JP2007269658A - Method for producing dialkylimidazole and dialkyl imidazole obtained thereby - Google Patents
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本発明は、ジアルキルイミダゾールの製造に際して生成する不純物を効果的に除去して不純物の少ないジアルキルイミダゾールを得ることを目的とするジアルキルイミダゾールの製造方法、およびそれにより得られるジアルキルイミダゾールに関するものである。 The present invention relates to a method for producing a dialkylimidazole for the purpose of obtaining a dialkylimidazole with few impurities by effectively removing impurities produced during the production of the dialkylimidazole, and a dialkylimidazole obtained thereby.
ジアルキルイミダゾールは、医薬品の中間体として、または各種樹脂の触媒用等、各種有機薬品分野においてその有用性が期待される化合物である。上記ジアルキルイミダゾールは、例えば、アンモニアと、第一級アミンと、アルデヒド化合物と、グリオキザールを反応させることにより製造することが知られている。 Dialkylimidazole is a compound that is expected to be useful in various organic drug fields, such as an intermediate for pharmaceuticals or as a catalyst for various resins. It is known that the dialkylimidazole is produced, for example, by reacting ammonia, a primary amine, an aldehyde compound, and glyoxal.
上記製造方法では、目的とするジアルキルイミダゾール以外に、アルキルイミダゾール等の副生成物が生成されるため、通常、これら副生成物を含む粗ジアルキルイミダゾールを蒸留することにより精製してジアルキルイミダゾールを得ることが行われている。 In the production method described above, by-products such as alkyl imidazole are produced in addition to the target dialkyl imidazole, usually, dialkyl imidazole is obtained by purification by distillation of the crude dialkyl imidazole containing these by-products. Has been done.
しかしながら、上記粗ジアルキルイミダゾールにはジアルキルイミダゾールと沸点の近似したアルキルイミダゾールが含有されており、通常の蒸留工程ではアルキルイミダゾールを除去しきれず、結果的に不純物が含有されたジアルキルイミダゾールが得られることとなる。また、不純物としてはアルキルイミダゾリウム以外にもアルキル基の付いていないイミダゾールや製品を経時で着色させてしまうような不純物なども存在することとなる。したがって、蒸留直後では透明性を有しているが、経時的に黒褐色に変色するというような結果となり、高純度のジアルキルイミダゾールを得ることが非常に困難であった。 However, the crude dialkylimidazole contains an alkylimidazole having a boiling point close to that of the dialkylimidazole, and the alkylimidazole cannot be completely removed in a normal distillation step, resulting in a dialkylimidazole containing impurities. Become. In addition to the alkyl imidazolium, there are also impurities such as imidazole having no alkyl group and impurities that cause the product to be colored over time. Therefore, although it has transparency immediately after distillation, it has resulted in a discoloration to black brown over time, and it was very difficult to obtain a high-purity dialkylimidazole.
本発明は、このような事情に鑑みなされたもので、不純物を効果的に除去し、高純度のジアルキルイミダゾールを得ることのできるジアルキルイミダゾールの製造方法およびそれにより得られるジアルキルイミダゾールの提供をその目的とする。 The present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for producing a dialkylimidazole capable of effectively removing impurities and obtaining a high-purity dialkylimidazole, and a dialkylimidazole obtained thereby. And
上記の目的を達成するため、本発明は、アンモニア、1級アミン、アルデヒドおよびグリオキザールを反応させて得た粗ジアルキルイミダゾールを蒸留しジアルキルイミダゾールを製造する方法において、粗ジアルキルイミダゾールを蒸留に先立って、60℃以上の温度で加熱処理するジアルキルイミダゾールの製造方法を第1の要旨とする。 In order to achieve the above object, the present invention provides a method for producing a dialkylimidazole by distilling a crude dialkylimidazole obtained by reacting ammonia, a primary amine, an aldehyde and glyoxal. The manufacturing method of the dialkylimidazole which heat-processes at the temperature of 60 degreeC or more is made into the 1st summary.
そして、上記ジアルキルイミダゾールの製造方法により得られてなるジアルキルイミダゾールを第2の要旨とする。 And let the dialkyl imidazole obtained by the manufacturing method of the said dialkyl imidazole be a 2nd summary.
