JP2558480B2 - Method for producing N-ethylpiperazine - Google Patents
Method for producing N-ethylpiperazineInfo
- Publication number
- JP2558480B2 JP2558480B2 JP62294662A JP29466287A JP2558480B2 JP 2558480 B2 JP2558480 B2 JP 2558480B2 JP 62294662 A JP62294662 A JP 62294662A JP 29466287 A JP29466287 A JP 29466287A JP 2558480 B2 JP2558480 B2 JP 2558480B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylpiperazine
- catalyst
- reaction
- producing
- piperazine
- 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.)
- Expired - Lifetime
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
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、下記式で示されるＮ−エチルピペラジンの
製造方法に関するものである。Ｎ−エチルピペラジン
は、医薬品原料、特に抗菌剤の主要原料として、近年需
要が高まってきた有用な化合物である。DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a method for producing N-ethylpiperazine represented by the following formula. N-Ethylpiperazine is a useful compound, which has been in increasing demand in recent years, as a main raw material for pharmaceutical raw materials, particularly antibacterial agents.
［従来の技術］ 従来、Ｎ−エチルピペラジンの製造方法としては、下
記の二つの方法が知られている。 [Prior Art] Conventionally, the following two methods are known as methods for producing N-ethylpiperazine.
（１） ジエタノールアミンとエチルアミンをヘテロポ
リ酸の存在下にオートクレーブ中、高温高圧下で反応さ
せ、Ｎ−エチルピペラジンを得る方法。（特開昭58−35
179号公報） （２） ピペラジンとエタノールをラネーニッケル触媒
と水素の存在下に反応させる方法。（西独特許公開第34
40195号公報） 第一のヘテロポリ酸を触媒として使用する方法は、高
圧高圧の条件を必要とする為、工業的な実施には、難し
い面が多い。また、第二のエタノールを反応させる方法
は、副生物としてジエチルピペラジンの生成が多く、収
率的に満足できる方法ではない。(1) A method of obtaining N-ethylpiperazine by reacting diethanolamine and ethylamine in the presence of heteropolyacid in an autoclave under high temperature and high pressure. (JP-A-58-35
No. 179) (2) A method of reacting piperazine and ethanol in the presence of Raney nickel catalyst and hydrogen. (West German Patent Publication No. 34
The method using the first heteropolyacid as a catalyst requires high-pressure and high-pressure conditions, and therefore has many difficulties in industrial implementation. In addition, the method of reacting the second ethanol is not a method that is satisfactory in terms of yield because a large amount of diethylpiperazine is produced as a by-product.
［発明が解決しようとする問題点］ 本発明は、工業的に容易に実施可能で、収率的にも優
れたＮ−エチルピペラジンの新規な製造方法を提供す
る。[Problems to be Solved by the Invention] The present invention provides a novel method for producing N-ethylpiperazine, which can be easily carried out industrially and is excellent in yield.
［問題点を解決するための手段］ 一般にＮ−アルキルアミンを製造する方法としては、
従来技術の項で述べた方法の他に、アミンをアルデヒド
で還元アルキル化する方法、アミンとアルキルハロゲン
化物などのアルキル化剤を反応させる方法、アミンとア
ミンを還元雰囲気下で反応させ、脱アンモニア反応によ
りＮ−アルキルアミンを製造する方法等が考えられる。
しかし、Ｎ−アルキルピペラジンの場合には、ピペラジ
ンが第二級アミン化合物であること、両端アミンの片方
だけにアルキル化するように反応選択性を持たねばなら
ぬこと等の特殊性から、上記の方法は試みたがいずれも
満足な結果を得ることが出来なかった。本発明者等は、
更に鋭意研究の結果、アミンとアセトニトリルを還元雰
囲気下で反応させることによりＮ−エチルピペラジンが
好収率で得られることを見いだし、本発明を完成させた
ものである。[Means for Solving Problems] Generally, as a method for producing an N-alkylamine,
In addition to the method described in the section of the prior art, a method of reductively alkylating an amine with an aldehyde, a method of reacting an amine with an alkylating agent such as an alkyl halide, a reaction of an amine with an amine in a reducing atmosphere, and deammonification A method of producing an N-alkylamine by the reaction and the like can be considered.
