JP4542480B2 - Method for producing maleonitriles - Google Patents
Method for producing maleonitriles Download PDFInfo
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- JP4542480B2 JP4542480B2 JP2005242460A JP2005242460A JP4542480B2 JP 4542480 B2 JP4542480 B2 JP 4542480B2 JP 2005242460 A JP2005242460 A JP 2005242460A JP 2005242460 A JP2005242460 A JP 2005242460A JP 4542480 B2 JP4542480 B2 JP 4542480B2
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本発明はマレオニトリル化合物類の製造方法に関する。 The present invention relates to a process for producing maleonitrile compounds.
マレオニトリル化合物類は、液晶表示装置およびプラズマディスプレーパネルなどの光学フィルター用色素、電子写真感光体の感光層に用いられるテトラアザポルフィリン化合物類の製造原料として有用である（特許文献１および特許文献２を参照）。 Maleonitrile compounds are useful as raw materials for producing tetraazaporphyrin compounds used in dyes for optical filters such as liquid crystal display devices and plasma display panels, and photosensitive layers of electrophotographic photoreceptors (see Patent Documents 1 and 2). reference).
従来のマレオニトリル化合物類の製造方法としては、例えば、１,２−ジエチル−３,４−ジブロモエテンとシアン化銅をＮ，Ｎ´−ジメチルホルムアミドおよびアセトニトリル溶媒中で反応させて１,２−ジエチル−３,４−ジニトリルエテンを得る方法（非特許文献１を参照。）、１,２−ジヨードエテンとシアンイオンを反応させて１,２−ジシアノエテンを得る方法（非特許文献２を参照）、更に１,２−ジクロロ−Ｎ,Ｎ,Ｎ´,Ｎ´−テトラメチル−エテン−１,２−ジアミンとシアン化カリウムを１８−クラウン−６の存在下で反応させて１,２−ジシアノ−Ｎ,Ｎ,Ｎ´,Ｎ´−テトラメチル−エテン−１,２−ジアミンを得る方法（非特許文献３を参照）などが知られている。
前記のマレオニトリル化合物類の製造方法で得られるマレオニトリル化合物類の収率は、非特許文献１に記載の製造方法では５０％、非特許文献２に記載の製造方法でも４５％にすぎない。
したがって、本発明はマレオニトリル化合物を収率良く得られる製造方法を提供することを目的とする。
The yield of the maleonitrile compound obtained by the manufacturing method of the above-mentioned maleonitrile compound is 50% in the manufacturing method described in Non-Patent Document 1, and only 45% in the manufacturing method described in Non-Patent Document 2.
Therefore, an object of the present invention is to provide a production method capable of obtaining a maleonitrile compound in a high yield.
本発明者らは、前記課題を解決するため鋭意検討を重ねた結果、ｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンとシアン化銅とを１,３−ジアルキル−２−イミダゾリジノンを反応溶媒として用いて反応させることにより、高い選択率でｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained cis-1,2-dibromo-3,3-dimethyl-1-butene and copper cyanide as 1,3-dialkyl-2- It has been found that cis-tert-butylmaleonitrile can be obtained with high selectivity by reacting with imidazolidinone as a reaction solvent, and the present invention has been completed.
即ち、本発明は、一般式（１） That is, the present invention relates to the general formula (1)
（式中、ＲおよびＲ´はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基またはアリールチオ基を示し、Ｘはハロゲン原子を示し、Ｘ´はハロゲン原子またはニトリル基を示す）で表される化合物と、一般式（２） (Wherein R and R ′ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group or an arylthio group, X represents a halogen atom, X ′ represents a halogen atom or a nitrile group) and the general formula (2)
（式中、Ｍはアルカリ金属、アルカリ土類金属、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、ＨｇまたはＴｌを示す）で表される化合物を反応させて、一般式（３） (Wherein M represents an alkali metal, alkaline earth metal, Ni, Pd, Pt, Cu, Ag, Au, Zn, Hg, or Tl), and a compound represented by the general formula (3)
（式中、ＲおよびＲ´は前記一般式（１）中のＲおよびＲ´と同義である）で表される化合物を製造するに際し、１,３−ジアルキル−２−イミダゾリジノンを反応溶媒として用いることを特徴とする一般式（３）で表される化合物の製造方法に関するものである。 (In the formula, R and R 'have the same meanings as R and R' in the general formula (1)), and 1,3-dialkyl-2-imidazolidinone is used as a reaction solvent. It is related with the manufacturing method of the compound represented by General formula (3) characterized by using as.