さらに、25℃で2ヶ月放置した後のAPHA(ハーゼン単位色数)が200以下であるジアルキルイミダゾールを第3の要旨とする。 Furthermore, a third gist is a dialkylimidazole having an APHA (Hazen unit color number) of 200 or less after being left at 25 ° C. for 2 months.
すなわち、本発明者らは、粗ジアルキルイミダゾールにおける不純物を効果的に除去する方法について鋭意検討を重ねた。そして、経時的に黒褐色に変色する不純物は、製造直後の時点では着色されておらず、その状態で分離除去することが困難であることから、上記不純物を早期に着色させ除去する方法を突き止めるべくさらに研究を重ねた。その結果、粗ジアルキルイミダゾールを蒸留工程の前に、60℃以上の温度で加熱処理を行うことにより、経時的に黒褐色に変色する原因物質(不純物)の着色を促進させることが可能となることを突き止めた。そして、上記加熱後、加熱処理により着色させた不純物を蒸留により容易に除去することができ、結果、不純物の含有が極めて少ない、高純度のジアルキルイミダゾールを得ることが可能となることを見出し、本発明に到達した。 That is, the present inventors have made extensive studies on a method for effectively removing impurities in the crude dialkylimidazole. Impurities that turn blackish brown over time are not colored immediately after production and are difficult to separate and remove in that state, so a method for early coloring and removing the impurities should be determined. Further research was done. As a result, the crude dialkylimidazole can be heated at a temperature of 60 ° C. or higher before the distillation step, thereby facilitating the coloring of the causative substance (impurities) that turn blackish brown over time. I found it. Then, after the heating, the impurities colored by the heat treatment can be easily removed by distillation, and as a result, it has been found that it is possible to obtain a high-purity dialkylimidazole containing very little impurities. The invention has been reached.
このように、本発明は、粗ジアルキルイミダゾールを蒸留しジアルキルイミダゾールを製造するに際して、上記粗ジアルキルイミダゾールを蒸留に先立って、60℃以上で加熱処理するものである。このため、従来の方法では抽出等が困難であった不純物を蒸留前に着色させることができ、これを蒸留により容易に除去可能となる。このようにして得られるジアルキルイミダゾールは、ジアルキルイミダゾール生成時の副生成物である不純物の含有量の少ない高純度のジアルキルイミダゾールである。 Thus, in the present invention, when dialkylimidazole is produced by distilling crude dialkylimidazole, the crude dialkylimidazole is heat-treated at 60 ° C. or higher prior to distillation. For this reason, impurities that were difficult to extract by conventional methods can be colored before distillation, and can be easily removed by distillation. The dialkylimidazole thus obtained is a high-purity dialkylimidazole with a low content of impurities which is a by-product during the production of the dialkylimidazole.
そして、上記加熱処理を苛性アルカリ物質存在下で行うと、加熱温度を低く設定しても不純物を容易に着色させることが可能となり、蒸留により不純物を効果的に分離除去することができ、より一層高純度のジアルキルイミダゾールを得ることができる。 When the heat treatment is performed in the presence of a caustic substance, impurities can be easily colored even when the heating temperature is set low, and impurities can be effectively separated and removed by distillation. High purity dialkylimidazole can be obtained.
また、上記苛性アルカリ物質の配合量を、粗ジアルキルイミダゾールに対して1〜40モル%の範囲に設定すると、蒸留留出液に混入する水分量も調整され、より一層高純度の1,2−ジアルキルイミダゾールを得ることができる。 Moreover, when the blending amount of the caustic substance is set in the range of 1 to 40 mol% with respect to the crude dialkylimidazole, the amount of water mixed in the distilled distillate is also adjusted, and the 1,2-higher purity 1,2- Dialkylimidazoles can be obtained.
このようにして、25℃で2ヶ月放置した後のAPHAが200以下となる高純度のジアルキルイミダゾールが得られる。 In this way, a high-purity dialkylimidazole having an APHA of 200 or less after standing at 25 ° C. for 2 months is obtained.
