维持在150～180℃通入乙炔气体100g，通气结束后，在150～180℃高压反应4h，反应结束后，蒸馏，得2，2’-联吡啶240g。
实施例2：2，2’-联吡啶的制备
(1)环辛二烯基茂钴的制备
在250ml的三口瓶中，加入100ml四氢呋喃和5g金属钠，在搅拌状态下滴加环辛二烯20g，温度上升，滴加完毕后，升温回流3小时，反应结束后，降至常温，备用；在500ml的三口瓶中，加入无水100ml四氢呋喃和24g无水氯化钴，搅拌升温，当温度升至50℃时，缓慢滴加上述制备溶液，滴加完毕后，回流反应4h，反应完毕后，回收四氢呋喃，当四氢呋喃流量减少时，减压回收四氢呋喃，回收完全后，加入2-氰基吡啶50g，降至常温，密闭备用。
(2)对氯苄基吡啶的制备
在500ml高压釜中加入2-氰基吡啶200g和催化剂环辛二烯基茂钴20g，抽真空，升温至140℃，通入经处理的乙炔气体，温度上升，温度维持在150～190℃通入乙炔气体105g，通气结束后，在150～190℃高压反应2h，反应结束后，蒸馏，得2，2’-联吡啶250g。

Claims (3)

1.一种2，2’-联吡啶的合成方法，其特征在于包括如下顺序的步骤：
(1)环辛二烯基茂钴的制备
在四氢呋喃溶剂中加入氨基钠(或金属钠)，搅拌状态下滴加环辛二烯，滴加完毕后，回流反应2h，反应结束后，滴加至无水氯化钴的四氢呋喃溶液中，回流反应6小时，回收溶剂，回收完全后，加入2-氰基吡啶，搅拌均匀，密闭备用。
(2)2，2’-联吡啶的制备
在高压反应釜中加入2-氰基吡啶和环辛二烯基茂钴溶液，抽真空，升温至140℃，通入经处理的乙炔气体，温度上升，温度维持在140～180℃通入乙炔气体，压力≤2.0MPa，通气结束后，在150～180℃高压反应2h，反应结束后，减压蒸馏，得纯度较高的2，2’-联吡啶。
2.根据权利要求1所述，步骤(1)中，本发明特征在于，在四氢呋喃溶液中，环辛二烯在氨基钠(或金属钠)的参与下和无水氯化钴反应，生产环辛二烯基茂钴。
3.根据权利要求2所述，步骤(2)中，本发明特征在于，2-氰基吡啶在环辛二烯基茂钴的催化下和乙炔气体反应，生成2，2’-联吡啶。
CN201610052642.5A 2016-01-20 2016-01-20 一种2,2’-联吡啶的合成方法 Pending CN106986817A (zh)

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CN108658848A (zh) * 2018-05-05 2018-10-16 湖北荆洪生物科技股份有限公司 一种2,2`-联吡啶的生产工艺

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN108658848A (zh) * 2018-05-05 2018-10-16 湖北荆洪生物科技股份有限公司 一种2,2`-联吡啶的生产工艺
CN108658848B (zh) * 2018-05-05 2021-04-02 湖北荆洪生物科技股份有限公司 一种2，2’-联吡啶的生产工艺

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