JP6223705B2 - Extraction method of alkylimidazole compound - Google Patents
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Description
本発明は、複素環式化合物を抽出剤として用いるアルキルイミダゾール化合物を含有する水溶液からのアルキルイミダゾール化合物の抽出方法に関する。
アルキルイミダゾール化合物は、医薬、農薬、機能性材料等の中間体として有用な化合物である。
The present invention relates to a method for extracting an alkylimidazole compound from an aqueous solution containing an alkylimidazole compound using a heterocyclic compound as an extractant.
Alkylimidazole compounds are useful compounds as intermediates for pharmaceuticals, agricultural chemicals, functional materials and the like.
アルキルイミダゾール化合物は、医薬、農薬、機能性材料等の中間体として有用な化合物であり、特に、グリーンケミストリーの分野において、リサイクル可能な溶媒としてのイオン液体の原料として有用な化合物である。
アルキルイミダゾール化合物を製造する方法としては、グリオキサール、ホルムアルデヒド、アンモニア及びメチルアミンを液相バッチ反応させた後、得られた反応液を１−ブチルアルコールで３回抽出することにより、収率７０％で１−メチルイミダゾールを得たことが報告されている。また、同様の反応を行った後、酢酸エチルで３回抽出することにより、収率６９％で１−メチルイミダゾールを得たことが報告されている（特許文献１参照）。
Alkylimidazole compounds are useful compounds as intermediates for pharmaceuticals, agricultural chemicals, functional materials and the like, and are particularly useful as raw materials for ionic liquids as recyclable solvents in the field of green chemistry.
As a method for producing an alkylimidazole compound, glyoxal, formaldehyde, ammonia and methylamine were subjected to a liquid phase batch reaction, and then the obtained reaction solution was extracted three times with 1-butyl alcohol. It has been reported that 1-methylimidazole was obtained. In addition, it was reported that 1-methylimidazole was obtained with a yield of 69% by performing extraction with ethyl acetate three times after performing the same reaction (see Patent Document 1).
上記従来法において、グリオキサール、ホルムアルデヒド、アンモニア及びメチルアミンを液相バッチ反応させる方法は、水溶液での反応である上、反応工程においても水が副生するため、生成物である１−メチルイミダゾールを抽出等の方法で水と分離する必要がある。特許文献１の実施例には、前記の通り、反応液を１−ブチルアルコール、酢酸エチルを用いて１−メチルイミダゾールを抽出したことが記載されているが、本発明者らが特許文献１を参考に１−ブチルイミダゾール、酢酸エチル等によりアルキルイミダゾール化合物の抽出を試みたところ、これらの抽出剤ではアルキルイミダゾール化合物を効率よく抽出できないことがわかった（後述の比較例参照）。 In the above conventional method, the method of reacting glyoxal, formaldehyde, ammonia and methylamine in a liquid phase batch is a reaction in an aqueous solution, and water is also produced as a by-product in the reaction step. It must be separated from water by extraction or other means. In the Examples of Patent Document 1, as described above, it was described that 1-methylimidazole was extracted from the reaction solution using 1-butyl alcohol and ethyl acetate. Attempts were made to extract the alkylimidazole compound with 1-butylimidazole, ethyl acetate or the like for reference, and it was found that these extractants could not extract the alkylimidazole compound efficiently (see Comparative Examples described later).
本発明者らは、かかる事情に鑑み鋭意検討した結果、アルキルイミダゾール化合物を含有する水溶液に対して、抽出剤として複素環式化合物を用いるとアルキルイミダゾール化合物を含有する水溶液からアルキルイミダゾール化合物を効率よく抽出できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of such circumstances, the present inventors have efficiently used an alkylimidazole compound from an aqueous solution containing an alkylimidazole compound when a heterocyclic compound is used as an extractant with respect to the aqueous solution containing the alkylimidazole compound. The inventors have found that it can be extracted and have completed the present invention.
即ち、本発明は、複素環式化合物を抽出剤として用いるアルキルイミダゾール化合物を含有する水溶液からのアルキルイミダゾール化合物の抽出方法に関する。 That is, this invention relates to the extraction method of the alkylimidazole compound from the aqueous solution containing the alkylimidazole compound which uses a heterocyclic compound as an extracting agent.
本発明によれば、アルキルイミダゾール化合物を含有する水溶液からアルキルイミダゾール化合物を効率よく抽出することができるため、本発明は工業的に有用な方法である。 According to the present invention, the alkylimidazole compound can be efficiently extracted from the aqueous solution containing the alkylimidazole compound, and thus the present invention is an industrially useful method.
以下、本発明を詳しく説明する。 The present invention will be described in detail below.