本発明のジアルキルイミダゾールの製造方法において、精製の対象となる粗ジアルキルイミダゾールは、従来公知の方法により反応、生成されるものである。例えば、アンモニア、第一級アミン、アルデヒドおよびグリオキザールを反応媒体中で反応させることにより製造される。上記アンモニア、第一級アミンおよびグリオキザールは、通常、それぞれ水溶液として反応に供され、具体的には、上記アンモニアは5〜30重量%のアンモニア水溶液として、上記第一級アミンは30〜50重量%の水溶液として、グリオキザールは、30〜50重量%、好ましくは40重量%程度の水溶液として供給される。また、上記アルデヒドにおいては、例えば、ホルムアルデヒド、アセトアルデヒドなどの沸点の低いアルデヒド化合物は水溶液またはメタノール、エタノール、プロパノール等の低級アルコールの20〜80重量%溶液として反応に供給され、高沸点のアルデヒド化合物、例えばブチルアルデヒドのような高沸点のアルデヒドは、そのまま反応に供給される。固体のアルデヒドに関しては、低級アルコール等の溶液として反応に使用しても良い。 In the method for producing a dialkylimidazole of the present invention, the crude dialkylimidazole to be purified is produced by reaction and production by a conventionally known method. For example, it is produced by reacting ammonia, primary amine, aldehyde and glyoxal in a reaction medium. The ammonia, primary amine, and glyoxal are usually each subjected to a reaction as an aqueous solution. Specifically, the ammonia is a 5-30 wt% aqueous ammonia solution, and the primary amine is 30-50 wt%. As the aqueous solution, glyoxal is supplied as an aqueous solution of 30 to 50% by weight, preferably about 40% by weight. In the aldehyde, for example, a low-boiling aldehyde compound such as formaldehyde or acetaldehyde is supplied to the reaction as an aqueous solution or a 20 to 80% by weight solution of a lower alcohol such as methanol, ethanol or propanol. For example, a high-boiling aldehyde such as butyraldehyde is supplied to the reaction as it is. Solid aldehydes may be used in the reaction as a solution of lower alcohol or the like.
上記原料成分の添加方法としては、特に限定するものではなく、従来公知の方法、例えば、一括方式、分割方式、滴下方式等の方法があげられ、適宜選択される。また、反応時間は、通常、30分間〜10時間程度に設定される。 The method for adding the raw material components is not particularly limited, and conventionally known methods such as a batch method, a division method, a dropping method, and the like can be mentioned and appropriately selected. The reaction time is usually set to about 30 minutes to 10 hours.
上記反応において用いられる反応媒体としては、特に限定するものではなく、通常、水が用いられ、必要に応じてメタノール,エタノール,プロパノール等の水と相溶性を有する有機溶媒を適宜使用しても差し支えない。そして、上記各原料成分の仕込み組成は、モル比基準で、グリオキザール/アルデヒド化合物/第一級アミン/アンモニア/=1/1〜1.5/1〜4/1〜1.5の範囲に設定することが好適である。 The reaction medium used in the above reaction is not particularly limited, and usually water is used. If necessary, an organic solvent having compatibility with water such as methanol, ethanol, propanol or the like may be appropriately used. Absent. And the preparation composition of each said raw material component is set in the range of a glyoxal / aldehyde compound / primary amine / ammonia / = 1 / 1-1.5 / 1-4 / 1-1.5 on the molar ratio basis. It is preferable to do.
そして、このような反応により生成される上記粗ジアルキルイミダゾールとしては、精製抽出されるジアルキルイミダゾールとともに、副生成物であるアルキルイミダゾールおよびイミダゾールを含有しており、例えば、上記ジアルキルイミダゾールが粗ジアルキルイミダゾール全体の50〜90モル%、好ましくは70〜90モル%の割合で含有されているものである。 And as said crude dialkyl imidazole produced | generated by such reaction, the alkyl imidazole and imidazole which are by-products are contained with the dialkyl imidazole refined | extracted, for example, the said dialkyl imidazole contains the whole crude dialkyl imidazole. In an amount of 50 to 90 mol%, preferably 70 to 90 mol%.
本発明において、ジアルキルイミダゾールの精製方法は、上記粗ジアルキルイミダゾールを用い、つぎのようにして行われる。すなわち、上記粗ジアルキルイミダゾールを所定時間加熱することにより、ジアルキルイミダゾールを含有する油層と、水層とに分液して水層を除去する。ついで、残りの油層を減圧蒸留することにより高純度のジアルキルイミダゾールを得ることができる。 In the present invention, the method for purifying dialkylimidazole is carried out as follows using the above-mentioned crude dialkylimidazole. That is, the crude dialkylimidazole is heated for a predetermined time to separate into an oil layer containing dialkylimidazole and an aqueous layer, and the aqueous layer is removed. Then, the remaining oil layer is distilled under reduced pressure to obtain high-purity dialkylimidazole.
