JPH07291910A - Production of n-chloro aromatic carboxylic acid amide - Google Patents
Production of n-chloro aromatic carboxylic acid amideInfo
- Publication number
- JPH07291910A JPH07291910A JP8834894A JP8834894A JPH07291910A JP H07291910 A JPH07291910 A JP H07291910A JP 8834894 A JP8834894 A JP 8834894A JP 8834894 A JP8834894 A JP 8834894A JP H07291910 A JPH07291910 A JP H07291910A
- Authority
- JP
- Japan
- Prior art keywords
- acid amide
- carboxylic acid
- aromatic carboxylic
- reaction
- solvent
- 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
Abstract
Description
【０００１】[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。FIELD OF THE INVENTION The present invention relates to a process for producing N-chloroaromatic carboxylic acid amides from aromatic carboxylic acid amides. N-chloroaromatic carboxylic acid amides are important substances as intermediates for the production of herbicides and agricultural chemicals, or intermediates for the production of aromatic amine compounds used as plastic raw materials.
【０００２】[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。As a method for producing N-chloroaromatic carboxylic acid amide from aromatic carboxylic acid amide, JP-A-49-125331 discloses a method of diluting terephthalic acid amide or isophthalic acid amide with a mineral acid acidic aqueous suspension. Carrying out the chlorination reaction in a liquid, the degree of dilution of the reaction mixture being such that the hydrogen chloride produced during the chlorination reaction remains almost completely dissolved in the reaction mixture until the completion of the reaction Has been done. According to this method, the yield of N-chloroaromatic carboxylic acid amide is as high as 92 to 99%, but the crystals of N-chloroaromatic carboxylic acid amide produced in the reaction are extremely fine and bulky, and therefore the crystals are filtered to obtain the crystals. Separation is extremely difficult, and since the concentration of the charged aromatic carboxylic acid amide needs to be lowered, industrialization is difficult from the viewpoint of operability.
【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。In addition to the above-mentioned method, 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. There is. In this method, the mineral acid impregnated in the crystals produced after the reaction and the alkali salt of the mineral acid generated from the alkali acetate must be removed by washing with water, so that the operation is complicated.
【０００４】[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。As a means for overcoming the drawbacks of the prior art, the present inventors have previously proposed a method of carrying out a chlorination reaction in methyl alcohol (Japanese Patent Laid-Open No. Hei 5-
65259). According to this method, N-chloroaromatic carboxylic acid amide having good stirring and filterability can be obtained in high concentration and high yield. However, according to this method, the purity of crystals obtained is 93.4% by weight with 4,4'-diphenyletherdicarboxylic acid-bis-N-chloroamide and 91.8% by weight with 2,6-naphthalenedicarboxylic acid-N-bis-chloroamide. %, Which is a problem that the crystal purity is low. An object of the present invention is to provide a method for industrially advantageously producing N-chloroaromatic carboxylic acid amide from aromatic carboxylic acid amide in high yield and high purity.
【０００５】[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。Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for producing an N-chloroaromatic carboxylic acid amide having the above-mentioned problems, and as a result, the conventional chlorination reaction of an aromatic carboxylic acid amide In the method for producing N-chloroaromatic carboxylic acid amide according to, since chlorine gas is introduced into the suspension of aromatic carboxylic acid amide, the chlorine concentration in the reaction solution at the initial stage of the reaction is extremely low and the reaction rate is low. Since the amount of by-products increases, the reaction rate is increased by previously dissolving chlorine in the solvent to increase the chlorine concentration at the initial stage of the reaction, and the N-chloroaromatic carboxylic acid amide is highly concentrated and highly concentrated in a short reaction time. The present invention has been achieved by finding that it can be obtained with high purity and high yield.
【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、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。That is, the present invention relates to the general formula Z (CONH 2 )
n [Z is benzene, biphenyl, diphenyl ether,
An aromatic carboxylic acid amide represented by diphenyl sulfone, diphenylmethane or a naphthalene group, n is an integer of 1 to 3] is mixed with a solvent in which chlorine is dissolved in advance to carry out a chlorination reaction. It is a method for producing an aromatic carboxylic acid amide.
【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（ＣＯＮＨ
Ｃl ）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。Aromatic carboxylic acid amides as raw materials in the present invention are benzene, biphenyl, diphenyl ether,
Carboxylic acid amides having a monocyclic, polycyclic or condensed aromatic ring such as diphenylsulfone, diphenylmethane or naphthalene groups, and corresponding N-chloroaromatic carboxamides are obtained. That is, by chlorinating the above aromatic carboxylic acid amide, a compound of the general formula Z (CONH
Cl) n [Z is a benzene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylmethane or naphthalene group, n is an integer of 1 to 3] to produce an N-chloroaromatic carboxylic acid amide.
【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。Specific examples of the raw material aromatic carboxylic acid amide include benzamide, phthalic acid amide, isophthalic acid amide, terephthalic acid amide, 4,4'-biphenyldicarboxylic acid amide, 4,4'-diphenyletherdicarboxylic acid amide, 4,4'-diphenylsulfone dicarboxylic acid amide, 4,4'-diphenylmethane dicarboxylic acid amide, 2,6-
Examples thereof include naphthalenedicarboxylic acid amide and 1,5-naphthalenedicarboxylic acid amide.
