JPH08295675A - Production of 2-imidazoline - Google Patents
Production of 2-imidazolineInfo
- Publication number
- JPH08295675A JPH08295675A JP7106224A JP10622495A JPH08295675A JP H08295675 A JPH08295675 A JP H08295675A JP 7106224 A JP7106224 A JP 7106224A JP 10622495 A JP10622495 A JP 10622495A JP H08295675 A JPH08295675 A JP H08295675A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- reaction
- compound
- metal oxide
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、イミダゾリン類の製造
法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing imidazolines.
【０００２】[0002]
【従来の技術】ジアミン化合物及びニトリル化合物を原
料とする２−イミダゾリンの製造には、以下の方法が知
られている。The following method is known for producing 2-imidazoline using a diamine compound and a nitrile compound as raw materials.
【０００３】特公昭３９−２４９６５号公報には、硫黄
の存在下で反応させる方法が記載されている。硫黄を触
媒とする方法は、反応中に極めて毒性の高い硫化水素が
副生する他、イミダゾリンからイミダゾールを製造する
場合、残存する硫黄が触媒のＮｉを被毒し、反応を阻害
する等の問題があった。Japanese Patent Publication No. 39-24965 discloses a method of reacting in the presence of sulfur. In the method using sulfur as a catalyst, extremely toxic hydrogen sulfide is produced as a by-product during the reaction, and when imidazole is produced from imidazoline, residual sulfur poisons Ni of the catalyst and inhibits the reaction. was there.
【０００４】この問題を解決するために、特公平５−３
９９４３号公報には酢酸銅、塩化銅等の銅塩触媒、特開
昭６２−１９５３６９号公報には酢酸亜鉛、塩化亜鉛等
亜鉛塩を触媒とする方法が記載されている。酢酸銅、酢
酸亜鉛を使うと、硫化水素の副生はみられないものの、
酢酸イオン等の不純物が反応系に入るため、生成物が酢
酸塩等の塩になり、精製を必要とする。また、銅、亜鉛
の塩化物を使用した場合は、塩化物イオンのため生じる
装置の腐食が問題となる。In order to solve this problem, Japanese Patent Publication No. 5-3
JP-A-9943 discloses a method of using a copper salt catalyst such as copper acetate and copper chloride, and JP-A-62-195369 discloses a method using a zinc salt such as zinc acetate and zinc chloride as a catalyst. When copper acetate and zinc acetate are used, hydrogen sulfide by-product is not seen,
Since impurities such as acetate ions enter the reaction system, the product becomes a salt such as acetate and requires purification. Further, when copper and zinc chlorides are used, the corrosion of the equipment caused by chloride ions poses a problem.
【０００５】[0005]
【発明が解決しようとする課題】従来の方法は、硫化水
素が副生する、反応を阻害する、精製を必要とする、装
置腐食がおこる等の問題があり、十分なレベルに達して
いるとは言い難い。The conventional method has problems that hydrogen sulfide is by-produced, reaction is hindered, purification is required, equipment corrosion occurs, etc., and it has reached a sufficient level. Is hard to say.
【０００６】本発明は上記の課題に鑑みてなされたもの
であり、その目的は、これらの欠点を解消したすなわ
ち、分離、精製が必要であり装置腐食の原因となる塩を
触媒とせず、硫化水素を副生しない２−イミダゾリン類
の製造法の提供にある。The present invention has been made in view of the above-mentioned problems, and an object thereof is to solve these drawbacks, that is, to perform sulfurization without using a salt that requires separation and purification and causes apparatus corrosion as a catalyst. The present invention provides a method for producing 2-imidazolines that do not produce hydrogen as a by-product.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、イミダゾ
リン類の製造法について鋭意検討した結果、触媒として
金属酸化物を使用することによって、硫化水素の発生も
無く、また塩触媒を使用した場合生じるイオンによる汚
染、腐食という問題も無く、イミダゾリン類の製造が可
能であるという新規な事実を見いだし、本発明を完成さ
せるに至った。すなわち、本発明は、１，２−ジアミン
化合物とニトリル化合物を反応させて２−イミダゾリン
類を製造する際に、金属酸化物の存在下で反応を行うこ
とを特徴とする２−イミダゾリン類の製造法である。Means for Solving the Problems The inventors of the present invention have made extensive studies on a method for producing imidazolines, and as a result, by using a metal oxide as a catalyst, hydrogen sulfide was not generated and a salt catalyst was used. The present invention has been completed by discovering the novel fact that imidazolines can be produced without the problems of ion contamination and corrosion that may occur. That is, the present invention is characterized in that, when a 1,2-diamine compound and a nitrile compound are reacted to produce a 2-imidazoline, the reaction is carried out in the presence of a metal oxide. Is the law.