本発明によれば、マレオニトリル化合物類を収率良く製造する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing a maleonitrile compound with a sufficient yield can be provided.
本発明の製造方法は、一般式（１）で表される化合物と一般式（２）で表される化合物との反応を、１,３−ジアルキル−２−イミダゾリジノンを反応溶媒として用いることを特徴とする。
一般式（１）中のＲおよびＲ´はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基またはアリールチオ基を表し、Ｘはハロゲン原子を表し、Ｘ´はハロゲン原子またはニトリル基を表す。
一般式（１）中のアルキル基は特に限定されないが、アルキル基として炭素数１〜２０のアルキル基が好ましいものとして挙げられる。
一般式（１）中のアラルキル基は特に限定されないが、アラルキル基として炭素数１〜２０のアラルキル基が好ましいものとして挙げられる。
なお、アラルキル基はアルキル基、ニトロ基、シアノ基、ヒドロキシ基、ハロゲノ基、ハロゲン化炭化水素基で置換されていてもよい。
一般式（１）中のアルコキシ基は特に限定されないが、アルコキシ基として炭素数１〜２０のアルコキシ基が好ましいものとして挙げられる。
一般式（１）中のアルキルチオ基は特に限定されないが、アルキルチオ基として炭素数１〜２０のアルキルチオ基が好ましいものとして挙げられる。
一般式（１）中のアリール基は特に限定されないが、アリール基として炭素数６〜２０のアリール基が好ましいものとして挙げられる。
なお、アリール基はアルコキシ基、アミノ基、アルコキ基、ニトロ基、シアノ基、ヒドロキシ基、ハロゲノ基、ハロゲン化炭化水素基で置換されていてもよい。
一般式（１）中のヘテロアリール基は特に限定されないが、ヘテロアリール基として炭素数４〜２０のヘテロアリール基が好ましいものとして挙げられる。
一般式（１）中のアリールオキシ基としては、炭素数６〜２０のアリールオキシ基が好ましいものとして挙げられる。
なお、アリールオキシ基はアルキル基および／またはアルコキシ基で置換されていてもよい。
一般式（１）中のアリールチオ基は特に限定されないが、アリールチオ基として炭素数６〜２０のアリールチオ基が好ましいものとして挙げられる。
なお、アリールチオ基はアルキル基および／またはアルコキシ基で置換されていてもよい。
In the production method of the present invention, the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is performed using 1,3-dialkyl-2-imidazolidinone as a reaction solvent. It is characterized by.
R and R ′ in the general formula (1) each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group or an arylthio group, and X is a halogen atom. X ′ represents a halogen atom or a nitrile group.
Although the alkyl group in General formula (1) is not specifically limited, A C1-C20 alkyl group is mentioned as a preferable thing as an alkyl group.
Although the aralkyl group in General formula (1) is not specifically limited, As a aralkyl group, a C1-C20 aralkyl group is mentioned as a preferable thing.
The aralkyl group may be substituted with an alkyl group, a nitro group, a cyano group, a hydroxy group, a halogeno group, or a halogenated hydrocarbon group.
Although the alkoxy group in General formula (1) is not specifically limited, A C1-C20 alkoxy group is mentioned as a preferable thing as an alkoxy group.
Although the alkylthio group in General formula (1) is not specifically limited, A C1-C20 alkylthio group is mentioned as a preferable thing as an alkylthio group.
Although the aryl group in General formula (1) is not specifically limited, A C6-C20 aryl group is mentioned as a preferable thing as an aryl group.
The aryl group may be substituted with an alkoxy group, amino group, alkoxy group, nitro group, cyano group, hydroxy group, halogeno group, or halogenated hydrocarbon group.
Although the heteroaryl group in General formula (1) is not specifically limited, As a heteroaryl group, a C4-C20 heteroaryl group is mentioned as a preferable thing.
As an aryloxy group in General formula (1), a C6-C20 aryloxy group is mentioned as a preferable thing.