上記粗ジアルキルイミダゾールの加熱条件としては、60℃以上に設定する必要があり、より好ましくは120℃以上に設定する。なお、通常、加熱温度の上限は、300℃である。すなわち、加熱温度が下限値未満では、温度が低過ぎて、蒸留のみでは除去しにくい不純物を着色させることができず、上限値を超えると目的とするイミダゾールのN位の置換基が脱離して目的のジアルキルイミダゾールの収率が低下してしまうからである。また、加熱時間としては、20分間以上に設定することが好ましく、より好ましくは2〜8時間である。 The heating conditions for the crude dialkylimidazole need to be set to 60 ° C. or higher, and more preferably set to 120 ° C. or higher. In general, the upper limit of the heating temperature is 300 ° C. That is, when the heating temperature is less than the lower limit, the temperature is too low to color impurities that are difficult to remove by distillation alone, and when the upper limit is exceeded, the N-position substituent of the target imidazole is eliminated. This is because the yield of the target dialkylimidazole is lowered. Moreover, as heating time, it is preferable to set to 20 minutes or more, More preferably, it is 2 to 8 hours.
また、本発明の加熱処理は、粗ジアルキルイミダゾール溶液の液相保持圧力下において実施される。 Further, the heat treatment of the present invention is carried out under the liquid phase holding pressure of the crude dialkylimidazole solution.
そして、さらには、上記粗ジアルキルイミダゾールを加熱処理するに際して、苛性アルカリ物質存在下で加熱処理を行うことが好ましい。このように苛性アルカリ物質を添加して加熱処理を行うことにより、不純物の着色反応を促進する作用を奏することから、加熱温度を低く設定しても不純物を効果的に分離除去することができ、結果、より一層高純度のジアルキルイミダゾールを得ることができるようになる。上記苛性アルカリ物質の配合時期としては、特に限定するものではなく、蒸留前の上記加熱処理を行う際に粗ジアルキルイミダゾールに配合されていればよい。 Further, when the crude dialkylimidazole is subjected to a heat treatment, it is preferable to perform the heat treatment in the presence of a caustic substance. By performing the heat treatment by adding the caustic substance in this way, the effect of promoting the color reaction of the impurities is exerted, so that the impurities can be effectively separated and removed even if the heating temperature is set low, As a result, it becomes possible to obtain a dialkylimidazole of even higher purity. The time for blending the caustic alkali material is not particularly limited, and it may be blended with the crude dialkylimidazole when the heat treatment before distillation is performed.
上記苛性アルカリ物質としては、例えば、水酸化カリウム、水酸化ナトリウム等があげられる。これらは単独でもしくは2種以上併せて用いられる。なかでも、水に対する溶解度が高く、加熱時に水が留去しても固化しにくいという観点から、水酸化カリウムを用いることが好ましい。また、苛性アルカリ物質を配合するに際しては固体のままでも水溶液にしてもどちらでもよいが、特には取り扱いの点から水溶液として添加することが好ましい。 Examples of the caustic alkali material include potassium hydroxide and sodium hydroxide. These may be used alone or in combination of two or more. Of these, potassium hydroxide is preferably used from the viewpoint of high solubility in water and difficulty in solidification even when water is distilled off during heating. In addition, when the caustic substance is blended, it may be either solid or aqueous solution, but it is particularly preferable to add it as an aqueous solution from the viewpoint of handling.
上記苛性アルカリ物質の配合量は、粗ジアルキルイミダゾールに対して1〜40モル%の範囲に設定することが好ましく、特に好ましくは10〜30モル%である。すなわち、苛性アルカリ物質が上限値を超えて多過ぎると、蒸留留出液中に含まれる水分が多くなり、得られたジアルキルイミダゾールの純度が低下し、また、蒸留中に固化する苛性アルカリの量が多くなり、蒸留残渣に残留するジアルキルイミダゾールが多くなるという傾向がみられるからである。 The blending amount of the caustic substance is preferably set in the range of 1 to 40 mol%, particularly preferably 10 to 30 mol%, based on the crude dialkylimidazole. That is, if the amount of caustic alkali material exceeds the upper limit, the amount of water contained in the distilled distillate increases, the purity of the resulting dialkylimidazole decreases, and the amount of caustic alkali that solidifies during distillation. This is because there is a tendency to increase the amount of dialkylimidazole remaining in the distillation residue.
