JP2016037448A - Method for producing 1,2-di(4-pyridyl)ethylene - Google Patents
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Description
本発明はジピリジル配位子を製造する方法に関する。さらに詳しくは、４−メチルピリジンと４−ピリジンカルボキシアルデヒド（ＩＵＰＡＣ名：ピリジン−４−カルバルデヒド）とをカップリングさせ、１，２−ジ（４−ピリジル）エチレンを製造する方法に関する。１，２−ジ（４−ピリジル）エチレンは、多孔性金属錯体の原料として有用なものである。 The present invention relates to a method for producing a dipyridyl ligand. More specifically, the present invention relates to a process for producing 1,2-di (4-pyridyl) ethylene by coupling 4-methylpyridine and 4-pyridinecarboxaldehyde (IUPAC name: pyridine-4-carbaldehyde). 1,2-di (4-pyridyl) ethylene is useful as a raw material for porous metal complexes.
１，２−ジ（４−ピリジル）エチレンに代表されるジピリジル配位子は、多孔性の金属錯体を構築する架橋性二座配位子として利用されている（特許文献１、２）。しかしながら、従来の当該配位子の製造法としては、比較的安価な４−メチルピリジンおよび４−メチルピリジンの部分酸化体である４−ピリジンカルボキシアルデヒドを反応させて製造する方法が知られているが、収率が低いため、１，２−ジ（４−ピリジル）エチレンのコストが高く、製造される多孔性金属錯体の高コスト化が不可避であった（非特許文献１〜３）。前記多孔性金属錯体は特定の化合物を選択的に吸着することが可能であるが、このような吸着材として利用する場合、さらなるコスト削減が求められているのが現状であり、これを達成するためには、より収率の高い製造法が求められている。 A dipyridyl ligand typified by 1,2-di (4-pyridyl) ethylene is used as a crosslinkable bidentate ligand for constructing a porous metal complex (Patent Documents 1 and 2). However, as a conventional method for producing the ligand, a method is known in which 4-methylpyridine which is relatively inexpensive and 4-pyridinecarboxaldehyde which is a partially oxidized form of 4-methylpyridine are reacted. However, since the yield is low, the cost of 1,2-di (4-pyridyl) ethylene is high, and it is inevitable to increase the cost of the produced porous metal complex (Non-Patent Documents 1 to 3). The porous metal complex can selectively adsorb a specific compound, but when used as such an adsorbent, the present situation is that further cost reduction is required, and this is achieved. Therefore, a production method with higher yield is required.
塩化亜鉛の存在下、４−メチルピリジンと４−ピリジンカルボキシアルデヒドと反応させることにより、１，２−ジ（４−ピリジル）エチレンを合成する方法が開示されている（非特許文献１、２）。しかしながら、収率が１３〜１７％と低い。 A method of synthesizing 1,2-di (4-pyridyl) ethylene by reacting 4-methylpyridine and 4-pyridinecarboxaldehyde in the presence of zinc chloride is disclosed (Non-patent Documents 1 and 2). . However, the yield is as low as 13-17%.
無水酢酸を用い、４−メチルピリジンとベンズアルデヒドから４−スチルピリジンを合成する方法が開示されている（非特許文献３）。しかしながら、４−スチルピリジンは医農薬用途として合成されており、かつ、４-メチルピリジンと４−ピリジンカルボキシアルデヒドからの１，２−ジ（４−ピリジル）エチレン合成については何ら言及されていない。 A method of synthesizing 4-stilpyridine from 4-methylpyridine and benzaldehyde using acetic anhydride is disclosed (Non-patent Document 3). However, 4-stilpyridine has been synthesized for medical and agrochemical applications, and no mention is made of 1,2-di (4-pyridyl) ethylene synthesis from 4-methylpyridine and 4-pyridinecarboxaldehyde.
本発明の課題は、従来よりも高い収率で４−メチルピリジンと４−ピリジンカルボキシアルデヒドから、１，２−ジ（４−ピリジル）エチレンを製造する方法を提供することである。 An object of the present invention is to provide a method for producing 1,2-di (4-pyridyl) ethylene from 4-methylpyridine and 4-pyridinecarboxaldehyde in a higher yield than before.
本発明者らは鋭意検討した結果、４−メチルピリジンと４−ピリジンカルボキシアルデヒドとを、特定のアシル化剤の存在下で反応させることにより、１，２−ジ（４−ピリジル）エチレンを従来技術よりも高い収率で製造できることを見出し、本発明に至った。すなわち、本発明は以下の［１］〜［４］に関する。 As a result of intensive studies, the present inventors have made 1,2-di (4-pyridyl) ethylene conventional by reacting 4-methylpyridine and 4-pyridinecarboxaldehyde in the presence of a specific acylating agent. The present inventors have found that it can be produced at a higher yield than the technology, and have reached the present invention. That is, the present invention relates to the following [1] to [4].