【０００８】以下に本発明をさらに詳細に説明する。The present invention will be described in more detail below.
【０００９】本発明の方法において使用される触媒は金
属酸化物である。本発明においては金属酸化物として金
属水酸化物を含む。The catalyst used in the method of the present invention is a metal oxide. In the present invention, a metal hydroxide is included as the metal oxide.
【００１０】本発明においていう金属酸化物としては、
例えば酸化アルミニウム、二酸化ケイ素、酸化チタン、
酸化バナジウム、酸化クロム、酸化マンガン、酸化鉄、
酸化コバルト、酸化ニッケル、酸化銅、酸化亜鉛、酸化
イットリウム、酸化ジルコニウム、酸化ニオブ、酸化モ
リブデン、酸化銀、酸化カドミウム、酸化インジウム、
酸化すず、酸化タンタル、酸化タングステン、酸化レニ
ウム、酸化鉛、酸化ランタン、酸化セリウム等が挙げら
れるが、その中でも酸化銅、酸化亜鉛、酸化ニオブが特
に好ましい。酸化銅には、酸化銅（Ｉ）、酸化銅（Ｉ
Ｉ）があるが、どちらを使用しても良い。また、銅水酸
化物も酸化物と同様に使用することができる。亜鉛、ニ
オブについても、酸化物と同様に水酸化物を使用でき
る。The metal oxide in the present invention includes
For example, aluminum oxide, silicon dioxide, titanium oxide,
Vanadium oxide, chromium oxide, manganese oxide, iron oxide,
Cobalt oxide, nickel oxide, copper oxide, zinc oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide, silver oxide, cadmium oxide, indium oxide,
Examples thereof include tin oxide, tantalum oxide, tungsten oxide, rhenium oxide, lead oxide, lanthanum oxide, and cerium oxide. Among them, copper oxide, zinc oxide, and niobium oxide are particularly preferable. Copper oxide includes copper oxide (I) and copper oxide (I
I), but either may be used. Further, copper hydroxide can be used as well as the oxide. For zinc and niobium, hydroxides can be used as well as oxides.
【００１１】本発明において金属酸化物を担体に担持し
て使用しても良い。担体としては、シリカ、アルミナ等
の酸化物、シリカ−アルミナ等の複合酸化物、活性炭、
多孔質ガラス、多孔質セラミックス等が使用できる。In the present invention, a metal oxide may be supported on a carrier and used. As the carrier, silica, oxides such as alumina, composite oxides such as silica-alumina, activated carbon,
Porous glass, porous ceramics, etc. can be used.
【００１２】また金属酸化物は他の金属酸化物と混合し
ても使用できる。例えば、銅クロマイト、酸化銅−酸化
亜鉛等も使用できる。The metal oxide can also be used by mixing with other metal oxides. For example, copper chromite, copper oxide-zinc oxide and the like can also be used.
【００１３】本発明の方法において使用される原料は、
１，２−ジアミン化合物とニトリル化合物である。１，
２−ジアミン化合物は下記一般式（１）で示される化合
物であり、 Ｈ2ＮＣＨＲ1ＣＨＲ2ＮＨＲ3 （１） （式中、Ｒ1、Ｒ2、Ｒ3は、各々独立して水素、脂肪
族、芳香脂肪族、芳香族の基を意味する）ニトリル化合
物は下記一般式（２）で示される化合物である。The raw materials used in the method of the present invention are:
A 1,2-diamine compound and a nitrile compound. 1,
The 2-diamine compound is a compound represented by the following general formula (1): H 2 NCHR 1 CHR 2 NHR 3 (1) (In the formula, R 1 , R 2 , and R 3 are independently hydrogen and fat. A nitrile compound (meaning an aromatic group, an araliphatic group, or an aromatic group) is a compound represented by the following general formula (2).
