JP2612645B2 - Method for producing carboxamide compound - Google Patents
Method for producing carboxamide compoundInfo
- Publication number
- JP2612645B2 JP2612645B2 JP10037191A JP10037191A JP2612645B2 JP 2612645 B2 JP2612645 B2 JP 2612645B2 JP 10037191 A JP10037191 A JP 10037191A JP 10037191 A JP10037191 A JP 10037191A JP 2612645 B2 JP2612645 B2 JP 2612645B2
- Authority
- JP
- Japan
- Prior art keywords
- carboxylic acid
- reaction
- chloride
- amine
- acetic acid
- 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 - Fee Related
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、染料及び染料中間体、
顔料及び顔料中間体、医薬品等の種々の分野で有用なカ
ルボン酸クロリド化合物を、カルボン酸クロリドと、１
級または２級アミンとの反応により製造する方法におい
て、酢酸水溶液を溶媒とすることを特徴とする新規な製
造方法に関するものである。This invention relates to dyes and dye intermediates,
Carboxylic acid chloride compounds useful in various fields such as pigments and pigment intermediates, pharmaceuticals, etc.
The present invention relates to a novel method for producing by a reaction with a secondary or secondary amine, wherein an aqueous acetic acid solution is used as a solvent.
【０００２】[0002]
【従来の技術】カルボン酸クロリドが、１級もしくは２
級アミンと反応してカルボン酸アミド化合物を生成する
ことは良く知られている。この種の反応は、一般に有機
溶媒中で行われることが多いが、脱塩化水素反応である
ため、副生する塩化水素を中和除去するために塩基の存
在が必要となる。塩基が共存していないと、反応成分で
あるアミンが、副生した塩化水素と塩酸塩を形成し、カ
ルボン酸クロリドとの反応性を失ってしまう。そのた
め、一般的には、副生する塩化水素を除去する目的で、
ピリジン、トリエチルアミン等の３級アミンを反応成分
であるカルボン酸クロリドやアミンと当量分加えるか、
もしくは、反応成分であるアミンを化学量論量の２倍使
用することが行われている。2. Description of the Related Art Carboxylic acid chlorides are primary or secondary.
It is well known to react with secondary amines to form carboxylic acid amide compounds. This type of reaction is generally performed in an organic solvent in many cases. However, since it is a dehydrochlorination reaction, the presence of a base is required to neutralize and remove by-produced hydrogen chloride. If the base does not coexist, the amine as a reaction component forms hydrochloride with by-produced hydrogen chloride, and loses reactivity with carboxylic acid chloride. Therefore, in general, in order to remove hydrogen chloride produced as a by-product,
A tertiary amine such as pyridine or triethylamine is added in an amount equivalent to the carboxylic acid chloride or amine as a reaction component,
Alternatively, the reaction component, amine, is used twice as much as the stoichiometric amount.
【０００３】一方、有機溶媒を使用せず、水を溶媒とす
る反応方法も知られている。これは、Ｓｃｈｏｔｔｅｎ
−Ｂａｕｍａｎｎ反応と呼ばれる反応方法であり、副生
塩化水素除去剤である水酸化ナトリウム、炭酸ナトリウ
ム、酢酸ナトリウム等を含有したアルカリ水溶液を溶媒
として用いる方法である。一般に、カルボン酸クロリド
は加水分解性を有するが、カルボン酸クロリドの加水分
解速度よりもカルボン酸クロリドとアミンとの反応速度
の方が速いため、カルボン酸アミドの生成が有利に行わ
れることになる。このＳｃｈｏｔｔｅｎ−Ｂａｕｍａｎ
ｎ反応の応用としては、水を溶媒とし、水酸化ナトリウ
ム等のアルカリ水溶液を徐々に滴下して、反応系のｐＨ
を常に中性付近に調整しながら反応を行う方法もある。On the other hand, a reaction method using water as a solvent without using an organic solvent is also known. This is Schotten
This is a reaction method called a -Baumann reaction, in which an aqueous alkali solution containing sodium hydroxide, sodium carbonate, sodium acetate, and the like as by-product hydrogen chloride removing agents is used as a solvent. In general, carboxylic acid chloride has hydrolyzability, but since the reaction rate between carboxylic acid chloride and amine is faster than the rate of hydrolysis of carboxylic acid chloride, formation of carboxylic acid amide is advantageously performed. . This Schotten-Bauman
As an application of the n-reaction, use water as a solvent, and gradually drop an alkaline aqueous solution such as sodium hydroxide to adjust the pH of the reaction system.