さらに、前述の粗ジアルキルイミダゾールの加熱条件についてより詳しく述べる。すなわち、上記加熱処理に際して苛性アルカリ物質の存在の有無により、加熱条件を細かく設定することができる。(1)苛性アルカリ物質を配合して苛性アルカリ物質存在下で加熱処理を行う場合、その加熱温度は、60〜200℃に設定することが好ましく、特に好ましくは100〜150℃である。(2)苛性アルカリ物質を用いずに苛性アルカリ物質の存在無しで加熱処理を行う場合、その加熱温度は、60〜300℃に設定することが好ましく、特に好ましくは120〜200℃である。このように、苛性アルカリ物質を用い、苛性アルカリ物質存在下で加熱処理を行う方が、苛性アルカリ物質を用いない場合よりも加熱温度を低く設定することができる。これは、苛性アルカリの存在により、不純物の着色反応が促進されているためと考えられる。 Furthermore, the heating conditions for the aforementioned crude dialkylimidazole will be described in more detail. That is, the heating conditions can be set finely depending on the presence or absence of a caustic alkali substance during the heat treatment. (1) When a caustic substance is added and heat treatment is performed in the presence of the caustic substance, the heating temperature is preferably set to 60 to 200 ° C, particularly preferably 100 to 150 ° C. (2) When heat treatment is carried out without using caustic substances without using caustic substances, the heating temperature is preferably set to 60 to 300 ° C, particularly preferably 120 to 200 ° C. As described above, the heating temperature can be set lower when the caustic substance is used and the heat treatment is performed in the presence of the caustic substance than when the caustic substance is not used. This is presumably because the coloring reaction of impurities is promoted by the presence of caustic.
つぎに、上記粗ジアルキルイミダゾールを所定条件で加熱処理した後、静置して油層と水層に分液して、水層を除去する。ついで、上記油層を減圧蒸留することにより目的とするジアルキルイミダゾールを得ることができる。 Next, the above-mentioned crude dialkylimidazole is heat-treated under predetermined conditions, and then allowed to stand to separate into an oil layer and an aqueous layer, and the aqueous layer is removed. Subsequently, the target dialkylimidazole can be obtained by distilling the oil layer under reduced pressure.
上記油層の減圧蒸留としては、従来公知の方法にて行うことができ、例えば、圧力250〜14000Paの減圧条件下、温度60〜180℃での蒸留、特に好ましくは250〜7000Paで温度60〜130℃での蒸留を行い、不純物を留去して目的とする高純度のジアルキルイミダゾールを得ることができる。 The distillation under reduced pressure of the oil layer can be carried out by a conventionally known method. For example, distillation at a temperature of 60 to 180 ° C., particularly preferably 250 to 7000 Pa and a temperature of 60 to 130, under a reduced pressure of 250 to 14000 Pa. Distillation at 0 ° C. allows the impurities to be distilled off to obtain the desired high-purity dialkylimidazole.
このようにして得られるジアルキルイミダゾールは、不純物の含有合計量が2.5重量%未満の高純度のものである。なお、上記不純物の含有合計量、すなわち純度の定量としては、通常、水素炎イオン化検出器を付帯したガスクロマトグラフが用いられる。 The dialkylimidazole thus obtained has a high purity with the total content of impurities being less than 2.5% by weight. Note that a gas chromatograph with a flame ionization detector is usually used as a quantitative determination of the total content of impurities, that is, purity.
そして、このようにして得られたジアルキルイミダゾールとしては、濃度99%以上で、25℃で2ヶ月放置した後のAPHA(ハーゼン単位色数)が200以下となるようなジアルキルイミダゾールが得られる。好ましくは、25℃で2ヶ月放置後のAPHA(ハーゼン単位色数)が100以下である。なお、上記APHA(ハーゼン単位色数)は、色の判定方法であり、JIS K0071−1におけるハーゼン単位色数であって、ISO 6271に準拠するものである。 As the dialkylimidazole thus obtained, a dialkylimidazole having a concentration of 99% or more and an APHA (Hazen unit color number) of 200 or less after standing at 25 ° C. for 2 months is obtained. Preferably, APHA (Hazen unit color number) after standing at 25 ° C. for 2 months is 100 or less. The APHA (Hazen unit color number) is a color determination method, which is the Hazen unit color number in JIS K0071-1, and conforms to ISO 6271.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。また、以下、「%」は重量基準である。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example, unless the summary is exceeded. Hereinafter, “%” is based on weight.
