JP4045604B2 - Method for producing 2-methylimidazole - Google Patents
Method for producing 2-methylimidazole Download PDFInfo
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- JP4045604B2 JP4045604B2 JP03475796A JP3475796A JP4045604B2 JP 4045604 B2 JP4045604 B2 JP 4045604B2 JP 03475796 A JP03475796 A JP 03475796A JP 3475796 A JP3475796 A JP 3475796A JP 4045604 B2 JP4045604 B2 JP 4045604B2
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- methylimidazole
- alcohol
- methylimidazoline
- nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、２−メチルイミダゾールの製造法に関する。
【０００２】
一般に、２−メチルイミダゾールは、エポキシ樹脂、ポリウレタン樹脂等の樹脂硬化剤、硬化促進剤、各種農薬、医薬又は染料中間体として極めて有用な化合物である。
【０００３】
【従来の技術】
２−メチルイミダゾリンを脱水素することにより２−メチルイミダゾールを製造する方法としては多くの方法が知られている。
【０００４】
特公昭３９−２６４０５号公報には、ニッケル触媒存在下で反応させる方法が記載されている。特公昭６１−２３７９１号公報には、触媒として酸化亜鉛を用いる方法が記載されており、特公平３−２８４２６号公報には、酸化モリブデン，酸化ニッケル，酸化アルミニウム，酸化リン等を触媒とする方法が記載されている。
【０００５】
しかしながら、原料の２−メチルイミダゾリンは融点が高く、また昇華性があるため、取扱いが容易ではなく、工業的に生産する際には、反応装置内で２−メチルイミダゾリンが固結したり、配管が閉塞する等のトラブルが生じる。特公昭６１−２３７９１号公報及び特公平３−２８４２６号公報には、溶媒として、水と共沸混合物を形成しない溶剤、例えば、脂肪族炭化水素，石油エーテル，リグロインを使用することが記載されているが、これらの溶媒に２−メチルイミダゾリンは溶解しない為、固結等のトラブルを解消する手段にならない。
【０００６】
【発明が解決しようとする課題】
従来の方法では、２−メチルイミダゾールを固結等の問題なしに効率よく製造するには十分ではない。したがって、固結の問題なく、２−メチルイミダゾールを製造する方法の開発が望まれていた。
【０００７】
【課題を解決するための手段】
本発明者らは、２−メチルイミダゾールの製造法について鋭意検討をした結果、アルコール存在下で反応を行うことによって、原料の２−メチルイミダゾリンが固結することなく、高収率で目的物を得られることを見出し、２−メチルイミダゾールの新規な工業的製造法として、本発明を完成するに至った。
【０００８】
すなわち、本発明は、２−メチルイミダゾリンから２−メチルイミダゾールを製造する際に、アルコール存在下で反応を行うことを特徴とする２−メチルイミダゾールの製造法である。
【０００９】
【発明の実施の形態】
以下に本発明を詳細に説明する。
【００１０】
本発明の方法は、２−メチルイミダゾリンから２−メチルイミダゾールを製造する際に、アルコール存在下で反応させることを特徴とする。
【００１１】
本発明の方法においてアルコール存在下とは、２−メチルイミダゾリンの閉塞を防ぐことができる量のアルコールを反応系中に存在させることをいい、具体的には、反応系中にこのような量のアルコールを予め仕込み反応中に凝縮器等により還流させること、又は、反応系中にアルコールを供給しながら反応させることをいう。アルコールの供給は、連続的であっても断続的であってもよい。連続的にアルコールを供給する場合、供給する速度については特に制限はなく、反応温度が一定に保てればよい。
【００１２】
本発明の方法において供給するアルコールとしては反応条件に不活性なものであれば特に制限はないが、イミダゾリンの良溶媒であり、水と共沸混合物を形成するアルコールの使用が好ましく、炭素数７以下のアルコール、具体的には、メチルアルコール，エチルアルコール，プロピルアルコール，ブチルアルコール，アミルアルコール，シクロヘキサノール，ベンジルアルコール等が例示される。これらアルコールの中でも、触媒を失活させない三級アルコールの使用が特に好ましい。本発明の方法において使用される三級アルコールとしては、例えば、ｔｅｒｔ−ブチルアルコール，ｔｅｒｔ−アミルアルコール，１−メチルシクロヘキサノール等が挙げられる。さらに、これら三級アルコールの中でも、沸点の点から、ｔｅｒｔ−ブチルアルコールの使用が特に好ましい。
【００１３】
本発明の方法において、使用されるアルコールの量は、２−メチルイミダゾリン１に対して重量比で０．１〜１０の範囲で反応を行うことが好ましい。０．１未満では、２−メチルイミダゾリンの固結等のトラブルを解消することは難しい場合があり、１０を越えてもアルコールを増やした効果は小さい。
【００１４】
本発明の方法においては、２−メチルイミダゾリンを触媒存在下で反応させる。触媒としては、金属を使用することができる。
【００１５】