［１］
４−メチルピリジンと４−ピリジンカルボキシアルデヒドとをカップリングさせ、１，２−ジ（４−ピリジル）エチレンを製造する方法において、
下記一般式（Ｉ）；
In a method for producing 1,2-di (4-pyridyl) ethylene by coupling 4-methylpyridine and 4-pyridinecarboxaldehyde,
The following general formula (I);
（式中、Ｒは置換基を有していてもよい炭素数１〜４のアルキル基、または置換基を有してもよいフェニル基のいずれかである。式中、Ｘは−Ｏ（Ｃ＝Ｏ）Ｒ１またはハロゲン原子を示す。Ｒ１は置換基を有していてもよい炭素数１〜４のアルキル基または置換基を有してもよいフェニル基のいずれかである。）で表されるアシル化剤を用いることを特徴とする１，２−ジ（４−ピリジル）エチレン製造方法。
［２］
４−メチルピリジンと前記アシル化剤の混合比率が、４−メチルピリジン：アシル化剤＝３：１〜１：３のモル比の範囲にある、［１］に記載の製造方法。
［３］
該アシル化剤が無水カルボン酸またはカルボン酸ハロゲン化物である、［１］または［２］に記載の製造方法。
［４］
該アシル化剤が、無水酢酸、無水安息香酸、塩化アセチルまたは塩化ベンゾイルである［１］または［２］に記載の製造方法。
(In the formula, R is either an optionally substituted alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group. In the formula, X represents —O (C = O) R 1 or a halogen atom, wherein R 1 is either an optionally substituted alkyl group having 1 to 4 carbon atoms or an optionally substituted phenyl group. A method for producing 1,2-di (4-pyridyl) ethylene, characterized by using an acylating agent represented.
[2]
The production method according to [1], wherein a mixing ratio of 4-methylpyridine and the acylating agent is in a range of a molar ratio of 4-methylpyridine: acylating agent = 3: 1 to 1: 3.
[3]
The production method according to [1] or [2], wherein the acylating agent is a carboxylic anhydride or a carboxylic acid halide.
[4]
The production method according to [1] or [2], wherein the acylating agent is acetic anhydride, benzoic anhydride, acetyl chloride or benzoyl chloride.
本発明により、４−メチルピリジンと４−ピリジンカルボキシアルデヒドから、１，２−ジ（４−ピリジル）エチレンを従来よりも高い収率で製造することができる。 According to the present invention, 1,2-di (4-pyridyl) ethylene can be produced from 4-methylpyridine and 4-pyridinecarboxaldehyde at a higher yield than before.
本発明の製造法は、４−メチルピリジンと４−ピリジンカルボキシアルデヒドとを下記一般式（Ｉ）
で表されるアシル化剤存在下で反応させることで１，２−ジ（４−ピリジル）エチレンの製造法を得る。アシル化剤が無水酢酸の場合の反応式は以下のようになる。
In the production method of the present invention, 4-methylpyridine and 4-pyridinecarboxaldehyde are represented by the following general formula (I):
To produce 1,2-di (4-pyridyl) ethylene. The reaction formula when the acylating agent is acetic anhydride is as follows.
＜アシル化剤＞
本発明に用いられるアシル化剤は下記一般式（Ｉ）；
The acylating agent used in the present invention is represented by the following general formula (I):
Ｒ、Ｒ１の炭素数１〜４のアルキル基としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基などの直鎖または分岐を有するアルキル基が挙げられる。Ｒ、Ｒ１のアルキル基は同じであっても異なっていてもよいが、反応後の回収、精製、再利用を考慮すると同一であることが好ましい。 Examples of the alkyl group having 1 to 4 carbon atoms of R and R 1 include linear or branched alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl Groups. The alkyl groups for R and R 1 may be the same or different, but are preferably the same in consideration of recovery, purification, and reuse after the reaction.
Ｒ、Ｒ１の炭素数１〜４のアルキル基、フェニル基が有していてもよい置換基の例としては、フッ素、塩素などのハロゲン原子が挙げられる。Ｘの示すハロゲン原子としては塩素、臭素、沃素が挙げられる。コストの観点から塩素が好ましい。 Examples of the substituent that the R and R 1 alkyl groups having 1 to 4 carbon atoms and the phenyl group may have include halogen atoms such as fluorine and chlorine. Examples of the halogen atom represented by X include chlorine, bromine and iodine. Chlorine is preferred from the viewpoint of cost.