〔KOH使用+加熱温度120℃〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液に、粗1,2−ジメチルイミダゾールに対して水酸化カリウムを10モル%加えて常圧濃縮し、濃縮液温が120℃になった時点で2時間還流させた。ついで、これを静置して下層の水層と上層の油層とに分液し、下層の水層を除去した後、残りの油層を減圧蒸留(条件:2670Pa、90〜130℃)することにより純度99.8%の1,2−ジメチルイミダゾールを79g(収率82%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは40)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視により観察した結果、わずかに色度合いが変化したのみであり、そのときのAPHAは50であった。
[KOH use + heating temperature 120 ° C]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. To the obtained yellow solution, 10 mol% of potassium hydroxide was added to the crude 1,2-dimethylimidazole and concentrated under normal pressure, and the mixture was refluxed for 2 hours when the temperature of the concentrated solution reached 120 ° C. Next, this is left standing to separate into a lower aqueous layer and an upper oil layer, and after removing the lower aqueous layer, the remaining oil layer is distilled under reduced pressure (conditions: 2670 Pa, 90 to 130 ° C.). This was obtained as 79 g of 1,2-dimethylimidazole having a purity of 99.8% (yield 82%, charged glyoxal) as a slightly yellow solid (APHA in the melt was 40). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, the color degree was slightly changed, and the APHA at that time was 50.
なお、上記収率の測定には、ガスクロマトグラフを用い、詳細には、カラム:Agilent製 HP−WAX 0.53mm×30m×1.0μm、カラム温度:70℃から10℃/分で220℃まで昇温し220℃で10分保持、注入口:220℃、検出器(水素炎イオン化検出器):250℃、キャリアーガス:ヘリウム 20mL/分の条件にて、内部標準法にて測定した。 In addition, a gas chromatograph was used for the measurement of the yield, and in detail, column: HP-WAX 0.53 mm × 30 m × 1.0 μm manufactured by Agilent, column temperature: from 70 ° C. to 220 ° C. at 10 ° C./min. The temperature was raised and held at 220 ° C. for 10 minutes, the inlet: 220 ° C., detector (hydrogen flame ionization detector): 250 ° C., carrier gas: helium 20 mL / min.
また、上記純度の測定には、ガスクロマトグラフを用い、詳細には上記収率と同じ測定条件で、融解した1,2−ジメチルイミダゾールを測定し得られたクロマトクロマトグラムの面積%を純度とした。 The purity was measured using a gas chromatograph, and in detail, the area% of the chromatochromatogram obtained by measuring melted 1,2-dimethylimidazole under the same measurement conditions as the yield was defined as the purity. .
そして、上記APHAは、APHA標準液との比色を行い測定した。 The APHA was measured by performing colorimetry with the APHA standard solution.
〔KOH使用+加熱温度60℃〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液に、粗1,2−ジメチルイミダゾールに対して水酸化カリウムを30モル%加えて、6670Paで減圧濃縮し、60℃になった時点で8時間還流させた。ついで、これを静置して下層の水層と上層の油層とに分液し、下層の水層を除去した後、残りの油層を減圧蒸留(条件:2670Pa、90〜130℃)することにより、99.1%の1,2−ジメチルイミダゾールを75g、(収率78%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは50)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視により観察したところ、わずかに色度合いが進行しており、そのときのAPHAは70であった。
[KOH use + heating temperature 60 ° C]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. To the obtained yellow solution, 30 mol% of potassium hydroxide was added to the crude 1,2-dimethylimidazole, concentrated under reduced pressure at 6670 Pa, and refluxed for 8 hours when the temperature reached 60 ° C. Next, this is left standing to separate into a lower aqueous layer and an upper oil layer, and after removing the lower aqueous layer, the remaining oil layer is distilled under reduced pressure (conditions: 2670 Pa, 90 to 130 ° C.). , 99.1% of 1,2-dimethylimidazole (yield 78%, charged glyoxal), a pale yellow solid (APHA in the melt was 50). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, the color degree was slightly advanced, and the APHA at that time was 70.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行い測定した。 The above yield and purity were measured in the same manner as in Example 1. Further, the APHA was also measured by performing colorimetry with the APHA standard solution in the same manner as in Example 1.