The aryloxy group may be substituted with an alkyl group and / or an alkoxy group.
Although the arylthio group in General formula (1) is not specifically limited, A C6-C20 arylthio group is mentioned as a preferable thing as an arylthio group.
The arylthio group may be substituted with an alkyl group and / or an alkoxy group.
一般式（２）中のＭは、アルカリ金属、アルカリ土類金属、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、ＨｇまたはＴｌを表す。
一般式（２）中のアルカリ金属は特に限定されないが、アルカリ金属としてＮａ、Ｋ、Ｃｓが好ましいものとして挙げられる。
一般式（２）中のアルカリ土類金属は特に限定されないが、Ｂａが好ましいものとして挙げられる。
一般式（２）中のＭとして、Ｃｕは特に好ましい。
M in the general formula (2) represents an alkali metal, an alkaline earth metal, Ni, Pd, Pt, Cu, Ag, Au, Zn, Hg, or Tl.
Although the alkali metal in General formula (2) is not specifically limited, Na, K, and Cs are mentioned as a preferable thing as an alkali metal.
Although the alkaline-earth metal in General formula (2) is not specifically limited, Ba is mentioned as a preferable thing.
Cu is particularly preferable as M in the general formula (2).
一般式（３）中のＲおよびＲ´はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基またはアリールチオ基を表す。
一般式（３）中のアルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基およびアリールチオ基は、前記の一般式（１）中の各基の定義と同義である。
R and R ′ in the general formula (3) each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group or an arylthio group.
The alkyl group, aralkyl group, alkoxy group, alkylthio group, aryl group, heteroaryl group, aryloxy group and arylthio group in the general formula (3) have the same definitions as the respective groups in the general formula (1). is there.
一般式（１）で表される化合物と一般式（２）で表される化合物の使用量は、化学量論的な１．０：２．０のモル比であればよいが、好ましくは１．０：１．６〜１．０：２．４のモル比から選択することができる。
一般式（１）で表される化合物と一般式（２）で表される化合物との反応には、反応溶媒として１,３−ジアルキル−２−イミダゾリジノンを用いる。
１,３−ジアルキル−２−イミダゾリジノンとしては、１,３−ジメチル−２−イミダゾリジノン、１,３−ジエチル−２−イミダゾリジノン、１,３−ジプロピル−２−イミダゾリジノンおよび１,３−ジブチル−２−イミダゾリジノンなどが挙げられ、これらは単独または２種以上組み合わせて用いても良い。
The amount of the compound represented by the general formula (1) and the compound represented by the general formula (2) may be a stoichiometric molar ratio of 1.0: 2.0, preferably 1 It can be selected from a molar ratio of 0.0: 1.6 to 1.0: 2.4.
For the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2), 1,3-dialkyl-2-imidazolidinone is used as a reaction solvent.
1,3-dialkyl-2-imidazolidinone includes 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone and 1,3-dibutyl-2-imidazolidinone and the like may be mentioned, and these may be used alone or in combination of two or more.
１,３−ジアルキル−２−イミダゾリジノンの使用量は特に制限されないが、一般式（１）で表される化合物１００重量部に対し、２０〜２０００重量部が好ましい。
一般式（１）で表される化合物と一般式（２）で表される化合物との反応の温度は、６０〜１８０℃が好ましい。６０℃未満だと反応速度が小さく、１８０℃を超えると目的物である一般式（３）で表される化合物が分解するため好ましくない。
一般式（１）で表される化合物と一般式（２）で表される化合物との反応の圧力は特に制限されないが、通常、大気圧下である。
一般式（１）で表される化合物と一般式（２）で表される化合物との反応の雰囲気は、空気および／または窒素、ヘリウム、ネオン、アルゴン、クリプトン、キセノンおよびラドンなどの不活性気体である。
The amount of 1,3-dialkyl-2-imidazolidinone used is not particularly limited, but is preferably 20 to 2000 parts by weight with respect to 100 parts by weight of the compound represented by the general formula (1).
The temperature of the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is preferably 60 to 180 ° C. If it is less than 60 ° C., the reaction rate is low, and if it exceeds 180 ° C., the compound represented by the general formula (3), which is the target, is decomposed, which is not preferable.
The pressure of the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is not particularly limited, but is usually atmospheric pressure.
