JP3637924B2 - Process for producing N-chloroaromatic carboxylic acid amide - Google Patents
Process for producing N-chloroaromatic carboxylic acid amide Download PDFInfo
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- JP3637924B2 JP3637924B2 JP08834894A JP8834894A JP3637924B2 JP 3637924 B2 JP3637924 B2 JP 3637924B2 JP 08834894 A JP08834894 A JP 08834894A JP 8834894 A JP8834894 A JP 8834894A JP 3637924 B2 JP3637924 B2 JP 3637924B2
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- acid amide
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Description
【０００１】
【産業上の利用分野】
本発明は芳香族カルボン酸アミドからＮ−クロル芳香族カルボン酸アミドを製造する方法に関する。Ｎ−クロル芳香族カルボン酸アミドは、除草剤や農薬の製造中間体、或いはプラスチック原料として使用される芳香族アミン化合物を製造する為の中間体として重要な物質である。
【０００２】
【従来の技術】
芳香族カルボン酸アミドからＮ−クロル芳香族カルボン酸アミドを製造する方法としては、特開昭４９−１２５３３１号にテレフタル酸アミドやイソフタル酸アミドの希釈した鉱酸酸性水性懸濁液中で塩素化反応を実施し、その際反応混合物の希釈度を塩素化反応の際に生じる塩化水素が反応の完結までほぼ完全に反応混合物中に溶解したままであるようにすることが記載されている。この方法ではＮ−クロル芳香族カルボン酸アミドの収率が９２〜９９％と極めて高いが、反応で生成するＮ−クロル芳香族カルボン酸アミドの結晶が極めて細かく嵩ばるため、濾過により該結晶を分離することがが極めて困難であり、また仕込芳香族カルボン酸アミドの濃度を低くする必要があるので、操作性の点から工業化が困難である。
【０００３】
また特開昭５１−９８２３６号には、上記の方法の外に、芳香族及び脂環式カルボン酸アミドを氷酢酸または酢酸アルカリ塩との混合物中で塩素化する方法が記載されている。この方法では反応後生成した結晶に含浸している鉱酸と酢酸アルカリ塩から生成する鉱酸のアルカリ塩を水による洗浄により除去しなければならないので操作が繁雑である。
【０００４】
【発明が解決しようとする課題】
従来技術の欠点を克服するための手段として、本発明者等は先にメチルアルコール中で塩素化反応を行う方法を提案した（特開平５−６５２５９号）。
この方法では撹拌および濾過性の良好なＮ−クロル芳香族カルボン酸アミドを高濃度、高収率で得られる。しかしながらこの方法では、得られる結晶の純度が 4,4'-ジフェニルエーテルジカルボン酸−ビス−Ｎ−クロルアミドで９３．４重量％、2,6-ナフタレンジカルボン酸−Ｎ−ビス−クロルアミドで９１．８重量％であり、結晶の純度が低いことが難点である。
本発明の目的は、芳香族カルボン酸アミドからＮ−クロル芳香族カルボン酸アミドを高収率、高純度で工業的に有利に製造する方法を提供することである。
【０００５】
【課題を解決するための手段】
発明者等は、上記の如き課題を有するＮ−クロル芳香族カルボン酸アミドの製造法について鋭意研究を行った結果、従来の芳香族カルボン酸アミドの塩素化反応によるＮ−クロル芳香族カルボン酸アミドの製造法は、芳香族カルボン酸アミドの懸濁液中へ塩素ガスを導入しているので反応初期における反応液中の塩素濃度が極めて低く反応速度が小さいので副生物が多くなること、従って予め溶媒中に塩素を溶解して反応初期の塩素濃度を高めることにより反応速度が大きくなり、Ｎ−クロル芳香族カルボン酸アミドが短時間の反応で高濃度、高純度、高収率で得られるようになることを見い出し、本発明に到達した。
【０００６】
即ち本発明は、一般式 Ｚ（ＣＯＮＨ２）ｎ〔Ｚはベンゼン、ビフェニル、ジフェニルエーテル、ジフェニルスルホン、ジフェニルメタンまたはナフタレン基、ｎは１〜３の整数〕で表される芳香族カルボン酸アミドを、少なくともメチルアルコールまたはジメチルホルムアミドを含み、予め塩素を溶解した溶媒と混合して塩素化反応を行うことを特徴とするＮ−クロル芳香族カルボン酸アミドの製造法である。
【０００７】
本発明における原料の芳香族カルボン酸アミドは、ベンゼン、ビフェニル、ジフェニルエーテル、ジフェニルスルホン、ジフェニルメタンまたはナフタレン基の如き単環、複環または縮合環の芳香環を有するカルボン酸アミドであり、対応するＮ−クロル芳香族カルボン酸アミドが得られる。
即ち上記の芳香族カルボン酸アミドを塩素化することにより、一般式 Ｚ（ＣＯＮＨＣl ）n 〔Ｚはベンゼン、ビフェニル、ジフェニルエーテル、ジフェニルスルホン、ジフェニルメタンまたはナフタレン基、n は１〜３の整数〕で表されるＮ−クロル芳香族カルボン酸アミドが製造される。
【０００８】