There is also a method in which the reaction is carried out while always adjusting the pH to near neutrality.
【０００４】工業的にカルボン酸アミド化合物を製造す
る場合には、有機溶媒を使用せずにアルカリ水溶液中で
反応を行う方法が、生産コスト面からも、また、簡単な
装置で製造を行えることからも有利である。しかし、ア
ルカリ水溶液を溶媒とした場合には、有機溶媒を使用し
た場合に比べて反応成分であるカルボン酸クロリド及び
アミンの溶解性が劣るため、反応系内でハルツが発生し
たり、もっと悪い場合には反応が進行しないこともあ
る。In the case of industrially producing a carboxylic acid amide compound, a method in which the reaction is carried out in an aqueous alkali solution without using an organic solvent requires a simple apparatus from the viewpoint of production cost. Is also advantageous. However, when an alkaline aqueous solution is used as a solvent, the solubility of the carboxylic acid chloride and the amine as the reaction components is inferior to that in the case where an organic solvent is used, so that Harz is generated in the reaction system or worse. In some cases, the reaction does not proceed.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、カルボン酸
クロリドとアミンとの反応において、有機溶媒を使用せ
ず、しかも、副生する塩化水素を除去するための塩基を
共存させることなしに、容易にカルボン酸アミド化合物
を製造する方法を提供するものである。DISCLOSURE OF THE INVENTION The present invention provides a reaction between a carboxylic acid chloride and an amine without using an organic solvent and without coexisting a base for removing by-produced hydrogen chloride. It is intended to provide a method for easily producing a carboxylic acid amide compound.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明は、酢酸水
溶液中でカルボン酸クロリドと１級または２級アミンを
反応させることを特徴とするカルボン酸アミド化合物の
製造方法に関する。That is, the present invention relates to a method for producing a carboxylic acid amide compound, which comprises reacting a carboxylic acid chloride with a primary or secondary amine in an aqueous acetic acid solution.
【０００７】カルボン酸クロリドとアミンの反応は、酸
性水溶液中では進行しないと考えられており、実際に、
酢酸水溶液中で反応を行った例も知られていない。しか
し、本発明者らか検討を行った結果、カルボン酸クロリ
ドとアミンは酢酸酸性水溶液中で容易に反応し、カルボ
ン酸アミド化合物を生成することがわかった。しかも、
本発明によれば、副生塩化水素の中和除去剤を特に使用
しなくてもよいという利点がある。また、一般に、アミ
ン類は酢酸水溶液に対して良好な溶解性を示す場合が多
いため、水や有機溶媒に対して溶解度の小さなアミンを
反応成分として使用するような場合には、酢酸水溶液を
溶媒として使用することにより反応を容易に進行させる
ことができるため、本発明は特に有利である。It is believed that the reaction between carboxylic chloride and amine does not proceed in an acidic aqueous solution.
There is no known example of performing the reaction in an acetic acid aqueous solution. However, as a result of investigations by the present inventors, it was found that carboxylic acid chloride and amine easily react in an aqueous acetic acid solution to produce a carboxylic acid amide compound. Moreover,
Advantageous Effects of Invention According to the present invention, there is an advantage that a neutralizing and removing agent for by-product hydrogen chloride need not be particularly used. In general, amines often show good solubility in an aqueous acetic acid solution. Therefore, when an amine having low solubility in water or an organic solvent is used as a reaction component, the aqueous acetic acid solution is used as a solvent. The present invention is particularly advantageous since the reaction can be easily advanced by using the compound.