【００１４】Ｒ4ＣＮ （２） （式中、Ｒ4は、各々独立して水素、脂肪族、芳香脂肪
族、芳香族の基を意味する） １，２−ジアミン化合物としては、特に限定するもので
はないが、エチレンジアミン、プロピレンジアミン、ブ
チレンジアミン、ペンチレンジアミン、ヘキシレンジア
ミン、オクチレンジアミン、ノニレンジアミン、デシレ
ンジアミン、シクロヘキシルエチレンジアミン、ベンジ
ルエチレンジアミン、フェニルエチレンジアミン、メト
キシフェニルエチレンジアミン、ジメチルフェニルエチ
レンジアミン、トリルエチレンジアミン、Ｎ−ブチルエ
チレンジアミン、Ｎ−イソブチルエチレンジアミン、Ｎ
−メチルエチレンジアミン、Ｎ−エチルエチレンジアミ
ン、Ｎ−シクロヘキシルエチレンジアミン、Ｎ−ベンジ
ルエチレンジアミン、Ｎ−フェニルエチレンジアミン、
Ｎ−メトキシフェニルエチレンジアミン、Ｎ−ジメチル
フェニルエチレンジアミン、Ｎ−トリルエチレンジアミ
ン等が例示される。R 4 CN (2) (In the formula, each R 4 independently represents hydrogen, aliphatic, araliphatic or aromatic group.) The 1,2-diamine compound is not particularly limited. Although not a thing, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, octylenediamine, nonylenediamine, decylenediamine, cyclohexylethylenediamine, benzylethylenediamine, phenylethylenediamine, methoxyphenylethylenediamine, dimethylphenylethylenediamine, Tolylethylenediamine, N-butylethylenediamine, N-isobutylethylenediamine, N
-Methylethylenediamine, N-ethylethylenediamine, N-cyclohexylethylenediamine, N-benzylethylenediamine, N-phenylethylenediamine,
Examples include N-methoxyphenylethylenediamine, N-dimethylphenylethylenediamine, N-tolylethylenediamine and the like.
【００１５】またニトリル化合物としては、特に限定す
るものではないが、アセトニトリル、プロピオニトリ
ル、イソブチロニトリル、２−エチルヘキシロニトリ
ル、ラウロニトリル、ステアロニトリル、シクロヘキシ
ルニトリル、フェニルアセトニトリル、フェニルプロピ
オニトリル、ベンゾニトリル、メチルベンゾニトリル、
ジメチルベンゾニトリル、メトキシベンゾニトリル、ジ
メチルベンゾニトリル、ナフトニトリル、シアノピリジ
ン、マロンニトリル、アジポニトリル、フタロニトリ
ル、ジシアノジフェニル等が例示される。１，２−ジア
ミン化合物とニトリル化合物は化学当量又は一方の過剰
で反応を行うことができる。The nitrile compound is not particularly limited, but acetonitrile, propionitrile, isobutyronitrile, 2-ethylhexylonitrile, lauronitrile, stearonitrile, cyclohexylnitrile, phenylacetonitrile, phenylpropiotium is used. Nitrile, benzonitrile, methylbenzonitrile,
Examples thereof include dimethylbenzonitrile, methoxybenzonitrile, dimethylbenzonitrile, naphthonitrile, cyanopyridine, malonnitrile, adiponitrile, phthalonitrile and dicyanodiphenyl. The 1,2-diamine compound and the nitrile compound can be reacted in stoichiometric equivalent or in excess of one.
【００１６】本発明の方法において、反応温度は通常１
００〜３００℃の範囲で行うことができるが、１５０〜
２５０℃で行うことが好ましい。１００℃未満では、反
応は実用的でないほど遅く、３００℃以上では、アミン
類の分解が生じ、イミダゾリン類の収率が低下する。In the method of the present invention, the reaction temperature is usually 1.
It can be carried out in the range of 00 to 300 ° C., but 150 to
It is preferable to carry out at 250 ° C. If the temperature is lower than 100 ° C, the reaction is impractically slow, and if the temperature is higher than 300 ° C, the amines are decomposed and the yield of the imidazolines is lowered.
【００１７】本発明の方法は通常液相で実施される。The process of the invention is usually carried out in the liquid phase.
