JPH06192225A - Production of 1@(3754/24)-4-pyridyl)piperazines - Google Patents
Production of 1@(3754/24)-4-pyridyl)piperazinesInfo
- Publication number
- JPH06192225A JPH06192225A JP4358339A JP35833992A JPH06192225A JP H06192225 A JPH06192225 A JP H06192225A JP 4358339 A JP4358339 A JP 4358339A JP 35833992 A JP35833992 A JP 35833992A JP H06192225 A JPH06192225 A JP H06192225A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- piperazines
- halopyridine
- pyridyl
- strong base
- 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
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は１−（４−ピリジル）ピ
ペラジン類の製造法に関する。１−（４−ピリジル）ピ
ペラジンは医農薬の中間体として極めて重要な化合物で
ある。FIELD OF THE INVENTION The present invention relates to a process for producing 1- (4-pyridyl) piperazines. 1- (4-Pyridyl) piperazine is a very important compound as an intermediate for medical and agricultural chemicals.
【０００２】[0002]
【従来の技術】従来、１−（４−ピリジル）ピペラジン
類の製造法としては、炭酸カリウムの存在下に、ピペラ
ジンと４−ブロモピリジンを反応させる方法（Ｃｚｅｃ
ｈ．１５３８３４（ １９７４））が知られている。収
率の記載はない。2. Description of the Related Art Conventionally, as a method for producing 1- (4-pyridyl) piperazines, a method of reacting piperazine with 4-bromopyridine in the presence of potassium carbonate (Czec
h. 153834 (1974)) is known. There is no description of yield.
【０００３】[0003]
【本発明が解決しようとする課題】原料の４−ブロモピ
リジンに変えてこれよりも安価である４−クロロピリジ
ンを用いて、前記の方法を実施してところ、後述の比較
例１に示すように目的の１−（４−ピリジル）ピペラジ
ンは実質的に生成していなかった。このように、この従
来方法は工業的製造法としては不適なものである。The above method was carried out using 4-chloropyridine, which is cheaper than 4-bromopyridine as a raw material, as shown in Comparative Example 1 described later. The desired 1- (4-pyridyl) piperazine was not substantially formed. Thus, this conventional method is unsuitable as an industrial manufacturing method.
【０００４】[0004]
【課題を解決するための手段】本発明者等はかかる課題
を解決すべく鋭意研究を行った結果、４−ハロピリジン
又はその塩とピペラジン類を混合した後、この混合物に
強塩基を供給しながら４−ハロピリジン又はその塩とピ
ペラジン類を反応させると、４−ハロピリジンとして４
−クロロピリジン類を用いたときでも、好収率でかつ高
品質の１−（４−ピリジル）ピペラジン類を製造できる
ことを見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that after mixing 4-halopyridine or a salt thereof with piperazines, a strong base is supplied to the mixture. When 4-halopyridine or a salt thereof is reacted with piperazines, 4-halopyridine is converted into 4
The inventors have found that even when using -chloropyridines, it is possible to produce high-quality 1- (4-pyridyl) piperazines in good yield, and have completed the present invention.
【０００５】即ち、本発明は、アルカリ剤の存在下で一
般式（１）：That is, the present invention provides the compound represented by the general formula (1):
【化４】 （式中、Ｘはハロゲン原子を表わす。）で示されるハロ
ピリジン（以下、４−ハロピリジン（１）という）又は
その塩と一般式（２）：[Chemical 4] (In the formula, X represents a halogen atom.) Or a salt thereof and a general formula (2):
【化５】 （式中、Ｒ1は水素原子、低級アルキル基又は保護基を
表わす。Ｒ2及びＲ3は水素原子又は低級アルキル基を表
わす。）で示されるピペラジン類（以下、ピペラジン類
（２）という）を反応させて一般式（３）：[Chemical 5] (In the formula, R 1 represents a hydrogen atom, a lower alkyl group or a protective group, and R 2 and R 3 represent a hydrogen atom or a lower alkyl group.) (Hereinafter referred to as piperazine (2)) To react with the general formula (3):
【化６】 （式中、Ｒ1、Ｒ2及びＲ3は前記に同じ。）で示される
１−（４−ピリジル）ピペラジン類を製造するに当た
り、４−ハロピリジン（１）又はその塩とピペラジン類
（２）の混合物に、アルカリ剤としての強塩基を供給し
ながら反応させることを特徴とする１−（４−ピリジ
ル）ピペラジン類の製造法を提供するものでる。[Chemical 6] (In the formula, R 1 , R 2 and R 3 are the same as above.) In producing 1- (4-pyridyl) piperazine, 4-halopyridine (1) or a salt thereof and piperazine (2) A method for producing 1- (4-pyridyl) piperazines, which comprises reacting the mixture of item 1 with a strong base as an alkali agent.
【０００６】本発明の出発原料である４−ハロピリジン
（１）としては、４−クロロピリジン、４−ブロモピリ
ジン、４−ヨードピリジン、４−フルオロピリジンが挙
げられが、工業的には安価な４−クロルピリジンが好適
である。As 4-halopyridine (1) which is the starting material of the present invention, 4-chloropyridine, 4-bromopyridine, 4-iodopyridine and 4-fluoropyridine can be mentioned. -Chloropyridine is preferred.
【０００７】本発明で用いられる４−ハロピリジン
（１）の塩としては特に限定されないが、例えば４−ク
ロロピリジン・ＨＣｌ、４−ブロモピリジン・ＨＢｒ、
４−クロロピリジン・ＨＩ、４−クロロピリジン・ＨＣ
ＯＯＨ等が挙げられる。The salt of 4-halopyridine (1) used in the present invention is not particularly limited, but for example, 4-chloropyridine.HCl, 4-bromopyridine.HBr,
4-chloropyridine ・ HI, 4-chloropyridine ・ HC
OOH etc. are mentioned.
【０００８】本発明で４−ハロピリジン（１）の塩を原
料に選んだ場合には、反応を行う前に４−ハロピリジン
（１）の塩とピペラジン類（２）の中和反応を確認して
おかなければならない。即ち、４−ハロピリジン（１）
の塩とピペラジン類（２）の中和で、４−ハロピリジン
（１）とピペラジン類（２）の塩が生成されたことを確
認しなければならない。もし、４−ハロピリジン（１）
の塩とピペラジン類（２）を混合する温度が低すぎて、
これらの中和反応が行われていない時には、次の強塩基
の供給時に一気に中和反応が促進されることがあるので
注意を要する。通常、これらの中和反応は発熱による顕
著な温度上昇を容易に観察できる。When the salt of 4-halopyridine (1) is selected as the starting material in the present invention, the neutralization reaction between the salt of 4-halopyridine (1) and the piperazine (2) is confirmed before the reaction. I have to go. That is, 4-halopyridine (1)
It must be confirmed that the salt of 4-halopyridine (1) and the piperazine (2) was produced by the neutralization of the salt of 1 and the piperazine (2). If 4-halopyridine (1)
Is too low to mix the salt with piperazine (2),
When these neutralization reactions are not carried out, the neutralization reaction may be accelerated at the next supply of the strong base, so caution is required. Usually, in these neutralization reactions, a remarkable temperature rise due to exotherm can be easily observed.
【０００９】本発明の一般式（２）において、Ｒ1、Ｒ2
及びＲ3で示される低級アルキル基としてはメチル基、
エチル基、プロピル基、ブチル基などが挙げられる。ま
たＲ3で示される保護基としてはホルミル基、ベンジル
基などが挙げられる。ピペラジン類（２）の具体例とし
ては、ピペラジン、１−メチルピペラジン、２−メチル
ピペラジン、２，３−ジメチルピペラジン、２，５−ジ
メチルピペラジン、２，６−ジメチルピペラジン、１−
ホルミルピペラジン、１−エトキシカルボニル−２−メ
チルピペラジン、１−ベンジル−３−メチルピペラジン
等が挙げられる。ピペラジン類（２）の使用量は、通常
４−ハロピリジン（１）に対して等モルから２倍モルの
範囲である。In the general formula (2) of the present invention, R 1 , R 2
And a lower alkyl group represented by R 3 is a methyl group,
Examples thereof include ethyl group, propyl group and butyl group. Examples of the protecting group represented by R 3 include a formyl group and a benzyl group. Specific examples of the piperazines (2) include piperazine, 1-methylpiperazine, 2-methylpiperazine, 2,3-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-
Formylpiperazine, 1-ethoxycarbonyl-2-methylpiperazine, 1-benzyl-3-methylpiperazine and the like can be mentioned. The amount of piperazine (2) used is usually in the range of equimolar to 2 times the molar amount of 4-halopyridine (1).
【００１０】本発明で用いられる強塩基としては特に限
定されないが、工業的には安価でかつ扱いやすい水酸化
アルカリが好ましく、中でも水酸化ナトリウム、水酸化
カリウム等が選ばれる。強塩基の使用量は、通常４−ハ
ロピリジン（１）に対して２倍モルから４倍モルの範囲
である。強塩基の供給時間は通常３０分から５時間の範
囲である。本発明で用いられる強塩基はそれ単独で用い
るか、又は本発明の反応に用い得る溶媒に溶解もしくは
分散して用いても反応になんら影響を及ぼさない。The strong base used in the present invention is not particularly limited, but an industrially inexpensive and easy-to-handle alkali hydroxide is preferable, and among them, sodium hydroxide, potassium hydroxide and the like are selected. The amount of the strong base used is usually in the range of 2 times to 4 times the mol of 4-halopyridine (1). The supply time of the strong base is usually in the range of 30 minutes to 5 hours. The strong base used in the present invention does not affect the reaction even if it is used alone or is dissolved or dispersed in a solvent which can be used in the reaction of the present invention.
【００１１】本発明の反応で用い得る溶媒としては、原
料の４−ハロピリジン（１）及びその塩、ピペラジン類
（２）、さらに反応で生成される一般式（３）で示され
る１−（４−ピリジル）ピペラジン類を溶解又は分散さ
せるものであれば限定されないが、通常、水溶媒やメタ
ノール、エタノール、ブタノール等のアルコール溶媒、
ベンゼン、トルエン、キシレン等の炭化水素系溶媒が好
適である。溶媒の使用量は、通常４−ハロピリジン
（１）に対して等量から１０倍重量の範囲である。As the solvent which can be used in the reaction of the present invention, 4-halopyridine (1) as a raw material and its salt, piperazines (2), and 1- (4) represented by the general formula (3) produced by the reaction. -Pyridyl) piperazine is not limited as long as it can dissolve or disperse, usually, an alcohol solvent such as water solvent or methanol, ethanol, butanol,
Hydrocarbon solvents such as benzene, toluene and xylene are suitable. The amount of the solvent used is usually in the range of equivalent to 10 times the weight of 4-halopyridine (1).
【００１２】本発明の反応温度は８０℃以上であれば制
限されないが、１００〜１６０℃が好適であり、収率の
点からより好適には１３０〜１５０℃である。反応温度
が低いと、例えば、原料のハロピリジン類とピペラジン
類が存在する中で強塩基が蓄積し、急激に反応を起こす
ことがあるので、事前に各原料毎の適性温度を確認しす
るのが好ましい。本発明の反応における反応時間は原料
の組合せによって異なるが、通常は１〜１５時間の範囲
である。The reaction temperature of the present invention is not limited as long as it is 80 ° C. or higher, but 100 to 160 ° C. is preferable, and 130 to 150 ° C. is more preferable from the viewpoint of yield. If the reaction temperature is low, for example, strong bases may accumulate in the presence of halopyridines and piperazines as raw materials and cause a rapid reaction, so it is necessary to confirm the appropriate temperature for each raw material in advance. preferable. The reaction time in the reaction of the present invention varies depending on the combination of raw materials, but is usually in the range of 1 to 15 hours.
【００１３】このようにして得られた一般式（３）で示
される１−（４−ピリジル）ピペラジン類は、反応液を
一般的な濾過（又は分液）、濃縮、蒸留することによっ
て、単離精製される。The 1- (4-pyridyl) piperazines represented by the general formula (3) thus obtained are isolated by subjecting the reaction solution to general filtration (or liquid separation), concentration and distillation. It is isolated and purified.
【００１４】[0014]
【実施例】以下に、実施例を掲げて本発明を具体的に説
明するが、本発明はこれらの実施例に限定されるもので
はない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
【００１５】比較例１ 撹拌器、還流冷却器、温度計の備わった２リットルフラ
スコに、４−クロロピリジン・ＨＣｌ１５０ｇ、ピペラ
ジン１７２ｇ、炭酸カリウム６９ｇ及びエタノール４５
０ｇを仕込み、還流状態（内温８６℃）で１０時間撹拌
した。その後、冷却、濾過し、濾液をガスクロマトグラ
フィ分析したところ、それぞれの原料が確認されただけ
で、１−（４−ピリジル）ピペラジンは生成していなか
った。Comparative Example 1 In a 2 liter flask equipped with a stirrer, a reflux condenser and a thermometer, 150 g of 4-chloropyridine.HCl, 172 g of piperazine, 69 g of potassium carbonate and 45 ethanol.
0 g was charged, and the mixture was stirred under reflux (internal temperature 86 ° C.) for 10 hours. Then, the mixture was cooled, filtered, and the filtrate was subjected to gas chromatography analysis. As a result, only the respective raw materials were confirmed, and 1- (4-pyridyl) piperazine was not produced.
【００１６】比較例２ 炭酸カリウムの代りに４８％水酸化ナトリウム８２ｇ、
エタノールの代りに水３００ｇを用いた以外は、比較例
１と同様にして反応したところ、痕跡の１−（４−ピリ
ジル）ピペラジンを得た。Comparative Example 2 82 g of 48% sodium hydroxide in place of potassium carbonate,
When the reaction was performed in the same manner as in Comparative Example 1 except that 300 g of water was used instead of ethanol, traces of 1- (4-pyridyl) piperazine were obtained.
【００１７】実施例１ 撹拌器、還流冷却器、温度計、滴下ロートの備った３０
０ｍｌの反応フラスコに、４−クロロピリジン・ＨＣｌ
３７．５ｇ、水３５．５ｇ及びピペラジン４３ｇを仕込
んだ後、撹拌下に昇温すると、内温約７０℃で急な温度
上昇があった。内温が８０℃で治まった後、再び昇温し
た。この混合物を撹拌下１１０℃に保ちながら、滴下ロ
ートに入れた４８％水酸化ナトリウム６２．５ｇを約
１．５時間で供給した。供給終了後、還流状態（内温１
１２℃）で５時間撹拌を行った。その後、５０〜６０℃
に冷却し、ブタノール１００ｇ及び水１００ｇを反応液
に入れて、分液ロートで振盪した。分液した油分を濃縮
し、蒸留すると、ガスクロマトグラフィ純度９９．１％
の１−（４−ピリジル）ピペラジン３０ｇを得た。４−
クロロピリジン・ＨＣｌに対する１−（４−ピリジル）
ピペラジンの収率は７４％であった。Example 1 30 equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel
In a 0 ml reaction flask, add 4-chloropyridine.HCl.
After charging 37.5 g, 35.5 g of water and 43 g of piperazine and then raising the temperature with stirring, an abrupt temperature rise occurred at an internal temperature of about 70 ° C. After the internal temperature subsided at 80 ° C., the temperature was raised again. While maintaining the mixture at 110 ° C. with stirring, 62.5 g of 48% sodium hydroxide in a dropping funnel was supplied in about 1.5 hours. After the supply is completed, a reflux state (internal temperature 1
The mixture was stirred at 12 ° C for 5 hours. After that, 50-60 ℃
After cooling to 100 ° C., 100 g of butanol and 100 g of water were added to the reaction solution, and the mixture was shaken with a separating funnel. When the separated oil is concentrated and distilled, the gas chromatography purity is 99.1%.
30 g of 1- (4-pyridyl) piperazine was obtained. 4-
1- (4-pyridyl) for chloropyridine / HCl
The yield of piperazine was 74%.
【００１８】実施例２ ４−クロロピリジン・ＨＣｌの代りに４−ブロモピリジ
ン・ＨＢｒ６０ｇを用いた他は、実施例１と同様にして
反応したところ、４−ブロモピリジンに対する収率７８
％で１−（４−ピリジル）ピペラジンを得た。Example 2 A reaction was conducted in the same manner as in Example 1 except that 60 g of 4-bromopyridine.HBr was used instead of 4-chloropyridine.HCl, and the yield was 78 based on 4-bromopyridine.
% 1- (4-pyridyl) piperazine was obtained.
【００１９】実施例３ ３００ｍｌの鉄製オートクレーブに実施例１と同様に原
料を仕込み、撹拌下に昇温した。内温１４０℃、内圧約
３ｋｇ／ｃｍ2で、３０％水酸化ナトリウム１００ｇを
５時間で供給した。供給終了後、同温同圧で３時間撹拌
した。その後は実施例１と同様にして、４−クロロピリ
ジン・ＨＣｌに対する収率９３％で１−（４−ピリジ
ル）ピペラジンを得た。Example 3 A 300 ml iron autoclave was charged with the same raw materials as in Example 1, and the temperature was raised with stirring. At an inner temperature of 140 ° C. and an inner pressure of about 3 kg / cm 2 , 100 g of 30% sodium hydroxide was supplied for 5 hours. After the supply was completed, the mixture was stirred at the same temperature and the same pressure for 3 hours. Thereafter, in the same manner as in Example 1, 1- (4-pyridyl) piperazine was obtained with a yield of 93% based on 4-chloropyridine.HCl.
【００２０】[0020]
【発明の効果】本発明の方法によれば、従来技術では原
料として不適であった４−クロロピリジンを用いて、好
収率で１−（４−ピリジル）ピペラジン類を得ることが
でき、本発明は工業的に極めて有用な方法を提供するも
のである。According to the method of the present invention, 1- (4-pyridyl) piperazines can be obtained in good yield by using 4-chloropyridine, which was unsuitable as a raw material in the prior art. The invention provides an industrially extremely useful method.
Claims (4)
ピリジン又はその塩と一般式（２）： 【化２】 （式中、Ｒ1は水素原子、低級アルキル基又は保護基を
表わす。Ｒ2及びＲ3は水素原子又は低級アルキル基を表
わす。）で示されるピペラジン類を反応させて一般式
（３）： 【化３】 （式中、Ｒ1、Ｒ2及びＲ3は前記に同じ。）で示される
１−（４−ピリジル）ピペラジン類を製造するに当た
り、一般式（１）で示されるハロピリジン又はその塩と
一般式（２）で示されるピペラジン類の混合物に、アル
カリ剤としての強塩基を供給しながら反応させることを
特徴とする１−（４−ピリジル）ピペラジン類の製造
法。1. A compound represented by the general formula (1): embedded image in the presence of an alkaline agent. (Wherein, X represents a halogen atom) and a halopyridine represented by the formula or a salt thereof and a compound represented by the general formula (2): (Wherein R 1 represents a hydrogen atom, a lower alkyl group or a protective group, R 2 and R 3 represent a hydrogen atom or a lower alkyl group), and the piperazine compound represented by the formula (3): [Chemical 3] (In the formula, R 1 , R 2 and R 3 are the same as above.) In producing the 1- (4-pyridyl) piperazines represented by the formula, a halopyridine represented by the formula (1) or a salt thereof A method for producing 1- (4-pyridyl) piperazines, which comprises reacting a mixture of piperazines represented by (2) while supplying a strong base as an alkaline agent.
記載の製造法。2. The strong base is an alkali hydroxide.
The manufacturing method described.
はその塩と一般式（２）で示されるピペラジン類の混合
物が、水溶媒、アルコール溶媒又は炭化水素系溶媒で希
釈されていることを特徴とする請求項１、２又は３記載
の方法。3. A mixture of a halopyridine represented by the general formula (1) or a salt thereof and a piperazine represented by the general formula (2) is diluted with an aqueous solvent, an alcohol solvent or a hydrocarbon solvent. The method according to claim 1, 2 or 3.
項１〜４のいずれかに記載の方法。4. The method according to claim 1, wherein the reaction temperature is 100 to 160 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35833992A JP3238508B2 (en) | 1992-12-25 | 1992-12-25 | Method for producing 1- (4-pyridyl) piperazines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35833992A JP3238508B2 (en) | 1992-12-25 | 1992-12-25 | Method for producing 1- (4-pyridyl) piperazines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06192225A true JPH06192225A (en) | 1994-07-12 |
| JP3238508B2 JP3238508B2 (en) | 2001-12-17 |
Family
ID=18458791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35833992A Expired - Fee Related JP3238508B2 (en) | 1992-12-25 | 1992-12-25 | Method for producing 1- (4-pyridyl) piperazines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3238508B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089451A (en) * | 1999-09-14 | 2001-04-03 | Teikoku Chem Ind Corp Ltd | Production of aminopyridines |
| CZ303950B6 (en) * | 2011-12-12 | 2013-07-10 | Masarykova Univerzita | Process for preparing 1-(pyridin-4-yl)piperazine and 1,1-dialkyl-1-ium derivatives thereof |
-
1992
- 1992-12-25 JP JP35833992A patent/JP3238508B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089451A (en) * | 1999-09-14 | 2001-04-03 | Teikoku Chem Ind Corp Ltd | Production of aminopyridines |
| CZ303950B6 (en) * | 2011-12-12 | 2013-07-10 | Masarykova Univerzita | Process for preparing 1-(pyridin-4-yl)piperazine and 1,1-dialkyl-1-ium derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3238508B2 (en) | 2001-12-17 |
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