本発明の方法において、金属としては、特に限定するものではないが、例えば、マグネシウム，アルミニウム，カルシウム，スカンジウム，チタン，バナジウム，クロム，マンガン，鉄，コバルト，ニッケル，銅，亜鉛，ストロンチウム，イットリウム，ジルコニウム，ニオブ，モリブデン，ルテニウム，ロジウム，パラジウム，銀，カドニウム，バリウム，ランタン，ハフニウム，タンタル，タングステン，レニウム，オスミウム，イリジウム，白金，金，水銀等が挙げられる。その中でも触媒活性が高いことから、ニッケル，パラジウム，白及び銅からなる群より選ばれる１種又は２種以上を使用することが特に好ましい。ニッケルとしては、安定化ニッケル，ラネーニッケル，フレークニッケル等を使用することができる。
【００１６】
本発明の方法において、触媒の形態は、反応形式によって、最適なものを選べばよく、粉末で使用しても良いし、成形して使用してもよい。
【００１７】
本発明の方法において、使用される触媒の量は２−メチルイミダゾリンに対して０．１〜２０重量％の範囲で反応を行うことが好ましい。０．１重量％未満であると反応速度が遅くなるため未反応のイミダゾリンの分解が生じ、イミダゾールの収率が低下する場合がある。２０重量％を越えても触媒を増やした効果は小さい。
【００１８】
本発明の方法においては、副生成物及び着色防止を考慮して、水素、不活性ガス、例えば、窒素ガス，ヘリウム又はアルゴンガスで反応器を置換して行うことが好ましい。
【００１９】
本発明の方法において、反応温度は１５０〜２４０℃の範囲で行うことが好ましい。１５０℃未満では、反応は非常に遅いため未反応のイミダゾリンの分解が生じ、イミダゾールの収率が低下する。２４０℃を越える温度では、原料の分解が生じ、イミダゾールの収率が低下する。
【００２０】
本発明の方法は、液相で実施する。
【００２１】
本発明の方法において、反応は、原料を液状に保てればよく、常圧，加圧又は減圧下で行うことができる。この反応では、反応中に水素が生成するため反応圧力が上昇するが、この水素は反応途中で除去してもしなくてもよいが、除去することが好ましい。反応温度が原料の沸点を越えている場合は、加圧下で反応を行うか、凝縮器を設け原料を液化する必要がある。
【００２２】
【発明の効果】
以上のように本発明によれば、アルコール存在下で反応を行えば、２−メチルイミダゾールを固結等の問題なしに効率よく製造することができるため、工業上極めて有意義である。
【００２３】
【実施例】
以下、本発明の方法を実施例により説明するが、本発明はこれらに限定されるものではない。
【００２４】
実施例１
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾリン５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１８０℃に加熱した。温度が上昇したところで、常圧，窒素気流下、ｔｅｒｔ−ブチルアルコールを４ｍｌ／ｈｒの速度で供給しながら５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出した。配管の閉塞はなかった。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率９０％，２−メチルイミダゾールの選択率は９２％であった。
【００２５】
実施例２
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１６０℃に加熱した。温度が上昇したところで、常圧，窒素気流下、ｔｅｒｔ−ブチルアルコールを４ｍｌ／ｈｒの速度で供給しながら５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出した。配管の閉塞はなかった。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率８９％，２−メチルイミダゾールの選択率は９０％であった。
【００２６】
参考例
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１８０℃に加熱した。温度が上昇したところで、常圧，窒素気流下、メチルアルコールを４ｍｌ／ｈｒの速度で供給しながら５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出した。配管の閉塞はなかった。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率８５％，２−メチルイミダゾールの選択率は９１％であった。
【００２７】
実施例４
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１８０℃に加熱した。温度が上昇したところで、常圧，窒素気流下、ｔｅｒｔ−ブチルアルコールを３０ｍｌ／ｈｒの速度で供給しながら５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出した。配管の閉塞はなかった。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率８９％，２−メチルイミダゾールの選択率は９２％であった。
【００２８】
実施例５
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇ及びｔｅｒｔ−ブチルアルコール４４．３ｇを入れ、窒素置換した後、１８０℃に加熱した。反応中、圧力が２．５ＭＰａ以上になったら、内径１ｍｍの配管を通して脱圧し、圧力を下げ、５時間反応を行った。配管の閉塞はなかった。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率３４％，２−メチルイミダゾールの選択率は８１％であった。
【００２９】
比較例１