【０００８】本発明にかかわるカルボン酸クロリドと
は、官能基−ＣＯＣｌを有する化合物であり、芳香族化
合物であっても、脂肪族化合物であっても、脂環式化合
物であってもよい。[0008] The carboxylic acid chloride according to the present invention is a compound having a functional group -COCl, and may be an aromatic compound, an aliphatic compound, or an alicyclic compound.
【０００９】本発明にかかわるカルボン酸クロリドの一
例を示せば、ベンゾイルクロリド類、ナフトイルクロリ
ド類、アントラキノンカルボン酸クロリド類等の芳香族
カルボン酸クロリドや、ｎ−ブチリルクロリド、３，
３，５−トリメチルヘキサノイルクロリド、ｎ−デカノ
イルクロリド、ステアロイルクロリド、オレイルクロリ
ド等の脂肪族カルボン酸クロリド、または、テトラヒド
ロフルフリルクロリド等の脂環式カルボン酸クロリドが
挙げられる。Examples of the carboxylic acid chloride according to the present invention include aromatic carboxylic acid chlorides such as benzoyl chlorides, naphthoyl chlorides, anthraquinone carboxylic acid chlorides, n-butyryl chloride,
Examples thereof include aliphatic carboxylic acid chlorides such as 3,5-trimethylhexanoyl chloride, n-decanoyl chloride, stearoyl chloride and oleyl chloride, and alicyclic carboxylic acid chlorides such as tetrahydrofurfuryl chloride.
【００１０】また、本発明にかかわる１級または２級ア
ミンとは、官能基−ＮＨ2 または官能基−ＮＨ−を有す
る化合物であり、芳香族化合物であっても、脂肪族化合
物であっても、脂環式化合物であってもよい。The primary or secondary amine according to the present invention is a compound having a functional group -NH 2 or a functional group -NH-, and may be an aromatic compound or an aliphatic compound. And an alicyclic compound.
【００１１】本発明にかかわる１級または２級アミンの
一例を示せば、アニリン、ナフチルアミン、更には、ア
ニリン構造もしくはナフチルアミン構造を分子中に有す
るようなアミン類等の芳香族アミン、ｎ−プロピルアミ
ン、ｎ−ドデシルアミン、１−アミノデカン、ジブチル
アミン、ジ−ｎ−デシルアミン、エチレンジアミン、
１，６−ヘキサンジアミン、ジエチレントリアミン、ペ
ンタエチレンヘキサミン、Ｎ，Ｎ−ジエチルアミノプロ
ピルアミン、Ｎ，Ｎ−ジブチルアミノプロピルアミン、
Ｎ−アミノエチルピペリジン、Ｎ−アミノプロピルモル
ホリン等の脂肪族アミン、ピペラジン、モルホリン、ピ
ペリジン等の脂環式アミンが挙げられる。Examples of the primary or secondary amine according to the present invention include aniline, naphthylamine, aromatic amines such as amines having an aniline structure or a naphthylamine structure in the molecule, and n-propylamine. , N-dodecylamine, 1-aminodecane, dibutylamine, di-n-decylamine, ethylenediamine,
1,6-hexanediamine, diethylenetriamine, pentaethylenehexamine, N, N-diethylaminopropylamine, N, N-dibutylaminopropylamine,
Examples thereof include aliphatic amines such as N-aminoethylpiperidine and N-aminopropylmorpholine, and alicyclic amines such as piperazine, morpholine and piperidine.
