JPH0940651A - Production of 2-imidazoline compound - Google Patents
Production of 2-imidazoline compoundInfo
- Publication number
- JPH0940651A JPH0940651A JP7196525A JP19652595A JPH0940651A JP H0940651 A JPH0940651 A JP H0940651A JP 7196525 A JP7196525 A JP 7196525A JP 19652595 A JP19652595 A JP 19652595A JP H0940651 A JPH0940651 A JP H0940651A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- acid
- reaction
- compound
- metal oxide
- 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.)
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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。[0003] 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
酸亜鉛等の塩を使うと、触媒が反応液に溶解するため、
触媒の回収が困難であり、また触媒が生成物を汚染す
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 salts such as copper acetate and zinc acetate are used, the catalyst dissolves in the reaction solution,
The recovery of the catalyst is difficult and the catalyst contaminates the product. 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、触媒の回収が困難等の問題があり、十
分なレベルに達しているとは言い難い。したがって、塩
を触媒とせず、硫化水素を副生しない方法の開発が望ま
れていた。The conventional method has problems that hydrogen sulfide is by-produced, reaction is inhibited, purification is required, equipment corrosion occurs, and catalyst recovery is difficult. It is hard to say that you have reached the level. Therefore, it has been desired to develop a method which does not use salt as a catalyst and does not produce hydrogen sulfide as a by-product.
【０００６】[0006]
【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
金属酸化物及びカルボン酸を使用することによって、硫
化水素の発生も無く、触媒の回収も容易であり、また塩
触媒を使用した場合生じる汚染、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。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 and a carboxylic acid as a catalyst, hydrogen sulfide was not generated and the catalyst was recovered. The present invention has been completed by discovering the novel fact that imidazolines can be produced without any problems such as contamination and corrosion that occur when a salt catalyst is used.
【０００７】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、金属酸化物及びカルボン酸の存在下で
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。That is, the present invention is characterized in that when a 1,2-diamine compound and a nitrile compound are reacted to produce 2-imidazolines, they are carried out in the presence of a metal oxide and a carboxylic acid. This is a method for producing imidazolines.
【０００８】以下に本発明をさらに詳細に説明する。Hereinafter, the present invention will be described in more detail.
【０００９】本発明の方法において使用される触媒は金
属酸化物及びカルボン酸である。本発明の方法において
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、その中でも活性選
択性が向上するため、酸化銅、酸化クロム、酸化マンガ
ン、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（ＩＩ）があるが、どちらを
使用しても良く、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、同様に水酸化
物が使用できる。また、酸化銅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。The catalysts used in the process of the invention are metal oxides and carboxylic acids. Examples of the metal oxide referred to in the method of the present invention include 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. , Tin oxide, tantalum oxide,
Examples thereof include tungsten oxide, rhenium oxide, lead oxide, lanthanum oxide, and cerium oxide. Among them, copper oxide, chromium oxide, manganese oxide, zinc oxide, and niobium oxide are particularly preferable because the activity selectivity is improved. Although copper oxide includes copper oxide (I) and copper oxide (II), either of them may be used, and copper hydroxide may be used in the same manner as the oxide. Hydroxides can be similarly used for zinc and niobium. Further, copper oxide may be supported on a carrier and used. As the carrier, oxides such as silica and alumina, composite oxides such as silica-alumina, activated carbon, porous glass and porous ceramics can be used.
【００１０】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 as a mixture with other metal oxides. For example, copper chromite, copper oxide-zinc oxide and the like can also be used.