〔KOH使用+加熱温度200℃〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ、黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液に、粗1,2−ジメチルイミダゾールに対して水酸化カリウムを3モル%加えて常圧濃縮し、濃縮液が200℃になった時点で2時間還流させた。ついで、減圧蒸留をすることにより、98.7%の1,2−ジメチルイミダゾールを61g(収率63%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは20)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月放置した後、目視により観察した結果、わずかに色度合いが変化したのみであり、そのときのAPHAは50であった。
[KOH use + heating temperature 200 ° C]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. To the obtained yellow solution, 3 mol% of potassium hydroxide was added to the crude 1,2-dimethylimidazole and concentrated under normal pressure. When the concentrated solution reached 200 ° C., it was refluxed for 2 hours. Then, by distillation under reduced pressure, 98.7% of 1,2-dimethylimidazole was obtained as 61 g (yield 63%, charged glyoxal) as a slightly yellow solid (APHA of the melt was 20). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, the color degree slightly changed, and the APHA at that time was 50.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行い測定した。 The above yield and purity were measured in the same manner as in Example 1. Further, the APHA was also measured by performing colorimetry with the APHA standard solution in the same manner as in Example 1.
〔KOH無し+加熱温度180℃〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液を常圧濃縮し、濃縮液温が180℃になった時点で8時間還流させた。ついで、これを減圧蒸留(条件:2679Pa、90〜130℃)することにより純度97.6%の1,2−ジメチルイミダゾールを64g(収率67%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは90)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視により観察した結果、若干色度合いが変化したが極端な着色の変化はみられなかった。そのときのAPHAは180であった。
[No KOH + Heating temperature 180 ° C]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. The resulting yellow solution was concentrated under normal pressure, and refluxed for 8 hours when the temperature of the concentrated solution reached 180 ° C. Subsequently, this was distilled under reduced pressure (conditions: 2679 Pa, 90 to 130 ° C.) to give 64 g of 1,2-dimethylimidazole with a purity of 97.6% (yield 67%, charged glyoxal), slightly yellow solid (melt) APHA was obtained as 90). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then observed with the naked eye. As a result, the degree of color was slightly changed, but no extreme color change was observed. APHA at that time was 180.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行い測定した。 The above yield and purity were measured in the same manner as in Example 1. Further, the APHA was also measured by performing colorimetry with the APHA standard solution in the same manner as in Example 1.
〔KOH無し+加熱温度300℃〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液を常圧濃縮し、内温が180℃になった時点でオートクレーブに封じ込めて、850000〜900000Paになるよう調整しながら、300℃で4時間加熱した。ついで減圧蒸留(条件:2670Pa、90〜130℃)するにより純度97.8%の1,2−ジメチルイミダゾールを55g(収率57%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは60)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視で観察した結果、若干色度合いが変化したが極端な着色の変化は見られなかった。そのときのAPHAは160であった。
[No KOH + heating temperature 300 ° C]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. The obtained yellow solution was concentrated at normal pressure, and when the internal temperature reached 180 ° C., it was sealed in an autoclave and heated at 300 ° C. for 4 hours while adjusting to 850000 to 900,000 Pa. Subsequently, 55 g of 1,2-dimethylimidazole having a purity of 97.8% (yield 57%, charged glyoxal) by distillation under reduced pressure (conditions: 2670 Pa, 90 to 130 ° C.), slightly yellow solid (APHA of the melt was 60 ) Was obtained. The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, although the degree of color was slightly changed, no extreme color change was observed. APHA at that time was 160.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行い測定した。 The above yield and purity were measured in the same manner as in Example 1. Further, the APHA was also measured by performing colorimetry with the APHA standard solution in the same manner as in Example 1.