【００１８】本発明の方法において、反応は、原料を液
状に保てれば良く、常圧、又は加圧下で行うことができ
る。この反応では、反応中にアンモニアが生成するため
反応圧力が上昇するが、このアンモニアは反応途中で除
去することもできるし、反応が終了してから除去するこ
ともできる。反応温度が原料の沸点を越えている場合
は、加圧下で反応を実施するか、凝縮器を設け、原料を
液化する必要がある。In the method of the present invention, the reaction may be carried out at a normal pressure or under pressure as long as the raw materials are kept in a liquid state. In this reaction, the reaction pressure rises because ammonia is produced during the reaction, but this ammonia can be removed during the reaction or can be removed after the reaction is completed. When the reaction temperature exceeds the boiling point of the raw material, it is necessary to carry out the reaction under pressure or to liquefy the raw material by providing a condenser.
【００１９】本発明の方法においては、溶媒を使用して
もしなくても良い。溶媒としては、反応条件に不活性な
ものであれば特に制限はなく、水等イミダゾリン類を分
解するものの使用は好ましくない。A solvent may or may not be used in the method of the present invention. The solvent is not particularly limited as long as it is inert to the reaction conditions, and it is not preferable to use a solvent such as water that decomposes imidazolines.
【００２０】本発明の方法は、連続反応で実施しても良
いし、回分反応、半回分反応で実施しても良い。また、
固定床でも懸濁床でも反応できる。触媒の形態は、反応
形式によって、最適なものを選択すれば良く、粉末で使
用しても良いし、成型して使用しても良い。The method of the present invention may be carried out as a continuous reaction, a batch reaction or a semi-batch reaction. Also,
The reaction can be carried out on a fixed bed or a suspension bed. As for the form of the catalyst, an optimum one may be selected depending on the reaction mode, and it may be used in the form of powder or may be used by molding.
【００２１】本発明の方法においては、反応生成物のイ
ミダゾリン類は、精製しても、精製せずに、脱水素して
イミダゾールとしても良い。イミダゾリン類の精製方法
は蒸留、再結晶等種々の方法が知られているが、どの方
法を用いても一向に差支えない。In the method of the present invention, the imidazolines of the reaction product may be purified or may be dehydrogenated to be imidazole without being purified. Various methods such as distillation and recrystallization are known as methods for purifying imidazolines, but any method can be used.
【００２２】[0022]
【実施例】以下、本発明を実施例にて説明するが、本発
明はこれらに限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００２３】実施例１ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
酸化銅（ＩＩ）：４．５ｇを入れ、窒素置換した後、２
００℃に加熱した。反応圧力が２．５ＭＰａ以上になっ
たら、脱圧し、圧力を下げ、３時間反応した。反応終了
後、これを冷却し、ガスクロマトグラフィーで分析した
ところ、エチレンジアミン転化率は６８％であり、２−
メチルイミダゾリンの選択率は９５％であった。Example 1 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g and copper (II) oxide: 4.5 g were put in a 200 ml autoclave made of stainless steel, and after nitrogen substitution, 2
Heated to 00 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of ethylenediamine was 68%.
The selectivity of methylimidazoline was 95%.
【００２４】実施例２ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
酸化銅（Ｉ）：４．５ｇを入れ、窒素置換した後、２０
０℃に加熱した。反応圧力が２．５ＭＰａ以上になった
ら、脱圧し、圧力を下げ、３時間反応した。反応終了
後、これを冷却し、ガスクロマトグラフィーで分析した
ところ、エチレンジアミン転化率は４２％であり、２−
メチルイミダゾリンの選択率は８９％であった。Example 2 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g and copper (I) oxide: 4.5 g were put into a 200 ml autoclave made of stainless steel, and after purging with nitrogen, 20
Heated to 0 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the ethylenediamine conversion rate was 42%.
The selectivity of methyl imidazoline was 89%.
【００２５】実施例３ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
マンガン酸化物を添加した銅クロマイト（堺化学（株）
製）：４．５ｇを入れ、窒素置換した後、２００℃に加
熱した。反応圧力が２．５ＭＰａ以上になったら、脱圧
し、圧力を下げ、３時間反応した。反応終了後、これを
冷却し、ガスクロマトグラフィーで分析したところ、エ
チレンジアミン転化率は５１％であり、２−メチルイミ
ダゾリンの選択率は９７％であった。Example 3 Copper chromite (Sakai Chemical Co., Ltd.) in which ethylenediamine: 60.1 g, acetonitrile: 45.2 g and manganese oxide were added to a 200 ml stainless steel autoclave.