【００１１】カルボン酸に特に制限はないが、蟻酸、酢
酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、イソ吉草
酸、ピバル酸、ラウリン酸、ミリスチン酸、パルミチン
酸、ステアリン酸、２−エチルヘキサン酸等の脂肪族飽
和モノカルボン酸類、シュウ酸、マロン酸、こはく酸、
グルタル酸、アジピン酸、ピメリン酸、スベリン酸、ア
ゼライン酸、セバシン酸等の脂肪族飽和ジカルボン酸
類、アクリル酸、プロピオル酸、メタクリル酸、クロト
ン酸、イソクロトン酸、オレイン酸、エライジン酸、マ
レイン酸、フマル酸、シトラコン酸、メサコン酸等の脂
肪族不飽和カルボン酸類、しょのう酸、安息香酸、フタ
ル酸、イソフタル酸、テレフタル酸、ナフトエ酸、トル
イル酸、ヒドロアトロパ酸、アトロパ酸、けい皮酸等の
炭素環式カルボン酸類、フル酸、テン酸、ニコチン酸、
イソニコチン酸等の複素環式カルボン酸類、モノクロロ
酢酸、ジクロロ酢酸、トリフルオロ酢酸等が例示され
る。しかし、触媒が生成物純度に影響を与えないように
するために、原料のニトリルに対応するカルボン酸を使
用するのが好ましい。例えば、アセトニトリルを原料と
した場合は、触媒としては酢酸を使用するのが良い。The carboxylic acid is not particularly limited, but is formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexane. Aliphatic saturated monocarboxylic acids such as acids, oxalic acid, malonic acid, succinic acid,
Aliphatic saturated dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, elaidic acid, maleic acid, fumaric acid Acids, aliphatic unsaturated carboxylic acids such as citraconic acid, mesaconic acid, succinic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, toluic acid, hydroatropic acid, atropic acid, cinnamic acid, etc. Carbocyclic carboxylic acids, fulic acid, tenic acid, nicotinic acid,
Heterocyclic carboxylic acids such as isonicotinic acid, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and the like are exemplified. However, it is preferred to use the carboxylic acid corresponding to the starting nitrile so that the catalyst does not affect the product purity. For example, when acetonitrile is used as a raw material, acetic acid is preferably used as a catalyst.
【００１２】また、カルボン酸化合物は塩の形で使用し
ても一向に差支えない。Further, the carboxylic acid compound may be used in the form of a salt without any problem.
【００１３】金属酸化物とカルボン酸の比に特に制限は
ない。カルボン酸、又は金属酸化物だけでは、反応は遅
いが、両方が存在すると反応は大きく加速される。There is no particular limitation on the ratio of metal oxide to carboxylic acid. The reaction is slow only with carboxylic acid or metal oxide, but the reaction is greatly accelerated when both are present.
【００１４】なお本発明の方法における条件では、ジア
ミン化合物が存在するため系中は強塩基性になり、金属
酸化物とカルボン酸とが反応して塩を形成することはな
い。Under the conditions of the method of the present invention, the system is strongly basic because of the presence of the diamine compound, and the metal oxide and the carboxylic acid do not react to form a salt.
【００１５】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、
芳香脂肪族及び芳香族の基からなる群より選ばれる１種
以上を意味する） ニトリル化合物は式（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 formula (1), and H 2 NCHR 1 CHR 2 NHR 3 (1) (in the formula, R 1 , R 2 , and R 3 are each independently hydrogen, aliphatic,
Meaning one or more selected from the group consisting of araliphatic and aromatic groups) The nitrile compound is a compound represented by the formula (2).
【００１６】 Ｒ4ＣＮ （２） （式中、Ｒ4は水素、脂肪族、芳香脂肪族又は芳香族の
基を意味する） １，２−ジアミン化合物としては、例えば、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−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) (wherein R 4 represents hydrogen, aliphatic, araliphatic or aromatic group) Examples of the 1,2-diamine compound include ethylenediamine, propylenediamine and butylene. Diamine, pentylenediamine, hexylenediamine, octylenediamine, nonylenediamine, decylenediamine, cyclohexylethylenediamine, benzylethylenediamine,
Examples include phenylethylenediamine, methoxyphenylethylenediamine, dimethylphenylethylenediamine, tolylethylenediamine, N-cyclohexylethylenediamine, N-benzylethylenediamine, N-phenylethylenediamine, N-methoxyphenylethylenediamine, N-dimethylphenylethylenediamine and N-tolylethylenediamine. .
【００１７】また、ニトリル化合物としては、例えば、
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, for example,
Acetonitrile, propionitrile, isobutyronitrile, 2-ethylhexylonitrile, lauronitrile, stearonitrile, cyclohexylnitrile, phenylacetonitrile, phenylpropionitrile, benzonitrile, methylbenzonitrile, dimethylbenzonitrile, methoxybenzonitrile, Examples thereof include dimethylbenzonitrile, naphthonitrile, cyanopyridine, malonnitrile, adiponitrile, phthalonitrile, dicyanodiphenyl and the like. The 1,2-diamine compound and the nitrile compound can be reacted in stoichiometric equivalent or in excess of one.
