CN106946772B - 一种2,2’-联吡啶-4,4’-甲酸甲酯的合成方法 - Google Patents
一种2,2’-联吡啶-4,4’-甲酸甲酯的合成方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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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
- C07D213/60—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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
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Abstract
一种2,2'‑联吡啶‑4,4'‑甲酸甲酯的合成方法，包括以下步骤：1）将2,2’‑联吡啶，氯甲酸甲酯，缚酸剂，溶剂和催化剂混合，通入保护气，于90～120℃、3～4MPa下反应5～9h；2）反应结束后冷却，分离提纯即得产物2,2'‑联吡啶‑4,4'‑甲酸甲酯。本发明以2,2'‑联吡啶为初始原料，原料易得且价格便宜；反应步骤较短，为一步反应，操作更加简单；可避免使用重铬酸和硫酸等强腐蚀性物质，操作安全、简单；产率高，达到98%以上，且工艺成本低；后处理简单，污染少。
Description
技术领域
本发明属于有机合成技术领域，具体涉及一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法。
背景技术
2,2'-联吡啶-4,4'-甲酸甲酯为类白色晶体粉末，主要用作医药中间体和光敏染料配体中间体。2,2'-联吡啶-4,4'-甲酸甲酯可作为配体，与钌等多种金属形成具有共轭电子系统的配合物，具有显著的光电转换效应。
现有技术中，合成2,2'-联吡啶-4,4'-甲酸甲酯的基本方法是以4,4'-二甲基-2,2'-联吡啶为原料，在重铬酸钾等强氧化剂作用下，先进行氧化合成2,2'-联吡啶-4,4'-二甲酸，然后与甲醇进行酯化得到2,2'-联吡啶-4,4'-甲酸甲酯。如CN105294773、PCT2016025742、Angewandte Chemie, International Edition, 52(38), 9956-9960;2013、Chemical Communications (Cambridge, United Kingdom), (45), 6949-6951;2009等。
该方法需要两步才能完成，且产率较低，而且需要涉及使用重铬酸、硫酸等强腐蚀性物质，操作较为危险，容易产生设备腐蚀和水质污染，总产率不高。
发明内容
本发明目的在于提供了一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法。
基于上述目的，本发明采取了如下技术方案：一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，包括以下步骤：1）将2,2’-联吡啶，氯甲酸甲酯，缚酸剂，溶剂和催化剂混合，通入保护气，于90～120℃、3～4MPa下反应5～9h；2）反应结束后冷却，分离提纯即得产物2,2'-联吡啶-4,4'-甲酸甲酯。
所述催化剂采用以下方法制得：将磷钨酸和钨酸钠溶于水中，加入为磷钨酸重量的6～8倍的纳米二氧化钛和纳米氧化锆的混合物，于45～60℃下搅拌30～40h，真空抽干水分，120～160℃烘干2～5h即得；所述磷钨酸、钨酸钠与水三者的质量比为1:0.15～0.26:5～8。
分离提纯的具体操作为：先过滤除去不溶物（催化剂和可能没反应析出的2,2’-联吡啶），滤液经分离提取、浓缩、干燥，即得，再加水浓缩，即得2,2'-联吡啶-4,4'-甲酸甲酯。
步骤1）中所述2,2’-联吡啶、氯甲酸甲酯、缚酸剂的摩尔比1:（2～3.6）:（5～5.15）；2,2’-联吡啶、溶剂、催化剂的用量比为1mol:（500～800）ml:（0.3～0.8）g。
所述缚酸剂为三乙胺、二乙胺和乙二胺中的一种。
步骤1）中的溶剂为甲醇、四氢呋喃、二氯甲烷和氯仿中的一种。
所述保护气为氮气或氩气。
本发明中，两种主要原料2,2’-联吡啶、氯甲酸甲酯是在加压、催化剂和缚酸剂的共同作用下，直接合成2,2'-联吡啶-4,4'-甲酸甲酯；其反应机理在于催化剂使氯甲酸甲酯和2,2 '-联吡啶发生类似亲电反应；脱掉一分子氯化氢，然后缚酸剂可以迅速结合氯化氢，使得反应得以继续进行，采用该反应可有效增加产率；且整个反应过程中，不产生污染物排放。同时，本发明中，由于原料（尤其是氯甲酸甲酯和缚酸剂）沸点较低，加压可使反应物接触更充分，利于反应进行；同时加入保护气可避免在该反应条件下形成2,2 '-联吡啶的氮氧化物，减少副反应。
因此，与现有技术相比，本发明具有以下技术效果：
1）以2,2'-联吡啶为初始原料，原料易得且价格便宜；
2）反应步骤较短，为一步反应，操作更加简单；
3）避免使用重铬酸和硫酸等强腐蚀性物质，操作安全、简单；
4）产率高，达到98%以上（现有技术的产率最高仅达88%），且工艺成本低；
5）后处理简单，污染少。
附图说明
图1是实施例1的H1NMR图。
具体实施方式
下面结合具体实施例，对本发明作进一步的说明。
实施例1
一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，包括以下步骤：
1）将2,2’-联吡啶，氯甲酸甲酯，二乙胺，甲醇和催化剂混合，通入氮气，于90℃、3MPa下反应5h；步骤1）中，2,2’-联吡啶、氯甲酸甲酯、二乙胺的摩尔比1:2:5；2,2’-联吡啶、甲醇、催化剂的用量比为1mol:500ml:0.3g；
所述催化剂采用以下方法制得：将磷钨酸和钨酸钠溶于水中，加入为磷钨酸重量的6倍的纳米二氧化钛和纳米氧化锆的混合物（该混合物含70%重量的二氧化钛），于60℃下搅拌30h，真空抽干水分， 160℃烘干2h即得；所述磷钨酸、钨酸钠与水三者的质量比为1:0.15:5；
2）反应结束后冷却，先过滤除去不溶物，加入水中，然后用乙酸乙酯进行提取，经浓缩后即得白色固体2,2'-联吡啶-4,4'-甲酸甲酯，产率98.2%。