The reaction atmosphere between the compound represented by the general formula (1) and the compound represented by the general formula (2) is air and / or an inert gas such as nitrogen, helium, neon, argon, krypton, xenon and radon. It is.
一般式（１）で表される化合物と一般式（２）で表される化合物との反応は、回分式または連続式のどちらの方法でも実施できる。
例えば、回分式で反応を行なう場合は、一般式（１）で表される化合物と一般式（２）で表される化合物および１,３−ジアルキル−２−イミダゾリジノンを一括で仕込み、所望の温度で反応する方法や、一般式（１）で表される化合物または一般式（２）で表される化合物のどちらか一方の原料と１,３−ジアルキル−２−イミダゾリジノンを仕込み、所望の反応温度に加温し、もう一方の原料を添加しながら反応する方法が挙げられる。
連続式で反応を行なう場合は、反応溶媒である１,３−ジアルキル−２−イミダゾリジノンを所望の反応温度に保持しながら、一般式（１）で表される化合物と一般式（２）で表される化合物を連続的に添加し、反応生成物を連続的に抜出す方法が挙げられる。
前記の反応で得られる一般式（３）で表される化合物は、公知の方法で反応混合物から分離することができる。例えば反応混合物中に一般式（３）で表される化合物が析出した状態であれば、これを濾過して分離することができる。反応混合物中に一般式（３）で表される化合物の結晶が析出していない場合は、使用した１,３−ジアルキル−２−イミダゾリジノンを蒸留により留去するか、または一般式（３）で表される化合物を溶解しないが、１,３−ジアルキル−２−イミダゾリジノンとは混和する溶剤、例えば水やメタノールを添加して一般式（３）で表される化合物の結晶を析出させるなどして一般式（３）で表される化合物を分離することができる。
The reaction of the compound represented by the general formula (1) and the compound represented by the general formula (2) can be carried out by either a batch method or a continuous method.
For example, when the reaction is carried out batchwise, the compound represented by the general formula (1), the compound represented by the general formula (2), and 1,3-dialkyl-2-imidazolidinone are charged all at once. A method of reacting at a temperature of 1, a compound represented by general formula (1) or a compound represented by general formula (2) and 1,3-dialkyl-2-imidazolidinone, A method of reacting while heating to a desired reaction temperature and adding the other raw material can be mentioned.
When the reaction is carried out continuously, the compound represented by the general formula (1) and the general formula (2) while maintaining the reaction solvent 1,3-dialkyl-2-imidazolidinone at a desired reaction temperature. A method in which the compound represented by the above is continuously added and the reaction product is continuously withdrawn.
The compound represented by the general formula (3) obtained by the above reaction can be separated from the reaction mixture by a known method. For example, if the compound represented by the general formula (3) is precipitated in the reaction mixture, it can be separated by filtration. When crystals of the compound represented by the general formula (3) are not precipitated in the reaction mixture, the 1,3-dialkyl-2-imidazolidinone used is distilled off by distillation, or the general formula (3 The compound represented by formula (3) is not dissolved, but a solvent miscible with 1,3-dialkyl-2-imidazolidinone, such as water or methanol, is added to precipitate crystals of the compound represented by formula (3) For example, the compound represented by the general formula (3) can be separated.
以下に本発明の実施例を示すが、本発明はこれにより何ら限定されるものではない。
なお一般式（１）で表される化合物および一般式（３）で表される化合物の分析は液クロマトグラフィー（以下、「ＨＰＬＣ」と略記する）に依った。
ＨＰＬＣ分析条件を以下に記す。
カラム：ＹＭＣ−Ｐａｃｋ ＯＤＳ−Ａ φ６ｍｍ×１５０ｍｍ
溶離液：アセトニトリル／水＝７／３
Examples of the present invention will be shown below, but the present invention is not limited thereto.
The analysis of the compound represented by the general formula (1) and the compound represented by the general formula (3) depended on liquid chromatography (hereinafter abbreviated as “HPLC”).
The HPLC analysis conditions are described below.