【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。A polar solvent inert to chlorine is used as the solvent in the present invention. Specific examples of the solvent include H 2 O and
Examples thereof include methyl alcohol and dimethylformamide. You may use these solvents as a mixed solvent of 2 or more types. The amount of the solvent used for the aromatic carboxylic acid amide may be within a range in which the reaction system can be stirred, since the aromatic carboxylic acid amide is a crystal under the chlorination reaction condition, and usually, 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 it is too large, the cost of solvent recovery is high, which is not economically preferable.
【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。The amount of chlorine to be dissolved in the solvent for carrying out the chlorination reaction is 1 to 3 equivalents relative to (-CONH 2 ) of the aromatic carboxylic acid amide usually supplied. If the amount of chlorine is too small, the reaction rate will decrease and unreacted aromatic carboxylic acid amide will increase. If it is too large, the amount of unreacted chlorine will increase, which is not economically advantageous.
Although the above-mentioned amount of chlorine is previously dissolved in a solvent to react with the aromatic carboxylic acid amide, chlorine can be introduced after the addition of the raw material aromatic carboxylic acid amide to accelerate the chlorination reaction.
【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。The reaction temperature of the chlorination reaction is in the range of 0 to 50 ° C. If the reaction temperature is too high, the N-chloroaromatic carboxylic acid amide produced in the reaction is decomposed and the yield is lowered.
Further, if the reaction temperature is too low, the reaction rate will decrease. The reaction time varies depending on the kind 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】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。The crystals of N-chloroaromatic carboxylic acid amide produced in the reaction are easily separated and recovered by distilling off the by-product hydrogen chloride and the solvent under reduced pressure or by filtering. According to the method of the present invention, N-chloroaromatic carboxylic acid amide having good stirring property and filterability is produced in a short reaction time in high concentration, high purity and high yield. The reaction of the present invention can be performed by either a batch method or a continuous method.
【００１３】[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。EXAMPLES The present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.
【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。Example 1 500 ml of 4 equipped with a stirrer, thermometer and chlorine inlet tube
Put 300 g of methyl alcohol in a neck flask and
With vigorous stirring at 0 ° C., 99.3 g of chlorine were introduced in 2 hours. Next, 100 g of isophthalic acid amide was added, and the reaction solution was heated to 25 ° C. with stirring and stirred for 0.5 hours while maintaining this temperature. The crystals obtained by the reaction had good stirrability and filterability. After completion of the reaction, crystals in the reaction solution are filtered and washed with a small amount of methyl alcohol,
It was dried to obtain 141.8 g of white crystals. When the crystals were analyzed by liquid chromatography, the content of N, N'-dichloroisophthalic acid amide was 99.3% by weight,
The yield based on the raw material isophthalic acid amide was 99.2 mol%.
【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１５０
ｇ、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。Example 2 A reactor similar to that used in Example 1 was charged with methyl alcohol 150.
and 150 g of H 2 O were added, and 14.5 g of chlorine was introduced in 1 hour while vigorously stirring at 0 ° C. Next, 12.5 g of 2,6-naphthalenedicarboxylic acid amide was added, the reaction solution was heated to 25 ° C. with stirring, and the mixture was stirred for 1 hour while maintaining this temperature. The crystals obtained by the reaction had good stirrability and filterability. After the reaction was completed, the 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-chloroamide was 98.0% by weight, and the yield based on the naphthalenedicarboxylic acid amide as a raw material was 95.1 mol. %Met.
【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３０
０ｇ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。Example 3 A reactor similar to that used in Example 1 was charged with dimethylformamide 30.
0 g was added and chlorine 28.
9 g were introduced in 1 hour. 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 to find that the yield of 4,4'-diphenyletherdicarboxylic acid-bis-N-chloroamide was 98.7 with respect to the starting 4,4'-diphenyletherdicarboxylic acid amide.
It was mol%.
【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。Example 4 300 g of methyl alcohol was placed in the same reactor as in Example 1.
99.3g chlorine with vigorous stirring at 0 ° C
Was introduced in 2 hours. Next, 100 g of terephthalic acid amide
The reaction liquid was heated to 5 ° C. with stirring, and the mixture was stirred for 2 hours while maintaining this temperature. After the completion of the reaction, the reaction solution was analyzed by liquid chromatography. As a result, the yield of N, N'-dichloroterephthalic acid amide was 99.3 mol% based on the starting material terephthalic acid amide.
【００１８】[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。As is apparent from the examples, according to the method of the present invention, N-chloro aromatic carboxylic acid amide having good stirring and filterability is converted from aromatic carboxylic acid amide in a short reaction at a high concentration, It is manufactured with high purity and high yield. Therefore, according to the present invention, an N-chloroaromatic carboxylic acid amide can be produced industrially very advantageously, and the industrial significance of the present invention is great.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大川 隆 新潟県新潟市太夫浜字新割182番地 三菱 瓦斯化学株式会社新潟研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takashi Okawa Niigata City, Niigata City, Tayuhama, Niiwari 182 Shinwari, Mitsubishi Gas Chemical Co., Ltd. Niigata Research Center
Claims (1)
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、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1. A compound represented by the general formula Z (CONH 2 ) n [Z is a benzene, biphenyl, diphenyl ether, diphenyl sulfone, diphenylmethane or naphthalene group, and n is 1 to 1
An integer of 3], and a chlorination reaction is carried out by mixing an aromatic carboxylic acid amide represented by the formula [3] with a solvent in which chlorine is dissolved in advance.
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 true JPH07291910A (en) | 1995-11-07 |
| JP3637924B2 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 |
|---|---|
| JP3637924B2 (en) | 2005-04-13 |
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