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１８０℃に加熱した。常圧，窒素気流下、リグロインを４ｍｌ／ｈｒの速度で供給しながら５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出しながら反応を行ったところ、１時間３０分後、配管が閉塞した。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率８２％，２−メチルイミダゾールの選択率は９１％であった。
比較例２
２００ｍｌのステンレス製オートクレーブに２−メチルイミダゾール５０．５ｇ（０．６０モル），安定化ニッケル３．０ｇを入れ、窒素置換した後、１８０℃に加熱した。常圧，窒素気流下、溶媒を供給しないで５時間反応を行った。反応中、発生する水素を内径１ｍｍの配管を通して抜き出しながら反応を行ったところ、１時間３０分後、配管が閉塞した。反応終了後、室温まで冷却し、ガスクロマトグラフィーで分析したところ、２−メチルイミダゾリンの転化率８７％，２−メチルイミダゾールの選択率は９０％であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 2-methylimidazole.
[0002]
In general, 2-methylimidazole is a very useful compound as a resin curing agent such as an epoxy resin and a polyurethane resin, a curing accelerator, various agricultural chemicals, pharmaceuticals, or dye intermediates.
[0003]
[Prior art]
Many methods are known for producing 2-methylimidazole by dehydrogenating 2-methylimidazoline.
[0004]
Japanese Examined Patent Publication No. 39-26405 describes a method of reacting in the presence of a nickel catalyst. Japanese Patent Publication No. 61-23791 discloses a method using zinc oxide as a catalyst, and Japanese Patent Publication No. 3-28426 is a method using molybdenum oxide, nickel oxide, aluminum oxide, phosphorus oxide or the like as a catalyst. Is described.
[0005]
However, since 2-methylimidazoline, which is a raw material, has a high melting point and sublimation properties, it is not easy to handle. When industrially produced, 2-methylimidazoline is solidified in a reaction apparatus or piping. Troubles such as blockage occur. Japanese Patent Publication No. 61-23791 and Japanese Patent Publication No. 3-28426 describe the use of a solvent that does not form an azeotrope with water, such as aliphatic hydrocarbons, petroleum ether, or ligroin. However, since 2-methylimidazoline does not dissolve in these solvents, it does not provide a means for solving troubles such as caking.
[0006]
[Problems to be solved by the invention]
Conventional methods are not sufficient to efficiently produce 2-methylimidazole without problems such as consolidation. Therefore, development of a method for producing 2-methylimidazole without caking problem has been desired.
[0007]
[Means for Solving the Problems]
As a result of intensive studies on the production method of 2-methylimidazole, the present inventors have conducted the reaction in the presence of alcohol, so that the desired product can be obtained in high yield without solidifying 2-methylimidazoline as a raw material. As a result, the present invention was completed as a new industrial production method of 2-methylimidazole.