实施例2
一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，包括以下步骤：
1）将2,2’-联吡啶，氯甲酸甲酯，三乙胺，四氢呋喃和催化剂混合，通入氩气，于120℃、4 MPa下反应8 h；步骤1）中，2,2’-联吡啶、氯甲酸甲酯、三乙胺的摩尔比1:3.6:5.15；2,2’-联吡啶、四氢呋喃、催化剂的用量比为1mol:700ml:0.6g；
所述催化剂采用以下方法制得：将磷钨酸和钨酸钠溶于水中，磷钨酸、钨酸钠与水三者的质量比为1:0.20:6；然后加入为磷钨酸重量的7倍的纳米二氧化钛和纳米氧化锆的混合物（该混合物含66%重量的二氧化钛），于55 ℃下搅拌28 h，真空抽干水分，160℃烘干2h得到催化剂；
2）反应结束后冷却，先过滤除去不溶物，加入水中，然后用氯仿进行提取，经浓缩后即得白色固体2,2'-联吡啶-4,4'-甲酸甲酯，产率99.5 %。
实施例3
一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，包括以下步骤：
1）将2,2’-联吡啶，氯甲酸甲酯，乙二胺，氯仿和催化剂混合，通入氮气，于100℃、3.5 MPa下反应9 h；步骤1）中，2,2’-联吡啶、氯甲酸甲酯、乙二胺的摩尔比1:3:5.1；2,2’-联吡啶、四氢呋喃、催化剂的用量比为1mol:800ml:0.8g；
所述催化剂采用以下方法制得：将磷钨酸和钨酸钠溶于水中，磷钨酸、钨酸钠与水三者的质量比为1:0.26:8；然后加入为磷钨酸重量的8倍的纳米二氧化钛和纳米氧化锆的混合物（该混合物含60%重量的二氧化钛），于45℃下搅拌40h，真空抽干水分，120℃烘干5h得到催化剂；
2）反应结束后冷却，先过滤除去不溶物，加入水中，然后用氯仿进行提取，经浓缩后即得白色固体2,2'-联吡啶-4,4'-甲酸甲酯，产率99.0 %。
产物确认
实施例1-3得到的产物为白色固体，同时对各产物进行熔点测试、HNMR测试及质谱分析，经分析确认所得产物确为目标产物2,2'-联吡啶-4,4'-甲酸甲酯，其产物H1NMR见图1所示产物熔点：熔点211.1～211.9℃；质谱分析：分子离子峰m/z =272，对应产物分子量。
Claims (6)
1.一种2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，包括以下步骤：1）将2,2’-联吡啶、氯甲酸甲酯、缚酸剂、溶剂和催化剂混合，通入保护气，于90～120℃、3～4MPa下反应5～9h；2）反应结束后冷却，分离提纯即得产物2,2'-联吡啶-4,4'-甲酸甲酯；
所述催化剂采用以下方法制得：将磷钨酸和钨酸钠溶于水中，加入磷钨酸重量的6～8倍的纳米二氧化钛和纳米氧化锆的混合物，于45～60℃下搅拌30～40h，真空抽干水分，120℃～160℃烘干2～5h即可；所述磷钨酸、钨酸钠与水三者的质量比为1:0.15～0.26:5～8。
2.如权利要求1所述的2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，分离提纯的具体操作为：先过滤除去不溶物，滤液经分离提取、浓缩、干燥，即得2,2'-联吡啶-4,4'-甲酸甲酯。
3.如权利要求1-2任一所述的2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，步骤1）中所述2,2’-联吡啶、氯甲酸甲酯、缚酸剂的摩尔比1:（2～3.6）:（5～5.15）；2,2’-联吡啶、溶剂、催化剂的用量比为1mol:（500～800）ml:（0.3～0.8）g。
4.如权利要求3所述的2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，所述缚酸剂为三乙胺、二乙胺和乙二胺中的一种。
5.如权利要求3所述的2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，步骤1）中的溶剂为甲醇、四氢呋喃、二氯甲烷和氯仿中的一种。
6.如权利要求3所述的2,2'-联吡啶-4,4'-甲酸甲酯的合成方法，其特征在于，所述保护气为氮气或氩气。
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| CN105503738A (zh) * | 2015-12-21 | 2016-04-20 | 哈尔滨工业大学 | 合成仿生氧化还原电对2-(3,5-二叔丁基-2-羟苯基)苯并咪唑-5-羧酸的方法 |
| WO2016090317A1 (en) * | 2014-12-05 | 2016-06-09 | Aquinnah Pharmaceuticals, Inc. | Sulfonamide derivatives, compositions and methods of use in the treatment of neurodegenerative diseases |
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| WO2010132999A1 (en) * | 2009-05-21 | 2010-11-25 | Chlorion Pharma, Inc. | Methyl sulfanyl pyrmidmes useful as antiinflammatories, analgesics, and antiepileptics |
| WO2016090317A1 (en) * | 2014-12-05 | 2016-06-09 | Aquinnah Pharmaceuticals, Inc. | Sulfonamide derivatives, compositions and methods of use in the treatment of neurodegenerative diseases |
| CN105503738A (zh) * | 2015-12-21 | 2016-04-20 | 哈尔滨工业大学 | 合成仿生氧化还原电对2-(3,5-二叔丁基-2-羟苯基)苯并咪唑-5-羧酸的方法 |
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