当該アシル化剤としては、無水酢酸、無水トリフルオロ酢酸、無水安息香酸、塩化アセチル、塩化ベンゾイルが好ましく、コストの観点から、無水酢酸が最も好ましい。 As the acylating agent, acetic anhydride, trifluoroacetic anhydride, benzoic anhydride, acetyl chloride, and benzoyl chloride are preferable, and acetic anhydride is most preferable from the viewpoint of cost.
＜１，２−ジ（４−ピリジル）エチレンの製造方法＞
本発明の製造法では、４−メチルピリジンと４−ピリジンカルボキシアルデヒドとを一般式（Ｉ）のアシル化剤存在下で反応させ、目的とする１，２−ジ（４−ピリジル）エチレンを得ることができる。
<Method for producing 1,2-di (4-pyridyl) ethylene>
In the production method of the present invention, 4-methylpyridine and 4-pyridinecarboxaldehyde are reacted in the presence of an acylating agent of the general formula (I) to obtain the desired 1,2-di (4-pyridyl) ethylene. be able to.
４−メチルピリジンと４−ピリジンカルボキシアルデヒド の混合比率は、４−メチルピリジン：４−ピリジンカルボキシアルデヒド ＝１：３〜３：１のモル比の範囲内が好ましく、１：１．５〜１．５：１のモル比の範囲内がより好ましい。この範囲で反応を行うと収率が高く、副反応も抑えることができる。 The mixing ratio of 4-methylpyridine and 4-pyridinecarboxaldehyde is preferably in the range of a molar ratio of 4-methylpyridine: 4-pyridinecarboxaldehyde = 1: 3 to 3: 1. A range of 5: 1 molar ratio is more preferred. When the reaction is carried out in this range, the yield is high and side reactions can be suppressed.
４−メチルピリジンとアシル化剤の混合比率は、４−メチルピリジン：アシル化剤＝３：１〜１：３のモル比の範囲内が好ましく、２：１〜１：２のモル比の範囲内がより好ましい。この範囲で反応を行うと収率が高く、未反応の原料が残留も少なくなるので得られた１，２−ジ（４―ピリジル）エチレンの精製が容易になる。
反応温度は、６０〜１５０℃が好ましく、８０〜１３０℃がより好ましい。反応時間は１〜２４時間が好ましく、２〜４時間がより好ましい。
The mixing ratio of 4-methylpyridine and the acylating agent is preferably within the range of the molar ratio of 4-methylpyridine: acylating agent = 3: 1 to 1: 3, and the range of the molar ratio of 2: 1 to 1: 2. The inside is more preferable. When the reaction is carried out in this range, the yield is high and the amount of unreacted raw material is reduced, so that the obtained 1,2-di (4-pyridyl) ethylene can be easily purified.
The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 130 ° C. The reaction time is preferably 1 to 24 hours, more preferably 2 to 4 hours.
反応は務溶媒でも、反応に不活性な溶媒を用いてもよい。反応に利用できる溶媒としては、クロロホルム、ジクロロメタン、トルエン、テトラヒドロフラン等が好ましい。 The reaction may be a working solvent or a solvent inert to the reaction. As a solvent usable for the reaction, chloroform, dichloromethane, toluene, tetrahydrofuran and the like are preferable.
反応は、アルデヒドの安定性の観点から、嫌気下で行うのが好ましい。より具体的には、アルゴンまたは窒素ガス等の不活性ガス雰囲気下で行うことが好ましい。 The reaction is preferably carried out under anaerobic conditions from the viewpoint of aldehyde stability. More specifically, it is preferably performed in an inert gas atmosphere such as argon or nitrogen gas.
反応が終了したことは、核磁気共鳴法（ＮＭＲ）、ガスクロマトグラフィー、高速液体クロマトグラフィーにより原料の残存量を定量することにより確認することができる。反応終了後、得られた混合液に塩基性水溶液を加え、濾過により沈殿物を集め、有機溶媒または水を用いて再結晶することにより、目的とする１，２−ジ（４―ピリジル）エチレンを得ることができる。 The completion of the reaction can be confirmed by quantifying the remaining amount of the raw material by nuclear magnetic resonance (NMR), gas chromatography, or high performance liquid chromatography. After completion of the reaction, a basic aqueous solution is added to the obtained mixture, and the precipitate is collected by filtration and recrystallized using an organic solvent or water to obtain the desired 1,2-di (4-pyridyl) ethylene. Can be obtained.
以下、本発明を実施例によって具体的に説明するが、本発明はこれらに限定されるものではない。以下の実施例および比較例における分析は次のようにして行った。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. Analysis in the following Examples and Comparative Examples was performed as follows.