[0008]
That is, this invention is a manufacturing method of 2-methylimidazole characterized by reacting in the presence of alcohol when manufacturing 2-methylimidazole from 2-methylimidazoline.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0010]
The method of the present invention is characterized by reacting in the presence of alcohol when 2-methylimidazole is produced from 2-methylimidazoline.
[0011]
In the method of the present invention, the presence of alcohol refers to the presence of an amount of alcohol in the reaction system that can prevent clogging of 2-methylimidazoline. Specifically, such an amount of alcohol is present in the reaction system. It means that the alcohol is charged in advance and refluxed by a condenser or the like during the reaction, or the reaction is carried out while supplying the alcohol into the reaction system. The supply of alcohol may be continuous or intermittent. When supplying alcohol continuously, there is no restriction | limiting in particular about the supply speed, What is necessary is just to keep reaction temperature constant.
[0012]
The alcohol supplied in the method of the present invention is not particularly limited as long as it is inert to the reaction conditions. However, it is preferable to use an alcohol that is a good solvent for imidazoline and forms an azeotrope with water. The following alcohols, specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, cyclohexanol, benzyl alcohol and the like are exemplified. Among these alcohols, it is particularly preferable to use a tertiary alcohol that does not deactivate the catalyst. Examples of the tertiary alcohol used in the method of the present invention include tert-butyl alcohol, tert-amyl alcohol, 1-methylcyclohexanol and the like. Further, among these tertiary alcohols, tert-butyl alcohol is particularly preferable from the viewpoint of boiling point.
[0013]
In the method of the present invention, the alcohol used is preferably reacted in a weight ratio of 0.1 to 10 with respect to 2-methylimidazoline 1. If it is less than 0.1, it may be difficult to eliminate troubles such as consolidation of 2-methylimidazoline, and even if it exceeds 10, the effect of increasing alcohol is small.
[0014]
In the method of the present invention, 2-methylimidazoline is reacted in the presence of a catalyst. A metal can be used as the catalyst.
[0015]
In the method of the present invention, the metal is not particularly limited. For example, magnesium, aluminum, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, yttrium, Zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury and the like. Among them, it is particularly preferable to use one or more selected from the group consisting of nickel, palladium, white and copper because of its high catalytic activity. As nickel, stabilized nickel, Raney nickel, flake nickel, or the like can be used.
[0016]
In the method of the present invention, an optimum catalyst form may be selected depending on the reaction mode, and it may be used in powder form or may be used after being molded.
[0017]
In the method of the present invention, the reaction is preferably carried out in an amount of 0.1 to 20% by weight based on 2-methylimidazoline. If it is less than 0.1% by weight, the reaction rate becomes slow, so that unreacted imidazoline is decomposed, and the yield of imidazole may be lowered. Even if it exceeds 20% by weight, the effect of increasing the catalyst is small.
[0018]
In the method of the present invention, it is preferable to replace the reactor with hydrogen or an inert gas such as nitrogen gas, helium or argon gas in consideration of by-products and coloring prevention.
[0019]
In the method of the present invention, the reaction temperature is preferably in the range of 150 to 240 ° C. Below 150 ° C., the reaction is so slow that decomposition of unreacted imidazoline occurs and the yield of imidazole decreases. When the temperature exceeds 240 ° C., decomposition of the raw material occurs, and the yield of imidazole decreases.
[0020]
The process according to the invention is carried out in the liquid phase.
[0021]
In the method of the present invention, the reaction may be carried out under normal pressure, increased pressure or reduced pressure as long as the raw material is kept in a liquid state. In this reaction, since hydrogen is generated during the reaction, the reaction pressure rises. This hydrogen may or may not be removed during the reaction, but it is preferably removed. When the reaction temperature exceeds the boiling point of the raw material, it is necessary to carry out the reaction under pressure or to provide a condenser to liquefy the raw material.
[0022]
【The invention's effect】
As described above, according to the present invention, if the reaction is carried out in the presence of alcohol, 2-methylimidazole can be efficiently produced without problems such as solidification, which is extremely significant industrially.