【００１２】本発明に従って、酢酸水溶液を溶媒として
カルボン酸クロリドとアミンとの反応によりカルボン酸
アミド化合物を製造する場合、酢酸水溶液の濃度は特に
限定されるものではないが、好ましくは５〜９０重量
％、更に好ましくは２０〜８０重量％である。また、酢
酸水溶液の使用量は、反応系が充分に攪拌できる量であ
れば差し支えないが、反応成分であるアミンの５重量倍
以上とすることが好ましい。また、反応温度及び反応時
間は、反応成分であるカルボン酸クロリドとアミンの反
応性により左右されるが、通常は０〜１００℃、好まし
くは２０〜７０℃の温度範囲で、１〜１０時間程度の反
応を行う。カルボン酸クロリドとアミンの種類により、
酢酸水溶液の濃度、反応温度、反応時間をコントロ−ル
することが望ましい。According to the present invention, when a carboxylic acid amide compound is produced by reacting a carboxylic acid chloride with an amine using an aqueous acetic acid solution as a solvent, the concentration of the aqueous acetic acid solution is not particularly limited, but is preferably 5 to 90% by weight. %, More preferably 20 to 80% by weight. The amount of the acetic acid aqueous solution may be used as long as the reaction system can be sufficiently stirred, but is preferably at least 5 times the weight of the amine as a reaction component. The reaction temperature and the reaction time depend on the reactivity of the carboxylic acid chloride as a reaction component and the amine, but are usually from 0 to 100 ° C, preferably from 20 to 70 ° C, for about 1 to 10 hours. Is performed. Depending on the type of carboxylic acid chloride and amine,
It is desirable to control the concentration of the acetic acid aqueous solution, the reaction temperature, and the reaction time.
【００１３】本発明における反応成分であるカルボン酸
クロリドとアミンの使用量は、化学量論量であってもよ
く、場合によってはどちらかの成分を過剰に使用しても
よい。また、本発明に従ってカルボン酸アミド化合物を
製造する場合には、副生する塩化水素を除去するための
塩基を反応系に共存させる必要はないが、塩基共存下で
反応を行うことも可能である。The amounts of the carboxylic acid chloride and amine used as the reaction components in the present invention may be stoichiometric amounts, and in some cases, either component may be used in excess. In the case of producing a carboxylic acid amide compound according to the present invention, it is not necessary to allow a base for removing by-produced hydrogen chloride to coexist in the reaction system, but the reaction can be performed in the coexistence of a base. .
【００１４】本発明の好ましい実施形態としては、ま
ず、アミン成分を酢酸水溶液に加えて溶解させた後、カ
ルボン酸クロリドを加えて反応を行う方法が考えられ
る。なお、カルボン酸クロリドやアミンが酢酸水溶液に
対して溶解度の低い固体であるような場合には、予め、
それらの固体を粉砕して微粉化しておくことが好まし
い。As a preferred embodiment of the present invention, a method is conceivable in which, first, an amine component is added to and dissolved in an aqueous acetic acid solution, and then carboxylic acid chloride is added to carry out the reaction. In the case where carboxylic acid chloride or amine is a solid having low solubility in acetic acid aqueous solution,
It is preferable to pulverize those solids to make them fine.
【００１５】次に本発明にかかわる実施例を示すが、本
発明は以下の実施例により限定されるものではない。な
お、実施例中の「部」は重量部を、「％」は重量％を表
す。Next, examples according to the present invention will be described, but the present invention is not limited to the following examples. In the examples, "parts" indicates parts by weight, and "%" indicates% by weight.
【００１６】[0016]
【実施例１】５０％酢酸水溶液１８０部にアニリン３．
４４部を加えて５分間攪拌し、アニリンを酢酸水溶液に
完全に溶解させた。次いで、アントラキノン−２−カル
ボン酸クロリド１０．００部を加え、４５℃まで昇温し
て、同温度で５時間攪拌を行った。室温まで冷却後、水
酸化ナトリウム水溶液を用いて反応系のｐＨを８〜９に
調整し、沈殿物を瀘過、水洗、乾燥して、下記化合物１
０．３７部を得た。生成物をＦＤ−ＭＳ分析した結果、
分子量３２７のピ−クが確認された。Example 1 Aniline was added to 180 parts of a 50% aqueous acetic acid solution.
44 parts were added and stirred for 5 minutes to completely dissolve the aniline in the acetic acid aqueous solution. Next, 10.00 parts of anthraquinone-2-carboxylic acid chloride was added, the temperature was raised to 45 ° C, and the mixture was stirred at the same temperature for 5 hours. After cooling to room temperature, the pH of the reaction system was adjusted to 8 to 9 using an aqueous sodium hydroxide solution, and the precipitate was filtered, washed with water and dried to obtain the following compound 1
0.37 parts were obtained. As a result of FD-MS analysis of the product,
A peak having a molecular weight of 327 was confirmed.
【００１７】[0017]
【化１】 Embedded image
【００１８】[0018]
【実施例２】６０％酢酸水溶液１５０部にｐ−ｎ−ヘキ
シルアニリン１９．１７部を加えて５分間攪拌し、ｐ−
ｎ−ヘキシルアニリンを酢酸水溶液に完全に溶解させ
た。次いで、プロピオニルクロリド１０．００部を加
え、５０℃まで昇温して、同温度で４時間攪拌を行っ
た。室温まで冷却後、水酸化ナトリウム水溶液を用いて
反応系のｐＨを８〜９に調整し、オイル状の生成物を水
層から上層に分離した。分液操作により下記化合物２
０．０５部を得た。生成物をＦＤ−ＭＳ分析した結果、
分子量２３３のピ−クが確認された。Example 2 19.17 parts of pn-hexylaniline was added to 150 parts of a 60% aqueous solution of acetic acid, and the mixture was stirred for 5 minutes.
n-Hexylaniline was completely dissolved in the acetic acid aqueous solution. Next, 10.00 parts of propionyl chloride was added, the temperature was raised to 50 ° C., and the mixture was stirred at the same temperature for 4 hours. After cooling to room temperature, the pH of the reaction system was adjusted to 8 to 9 using an aqueous sodium hydroxide solution, and the oily product was separated from the aqueous layer to the upper layer. Compound 2 shown below by liquid separation operation
0.05 parts were obtained. As a result of FD-MS analysis of the product,
A peak having a molecular weight of 233 was confirmed.
【００１９】[0019]
【化２】 Embedded image
【００２０】[0020]
【実施例３】４５％酢酸水溶液１７０部、ジ−ｎ−オク
チルアミン８．９１部、アントラキノン−２−カルボン
酸クロリド１０．００部を使用し、反応温度を４０℃と
して、実施例１と同様の方法により、下記化合物１７．
３０部を得た。生成物をＦＤ−ＭＳ分析した結果、分子
量４７５のピ−クが確認された。Example 3 The same procedure as in Example 1 was carried out except that 170 parts of a 45% aqueous acetic acid solution, 8.91 parts of di-n-octylamine, and 10.00 parts of anthraquinone-2-carboxylic acid chloride were used at a reaction temperature of 40 ° C. The following compound 17.
30 parts were obtained. As a result of FD-MS analysis of the product, a peak having a molecular weight of 475 was confirmed.
【００２１】[0021]
【化３】 Embedded image
【００２２】[0022]
【実施例４】５０％酢酸水溶液１２０部、ベンジルアミ
ン５．６１部、２−ナフトイルクロリド１０．００部を
使用し、反応温度を５５℃として、実施例１と同様の方
法により、下記化合物５．８３部を得た。生成物をＦＤ
−ＭＳ分析した結果、分子量２６１のピ−クが確認され
た。Example 4 The following compound was prepared in the same manner as in Example 1 using 120 parts of a 50% aqueous acetic acid solution, 5.61 parts of benzylamine, and 10.00 parts of 2-naphthoyl chloride at a reaction temperature of 55 ° C. 5.83 parts were obtained. FD the product
As a result of -MS analysis, a peak having a molecular weight of 261 was confirmed.