(Manufactured): 4.5 g was added, and the atmosphere was replaced with nitrogen, and then heated to 200 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours. After completion of the reaction, this was cooled and analyzed by gas chromatography. As a result, the ethylenediamine conversion rate was 51% and the 2-methylimidazoline selectivity was 97%.
【００２６】実施例４ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
酸化銅（ＩＩ）：４．５ｇを入れ、窒素置換した後、１
８０℃に加熱した。反応圧力が２．５ＭＰａ以上になっ
たら、脱圧し、圧力を下げ、３時間反応した。反応終了
後、これを冷却し、ガスクロマトグラフィーで分析した
ところ、エチレンジアミン転化率は６２％であり、２−
メチルイミダゾリンの選択率は７４％であった。Example 4 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g and copper (II) oxide: 4.5 g were put into a 200 ml stainless steel autoclave, and the atmosphere was replaced with nitrogen.
Heated to 80 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours. After completion of the reaction, this was cooled and analyzed by gas chromatography to find that the ethylenediamine conversion rate was 62%.
The selectivity of methyl imidazoline was 74%.
【００２７】実施例５ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
酸化ニオブ（ＣＢＭＭ社製）：４．５ｇを入れ、窒素置
換した後、２００℃に加熱した。反応圧力が２．５ＭＰ
ａ以上になったら、脱圧し、圧力を下げ、３時間反応し
た。反応終了後、これを冷却し、ガスクロマトグラフィ
ーで分析したところ、エチレンジアミン転化率は５３％
であり、２−メチルイミダゾリンの選択率は１００％で
あった。Example 5 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g and niobium oxide (manufactured by CBMM): 4.5 g were put into a 200 ml stainless steel autoclave, and after nitrogen substitution, the mixture was heated to 200 ° C. Reaction pressure is 2.5MP
When it became a or more, the pressure was released, the pressure was lowered, and the reaction was carried out for 3 hours. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of ethylenediamine was 53%.
And the selectivity for 2-methylimidazoline was 100%.
【００２８】実施例６ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
酸化亜鉛をシリカに担持した触媒（２０重量％酸化亜
鉛、８０重量％シリカ）：４．５ｇを入れ、窒素置換し
た後、２００℃に加熱した。反応圧力が２．５ＭＰａ以
上になったら、脱圧し、圧力を下げ、３時間反応した。
反応終了後、これを冷却し、ガスクロマトグラフィーで
分析したところ、エチレンジアミン転化率は２０％であ
り、２−メチルイミダゾリンの選択率は９６％であっ
た。Example 6 A 200 ml stainless autoclave was charged with ethylenediamine: 60.1 g, acetonitrile: 45.2 g, and a catalyst in which zinc oxide was supported on silica (20 wt% zinc oxide, 80 wt% silica): 4.5 g. After purging with nitrogen, it was heated to 200 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours.
After completion of the reaction, this was cooled and analyzed by gas chromatography. As a result, the ethylenediamine conversion rate was 20% and the 2-methylimidazoline selectivity was 96%.
【００２９】実施例７ ２００ｍｌのステンレス製オートクレーブにエチレンジ
アミン：６０．１ｇ、アセトニトリル：４５．２ｇ及び
水酸化亜鉛：４．５ｇを入れ、窒素置換した後、２００
℃に加熱した。反応圧力が２．５ＭＰａ以上になった
ら、脱圧し、圧力を下げ、３時間反応した。反応終了
後、これを冷却し、ガスクロマトグラフィーで分析した
ところ、エチレンジアミン転化率は２１％であり、２−
メチルイミダゾリンの選択率は８３％であった。Example 7 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g and zinc hydroxide: 4.5 g were put into a 200 ml stainless steel autoclave, and after nitrogen substitution, 200
Heated to ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours. After completion of the reaction, this was cooled and analyzed by gas chromatography to find that the ethylenediamine conversion rate was 21%.
The selectivity of methylimidazoline was 83%.