[0023]
【Example】
Hereinafter, the method of the present invention will be described with reference to examples, but the present invention is not limited thereto.
[0024]
Example 1
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazoline and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 180 ° C. When the temperature rose, the reaction was carried out for 5 hours while supplying tert-butyl alcohol at a rate of 4 ml / hr under normal pressure and nitrogen flow. During the reaction, generated hydrogen was extracted through a pipe having an inner diameter of 1 mm. There was no blockage of the piping. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion rate of 2-methylimidazoline was 90% and the selectivity of 2-methylimidazole was 92%.
[0025]
Example 2
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 160 ° C. When the temperature rose, the reaction was carried out for 5 hours while supplying tert-butyl alcohol at a rate of 4 ml / hr under normal pressure and nitrogen flow. During the reaction, generated hydrogen was extracted through a pipe having an inner diameter of 1 mm. There was no blockage of the piping. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 89%, and the selectivity of 2-methylimidazole was 90%.
[0026]
Reference Example A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 180 ° C. When the temperature rose, the reaction was carried out for 5 hours while supplying methyl alcohol at a rate of 4 ml / hr under normal pressure and a nitrogen stream. During the reaction, generated hydrogen was extracted through a pipe having an inner diameter of 1 mm. There was no blockage of the piping. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 85% and the selectivity for 2-methylimidazole was 91%.
[0027]
Example 4
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 180 ° C. When the temperature rose, the reaction was carried out for 5 hours while supplying tert-butyl alcohol at a rate of 30 ml / hr under normal pressure and nitrogen flow. During the reaction, generated hydrogen was extracted through a pipe having an inner diameter of 1 mm. There was no blockage of the piping. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 89% and the selectivity of 2-methylimidazole was 92%.
[0028]
Example 5
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole, 3.0 g of stabilized nickel, and 44.3 g of tert-butyl alcohol. After purging with nitrogen, the mixture was heated to 180 ° C. When the pressure became 2.5 MPa or more during the reaction, the pressure was released through a pipe having an inner diameter of 1 mm, the pressure was lowered, and the reaction was carried out for 5 hours. There was no blockage of the piping. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 34% and the selectivity for 2-methylimidazole was 81%.
[0029]
Comparative Example 1
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 180 ° C. The reaction was carried out for 5 hours while supplying ligroin at a rate of 4 ml / hr under normal pressure and nitrogen flow. During the reaction, the reaction was carried out while extracting generated hydrogen through a pipe having an inner diameter of 1 mm. After 1 hour and 30 minutes, the pipe was blocked. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 82% and the selectivity for 2-methylimidazole was 91%.
Comparative Example 2
A 200 ml stainless steel autoclave was charged with 50.5 g (0.60 mol) of 2-methylimidazole and 3.0 g of stabilized nickel, purged with nitrogen, and then heated to 180 ° C. The reaction was carried out for 5 hours without supplying solvent under normal pressure and nitrogen flow. During the reaction, the reaction was carried out while extracting generated hydrogen through a pipe having an inner diameter of 1 mm. After 1 hour and 30 minutes, the pipe was blocked. After completion of the reaction, the reaction mixture was cooled to room temperature and analyzed by gas chromatography. As a result, the conversion of 2-methylimidazoline was 87% and the selectivity for 2-methylimidazole was 90%.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03475796A JP4045604B2 (en) | 1996-02-22 | 1996-02-22 | Method for producing 2-methylimidazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03475796A JP4045604B2 (en) | 1996-02-22 | 1996-02-22 | Method for producing 2-methylimidazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09227525A JPH09227525A (en) | 1997-09-02 |
| JP4045604B2 true JP4045604B2 (en) | 2008-02-13 |
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| JP03475796A Expired - Fee Related JP4045604B2 (en) | 1996-02-22 | 1996-02-22 | Method for producing 2-methylimidazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003313172A (en) * | 2002-04-23 | 2003-11-06 | Tosoh Corp | Method for producing n-substituted imidazole |
| CN111393369B (en) * | 2020-05-13 | 2022-12-16 | 宁夏大学 | Preparation method of 2-hexyl imidazole |
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1996
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