Column: YMC-Pack ODS-A φ6mm × 150mm
Eluent: acetonitrile / water = 7/3
シアン化銅１７．９ｇ（０．２モル）と１，３−ジメチル−２−イミダゾリジノン１１０ｇおよびｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテン２１．６ｇ（０．０８９モル）を仕込み、１４０℃に加温して同温度で１０時間保持した。室温まで冷却して得られた反応マスを濾過して無機塩を除き、濾過マスを１６７．７ｇ得た。この濾過マスを分析した結果、原料であるｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンは不検出、目的物のｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルは濃度６．５重量％で１０．９ｇ含まれており、収率は仕込んだｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンに対し９１モル％であった。 17.9 g (0.2 mol) of copper cyanide, 110 g of 1,3-dimethyl-2-imidazolidinone and 21.6 g (0.089) of cis-1,2-dibromo-3,3-dimethyl-1-butene Mol) was added, heated to 140 ° C. and held at the same temperature for 10 hours. The reaction mass obtained by cooling to room temperature was filtered to remove inorganic salts, thereby obtaining 167.7 g of a filtration mass. As a result of analyzing this filtration mass, the raw material cis-1,2-dibromo-3,3-dimethyl-1-butene was not detected, and the target cis-tert-butylmaleonitrile was 6.5% by weight. 10.9 g was contained, and the yield was 91 mol% with respect to the charged cis-1,2-dibromo-3,3-dimethyl-1-butene.
引き続き濾過マスにトルエン１５０ｇ添加し、更にアンモニア水を２５０ｇ加えて抽出処理を行なった後に有機相と水相に分離し、ｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルを含む有機相を得、エバポレーターでトルエンを留去して純度９６．８重量％のｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルを９．５１ｇ得た。 Subsequently, 150 g of toluene was added to the filtration mass, and 250 g of ammonia water was further added, followed by extraction treatment, separation into an organic phase and an aqueous phase to obtain an organic phase containing cis-tert-butylmaleonitrile, and toluene was distilled off with an evaporator. As a result, 9.51 g of cis-tert-butylmaleonitrile having a purity of 96.8% by weight was obtained.
［比較例１］
溶媒をＮ，Ｎ´−ジメチルフォルムアミドに変えた以外は実施例１と同様に仕込み、反応を行い、実施例１と同様に濾過して濾過マスを２０８．５ｇ得た。この濾過マスを分析した結果、原料であるｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンは不検出、目的物のｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルは濃度３．９８重量％で８．３ｇ含まれており、収率は仕込んだｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンに対し６９．５モル％であった。
[Comparative Example 1]
The reaction was conducted in the same manner as in Example 1 except that the solvent was changed to N, N′-dimethylformamide, the reaction was performed, and filtration was performed in the same manner as in Example 1 to obtain 208.5 g of a filtration mass. As a result of analyzing this filtration mass, the raw material cis-1,2-dibromo-3,3-dimethyl-1-butene was not detected, and the target cis-tert-butylmaleonitrile was found to have a concentration of 3.98% by weight. 8.3 g was contained, and the yield was 69.5 mol% based on the charged cis-1,2-dibromo-3,3-dimethyl-1-butene.
［比較例２］
溶媒をジメチルスルフォキシドに変えた以外は実施例１と同様に仕込み、反応を行い、実施例１と同様に濾過して濾過マスを１４７．９ｇ得た。この濾過マスを分析した結果、原料であるｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンは不検出、目的物のｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルは濃度５．７重量％で８．４ｇ含まれており、収率は仕込んだｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンに対し７０．６モル％であった。
[Comparative Example 2]
The reaction was carried out in the same manner as in Example 1 except that the solvent was changed to dimethyl sulfoxide, the reaction was performed, and filtration was performed in the same manner as in Example 1 to obtain 147.9 g of a filtration mass. As a result of analyzing this filtration mass, the raw material cis-1,2-dibromo-3,3-dimethyl-1-butene was not detected, and the target cis-tert-butylmaleonitrile was at a concentration of 5.7% by weight. 8.4 g was contained, and the yield was 70.6 mol% based on the charged cis-1,2-dibromo-3,3-dimethyl-1-butene.