原料の芳香族カルボン酸アミドの具体例としては、ベンズアミド、フタル酸アミド、イソフタル酸アミド、テレフタル酸アミド、 4,4'-ビフェニルジカルボン酸アミド、 4,4'-ジフェニルエーテルジカルボン酸アミド、 4,4'-ジフェニルスルホンジカルボン酸アミド、 4,4'-ジフェニルメタンジカルボン酸アミド、2,6-ナフタレンジカルボン酸アミド、1,5-ナフタレンジカルボン酸アミド等が挙げられる。
【０００９】
本発明における溶媒は塩素に対し不活性な極性溶媒が用いられ、溶媒の具体例としては、Ｈ2 Ｏ、メチルアルコール、ジメチルホルムアミド等が挙げられる。これらの溶媒は２種類以上の混合溶媒として用いても良い。
芳香族カルボン酸アミドに対して使用される溶媒の量は、芳香族カルボン酸アミドが塩素化反応条件下では結晶であることから、反応系が撹拌可能となる範囲であれば良く、通常、仕込芳香族カルボン酸アミドの濃度が２〜３０％である。溶媒の量が少なすぎると反応系内の撹拌が困難となり、また多すぎると溶媒回収の費用がかかるので経済的に好ましくない。
【００１０】
塩素化反応を行うために溶媒中に溶解させる塩素の量は、通常供給される芳香族カルボン酸アミドの（−ＣＯＮＨ2 ）に対し１〜３当量である。塩素量が少なすぎる場合には、反応速度が低下すると共に、未反応芳香族カルボン酸アミドが増加し、多すぎる場合には、未反応塩素が増加するので経済的に得策ではない。なお上記量の塩素を予め溶媒中に溶解して芳香族カルボン酸アミドと反応させるが、原料の芳香族カルボン酸アミドの添加後、更に塩素を導入して塩素化反応を促進させることもできる。
【００１１】
塩素化反応の反応温度は０〜５０℃の範囲である。反応温度が高すぎると反応で生成するＮ−クロル芳香族カルボン酸アミドが分解し、収率が低下する。また、反応温度が低すぎると反応速度が低下する。
反応時間は、芳香族カルボン酸アミドの種類及び量や反応温度等により異なるが、通常０．１〜２時間である。本発明の反応は常圧下でも加圧下でも行うことができる。
【００１２】
反応で生成したＮ−クロル芳香族カルボン酸アミドの結晶は、副生塩化水素及び溶媒を減圧留去することにより、或いは濾過することによって容易に分離回収される。
本発明の方法では撹拌性及び濾過性の良好なＮ−クロル芳香族カルボン酸アミドが短時間の反応で高濃度、高純度、高収率で製造される。
なお本発明の反応は回分式、連続式の何れの方法でも行うことができる。
【００１３】
【実施例】
次に実施例により本発明を具体的に説明する。但し本発明はこれらの実施例により制限されるものではない。
【００１４】
実施例１
撹拌機、温度計及び塩素導入管を付した５００ｍｌの４ッ口フラスコに、メチルアルコール３００ｇを入れ、０℃にて激しく撹拌しながら、塩素９９．３ｇを２時間で導入した。次にイソフタル酸アミド１００ｇを入れ、撹拌下、反応液を２５℃まで昇温し、この温度を保ちつつ０．５時間撹拌した。
反応により得られた結晶は良好な撹拌性及び濾過性を有していた。反応終了後、反応液中の結晶を濾過し、少量のメチルアルコールにて洗浄後、乾燥して白色結晶１４１．８ｇを得た。この結晶を液体クロマトグラフィーにて分析したところ、 N,N'-ジクロルイソフタル酸アミドの含量は９９．３重量％であり、原料のイソフタル酸アミドに対する収率は９９．２モル％であった。
【００１５】
実施例２
実施例１と同様な反応器に、メチルアルコール１５０ｇ、Ｈ2 Ｏ１５０ｇを入れ、０℃にて激しく撹拌しながら塩素１４．５ｇを１時間で導入した。次に2,6-ナフタレンジカルボン酸アミド１２．５ｇを入れ、撹拌下、反応液を２５℃まで昇温し、この温度を保ちつつ１時間撹拌した。
反応により得られた結晶は良好な撹拌性及び濾過性を有していた。反応終了後、反応液中の結晶を濾過し、少量のメチルアルコールにて洗浄後、乾燥して淡黄色結晶１６．０ｇを得た。この結晶を液体クロマトグラフィーにて分析したところ、2,6-ナフタレンジカルボン酸−ビス−Ｎ−クロルアミドの含量は９８．０重量％であり、原料のナフタレンジカルボン酸アミドに対する収率は９５．１モル％であった。
【００１６】
実施例３
実施例１と同様な反応器に、ジメチルホルムアミド３００ｇを入れ、０℃にて激しく撹拌しながら、塩素２８．９ｇを１時間で導入した。次に 4,4'-ジフェニルエーテルジカルボン酸アミド２６．１ｇを入れ、撹拌下、反応液を２５℃まで昇温し、この温度を保ちつつ１時間撹拌した。
反応終了後、反応液を液体クロマトグラフィーにて分析したところ、原料の4,4'- ジフェニルエーテルジカルボン酸アミドに対する 4,4'-ジフェニルエーテルジカルボン酸−ビス−Ｎ−クロルアミドの収率は９８．７モル％であった。
【００１７】
実施例４
実施例１と同様な反応器に、メチルアルコール３００ｇを入れ、０℃にて激しく撹拌しながら、塩素９９．３ｇを２時間で導入した。次にテレフタル酸アミド１００ｇを入れ、撹拌下、反応液を５℃まで昇温し、この温度を保ちつつ２時間撹拌した。
反応終了後、反応液を液体クロマトグラフィーにて分析したところ、原料のテレフタル酸アミドに対する N,N'-ジクロルテレフタル酸アミドの収率は９９．３モル％であった。
【００１８】
【発明の効果】
実施例から明らかなように、本発明の方法によれば芳香族カルボン酸アミドから撹拌及び濾過性の良いＮ−クロル芳香族カルボン酸アミドが短時間の反応で、高濃度、高純度、高収率で製造される。
従って本発明によりＮ−クロル芳香族カルボン酸アミドを工業的に非常に有利に製造することができ、本発明の工業的意義が大きい。[0001]
[Industrial application fields]