〔比較例1〕
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(75.5g、1.2mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液を減圧蒸留(条件:2670Pa、95〜130℃)することにより純度95%の1,2−ジメチルイミダゾールを70g(収率73%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは200)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視により観察した結果、黒褐色に変色していた。そのときのAPHAは1000以上であり、測定不能であった。
[Comparative Example 1]
40% aqueous solution of glyoxal (145.0 g, 1 mol), 40% aqueous solution of methylamine (77.8 g, 1 mol), 25% aqueous solution of ammonia (68.0 g, 1 mol) and 70% aqueous solution of acetaldehyde (75.5 g, 1.2 mol) Was reacted at 50 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. The obtained yellow solution was distilled under reduced pressure (conditions: 2670 Pa, 95-130 ° C.) to obtain 70 g of 1,2-dimethylimidazole having a purity of 95% (yield 73%, charged glyoxal), slightly yellow solid (melting solution) APHA was obtained as 200). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, the color turned blackish brown. APHA at that time was 1000 or more, and measurement was impossible.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行った。 The above yield and purity were measured in the same manner as in Example 1. The APHA was also colorimetrically compared with the APHA standard solution, as in Example 1.
〔比較例2〕
(加熱温度が50℃)
40%グリオキザール水溶液(145.0g、1mol)、40%メチルアミン水溶液(77.8g、1mol)、25%アンモニア水溶液(68.0g、1mol)および70%アセトアルデヒド水溶液(62.9g、1mol)を50℃で3時間反応させ黄色溶液(粗ジアルキルイミダゾール溶液)が得られた。そして、上記黄色溶液である反応混合物をガスクロマトグラフで定量した結果、1,2−ジメチルイミダゾールが87g(収率90%)含有されていた。得られた黄色溶液を6670Paにて減圧濃縮し、濃縮液温が50℃になった時点で2時間還流させた。ついで、これを静置して下層の水層と上層の油層とに分液し、下層の水層を除去した後、油層を減圧蒸留(条件:2670Pa、95〜130℃)することにより純度95%の1,2−ジメチルイミダゾールを66g(収率69%、対仕込みグリオキザール)、微黄色固体(融解液のAPHAは150)として得られた。得られた1,2−ジメチルイミダゾールを25℃で2ヶ月間放置した後、目視により観察した結果、黒褐色に変化していた。そのときのAPHAは1000以上であり、測定不能であった。
[Comparative Example 2]
(Heating temperature is 50 ° C)
50% aqueous 40% glyoxal solution (145.0 g, 1 mol), 40% aqueous methylamine solution (77.8 g, 1 mol), 25% aqueous ammonia solution (68.0 g, 1 mol) and 70% aqueous acetaldehyde solution (62.9 g, 1 mol) The reaction was carried out at 0 ° C. for 3 hours to obtain a yellow solution (crude dialkylimidazole solution). And as a result of quantifying the reaction mixture which is the said yellow solution with a gas chromatograph, 87g (yield 90%) of 1, 2- dimethylimidazole was contained. The resulting yellow solution was concentrated under reduced pressure at 6670 Pa, and refluxed for 2 hours when the temperature of the concentrated solution reached 50 ° C. Next, this was allowed to stand to separate into a lower aqueous layer and an upper oil layer, and after removing the lower aqueous layer, the oil layer was distilled under reduced pressure (conditions: 2670 Pa, 95 to 130 ° C.) to obtain a purity of 95. % 1,2-dimethylimidazole (yield 69%, vs. charged glyoxal) as a pale yellow solid (APHA in the melt was 150). The obtained 1,2-dimethylimidazole was allowed to stand at 25 ° C. for 2 months and then visually observed. As a result, it turned blackish brown. APHA at that time was 1000 or more, and measurement was impossible.
なお、上記収率,純度の測定は、実施例1と同様にして行った。また、上記APHAも、実施例1と同様、APHA標準液との比色を行った。 The above yield and purity were measured in the same manner as in Example 1. The APHA was also colorimetrically compared with the APHA standard solution, as in Example 1.
本発明は、例えば、医薬品中間体、染料の中間体、さらにはエポキシ樹脂やポリウレタン樹脂等の各種樹脂の触媒等に有用となる高純度なジアルキルイミダゾールを得るための製造方法である。
The present invention is a production method for obtaining a high-purity dialkylimidazole useful for, for example, pharmaceutical intermediates, dye intermediates, and catalysts for various resins such as epoxy resins and polyurethane resins.
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JPS62164672A (en) * | 1986-01-16 | 1987-07-21 | Nippon Synthetic Chem Ind Co Ltd:The | Production of 1,2-dimethylimidazole |
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