本発明におけるアルキルイミダゾール化合物は、式（１）： The alkylimidazole compound in the present invention has the formula (1):
式（１）中、炭素数１〜８のアルキル基としては、具体的には、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、オクチル基等が挙げられ、メチル基が好ましい。炭素数５〜８のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。 In the formula (1), as the alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group , Neopentyl group, hexyl group, octyl group and the like, and methyl group is preferable. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
アルキルイミダゾール（１）の具体例としては、１−メチルイミダゾール、１−エチルイミダゾール、１−プロピルイミダゾール、１−ブチルイミダゾール、１−ペンチルイミダゾール、１−ヘキシルイミダゾール、１−ヘプチルイミダゾール、１−オクチルイミダゾール、１，２−ジメチルイミダゾール、１，４−ジメチルイミダゾール、１，５−ジメチルイミダゾール、１，２，４−トリメチルイミダゾール、１，２，５−トリメチルイミダゾール、１，２，４，５−テトラメチルイミダゾール等が挙げられ、１−メチルイミダゾールが好ましい。 Specific examples of alkylimidazole (1) include 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-pentylimidazole, 1-hexylimidazole, 1-heptylimidazole, 1-octylimidazole. 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,2,5-trimethylimidazole, 1,2,4,5-tetramethyl Examples include imidazole, and 1-methylimidazole is preferable.
本発明のアルキルイミダゾール化合物を含有する水溶液は、水溶液中に少なくともアルキルイミダゾール（１）を含有していればよく、アルキルイミダゾール（１）以外の不純物を含有していてもよい。アルキルイミダゾール（１）を含有する水溶液は、例えば、特許文献１に記載の方法により製造することができる。アルキルイミダゾール（１）を含有する水溶液の濃度は、アルキルイミダゾール（１）の含有量が１〜９５重量％の範囲であり、好ましくは１０〜８０重量％の範囲である。 The aqueous solution containing the alkylimidazole compound of the present invention only needs to contain at least the alkylimidazole (1) in the aqueous solution, and may contain impurities other than the alkylimidazole (1). The aqueous solution containing the alkylimidazole (1) can be produced, for example, by the method described in Patent Document 1. The concentration of the aqueous solution containing the alkylimidazole (1) is such that the content of the alkylimidazole (1) is in the range of 1 to 95% by weight, and preferably in the range of 10 to 80% by weight.
本発明では、抽出剤として複素環式化合物を用いる。複素環式化合物としては、通常、複素環式芳香族化合物が用いられ、中でも分子内に１個以上の窒素原子を有する複素環式芳香族化合物が好ましく用いられる。 In the present invention, a heterocyclic compound is used as the extractant. As the heterocyclic compound, a heterocyclic aromatic compound is usually used, and among them, a heterocyclic aromatic compound having one or more nitrogen atoms in the molecule is preferably used.
分子内に１個以上の窒素原子を有する複素環式芳香族化合物としては、ピロール、イミダゾール、ピラゾール、ピリジン、ピリミジン、ピラジン、トリアジン及びそれら化合物の芳香環上の少なくとも１つの水素原子がアルキル基に置換された化合物が挙げられ、それら化合物の２種以上の混合物を用いてもよい。 Heteroaromatic compounds having one or more nitrogen atoms in the molecule include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, triazine and at least one hydrogen atom on the aromatic ring of the compound as an alkyl group. Examples include substituted compounds, and a mixture of two or more of these compounds may be used.
分子内に１個以上の窒素原子を有する複素環式芳香族化合物として特に好ましいのは、下記式（２）で示されるピロール化合物（以下、ピロール（２）という。）である。 Particularly preferred as the heterocyclic aromatic compound having one or more nitrogen atoms in the molecule is a pyrrole compound represented by the following formula (2) (hereinafter referred to as pyrrole (2)).
式（２）中、炭素数１〜８のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、オクチル基等が挙げられる。炭素数５〜８のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。 In formula (2), the alkyl group having 1 to 8 carbon atoms includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and hexyl. Group, octyl group and the like. Examples of the cycloalkyl group having 5 to 8 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
ピロール（２）としては、ピロール、２−メチルピロール、３−メチルピロール、２，３−ジメチルピロール、２，４−ジメチルピロール、２，５−ジメチルピロール等が挙げられ、それら化合物の２種類以上の混合物も用いることができる。中でも好ましく用いられるのは、ピロールである。 Examples of pyrrole (2) include pyrrole, 2-methylpyrrole, 3-methylpyrrole, 2,3-dimethylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, etc., and two or more of these compounds A mixture of these can also be used. Of these, pyrrole is preferably used.
本発明は、通常０〜１００℃の範囲の温度で、好ましくは１０〜４０℃の範囲の温度で、実施できる。抽出の方法としては特に制限されず、バッチ式、連続式のいずれの方式も採用することができる。 The present invention can be carried out usually at a temperature in the range of 0 to 100 ° C, preferably at a temperature in the range of 10 to 40 ° C. The extraction method is not particularly limited, and either a batch method or a continuous method can be employed.