The present invention relates to a method for producing an N-chloro aromatic carboxylic acid amide from an aromatic carboxylic acid amide. N-chloroaromatic carboxylic acid amide is an important substance as an intermediate for producing an aromatic amine compound used as an intermediate for producing herbicides and agricultural chemicals or as a raw material for plastics.
[0002]
[Prior art]
As a method for producing N-chloroaromatic carboxylic acid amide from aromatic carboxylic acid amide, JP-A-49-125331 discloses chlorination in a dilute acidic acidic aqueous suspension of terephthalic acid amide or isophthalic acid amide. It is described that the reaction is carried out so that the dilution of the reaction mixture is such that the hydrogen chloride produced during the chlorination reaction remains almost completely dissolved in the reaction mixture until the completion of the reaction. In this method, the yield of N-chloroaromatic carboxylic acid amide is extremely high at 92 to 99%, but the crystals of N-chloroaromatic carboxylic acid amide produced by the reaction are very fine and bulky. It is extremely difficult to separate, and since it is necessary to reduce the concentration of the charged aromatic carboxylic acid amide, it is difficult to industrialize from the viewpoint of operability.
[0003]
JP-A-51-98236 describes a method of chlorinating aromatic and alicyclic carboxylic acid amides in a mixture with glacial acetic acid or alkali acetate, in addition to the above method. In this method, since the mineral acid impregnated in the crystals formed after the reaction and the alkali salt of the mineral acid generated from the alkali acetate must be removed by washing with water, the operation is complicated.
[0004]
[Problems to be solved by the invention]
As a means for overcoming the drawbacks of the prior art, the present inventors previously proposed a method of performing a chlorination reaction in methyl alcohol (Japanese Patent Laid-Open No. 5-65259).
In this method, an N-chloroaromatic carboxylic acid amide having good stirring and filterability can be obtained in high concentration and high yield. However, in this method, the purity of the crystals obtained is 93.4% by weight for 4,4′-diphenyl ether dicarboxylic acid-bis-N-chloramide and 91.8% by weight for 2,6-naphthalenedicarboxylic acid-N-bis-chloramide. %, And the crystal purity is low.