［比較例３］
溶媒を１−メチル−２−ピロリドンに変えた以外は実施例１と同様に仕込み、反応を行い、実施例１と同様に濾過して濾過マスを１４６．５ｇ得た。この濾過マスを分析した結果、原料であるｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンは不検出、目的物のｃｉｓ−ｔｅｒｔ−ブチルマレオニトリルは濃度２．６重量％で３．８ｇ含まれており、収率は仕込んだｃｉｓ−１,２−ジブロモ−３,３−ジメチル−１−ブテンに対し３１．９モル％であった。
[Comparative Example 3]
The reaction was carried out in the same manner as in Example 1 except that the solvent was changed to 1-methyl-2-pyrrolidone, and the reaction was carried out, followed by filtration in the same manner as in Example 1 to obtain 146.5 g of a filtration mass. As a result of analyzing this filtration mass, the raw material cis-1,2-dibromo-3,3-dimethyl-1-butene was not detected, and the target cis-tert-butylmaleonitrile was found to have a concentration of 2.6% by weight. The yield was 31.9 mol% based on the charged cis-1,2-dibromo-3,3-dimethyl-1-butene.
［参考例１］
下記の一般式（４）で表される化合物の合成
なお一般式（４）で表される化合物の分析は液クロマトグラフィー（以下、「ＨＰＬＣ」と略記する）に依った。
ＨＰＬＣ分析条件を以下に記す。
カラム：ＹＭＣ−Ｐａｃｋ ＯＤＳ−Ａ φ６ｍｍ×１５０ｍｍ
溶離液：メタノール／テトラヒドロフラン＝６／１
[Reference Example 1]
Synthesis of the compound represented by the following general formula (4) The analysis of the compound represented by the general formula (4) was based on liquid chromatography (hereinafter abbreviated as “HPLC”).
The HPLC analysis conditions are described below.
Column: YMC-Pack ODS-A φ6mm × 150mm
Eluent: methanol / tetrahydrofuran = 6/1
１−ペンタノール５０ｇに三塩化バナジウム１．５７ｇを装入し、２０℃でアンモニアガス１．０２ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃の反応温度で１時間攪拌を行った後、前述した実施例１で得られたｃｉｓ−ｔｅｒｔ−ブチルマレオニトリル５．３８ｇを装入し、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、メタノール水（メタノールと水の重量比は１：１）を装入して一般式（４）で表される化合物の結晶を析出させた。析出した一般式（４）で表される化合物を濾過により回収し、乾燥させて一般式（４）で表される化合物を得た。乾燥後の一般式（４）で表される化合物をＨＰＬＣ分析した結果、その純度は９４％、収率は８５％であった。一般式（４）で表される化合物の元素分析結果およびＦＤ−ＭＳ測定結果は次のとおりであった。
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（７） ６３．７０ ６．７１ １８．５５ ６０３
理論値（％） ６３．６７ ６．６８ １８．５６ ６０３
50 g of 1-pentanol was charged with 1.57 g of vanadium trichloride, and 1.02 g of ammonia gas was introduced at 20 ° C. over 1 hour. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring for 1 hour at a reaction temperature of 20 to 30 ° C., 5.38 g of cis-tert-butylmaleonitrile obtained in Example 1 was charged, and the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. About 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water (the weight ratio of methanol to water was 1: 1) was added to precipitate crystals of the compound represented by the general formula (4). . The precipitated compound represented by the general formula (4) was collected by filtration and dried to obtain a compound represented by the general formula (4). As a result of HPLC analysis of the compound represented by the general formula (4) after drying, the purity was 94% and the yield was 85%. The elemental analysis results and FD-MS measurement results of the compound represented by the general formula (4) were as follows.
Elemental analysis results C H N FD-MS
(M / z)
Compound (7) 63.70 6.71 18.55 603
Theoretical value (%) 63.67 6.68 18.56 603
本発明の製造方法は、マレオニトリル化合物類を収率良く製造する方法として有用である。また、本発明で得られるマレオニトリル化合物類はテトラアザポルフィリン化合物類の製造原料として有用である
The production method of the present invention is useful as a method for producing a maleonitrile compound with high yield. In addition, the maleonitrile compounds obtained in the present invention are useful as raw materials for producing tetraazaporphyrin compounds.
Claims (2)
1,3-dialkyl-2-imidazolidinone is 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-dipropyl-2-imidazolidinone and 1 A process for producing a compound represented by the general formula (3) according to claim 1, wherein at least one selected from 1,3-dibutyl-2-imidazolidinone is used as a solvent.
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