【００３０】実施例８ ２００ｍｌのステンレス製オートクレーブに１，２−プ
ロパンジアミン：７４．１ｇ、アセトニトリル：４５．
２ｇ及び酸化銅（ＩＩ）：４．５ｇを入れ、窒素置換し
た後、２００℃に加熱した。反応圧力が２．５ＭＰａ以
上になったら、脱圧し、圧力を下げ、３時間反応した。
反応終了後、これを冷却し、ガスクロマトグラフィーで
分析したところ、１，２−プロパンジアミン転化率は８
８％であり、２−メチル−４−メチルイミダゾリンの選
択率は９７％であった。Example 8 1,2-Propanediamine: 74.1 g, Acetonitrile: 45.
After adding 2 g and copper (II) oxide: 4.5 g and replacing the atmosphere with nitrogen, the mixture was heated to 200 ° C. When the reaction pressure became 2.5 MPa or more, the pressure was released, the pressure was reduced, and the reaction was performed for 3 hours.
After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of 1,2-propanediamine was 8
8% and the selectivity of 2-methyl-4-methylimidazoline was 97%.
【００３１】[0031]
【発明の効果】本発明は、硫化水素の発生も無く、また
塩触媒を使用した場合生じるイオンによる汚染、腐食と
いう問題も無い、イミダゾリン類の製造法を提供するも
のであり、極めて有意義である。INDUSTRIAL APPLICABILITY The present invention provides a method for producing imidazolines, which is free from the generation of hydrogen sulfide and is free from the problems of ion contamination and corrosion that occur when a salt catalyst is used, and is of great significance. .
Claims (7)
物を反応させて２−イミダゾリン類を製造する際に、金
属酸化物の存在下で反応を行うことを特徴とする２−イ
ミダゾリン類の製造法。1. A method for producing a 2-imidazoline compound, which comprises reacting a 1,2-diamine compound with a nitrile compound to produce a 2-imidazoline compound in the presence of a metal oxide. .
（１）で表されることを特徴とする請求項１に記載の方
法。 Ｈ2ＮＣＨＲ1ＣＨＲ2ＮＨＲ3 （１） （式中、Ｒ1、Ｒ2、Ｒ3は、各々独立して水素、脂肪
族、芳香脂肪族、芳香族の基を意味する）2. The method according to claim 1, wherein the 1,2-diamine compound is represented by the following general formula (1). H 2 NCHR 1 CHR 2 NHR 3 (1) (In the formula, R 1 , R 2 and R 3 each independently represent hydrogen, aliphatic, araliphatic or aromatic group)
されることを特徴とする請求項１又は請求項２に記載の
方法。 Ｒ4ＣＮ （２） （式中、Ｒ4は、各々独立して水素、脂肪族、芳香脂肪
族、芳香族の基を意味する）3. The method according to claim 1 or 2, wherein the nitrile compound is represented by the following general formula (2). R 4 CN (2) (In the formula, each R 4 independently represents hydrogen, an aliphatic group, an araliphatic group, or an aromatic group.)
請求項１乃至請求項３のいずれかに記載の方法。4. The method according to claim 1, wherein the reaction is performed in a liquid phase.
する請求項１乃至請求項４のいずれかに記載の方法。5. The method according to any one of claims 1 to 4, wherein the metal oxide is copper oxide.
とする請求項１乃至請求項４のいずれかに記載の方法。6. The method according to any one of claims 1 to 4, wherein the metal oxide is zinc oxide.
徴とする請求項１乃至請求項４のいずれかに記載の方
法。7. The method according to any one of claims 1 to 4, wherein the metal oxide is niobium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10622495A JP3849149B2 (en) | 1995-04-28 | 1995-04-28 | 2-Imidazoline production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10622495A JP3849149B2 (en) | 1995-04-28 | 1995-04-28 | 2-Imidazoline production method |
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| Publication Number | Publication Date |
|---|---|
| JPH08295675A true JPH08295675A (en) | 1996-11-12 |
| JP3849149B2 JP3849149B2 (en) | 2006-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402820A (en) * | 2014-12-02 | 2015-03-11 | 千辉药业（安徽）有限责任公司 | Synthesis method of 1-ethyl-2-methylimidazoline |
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1995
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402820A (en) * | 2014-12-02 | 2015-03-11 | 千辉药业（安徽）有限责任公司 | Synthesis method of 1-ethyl-2-methylimidazoline |
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|---|---|
| JP3849149B2 (en) | 2006-11-22 |
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