An object of the present invention is to provide a method for industrially advantageously producing N-chloro aromatic carboxylic acid amide from aromatic carboxylic acid amide with high yield and high purity.
[0005]
[Means for Solving the Problems]
As a result of diligent research on a method for producing N-chloro aromatic carboxylic acid amides having the above-mentioned problems, the inventors have found that N-chloro aromatic carboxylic acid amides by chlorination reaction of conventional aromatic carboxylic acid amides In this method, chlorine gas is introduced into the suspension of the aromatic carboxylic acid amide, so the chlorine concentration in the reaction solution at the initial stage of the reaction is extremely low and the reaction rate is low. By dissolving chlorine in the solvent and increasing the chlorine concentration at the initial stage of the reaction, the reaction rate increases, so that N-chloroaromatic carboxylic acid amide can be obtained in high concentration, high purity, and high yield in a short reaction. The present invention has been found.
[0006]
That is, the present invention provides at least an aromatic carboxylic acid amide represented by the general formula Z (CONH 2 ) n (Z is benzene, biphenyl, diphenyl ether, diphenylsulfone, diphenylmethane or naphthalene group, n is an integer of 1 to 3). A method for producing an N-chloroaromatic carboxylic acid amide, which comprises carrying out a chlorination reaction by mixing methyl alcohol or dimethylformamide with a solvent in which chlorine is previously dissolved.
[0007]
The starting aromatic carboxylic acid amide in the present invention is a carboxylic acid amide having a monocyclic, bicyclic or condensed aromatic ring such as benzene, biphenyl, diphenyl ether, diphenylsulfone, diphenylmethane or naphthalene group, and the corresponding N- A chloroaromatic carboxylic acid amide is obtained.
That is, by chlorinating the above aromatic carboxylic acid amide, it is represented by the general formula Z (CONHC1) n (Z is a benzene, biphenyl, diphenyl ether, diphenylsulfone, diphenylmethane or naphthalene group, and n is an integer of 1 to 3). N-chloroaromatic carboxylic acid amide is produced.
[0008]
Specific examples of the starting aromatic carboxylic acid amide include benzamide, phthalic acid amide, isophthalic acid amide, terephthalic acid amide, 4,4'-biphenyldicarboxylic acid amide, 4,4'-diphenyl ether dicarboxylic acid amide, 4,4 Examples include '-diphenylsulfone dicarboxylic acid amide, 4,4'-diphenylmethane dicarboxylic acid amide, 2,6-naphthalenedicarboxylic acid amide, 1,5-naphthalenedicarboxylic acid amide, and the like.
[0009]
As the solvent in the present invention, a polar solvent inert to chlorine is used, and specific examples of the solvent include H 2 O, methyl alcohol, dimethylformamide and the like. These solvents may be used as a mixed solvent of two or more types.
The amount of the solvent used for the aromatic carboxylic acid amide is not limited as long as the aromatic carboxylic acid amide is crystallized under the chlorination reaction conditions, so long as the reaction system can be stirred. The concentration of the aromatic carboxylic acid amide is 2 to 30%. If the amount of the solvent is too small, stirring in the reaction system becomes difficult, and if the amount is too large, the cost for recovering the solvent increases, which is not economically preferable.
[0010]
The amount of chlorine dissolved in the solvent to perform the chlorination reaction is 1 to 3 equivalents relative to (—CONH 2 ) of the aromatic carboxylic acid amide that is usually supplied. When the amount of chlorine is too small, the reaction rate decreases and unreacted aromatic carboxylic acid amide increases. When the amount is too large, unreacted chlorine increases, which is not economically advantageous. The above amount of chlorine is dissolved in a solvent in advance and reacted with the aromatic carboxylic acid amide. However, after addition of the raw material aromatic carboxylic acid amide, chlorine can be further introduced to promote the chlorination reaction.
[0011]
The reaction temperature of the chlorination reaction is in the range of 0-50 ° C. If the reaction temperature is too high, the N-chloroaromatic carboxylic acid amide produced by the reaction is decomposed and the yield decreases. On the other hand, if the reaction temperature is too low, the reaction rate decreases.
The reaction time varies depending on the type and amount of the aromatic carboxylic acid amide, the reaction temperature, etc., but is usually 0.1 to 2 hours. The reaction of the present invention can be carried out under normal pressure or under pressure.
[0012]
The crystals of N-chloroaromatic carboxylic acid amide produced by the reaction are easily separated and recovered by distilling off the by-product hydrogen chloride and the solvent under reduced pressure or by filtration.
In the method of the present invention, an N-chloroaromatic carboxylic acid amide having good stirring properties and filterability is produced in a high concentration, high purity and high yield by a short reaction.
The reaction of the present invention can be carried out by either a batch method or a continuous method.
[0013]
【Example】
Next, the present invention will be described specifically by way of examples. However, the present invention is not limited by these examples.
[0014]
Example 1
300 g of methyl alcohol was put into a 500 ml four-necked flask equipped with a stirrer, a thermometer and a chlorine inlet tube, and 99.3 g of chlorine was introduced in 2 hours with vigorous stirring at 0 ° C. Next, 100 g of isophthalic acid amide was added, and while stirring, the reaction solution was heated to 25 ° C. and stirred for 0.5 hour while maintaining this temperature.
The crystals obtained by the reaction had good stirring properties and filterability. After completion of the reaction, the crystals in the reaction solution were filtered, washed with a small amount of methyl alcohol, and dried to obtain 141.8 g of white crystals. When this crystal was analyzed by liquid chromatography, the content of N, N′-dichloroisophthalamide was 99.3% by weight, and the yield based on the raw material isophthalamide was 99.2 mol%. .
[0015]
Example 2
In a reactor similar to that of Example 1, 150 g of methyl alcohol and 150 g of H 2 O were introduced, and 14.5 g of chlorine was introduced in 1 hour with vigorous stirring at 0 ° C. Next, 12.5 g of 2,6-naphthalenedicarboxylic acid amide was added, and while stirring, the reaction solution was heated to 25 ° C. and stirred for 1 hour while maintaining this temperature.
The crystals obtained by the reaction had good stirring properties and filterability. After completion of the reaction, crystals in the reaction solution were filtered, washed with a small amount of methyl alcohol, and dried to obtain 16.0 g of pale yellow crystals. When the crystals were analyzed by liquid chromatography, the content of 2,6-naphthalenedicarboxylic acid-bis-N-chloramide was 98.0% by weight, and the yield based on naphthalenedicarboxylic acid amide as a raw material was 95.1 mol. %Met.
[0016]
Example 3
In a reactor similar to that in Example 1, 300 g of dimethylformamide was introduced, and 28.9 g of chlorine was introduced in 1 hour with vigorous stirring at 0 ° C. Next, 26.1 g of 4,4′-diphenyl ether dicarboxylic acid amide was added, and the reaction solution was heated to 25 ° C. with stirring, and stirred for 1 hour while maintaining this temperature.
After completion of the reaction, the reaction solution was analyzed by liquid chromatography. As a result, the yield of 4,4′-diphenyl ether dicarboxylic acid-bis-N-chloramide relative to 4,4′-diphenyl ether dicarboxylic acid amide as a raw material was 98.7 mol. %Met.
[0017]
Example 4
In a reactor similar to that in Example 1, 300 g of methyl alcohol was added, and 99.3 g of chlorine was introduced in 2 hours with vigorous stirring at 0 ° C. Next, 100 g of terephthalic acid amide was added, the reaction solution was heated to 5 ° C. with stirring, and stirred for 2 hours while maintaining this temperature.
When the reaction solution was analyzed by liquid chromatography after the completion of the reaction, the yield of N, N′-dichloroterephthalic acid amide with respect to the raw material terephthalic acid amide was 99.3 mol%.
[0018]
【The invention's effect】
As is apparent from the examples, according to the method of the present invention, N-chloroaromatic carboxylic acid amide with good stirring and filterability from aromatic carboxylic acid amide can be reacted in a short time with high concentration, high purity, and high yield. Manufactured at a rate.
Therefore, according to the present invention, N-chloroaromatic carboxylic acid amide can be produced industrially very advantageously, and the industrial significance of the present invention is great.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08834894A JP3637924B2 (en) | 1994-04-26 | 1994-04-26 | Process for producing N-chloroaromatic carboxylic acid amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08834894A JP3637924B2 (en) | 1994-04-26 | 1994-04-26 | Process for producing N-chloroaromatic carboxylic acid amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07291910A JPH07291910A (en) | 1995-11-07 |
| JP3637924B2 true JP3637924B2 (en) | 2005-04-13 |
Family
ID=13940335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08834894A Expired - Fee Related JP3637924B2 (en) | 1994-04-26 | 1994-04-26 | Process for producing N-chloroaromatic carboxylic acid amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3637924B2 (en) |
-
1994
- 1994-04-26 JP JP08834894A patent/JP3637924B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07291910A (en) | 1995-11-07 |
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