【００１８】本発明の方法において、反応温度は、反応
速度の向上、アミン類の分解抑制及びイミダゾリン類の
収率向上のため、通常１００〜３００℃の範囲で行われ
るが、１５０〜２５０℃で行うことが更に好ましい。In the method of the present invention, the reaction temperature is usually in the range of 100 to 300 ° C. in order to improve the reaction rate, suppress the decomposition of amines and improve the yield of imidazolines. It is more preferable to carry out.
【００１９】本発明の方法は通常液相で実施される。The process according to the invention is usually carried out in the liquid phase.
【００２０】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 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.
【００２１】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。In the method of the present invention, a solvent may or may not be used. The solvent is not particularly limited as long as it is inert to the reaction conditions. Use of a solvent that decomposes imidazolines, such as water, is not preferred.
【００２２】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 by 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.
【００２３】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 as a 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.
【００２４】[0024]
【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.
【００２５】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，活
性亜鉛華：３ｇ，酢酸：１．５ｇ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９９％であ
り、２−メチルイミダゾリンの選択率は９８％であっ
た。なお、活性亜鉛華は反応終了後も反応液に溶解せ
ず、回収された。Example 1 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g, activated zinc white: 3 g, acetic acid: 1.5 g were put into a 200 ml stainless steel autoclave, and after nitrogen substitution, 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, this was cooled and analyzed by gas chromatography to find that the conversion of ethylenediamine was 99% and the selectivity of 2-methylimidazoline was 98%. The active zinc white was not dissolved in the reaction solution even after the reaction was completed and was recovered.
【００２６】比較例１ 触媒として、活性亜鉛華：４．５ｇを使用し、酢酸を使
用しなかった以外は実施例１と同じ方法で反応をおこな
った。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１４
％であり、２−メチルイミダゾリンの選択率は８２％で
あった。Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that 4.5 g of active zinc white was used as a catalyst and acetic acid was not used. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of ethylenediamine was 14
%, And the selectivity for 2-methylimidazoline was 82%.
【００２７】比較例２ 触媒として、酢酸：４．５ｇを使用し、活性亜鉛華を使
用しなかった以外は実施例１と同じ方法で反応をおこな
った。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２２
％であり、２−メチルイミダゾリンの選択率は７１％で
あった。Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that acetic acid: 4.5 g was used as a catalyst and active zinc white was not used. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the ethylenediamine conversion rate was 22.
%, And the selectivity for 2-methylimidazoline was 71%.
【００２８】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，活
性亜鉛華：１．５ｇ，酢酸：１．５ｇを入れ、窒素置換
した後、１８０℃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、５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９７％
であり、２−メチルイミダゾリンの選択率は９６％であ
った。なお、活性亜鉛華は反応終了後も全く反応液に溶
解せず、回収された。Example 2 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g, activated zinc white: 1.5 g, acetic acid: 1.5 g were put in a 200 ml stainless steel autoclave, and after nitrogen substitution, the mixture was heated to 180 ° C. . Reaction pressure is 2.5 MPa
When the above was reached, the pressure was released and the pressure was lowered to react for 5 hours. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of ethylenediamine was 97%.
And the selectivity for 2-methylimidazoline was 96%. The active zinc oxide was not dissolved in the reaction solution even after the reaction was completed and was recovered.
【００２９】比較例３ 触媒として、酢酸亜鉛：３ｇを使用した以外は実施例２
と同じ方法で反応をおこなった。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９２％であり、２−メチルイミダ
ゾリンの選択率は９６％であった。なお、酢酸亜鉛は反
応終了後、反応液に溶解してしまい、回収できなかっ
た。Comparative Example 3 Example 2 except that zinc acetate: 3 g was used as the catalyst.
Reaction was carried out in the same manner as. After completion of the reaction, this was cooled and analyzed by gas chromatography. As a result, the ethylenediamine conversion rate was 92% and the 2-methylimidazoline selectivity was 96%. Note that zinc acetate could not be recovered because it dissolved in the reaction solution after the reaction was completed.
【００３０】実施例３ １Ｌのステンレス製オートクレーブにエチレンジアミ
ン：７５．１ｇ，アセトニトリル：２２６ｇ，活性亜鉛
華：７．５ｇ，酢酸：７．５ｇを入れ、窒素置換した
後、１８０℃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、２時間反応した。こ
れに、エチレンジアミン２２５．４ｇをポンプで５時間
かけて供給した。その後２時間１８０℃に維持した後、
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９８％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 Ethylenediamine: 75.1 g, acetonitrile: 226 g, activated zinc white: 7.5 g, acetic acid: 7.5 g were put into a 1 L stainless steel autoclave, and after nitrogen substitution, the mixture was heated to 180 ° 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 2 hours. To this, 225.4 g of ethylenediamine was pumped in over 5 hours. After maintaining at 180 ℃ for 2 hours,
When cooled and analyzed by gas chromatography, the conversion of ethylenediamine was 98% and the selectivity of 2-methylimidazoline was 97%.
【００３１】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，酸
化マンガン添加銅クロマイト：３ｇ，酢酸：１．５ｇ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９０％であり、２−メチルイミダゾリンの選択率
は９４％であった。Example 4 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g, manganese oxide-added copper chromite: 3 g, and acetic acid: 1.5 g were put in a 200 ml stainless steel autoclave, and after nitrogen substitution, the mixture was heated to 200 ° C. . When the reaction pressure exceeds 2.5 MPa, depressurize and lower the pressure.
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 90% and the 2-methylimidazoline selectivity was 94%.
【００３２】比較例４ 触媒として、銅クロマイト４．５ｇを使用し、酢酸を使
用しなかった以外は実施例１と同じ方法で反応をおこな
った。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。Comparative Example 4 The reaction was carried out in the same manner as in Example 1 except that 4.5 g of copper chromite was used as a catalyst and acetic acid was not used. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the ethylenediamine conversion rate was 51.
%, And the selectivity for 2-methylimidazoline was 97%.
【００３３】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、酸
化ニオブ：３ｇ，酢酸：１．５ｇ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９８％であ
り、２−メチルイミダゾリンの選択率は９８％であっ
た。Example 5 Ethylenediamine: 60.1 g, acetonitrile: 45.2 g, niobium oxide: 3 g, acetic acid: 1.5 g were put into a 200 ml stainless steel autoclave, and after nitrogen substitution, 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. As a result, the ethylenediamine conversion rate was 98% and the 2-methylimidazoline selectivity was 98%.
【００３４】実施例６ 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）：３ｇ，酢酸：１．５ｇ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９５％であり、２−メチル−４−メチルイ
ミダゾリンの選択率は９３％であった。Example 6 1,2-Propanediamine: 74.1 g, Acetonitrile: 45.
2 g and copper (II) oxide: 3 g and acetic acid: 1.5 g were added, and the atmosphere was replaced with nitrogen, and then heated to 200 ° C. When the reaction pressure exceeds 2.5 MPa, depressurize and reduce the pressure to 3
Reacted for hours. After completion of the reaction, it was cooled and analyzed by gas chromatography to find that the conversion of 1,2-propanediamine was 95% and the selectivity of 2-methyl-4-methylimidazoline was 93%.
【００３５】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，プロピオニトリル：６０．６ｇ、
酸化ニオブ：３ｇ，プロピオン酸：１．５ｇを入れ、窒
素置換した後、２００℃に加熱した。反応圧力が２．５
ＭＰａ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９
９％であり、２−エチルイミダゾリンの選択率は９２％
であった。Example 7 In a 200 ml stainless steel autoclave, ethylenediamine: 60.1 g, propionitrile: 60.6 g,
Niobium oxide (3 g) and propionic acid (1.5 g) were added, the atmosphere was replaced with nitrogen, and the mixture was heated to 200 ° C. Reaction pressure is 2.5
When the pressure became equal to or higher than MPa, 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 9
9%, the selectivity of 2-ethylimidazoline is 92%
Met.
【００３６】[0036]
【発明の効果】本発明は、硫化水素の発生も無く、また
触媒の回収も容易で、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
の製造方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 does not generate hydrogen sulfide, is easy to recover the catalyst, and is free from the problems of ion contamination and corrosion that occur when a salt catalyst is used. And is extremely meaningful.
Claims (9)
物を反応させて２−イミダゾリン類を製造する際に、金
属酸化物及びカルボン酸の存在下で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 and a carboxylic acid. Law.
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、
芳香脂肪族及び芳香族の基からなる群より選ばれる１種
以上を意味する）2. The method according to claim 1, wherein the 1,2-diamine compound is represented by the following formula. H 2 NCHR 1 CHR 2 NHR 3 (1) (wherein, R 1 , R 2 and R 3 are each independently hydrogen, aliphatic,
Meaning one or more selected from the group consisting of araliphatic and aromatic groups)
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、水素、脂肪族、芳香脂肪族又は芳香族
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 formula. R 4 CN (2) (wherein R 4 represents a hydrogen, aliphatic, araliphatic or 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.
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。8. The method according to any one of claims 1 to 4, wherein the metal oxide is chromium oxide.
特徴とする請求項１乃至請求項４のいずれかに記載の方
法。9. The method according to any one of claims 1 to 4, wherein the metal oxide is manganese oxide.
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|---|---|---|---|
| JP19652595A JP3849157B2 (en) | 1995-08-01 | 1995-08-01 | 2-Imidazoline production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19652595A JP3849157B2 (en) | 1995-08-01 | 1995-08-01 | 2-Imidazoline production method |
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| Publication Number | Publication Date |
|---|---|
| JPH0940651A true JPH0940651A (en) | 1997-02-10 |
| JP3849157B2 JP3849157B2 (en) | 2006-11-22 |
Family
ID=16359196
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|---|---|---|---|
| JP19652595A Expired - Fee Related JP3849157B2 (en) | 1995-08-01 | 1995-08-01 | 2-Imidazoline production method |
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| Country | Link |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007099730A (en) * | 2005-10-07 | 2007-04-19 | Chiba Univ | Bisimidazoline ligand and catalyst by using the same |
| US7361678B2 (en) | 2002-03-05 | 2008-04-22 | Transtech Pharma, Inc. | Azole derivatives and fused bicyclic azole derivatives as therapeutic agents |
| US7723369B2 (en) | 2006-01-30 | 2010-05-25 | Transtech Pharma, Inc. | Substituted imidazole derivatives, compositions, and methods of use as PTPase inhibitors |
| US8580833B2 (en) | 2009-09-30 | 2013-11-12 | Transtech Pharma, Inc. | Substituted imidazole derivatives and methods of use thereof |
| 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 |
-
1995
- 1995-08-01 JP JP19652595A patent/JP3849157B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7361678B2 (en) | 2002-03-05 | 2008-04-22 | Transtech Pharma, Inc. | Azole derivatives and fused bicyclic azole derivatives as therapeutic agents |
| US7714013B2 (en) | 2002-03-05 | 2010-05-11 | Transtech Pharma, Inc. | Azole derivatives and fused bicyclic azole derivatives as therapeutic agents |
| US7737285B2 (en) | 2002-03-05 | 2010-06-15 | Transtech Pharma, Inc. | Azole derivatives and fused bicyclic azole derivatives as therapeutic agents |
| JP2007099730A (en) * | 2005-10-07 | 2007-04-19 | Chiba Univ | Bisimidazoline ligand and catalyst by using the same |
| JP4747298B2 (en) * | 2005-10-07 | 2011-08-17 | 国立大学法人 千葉大学 | Bisimidazoline ligand and catalyst using the same |
| US7723369B2 (en) | 2006-01-30 | 2010-05-25 | Transtech Pharma, Inc. | Substituted imidazole derivatives, compositions, and methods of use as PTPase inhibitors |
| US8404731B2 (en) | 2006-01-30 | 2013-03-26 | Transtech Pharma, Inc. | Substituted imidazole derivatives, compositions, and methods of use as PTPase inhibitors |
| US8580833B2 (en) | 2009-09-30 | 2013-11-12 | Transtech Pharma, Inc. | Substituted imidazole derivatives and methods of use thereof |
| US10363241B2 (en) | 2009-09-30 | 2019-07-30 | Vtv Therapeutics Llc | Substituted imidazole derivatives and methods of use thereof |
| 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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| Publication number | Publication date |
|---|---|
| JP3849157B2 (en) | 2006-11-22 |
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