【００２３】[0023]
【化４】 Embedded image
【００２４】[0024]
【実施例５】５５％酢酸水溶液１５０部、ｎ−オクチル
アミン６．７８部、２−ナフトイルクロリド１０．００
部を使用し、反応温度を３５℃として、実施例１と同様
の方法により、下記化合物１３．６１部を得た。生成物
をＦＤ−ＭＳ分析した結果、分子量２８３のピ−クが確
認された。EXAMPLE 5 150 parts of 55% acetic acid aqueous solution, 6.78 parts of n-octylamine, and 10.00 of 2-naphthoyl chloride
In the same manner as in Example 1 except that the reaction temperature was 35 ° C., 13.61 parts of the following compound were obtained. As a result of FD-MS analysis of the product, a peak having a molecular weight of 283 was confirmed.
【００２５】[0025]
【化５】 Embedded image
【００２６】[0026]
【発明の効果】本発明によれば、カルボン酸クロリドと
１級もしくは２級アミンとの反応において酢酸水溶液を
溶媒として使用することにより、従来の有機溶媒を使用
した場合に比べ、工業的に簡単な装置でカルボン酸アミ
ド化合物の製造を行うことができる。また、一般にアミ
ン類は酢酸水溶液に対して良好な溶解性を示す場合が多
いため、従来、反応溶媒として使用されていた水及びア
ルカリ水溶液または有機溶媒に対して難溶性のアミンを
反応成分として使用する場合にも、容易に反応を行うこ
とができる。更に、本発明の製造方法によれば、従来、
カルボン酸クロリドとアミンからのカルボン酸アミド化
合物の製造において使用されている、副生塩化水素の除
去剤としての塩基を反応系に加えなくてもよいという利
点がある。According to the present invention, an aqueous acetic acid solution is used as a solvent in the reaction of a carboxylic acid chloride with a primary or secondary amine, so that it is industrially simpler than when a conventional organic solvent is used. The carboxylic acid amide compound can be produced with a simple apparatus. In addition, amines generally show good solubility in an aqueous acetic acid solution in many cases. Therefore, amines which have been conventionally used as a reaction solvent and are hardly soluble in water and an aqueous alkali solution or an organic solvent are used as reaction components. In this case, the reaction can be easily performed. Furthermore, according to the production method of the present invention,
There is an advantage that a base as a by-product hydrogen chloride removing agent used in the production of a carboxylic acid amide compound from a carboxylic acid chloride and an amine does not have to be added to the reaction system.
Claims (1)
級または２級アミンを反応させることを特徴とするカル
ボン酸アミド化合物の製造方法。1. A carboxylic acid chloride and an acetic acid solution in an aqueous acetic acid solution.
A method for producing a carboxylic acid amide compound, comprising reacting a secondary or secondary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10037191A JP2612645B2 (en) | 1991-04-05 | 1991-04-05 | Method for producing carboxamide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10037191A JP2612645B2 (en) | 1991-04-05 | 1991-04-05 | Method for producing carboxamide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04308558A JPH04308558A (en) | 1992-10-30 |
| JP2612645B2 true JP2612645B2 (en) | 1997-05-21 |
Family
ID=14272186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10037191A Expired - Fee Related JP2612645B2 (en) | 1991-04-05 | 1991-04-05 | Method for producing carboxamide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2612645B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010062308A1 (en) * | 2008-10-28 | 2010-06-03 | The Board Of Trustees Of The Leland Stanford Junior University | Modulators of aldehyde dehydrogenase and methods of use thereof |
| WO2012155199A1 (en) | 2011-05-16 | 2012-11-22 | Bionomics Limited | Amine derivatives as potassium channel blockers |
| JP6410790B2 (en) | 2013-03-14 | 2018-10-24 | ザ ボード オブ トラスティーズ オブ ザ レランド スタンフォード ジュニア ユニバーシティー | Mitochondrial aldehyde dehydrogenase-2 modulator and method of use thereof |
| WO2015086428A1 (en) | 2013-12-09 | 2015-06-18 | Unilever Plc | Process of making adamantanamides |
-
1991
- 1991-04-05 JP JP10037191A patent/JP2612645B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04308558A (en) | 1992-10-30 |
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