＜分析方法＞
合成反応で得た化合物の構造は、日本電子（株）製ＪＮＭ−ＥＣＳ４００を用いたＮＭＲ解析により決定した。より具体的には、溶媒として１，１，２，２−テトラクロロエタン−ｄ２を用い、２５℃において１Ｈ−ＮＭＲを測定することで決定した。
<Analysis method>
The structure of the compound obtained by the synthesis reaction was determined by NMR analysis using JNM-ECS400 manufactured by JEOL Ltd. More specifically, it was determined by measuring 1 H-NMR at 25 ° C. using 1,1,2,2-tetrachloroethane-d2 as a solvent.
＜実施例１＞
１００ ｍｌナスフラスコに、４−メチルピリジン（４．６８ｇ， ５０．３ ｍｍｏｌ）、４−ピリジンカルボキシアルデヒド（５．４０ ｇ， ５０．４ ｍｍｏｌ）、および無水酢酸（５．２０ｇ， ５１．０ ｍｍｏｌ）を加え、１２０℃で３時間加熱撹拌した。その後、得られた茶褐色溶液を室温まで冷却した後、ＮａＯＨ（４．０ｇ， １００ ｍｍｏｌ）の水溶液（４０ｍｌ）を加えて洗浄し、析出した固体を桐山漏斗（登録商標）を用いてろ過した。得られた茶褐色固体をエタノール（９ ｍｌ）、水（３５ ｍｌ）で再結晶した後、ろ過し、風乾した。目的とする１，２−ジ（４―ピリジル）エチレン５．２８ｇ（収率５８％）得た。
<Example 1>
In a 100 ml eggplant flask, 4-methylpyridine (4.68 g, 50.3 mmol), 4-pyridinecarboxaldehyde (5.40 g, 50.4 mmol), and acetic anhydride (5.20 g, 51.0 mmol). ) And heated and stirred at 120 ° C. for 3 hours. Then, after cooling the obtained brown solution to room temperature, it was washed by adding an aqueous solution (40 ml) of NaOH (4.0 g, 100 mmol), and the precipitated solid was filtered using a Kiriyama funnel (registered trademark). The resulting brown solid was recrystallized from ethanol (9 ml) and water (35 ml), filtered and air-dried. The target 1,2-di (4-pyridyl) ethylene (5.28 g, yield 58%) was obtained.
＜比較例１＞
非特許文献１および２では４−ピリジンカルボキシアルデヒドと４−メチルピリジンとを塩化亜鉛存在下で加熱することにより１、２−ジ（４―ピリジル）エチレンを得ている。より具体的には、４−ピリジンカルボキシアルデヒド（０．０２２ｍｏｌ）、塩化亜鉛（０．０２２ｍｏｌ）および４−メチルピリジン（０．０２２ｍｏｌ）を封じ切ったガラス管中で２００−２１５℃で１６時間加熱し、室温まで冷却後、リン酸水溶液（３Ｎ、４０ｍｌ）に溶解させ、その後、水酸化ナトリウムで塩基性にする。得られた塩基性溶液をエーテル（３０ｍｌ、２回）およびクロロホルム（３０ｍｌ、４回）で抽出し、溶媒除去後、アルミナカラムにより精製することで目的の化合物を得ている。このときの１、２−ジ（４―ピリジル）エチレンの収率は１３％（非特許文献１）および１７％（非特許文献２）である。
<Comparative Example 1>
In Non-patent Documents 1 and 2, 1,2-di (4-pyridyl) ethylene is obtained by heating 4-pyridinecarboxaldehyde and 4-methylpyridine in the presence of zinc chloride. More specifically, it is heated at 200-215 ° C. for 16 hours in a glass tube sealed with 4-pyridinecarboxaldehyde (0.022 mol), zinc chloride (0.022 mol) and 4-methylpyridine (0.022 mol). After cooling to room temperature, it is dissolved in an aqueous phosphoric acid solution (3N, 40 ml) and then made basic with sodium hydroxide. The obtained basic solution was extracted with ether (30 ml, 2 times) and chloroform (30 ml, 4 times), and after removing the solvent, the desired compound was obtained by purification with an alumina column. The yields of 1,2-di (4-pyridyl) ethylene at this time are 13% (Non-Patent Document 1) and 17% (Non-Patent Document 2).
実施例１と比較例１の文献の収率データから、本発明の製造法が優れていることは明らかである。
From the yield data in the literature of Example 1 and Comparative Example 1, it is clear that the production method of the present invention is excellent.
Claims (4)
下記一般式（Ｉ）；
The following general formula (I);
The method according to claim 1 or 2, wherein the acylating agent is acetic anhydride, benzoic anhydride, acetyl chloride or benzoyl chloride.
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