本発明における抽出剤の使用量は、アルキルイミダゾール（１）を含有する水溶液１重量部に対して、抽出剤０．１〜２０．０重量部の範囲であり、好ましくは０．５〜５．０重量部の範囲である。アルキルイミダゾール（１）を含有する水溶液からアルキルイミダゾール（１）を抽出する際の抽出操作回数は、特に制限されず、合計の抽出剤使用量が同じ場合、操作回数が多いほど効率が良くなるが、経済的には不利となるため、１〜１０回程度が好ましい。 The amount of the extractant used in the present invention is in the range of 0.1 to 20.0 parts by weight, preferably 0.5 to 5.0.0 parts by weight with respect to 1 part by weight of the aqueous solution containing the alkylimidazole (1). The range is 0 part by weight. The number of extraction operations when extracting the alkylimidazole (1) from the aqueous solution containing the alkylimidazole (1) is not particularly limited, and when the total amount of extractant used is the same, the higher the number of operations, the better the efficiency. Since it is economically disadvantageous, about 1 to 10 times is preferable.
抽出、分液によりアルキルイミダゾール（１）を含有するピロール（２）溶液を取得した後、蒸留等の通常の手段によって、アルキルイミダゾール（１）とピロール（２）を分離し、目的物であるアルキルイミダゾール（１）を得ることができる。 After obtaining pyrrole (2) solution containing alkylimidazole (1) by extraction and liquid separation, alkylimidazole (1) and pyrrole (2) are separated by ordinary means such as distillation to obtain the target alkyl Imidazole (1) can be obtained.
つぎに、本発明を実施例に基づいて具体的に説明するが、本発明はなんらこれらに限定されるものではない。なお、実施例中のガスクロマトグラフィーによる分析は以下の条件で、分配係数はガスクロマトグラフィーによる定量分析の結果から以下の定義に従って算出した。
１）ガスクロマトグラフィー分析条件
ガスクロマトグラフ：島津製作所製ＧＣ−２０１０
カラム：Ｊ＆Ｗ社製、ＤＢ−ＷＡＸ、３０ｍ、内径０．３２ｍｍ，膜厚０．２５μｍ
温度：５０℃（３ｍｉｎ）→（１５℃／ｍｉｎ）→２００℃（０ｍｉｎ）
→（２０℃／ｍｉｎ）→２５０℃（９．５ｍｉｎ）
２）分配係数
分配係数＝ピロール（２）層に含有されるアルキルイミダゾール（１）濃度（重量％）／水層中に含有されるアルキルイミダゾール（１）濃度（重量％）
Next, the present invention will be specifically described based on examples, but the present invention is not limited thereto. The analysis by gas chromatography in the examples was performed under the following conditions, and the distribution coefficient was calculated from the result of quantitative analysis by gas chromatography according to the following definition.
1) Gas chromatography analysis conditions Gas chromatograph: GC-2010 manufactured by Shimadzu Corporation
Column: J & W, DB-WAX, 30 m, inner diameter 0.32 mm, film thickness 0.25 μm
Temperature: 50 ° C. (3 min) → (15 ° C./min)→200° C. (0 min)
→ (20 ° C / min) → 250 ° C (9.5 min)
2) Partition coefficient Partition coefficient = alkylimidazole (1) concentration (wt%) contained in the pyrrole (2) layer / alkylimidazole (1) concentration (wt%) contained in the aqueous layer
実施例１
１−メチルイミダゾール８．９重量％、１，２−ジメチルイミダゾール０．９重量％、イミダゾール０．９重量％を含有する水溶液９．０ｇに対して、抽出剤としてピロールを８．０ｇ添加し室温で十分に撹拌混合した。得られた溶液を室温で静置後、同温度で分液し、得られたピロール（２）層及び水層中に含まれるアルキルイミダゾール（１）をガスクロマトグラフィーで分析した。その結果を表１に示す。
Example 1
To 9.0 g of an aqueous solution containing 8.9% by weight of 1-methylimidazole, 0.9% by weight of 1,2-dimethylimidazole and 0.9% by weight of imidazole, 8.0 g of pyrrole was added as an extractant. And mixed thoroughly. The resulting solution was allowed to stand at room temperature and then separated at the same temperature, and the resulting pyrrole (2) layer and alkylimidazole (1) contained in the aqueous layer were analyzed by gas chromatography. The results are shown in Table 1.
比較例１〜５
抽出剤として、ピロールに代えて表１に記載の抽出剤を用いた以外は、実施例１と同様に実施した。その結果を表１にまとめて示す。
Comparative Examples 1-5
It implemented like Example 1 except having replaced with the pyrrole and using the extractant of Table 1 as an extractant. The results are summarized in Table 1.
Claims (1)
式（１）：
Formula (1):
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| DE2932712A1 (en) * | 1979-08-13 | 1981-03-26 | Basf Ag, 67063 Ludwigshafen | METHOD FOR OBTAINING IMIDAZOLES |
| JPS6056961A (en) * | 1983-09-06 | 1985-04-02 | Mitsui Toatsu Chem Inc | Production of imidazole |
| JPH01149772A (en) * | 1987-12-07 | 1989-06-12 | Mitsui Toatsu Chem Inc | Production of 4-methylimidazole |
| JPH03169865A (en) * | 1989-11-29 | 1991-07-23 | Mitsui Toatsu Chem Inc | Production of 1-substituted imidazole |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |