JPH1135562A - Production of monoalkylaminopyridine - Google Patents
Production of monoalkylaminopyridineInfo
- Publication number
- JPH1135562A JPH1135562A JP9192116A JP19211697A JPH1135562A JP H1135562 A JPH1135562 A JP H1135562A JP 9192116 A JP9192116 A JP 9192116A JP 19211697 A JP19211697 A JP 19211697A JP H1135562 A JPH1135562 A JP H1135562A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- aminopyridine
- amino
- ketone
- reaction
- 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
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、モノアルキルアミ
ノピリジン化合物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a monoalkylaminopyridine compound.
【０００２】[0002]
【従来の技術】アミノピリジン化合物と脂肪族ケトン化
合物とを出発原料としてモノアルキルアミノピリジン化
合物を製造する方法としては、例えば該出発原料を四塩
化チタンで処理してケチミンを得、次いで得られるケチ
ミンをリチウムアルミニウムヒドリドで還元する方法が
知られている（Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔｓ
７５：２０１３７ｂ（１９７１）［Ｃ．Ｒ．Ａｃａｄ．
Ｓｃｉ．，Ｓｅｒ．Ｃ，２７１，１６２９（１９７
０）］。2. Description of the Related Art As a method for producing a monoalkylaminopyridine compound using an aminopyridine compound and an aliphatic ketone compound as starting materials, for example, the starting material is treated with titanium tetrachloride to obtain a ketimine, and then the obtained ketimine is obtained. Is known with lithium aluminum hydride (Chemical Abstracts)
75: 20137b (1971) [C. R. Acad.
Sci. , Ser. C, 271, 1629 (197
0)].
【０００３】しかしながら、上記従来法には種々の欠点
がある。即ち、従来の方法では、二工程の反応操作が必
要であり、煩雑である。またこの方法で使用される四塩
化チタン及びリチウムアルデヒドヒドリドは、いずれも
水と激しく反応するため、使用の際には水分との接触を
防止する措置が必要になる等、取り扱いに注意を要する
化合物である。従って、上記従来法は工業的に有利な製
造法ではない。However, the above-mentioned conventional method has various disadvantages. That is, the conventional method requires a two-step reaction operation, which is complicated. In addition, titanium tetrachloride and lithium aldehyde hydride used in this method both react violently with water, so when using, compounds that require careful handling such as measures to prevent contact with moisture are required. It is. Therefore, the above conventional method is not an industrially advantageous production method.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記従来法
のような欠点のないモノアルキルアミノピリジン化合物
の新規な製造方法を提供することを課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel method for producing a monoalkylaminopyridine compound which does not have the drawbacks of the above-mentioned conventional method.
【０００５】[0005]
【課題を解決するための手段】本発明者は、上記従来法
のような欠点のないモノアルキルアミノピリジン化合物
の新規な製造方法を開発すべく鋭意研究を重ねてきた。
その研究過程において、アミノピリジン化合物と脂肪族
ケトン化合物とを出発原料として用い、この原料化合物
を水素化触媒の存在下に水素化反応させて目的とするモ
ノアルキルアミノピリジン化合物を製造することに着目
した。この方法によれば、上記従来法のように取り扱い
が困難な四塩化チタン及びリチウムアルデヒドヒドリド
を使用する必要はなく、しかも二工程ではなく一工程で
目的化合物を得ることができる。そこで、水素化触媒と
して代表的なパラジウム触媒を用い、この触媒の存在下
にアミノピリジン化合物を脂肪族ケトン化合物及び水素
と反応させることを試みた。ところが、この反応ではア
ミノピリジン化合物のピリジン環の還元が起こる等の好
ましくない副反応が生じ、目的とするモノアルキルアミ
ノピリジン化合物を選択的に、収率よく製造し得ないこ
とが判明した（後記比較例参照）。本発明者は、更に研
究を続ける中で、水素化触媒の中でも特にラネー触媒を
用いた場合に、好ましくない副反応が殆ど生じず、目的
とするモノアルキルアミノピリジン化合物を高い選択率
で、収率よく製造し得ることを見い出した。本発明は斯
かる知見に基づき完成されたものである。Means for Solving the Problems The present inventors have intensively studied to develop a novel method for producing a monoalkylaminopyridine compound having no drawbacks as in the above-mentioned conventional method.
In the course of this research, we focused on producing the desired monoalkylaminopyridine compound by using an aminopyridine compound and an aliphatic ketone compound as starting materials, and subjecting the starting compounds to a hydrogenation reaction in the presence of a hydrogenation catalyst. did. According to this method, it is not necessary to use titanium tetrachloride and lithium aldehyde hydride which are difficult to handle as in the above-mentioned conventional method, and the target compound can be obtained in one step instead of two steps. Thus, an attempt was made to react an aminopyridine compound with an aliphatic ketone compound and hydrogen in the presence of a typical palladium catalyst as a hydrogenation catalyst. However, in this reaction, undesired side reactions such as reduction of the pyridine ring of the aminopyridine compound occurred, and it was found that the desired monoalkylaminopyridine compound could not be selectively produced with high yield (see below). See Comparative Example). The present inventor has continued his research and found that an undesired side reaction hardly occurs, particularly when a Raney catalyst is used among the hydrogenation catalysts, so that the target monoalkylaminopyridine compound can be recovered with a high selectivity. It has been found that it can be manufactured efficiently. The present invention has been completed based on such findings.
【０００６】本発明によれば、ラネー触媒の存在下、ア
ミノピリジン化合物を脂肪族ケトン化合物及び水素と反
応せしめることを特徴とするモノアルキルアミノピリジ
ン化合物の製造方法が提供される。According to the present invention, there is provided a process for producing a monoalkylaminopyridine compound, which comprises reacting an aminopyridine compound with an aliphatic ketone compound and hydrogen in the presence of a Raney catalyst.
【０００７】本発明の方法によれば、上記従来法のよう
に取り扱いが困難な四塩化チタン及びリチウムアルデヒ
ドヒドリドを使用する必要はなく、しかも二工程ではな
く一工程で目的化合物を得ることができる。According to the method of the present invention, it is not necessary to use titanium tetrachloride and lithium aldehyde hydride which are difficult to handle as in the above-mentioned conventional method, and the desired compound can be obtained in one step instead of two steps. .
【０００８】また、本発明の方法によれば、好ましくな
い副反応が殆ど生じず、目的とするモノアルキルアミノ
ピリジン化合物を高い選択率で、収率よく製造すること
ができる。According to the method of the present invention, an undesired side reaction hardly occurs, and the desired monoalkylaminopyridine compound can be produced with high selectivity and high yield.
【０００９】[0009]
【発明の実施の形態】本発明で出発原料として用いられ
るアミノピリジン化合物としては、ピリジン環上にアミ
ノ基が置換している化合物である限り、従来公知のもの
を広く使用することができる。このようなアミノピリジ
ン化合物の代表例を示せば、例えば一般式BEST MODE FOR CARRYING OUT THE INVENTION As the aminopyridine compound used as a starting material in the present invention, conventionally known compounds can be widely used as long as the compound has an amino group substituted on the pyridine ring. If a typical example of such an aminopyridine compound is shown, for example, the general formula
【００１０】[0010]
【化３】 Embedded image
【００１１】［式中Ｒはアルキル基を示す。ｎは０〜４
の整数を示す。］で表される化合物を挙げることができ
る。ここでＲで示されるアルキル基としては、例えばメ
チル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチ
ル、イソブチル、ｔｅｒｔ−ブチル基等の炭素数１〜４
のアルキル基を挙げることができる。またｎが２以上の
整数である場合には、ピリジン環上の複数のアルキル基
は、互いに同一であってもよいし異なっていてもよい。Wherein R represents an alkyl group. n is 0 to 4
Indicates an integer. ] The compound represented by this can be mentioned. Here, the alkyl group represented by R includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like having 1 to 4 carbon atoms.
Can be mentioned. When n is an integer of 2 or more, the plurality of alkyl groups on the pyridine ring may be the same or different.
【００１２】一般式（１）のアミノピリジン化合物の具
体例としては、例えば２−アミノピリジン、３−アミノ
ピリジン、４−アミノピリジン、２−アミノ−３−メチ
ルピリジン、２−アミノ−４−メチルピリジン、２−ア
ミノ−５−メチルピリジン、３−アミノピリジン、２−
アミノ−６−メチルピリジン、３−アミノ−２−メチル
ピリジン、３−アミノ−４−メチルピリジン、３−アミ
ノ−５−メチルピリジン、５−アミノ−２−メチルピリ
ジン、４−アミノ−２−メチルピリジン、４−アミノ−
３−メチルピリジン、２−アミノ−３−エチルピリジ
ン、２−アミノ−４−エチルピリジン、２−アミノ−５
−エチルピリジン、２−アミノ−６−エチルピリジン、
３−アミノ−２−エチルピリジン、３−アミノ−４−エ
チルピリジン、３−アミノ−５−エチルピリジン、５−
アミノ−２−エチルピリジン、４−アミノ−２−エチル
ピリジン、４−アミノ−３−エチルピリジン、２−アミ
ノ−３−ｎ−プロピルピリジン、２−アミノ−４−ｎ−
プロピルピリジン、２−アミノ−５−ｎ−プロピルピリ
ジン、２−アミノ−６−ｎ−プロピルピリジン、３−ア
ミノ−２−ｎ−プロピルピリジン、３−アミノ−４−ｎ
−プロピルピリジン、３−アミノ−５−ｎ−プロピルピ
リジン、５−アミノ−２−ｎ−プロピルピリジン、４−
アミノ−２−ｎ−プロピルピリジン、４−アミノ−３−
ｎ−プロピルピリジン、２−アミノ−３，５−ジメチル
ピリジン、２−アミノ−５，６−ジメチルピリジン、３
−アミノ−２，６−ジメチルピリジン、４−アミノ−
２，３−ジメチルピリジン、４−アミノ−２，６−ジメ
チルピリジン、５−アミノ−２，３−ジメチルピリジ
ン、２−アミノ−３，５，６−トリメチルピリジン、４
−アミノ−２，３，５−トリメチルピリジン等を挙げる
ことができる。Specific examples of the aminopyridine compound of the general formula (1) include, for example, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methyl Pyridine, 2-amino-5-methylpyridine, 3-aminopyridine, 2-
Amino-6-methylpyridine, 3-amino-2-methylpyridine, 3-amino-4-methylpyridine, 3-amino-5-methylpyridine, 5-amino-2-methylpyridine, 4-amino-2-methyl Pyridine, 4-amino-
3-methylpyridine, 2-amino-3-ethylpyridine, 2-amino-4-ethylpyridine, 2-amino-5
-Ethylpyridine, 2-amino-6-ethylpyridine,
3-amino-2-ethylpyridine, 3-amino-4-ethylpyridine, 3-amino-5-ethylpyridine, 5-
Amino-2-ethylpyridine, 4-amino-2-ethylpyridine, 4-amino-3-ethylpyridine, 2-amino-3-n-propylpyridine, 2-amino-4-n-
Propylpyridine, 2-amino-5-n-propylpyridine, 2-amino-6-n-propylpyridine, 3-amino-2-n-propylpyridine, 3-amino-4-n
-Propylpyridine, 3-amino-5-n-propylpyridine, 5-amino-2-n-propylpyridine, 4-
Amino-2-n-propylpyridine, 4-amino-3-
n-propylpyridine, 2-amino-3,5-dimethylpyridine, 2-amino-5,6-dimethylpyridine, 3
-Amino-2,6-dimethylpyridine, 4-amino-
2,3-dimethylpyridine, 4-amino-2,6-dimethylpyridine, 5-amino-2,3-dimethylpyridine, 2-amino-3,5,6-trimethylpyridine,
-Amino-2,3,5-trimethylpyridine and the like.
【００１３】これらアミノピリジン化合物の中でも、２
−アミノピリジン、３−アミノピリジン及び４−アミノ
ピリジンが特に好ましい。Among these aminopyridine compounds, 2
-Aminopyridine, 3-aminopyridine and 4-aminopyridine are particularly preferred.
【００１４】また他の一つの出発原料である脂肪族ケト
ン化合物としては、従来公知のものを広く使用すること
ができる。このような脂肪族ケトン化合物の代表例を示
せば、例えば一般式As the aliphatic ketone compound as another starting material, conventionally known compounds can be widely used. If a typical example of such an aliphatic ketone compound is shown, for example, the general formula
【００１５】[0015]
【化４】 Embedded image
【００１６】［式中Ｒ1及びＲ2は各々アルキル基を示
す。］で表される化合物を挙げることができる。ここで
Ｒ1及びＲ2で示されるアルキル基としては、例えばメチ
ル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチ
ル、イソブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｎ
−ヘキシル基等の炭素数１〜６のアルキル基を挙げるこ
とができる。Ｒ1及びＲ2のアルキル基は、同一であって
もよいし、異なっていてもよい。[Wherein R 1 and R 2 each represent an alkyl group. ] The compound represented by this can be mentioned. Here, as the alkyl group represented by R 1 and R 2 , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n
An alkyl group having 1 to 6 carbon atoms such as -hexyl group. The alkyl groups of R 1 and R 2 may be the same or different.
【００１７】一般式（２）の脂肪族ケトン化合物の具体
例としては、例えばアセトン、メチルエチルケトン、メ
チルイソプロピルケトン、メチルｎ−ブチルケトン、メ
チルイソブチルケトン、メチルｎ−ペンチルケトン、メ
チルｎ−ヘキシルケトン、ジエチルケトン、エチルイソ
プロピルケトン、エチルｎ−ブチルケトン、エチルイソ
ブチルケトン、エチルｎ−ペンチルケトン、エチルｎ−
ヘキシルケトン、ジｎ−プロピルケトン、ジイソプロピ
ルケトン、ジブチルケトン、ジペンチルケトン、ジヘキ
シルケトン等を挙げることができる。Specific examples of the aliphatic ketone compound represented by the general formula (2) include, for example, acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl n-butyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl Ketone, ethyl isopropyl ketone, ethyl n-butyl ketone, ethyl isobutyl ketone, ethyl n-pentyl ketone, ethyl n-
Hexyl ketone, di-n-propyl ketone, diisopropyl ketone, dibutyl ketone, dipentyl ketone, dihexyl ketone and the like can be mentioned.
【００１８】これら脂肪族ケトン化合物の中でも、一般
式（２）のＲ1及びＲ2の一方がメチル基であって、他方
が炭素数１〜４のアルキル基であるアセトン、メチルエ
チルケトン、メチルイソプロピルケトン、メチルｎ−ブ
チルケトン、メチルイソブチルケトン等が特に好まし
い。Among these aliphatic ketone compounds, acetone, methyl ethyl ketone and methyl isopropyl ketone in which one of R 1 and R 2 in the general formula (2) is a methyl group and the other is an alkyl group having 1 to 4 carbon atoms. , Methyl n-butyl ketone, methyl isobutyl ketone and the like are particularly preferred.
【００１９】上記一般式（１）のアミノピリジン化合物
と一般式（２）の脂肪族ケトン化合物とから製造される
本発明のモノアルキルアミノピリジン化合物を化学式で
示せば、次の通りである。The monoalkylaminopyridine compound of the present invention prepared from the aminopyridine compound of the general formula (1) and the aliphatic ketone compound of the general formula (2) can be represented by the following chemical formula.
【００２０】一般式General formula
【００２１】[0021]
【化５】 Embedded image
【００２２】［式中Ｒ、ｎ、Ｒ1及びＲ2は前記に同
じ。］アミノピリジン化合物及び脂肪族ケトン化合物の
使用割合としては、前者１モルに対して後者を通常１．
２〜６モル、好ましくは３〜５モルとする。Wherein R, n, R 1 and R 2 are as defined above. As for the use ratio of the aminopyridine compound and the aliphatic ketone compound, the former is usually 1 mol per mol of the former.
2 to 6 mol, preferably 3 to 5 mol.
【００２３】本発明では反応系内にラネー触媒を存在さ
せることを必須とする。ラネー触媒としては、従来公知
のものを広く使用でき、例えばラネーニッケル、ラネー
コバルト等を挙げることができる。斯かるラネー触媒
は、アミノピリジン化合物に対して通常５〜５０重量
％、好ましくは１０〜３０重量％使用する。In the present invention, it is essential that a Raney catalyst be present in the reaction system. As the Raney catalyst, conventionally known ones can be widely used, and examples thereof include Raney nickel and Raney cobalt. The Raney catalyst is used in an amount of usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the aminopyridine compound.
【００２４】本発明においては、例えば反応器にアミノ
ピリジン化合物、脂肪族ケトン化合物及びラネー触媒を
仕込み、加熱、撹拌下で水素を導入しながら反応を行う
のがよい。また、アミノピリジン化合物や脂肪族ケトン
化合物は、反応途中で適宜添加してもよい。In the present invention, for example, an aminopyridine compound, an aliphatic ketone compound and a Raney catalyst are charged into a reactor, and the reaction is preferably carried out while heating and stirring to introduce hydrogen. Further, the aminopyridine compound or the aliphatic ketone compound may be appropriately added during the reaction.
【００２５】本発明の反応を行うに当たっては、溶媒を
使用してもよい。溶媒としては、本発明の反応に悪影響
を及ぼさず、出発原料を溶解し得るものである限り従来
公知のものを広く使用でき、例えばメタノール、エタノ
ール、イソプロピルアルコール等のアルコール類、トル
エン、キシレン等の芳香族炭化水素類、ジエチルエーテ
ル、ジイソプロピルエーテル、ジｎ−ブチルエーテル等
の脂肪族エーテル類、テトラヒドロフラン、ジオキサン
等の環式エーテル類等を挙げることができる。尚、脂肪
族ケトン化合物をアミノピリジン化合物に対して過剰量
用いる場合には、脂肪族ケトン化合物は溶媒としても兼
用される。In carrying out the reaction of the present invention, a solvent may be used. As the solvent, those which do not adversely affect the reaction of the present invention and are conventionally known can be widely used as long as they can dissolve the starting materials.Examples include methanol, ethanol, alcohols such as isopropyl alcohol, toluene, xylene and the like. Examples thereof include aromatic hydrocarbons, aliphatic ethers such as diethyl ether, diisopropyl ether and di-n-butyl ether, and cyclic ethers such as tetrahydrofuran and dioxane. When the aliphatic ketone compound is used in an excess amount relative to the aminopyridine compound, the aliphatic ketone compound is also used as a solvent.
【００２６】本発明の反応温度は、通常１００〜２５０
℃、好ましくは１５０〜２００℃である。また水素圧
（ゲージ圧）は１０〜１００ｋｇ・ｆ／ｃｍ2（９８〜
９８０ｋＰａ）、好ましくは３０〜６０ｋｇ・ｆ／ｃｍ
2（２９４〜５８８ｋＰａ）である。本発明の反応は、
通常３〜８時間で終了する。The reaction temperature of the present invention is usually from 100 to 250.
° C, preferably 150 to 200 ° C. The hydrogen pressure (gauge pressure) is 10 to 100 kg · f / cm 2 (98 to
980 kPa), preferably 30 to 60 kg · f / cm
2 (294-588 kPa). The reaction of the present invention
It usually ends in 3 to 8 hours.
【００２７】上記反応終了後、本発明の目的化合物は、
従来公知の慣用手段に従い、反応混合物から容易に単離
精製され得る。After completion of the above reaction, the target compound of the present invention is
It can be easily isolated and purified from the reaction mixture according to conventionally known conventional means.
【００２８】[0028]
【実施例】以下に実施例及び比較例を掲げて、本発明を
より一層明らかにする。The present invention will be further clarified with reference to the following examples and comparative examples.
【００２９】実施例１ １００ｍｌのオートクレーブに３−アミノピリジン３
７．６ｇ（０．４モル）、アセトン９２．９ｇ（１．６
モル）及びラネーニッケル７．５ｇを仕込み、撹拌下、
水素を導入しながら１６０℃、水素圧４０ｋｇ・ｆ／ｃ
ｍ2（３９２ｋＰａ）にて４時間反応を行った。Example 1 In a 100 ml autoclave, 3-aminopyridine 3 was added.
7.6 g (0.4 mol), 92.9 g of acetone (1.6
Mol) and 7.5 g of Raney nickel
160 ° C, hydrogen pressure 40kg ・ f / c while introducing hydrogen
The reaction was performed at m 2 (392 kPa) for 4 hours.
【００３０】反応終了後、反応液を室温に冷却し、触媒
を濾別した。得られた濾液を濃縮し、濃縮物をガスクロ
マトグラフィーにより分析したところ、３−アミノピリ
ジンの転化率は８５％、３−（イソプロピルアミノ）ピ
リジンの選択率は７６％であった。また、３−（イソプ
ロピルアミノ）ピペリジン及び１−イソプロピル−３−
（イソプロピルアミノ）ピリジンが、各々選択率３．１
％、１２％で生成していた。After the completion of the reaction, the reaction solution was cooled to room temperature, and the catalyst was separated by filtration. The obtained filtrate was concentrated, and the concentrate was analyzed by gas chromatography. As a result, the conversion of 3-aminopyridine was 85%, and the selectivity of 3- (isopropylamino) pyridine was 76%. Also, 3- (isopropylamino) piperidine and 1-isopropyl-3-
(Isopropylamino) pyridine with selectivity of 3.1
% And 12%.
【００３１】実施例２ アセトンの使用量を３２．５ｇ（０．５６モル）とし、
反応を６時間行う以外は実施例１と同様に行った。その
結果、３−アミノピリジンの転化率は３６％、３−（イ
ソプロピルアミノ）ピリジンの選択率は７５％であっ
た。また、３−（イソプロピルアミノ）ピペリジン及び
１−イソプロピル−３−（イソプロピルアミノ）ピリジ
ンが、各々選択率５．３％、６．１％で生成していた。Example 2 The amount of acetone used was 32.5 g (0.56 mol).
The procedure was performed in the same manner as in Example 1 except that the reaction was performed for 6 hours. As a result, the conversion of 3-aminopyridine was 36%, and the selectivity of 3- (isopropylamino) pyridine was 75%. Also, 3- (isopropylamino) piperidine and 1-isopropyl-3- (isopropylamino) pyridine were produced at selectivities of 5.3% and 6.1%, respectively.
【００３２】実施例３ 反応を１８０℃で３時間行う以外は実施例１と同様に行
った。その結果、３−アミノピリジンの転化率は７５
％、３−（イソプロピルアミノ）ピリジンの選択率は７
６％であった。また、３−（イソプロピルアミノ）ピペ
リジン及び１−イソプロピル−３−（イソプロピルアミ
ノ）ピリジンが、各々選択率２．７％、１０．４％で生
成していた。Example 3 The procedure of Example 1 was repeated except that the reaction was carried out at 180 ° C. for 3 hours. As a result, the conversion of 3-aminopyridine is 75
%, Selectivity for 3- (isopropylamino) pyridine is 7
6%. In addition, 3- (isopropylamino) piperidine and 1-isopropyl-3- (isopropylamino) pyridine were produced with a selectivity of 2.7% and 10.4%, respectively.
【００３３】実施例４ 反応を１４０℃で５時間行う以外は実施例１と同様に行
った。その結果、３−アミノピリジンの転化率は６２
％、３−（イソプロピルアミノ）ピリジンの選択率は７
１％であった。また、３−（イソプロピルアミノ）ピペ
リジン及び１−イソプロピル−３−（イソプロピルアミ
ノ）ピリジンが、各々選択率２．６％、９．１％で生成
していた。Example 4 The procedure of Example 1 was repeated except that the reaction was carried out at 140 ° C. for 5 hours. As a result, the conversion of 3-aminopyridine was 62
%, Selectivity for 3- (isopropylamino) pyridine is 7
1%. Further, 3- (isopropylamino) piperidine and 1-isopropyl-3- (isopropylamino) pyridine were produced at selectivities of 2.6% and 9.1%, respectively.
【００３４】比較例１ １００ｍｌのオートクレーブに３−アミノピリジン３
７．６ｇ（０．４モル）、アセトン３２．５ｇ（０．５
６モル）及び５％パラジウム／カーボン０．７５ｇを仕
込み、撹拌下、水素を導入しながら８０℃、水素圧４０
ｋｇ・ｆ／ｃｍ2（３９２ｋＰａ）にて６時間反応を行
った。Comparative Example 1 3-aminopyridine 3 was added to a 100 ml autoclave.
7.6 g (0.4 mol), acetone 32.5 g (0.5
6 mol) and 0.75 g of 5% palladium / carbon, and stirred at 80 ° C. under a hydrogen pressure of 40 while introducing hydrogen.
The reaction was performed at kg · f / cm 2 (392 kPa) for 6 hours.
【００３５】反応終了後、反応液を室温に冷却し、触媒
を濾別した。得られた濾液を濃縮し、濃縮物をガスクロ
マトグラフィーにより分析したところ、３−アミノピリ
ジンの転化率は７９％であったが、３−（イソプロピル
アミノ）ピリジンの選択率は２８％に過ぎなかった。ま
た、３−（イソプロピルアミノ）ピペリジン及び１−イ
ソプロピル−３−（イソプロピルアミノ）ピリジンが、
各々選択率４４％、１４％で生成していた。After the completion of the reaction, the reaction solution was cooled to room temperature, and the catalyst was separated by filtration. The obtained filtrate was concentrated, and the concentrate was analyzed by gas chromatography. As a result, the conversion of 3-aminopyridine was 79%, but the selectivity of 3- (isopropylamino) pyridine was only 28%. Was. Also, 3- (isopropylamino) piperidine and 1-isopropyl-3- (isopropylamino) pyridine are
They were formed at selectivities of 44% and 14%, respectively.
【００３６】また、反応温度を１００℃に代えた以外は
上記と同様に反応を行った。その結果、３−アミノピリ
ジンの転化率は７７％、３−（イソプロピルアミノ）ピ
リジンの選択率は２５％に止まった。また、３−（イソ
プロピルアミノ）ピペリジン及び１−イソプロピル−３
−（イソプロピルアミノ）ピリジンが、各々選択率２２
％、３６％で生成していた。The reaction was carried out in the same manner as above except that the reaction temperature was changed to 100 ° C. As a result, the conversion of 3-aminopyridine was 77%, and the selectivity of 3- (isopropylamino) pyridine was only 25%. Also, 3- (isopropylamino) piperidine and 1-isopropyl-3
-(Isopropylamino) pyridine with a selectivity of 22
%, 36%.
Claims (3)
合物を脂肪族ケトン化合物及び水素と反応せしめること
を特徴とするモノアルキルアミノピリジン化合物の製造
方法。1. A method for producing a monoalkylaminopyridine compound, comprising reacting an aminopyridine compound with an aliphatic ketone compound and hydrogen in the presence of a Raney catalyst.
す。］で表される化合物であり、脂肪族ケトン化合物が
一般式 【化２】 ［式中Ｒ1及びＲ2は各々アルキル基を示す。］で表され
る化合物である請求項１記載の製造方法。2. An aminopyridine compound represented by the general formula: [Wherein R represents an alkyl group. n shows the integer of 0-4. And an aliphatic ketone compound represented by the general formula: [Wherein R 1 and R 2 each represent an alkyl group. The method according to claim 1, which is a compound represented by the formula:
肪族ケトン化合物を１．２〜６モル使用し、且つラネー
触媒をアミノピリジン化合物に対して５〜５０重量％使
用する請求項１記載の製造方法。3. The process according to claim 1, wherein 1.2 to 6 mol of the aliphatic ketone compound is used per 1 mol of the aminopyridine compound, and 5 to 50% by weight of the Raney catalyst is used relative to the aminopyridine compound. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19211697A JP4214322B2 (en) | 1997-07-17 | 1997-07-17 | Method for producing monoalkylaminopyridine compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19211697A JP4214322B2 (en) | 1997-07-17 | 1997-07-17 | Method for producing monoalkylaminopyridine compound |
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| Publication Number | Publication Date |
|---|---|
| JPH1135562A true JPH1135562A (en) | 1999-02-09 |
| JP4214322B2 JP4214322B2 (en) | 2009-01-28 |
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ID=16285943
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19211697A Expired - Fee Related JP4214322B2 (en) | 1997-07-17 | 1997-07-17 | Method for producing monoalkylaminopyridine compound |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351835B2 (en) | 2004-07-12 | 2008-04-01 | Meiji Seika Kaisha Ltd. | Organic molecular cataylst having binaphthol skeleton and processes for producing the same and application thereof |
| CN114790168A (en) * | 2021-05-18 | 2022-07-26 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethylpyridine and 2-amino-4-trifluoromethylpyridine |
-
1997
- 1997-07-17 JP JP19211697A patent/JP4214322B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351835B2 (en) | 2004-07-12 | 2008-04-01 | Meiji Seika Kaisha Ltd. | Organic molecular cataylst having binaphthol skeleton and processes for producing the same and application thereof |
| CN114790168A (en) * | 2021-05-18 | 2022-07-26 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethylpyridine and 2-amino-4-trifluoromethylpyridine |
| CN114790168B (en) * | 2021-05-18 | 2024-02-09 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethyl pyridine and 2-amino-4-trifluoromethyl pyridine |
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| Publication number | Publication date |
|---|---|
| JP4214322B2 (en) | 2009-01-28 |
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