However, in the case of N-alkylpiperazine, due to the peculiarities such as that the piperazine is a secondary amine compound and that it must have reaction selectivity so that it is alkylated on only one of the amines on both ends, I tried the methods but none of them yielded satisfactory results. The present inventors
As a result of further earnest research, it was found that N-ethylpiperazine can be obtained in good yield by reacting amine with acetonitrile in a reducing atmosphere, and completed the present invention.
すなわち本発明は、ピペラジンとアセトニトリルを水
素および水素化触媒の存在下に反応させることを特徴と
するＮ−エチルピペラジンの製造方法である。That is, the present invention is a method for producing N-ethylpiperazine, which comprises reacting piperazine and acetonitrile in the presence of hydrogen and a hydrogenation catalyst.
本発明で使用される水素化触媒は、ラネーニッケル触
媒、還元ニッケル触媒および白金炭素触媒からなる群よ
り選ばれる一種の触媒である。特に白金炭素触媒が最も
好ましい結果を与える。The hydrogenation catalyst used in the present invention is a catalyst selected from the group consisting of Raney nickel catalyst, reduced nickel catalyst and platinum carbon catalyst. In particular, a platinum carbon catalyst gives the most favorable results.
本発明は、溶媒の存在下または無溶媒のいずれでも実
施できる。無溶媒の場合は、アセトニトリル自体が溶媒
として作用するので、多めに使用する必要がある。本発
明で使用される溶媒としてはピペラジンを溶解し、反応
に不活性なものであれば、いずれでも使用できる。具体
的には、水およびメタノール、エタノール、イソプロパ
ノール、ブタノール等のアルコール類、並びにジオキサ
ン類等が挙げられる。The present invention can be carried out in the presence of a solvent or without a solvent. In the case of no solvent, acetonitrile itself acts as a solvent, so it is necessary to use a large amount. As the solvent used in the present invention, any solvent can be used as long as it dissolves piperazine and is inert to the reaction. Specific examples include water and alcohols such as methanol, ethanol, isopropanol and butanol, and dioxane.
本発明を実施する場合の好ましい反応条件としては、
アセトニトリルはビペラジンに対して２倍モル前後、溶
媒はビペラジンと同量程度、触媒はビペラジンに対し５
〜10重量％程度を使用するのが良い。反応水素圧として
は30ないし110kg/cm2の間、反応温度は40ないし120℃の
間で行うことが好適である。反応終了後は触媒を濾過で
取り除き、濾液を精留して、溶媒留分、未反応ピペラジ
ン留分についてＮ−エチルピペラジンの留分を得ること
が出来る。Preferred reaction conditions for carrying out the present invention include:
Acetonitrile is about twice the molar amount of biperazine, the solvent is about the same amount as biperazine, and the catalyst is 5 times the amount of biperazine.
It is recommended to use about 10% by weight. The reaction hydrogen pressure is preferably 30 to 110 kg / cm 2 , and the reaction temperature is preferably 40 to 120 ° C. After completion of the reaction, the catalyst is removed by filtration, and the filtrate is rectified to obtain a solvent fraction and an unreacted piperazine fraction, which is N-ethylpiperazine fraction.
以下、実施例により、本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例 １ 200mlステンレス製オートクレーブに、ピペラジン30.
1g、アセトニトリル28.7g、ｔ−ブタノール30gおよび５
％担持白金炭素触媒2.25g（ピペラジンに対し7.5％）を
仕込み、水素圧100kg/cm2、反応温度110℃で16時間反応
した。触媒を濾過した反応液についてガスクロマトグラ
フィーにより分析した結果、Ｎ−エチルピプラジンが77
％、未反応ピペラジンが16％およびN,N′−ジエチルピ
ペラジンが７％の組成であった。精留によりＮ−エチル
ピペラジン26.0g（収率65％）を得ることが出来た。Example 1 30 ml of piperazine was added to a 200 ml stainless steel autoclave.
1 g, acetonitrile 28.7 g, t-butanol 30 g and 5
% Support platinum carbon catalyst 2.25 g (7.5% relative to piperazine) was charged, and the reaction was carried out for 16 hours at a hydrogen pressure of 100 kg / cm 2 and a reaction temperature of 110 ° C. The reaction liquid obtained by filtering the catalyst was analyzed by gas chromatography to find that N-ethylpiprazine was 77%.
%, Unreacted piperazine 16% and N, N'-diethylpiperazine 7%. By rectification, 26.0 g (yield 65%) of N-ethylpiperazine could be obtained.
実施例 ２ 触媒をラネーニッケル触媒3gに代えたほかは実施例１
とほぼ同様に反応を行い、Ｎ−エチルピペラジン57％、
ピペラジン40％、N,N′−ジエチルビペラジン３％の組
成の反応液を得た。Example 2 Example 1 except that the catalyst was changed to 3 g of Raney nickel catalyst.
The reaction is performed in the same manner as in, N-ethylpiperazine 57%,
A reaction solution having a composition of 40% piperazine and 3% N, N'-diethylbiperazine was obtained.
実施例 ３ 500mlオートクレーブに無水ピペラジン86g（１モ
ル）、アセトニトリル82g（２モル）ｔ−ブタノール80g
および還元ニッケル3gを仕込み、水素置換した。水素圧
30ないし100kg/cm2、反応温度100ないし140℃で１時間
反応した。反応液を冷却すると未反応ピペラジンが析出
してきたのでそれを濾別し、母液は単蒸留し、140〜158
℃のＮ−エチルピペラジンの留分42g（収率47.8％）を
得た。Example 3 86 g (1 mol) of anhydrous piperazine, 82 g (2 mol) of acetonitrile and 80 g of t-butanol in a 500 ml autoclave.
Then, 3 g of reduced nickel was charged and the atmosphere was replaced with hydrogen. Hydrogen pressure
The reaction was carried out at 30 to 100 kg / cm 2 and a reaction temperature of 100 to 140 ° C. for 1 hour. When the reaction solution was cooled, unreacted piperazine began to precipitate, which was filtered off, and the mother liquor was subjected to simple distillation to 140-158.
42 g (yield 47.8%) of a fraction of N-ethylpiperazine at ℃ was obtained.
［発明の効果］ 本発明により、Ｎ−エチルピペラジンを工業的に容易
にかつ好収率で得ることが出来る。[Effects of the Invention] According to the present invention, N-ethylpiperazine can be obtained industrially easily and in good yield.
Claims (2)
水素化触媒の存在下に反応させることを特徴とするＮ−
エチルピペラジンの製造方法。1. N-characterized by reacting piperazine and acetonitrile in the presence of hydrogen and a hydrogenation catalyst.
Method for producing ethylpiperazine.
ニッケル触媒および白金炭素触媒からなる群より選ばれ
る一種である特許請求の範囲第１項記載の方法。2. The method according to claim 1, wherein the hydrogenation catalyst is one selected from the group consisting of Raney nickel catalyst, reduced nickel catalyst and platinum carbon catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294662A JP2558480B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing N-ethylpiperazine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294662A JP2558480B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing N-ethylpiperazine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01135779A JPH01135779A (en) | 1989-05-29 |
| JP2558480B2 true JP2558480B2 (en) | 1996-11-27 |
Family
ID=17810673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62294662A Expired - Lifetime JP2558480B2 (en) | 1987-11-20 | 1987-11-20 | Method for producing N-ethylpiperazine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2558480B2 (en) |
-
1987
- 1987-11-20 JP JP62294662A patent/JP2558480B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01135779A (en) | 1989-05-29 |
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