JPH09157239A - Production of 4,6-bis(substituted)phenyl azoresorcinol - Google Patents
Production of 4,6-bis(substituted)phenyl azoresorcinolInfo
- Publication number
- JPH09157239A JPH09157239A JP34648395A JP34648395A JPH09157239A JP H09157239 A JPH09157239 A JP H09157239A JP 34648395 A JP34648395 A JP 34648395A JP 34648395 A JP34648395 A JP 34648395A JP H09157239 A JPH09157239 A JP H09157239A
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- substituted
- salt
- solution
- alkaline earth
- alkali metal
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、（置換）ベンゼン
ジアゾニウム塩溶液にアルカリ金属又はアルカリ土類金
属の水酸化物の溶液又は懸濁液を混合しアルカリ性と
し、このアルカリ性の混合液にレゾルシノール及び／又
はそのアルカリ金属塩若しくはアルカリ土類金属塩に混
合して反応させることを特徴とする４，６−ビス（置
換）フェニルアゾレゾルシノールの製造法に関する。TECHNICAL FIELD The present invention relates to a (substituted) benzenediazonium salt solution which is mixed with a solution or suspension of an alkali metal or alkaline earth metal hydroxide to make it alkaline, and the alkaline mixed solution is mixed with resorcinol and And / or a method for producing 4,6-bis (substituted) phenylazoresorcinol, which comprises reacting with an alkali metal salt or alkaline earth metal salt thereof.
【０００２】４，６−ビス（置換）フェニルアゾレゾル
シノールからは還元することにより容易に４，６−ジア
ミノレゾルシノールが得られる（参照：Advanced Organ
ic Chemistry,4th Edition,John Wiley and Sons,(199
2) page 1224)。4,6-bis (substituted) phenylazoresorcinol can be easily reduced to give 4,6-diaminoresorcinol (see Advanced Organ).
ic Chemistry, 4th Edition, John Wiley and Sons, (199
2) page 1224).
【０００３】[0003]
【化３】 ４，６−ジアミノレゾルシノール〔ＤＡＲ〕は、テレフ
タル酸と縮合させると、種々の優れた特徴を持つポリベ
ンズビスオキサゾール（ＰＢＯ）となるので、その原料
として重要である。Embedded image When condensed with terephthalic acid, 4,6-diaminoresorcinol [DAR] becomes polybenzbisoxazole (PBO) having various excellent characteristics and is important as a raw material thereof.
【０００４】ＰＢＯは、強度、弾性率、耐熱性、耐薬品
性等の諸点に於て、従来のスーパー繊維より優れて居
り、超スーパー繊維として開発が待望されている（特表
昭６１−５０１４５２号公報）。PBO is superior to the conventional super fiber in various points such as strength, elastic modulus, heat resistance and chemical resistance, and is expected to be developed as an ultra super fiber (Japanese Patent Publication No. 61-501452). Issue).
【０００５】[0005]
【従来の技術】これまで、４，６−ジアミノレゾルシノ
ール〔ＤＡＲ〕を製造する方法としては、いくつか知ら
れているが、レゾルシノールと塩化ベンゼンジアゾニウ
ムからカップリング反応で４，６−ビスフェニルアゾレ
ゾルシノールを得る方法としては、Ｚｏｌｌｉｎｇｅｒ
らが緩衝溶液中、塩基性条件下で好収率で４，６−ビス
フェニルアゾレゾルシノールを得ている〔参照：Helvet
ica Chimca Acta, XLI 1816-1823(1958)〕。しかし、こ
のレゾルシノールを原料とする方法は、短工程でＤＡＲ
を得ることができる点で有利であるがレゾルシノールの
濃度は、０．１重量％であり、実用的には、生産性上問
題がある。2. Description of the Related Art There are several known methods for producing 4,6-diaminoresorcinol [DAR]. 4,6-bisphenylazoresorcinol is obtained by a coupling reaction from resorcinol and benzenediazonium chloride. The method of obtaining Zollinger
Et al. Obtained 4,6-bisphenylazoresorcinol in a good yield in a buffer solution under basic conditions [Ref: Helvet
ica Chimca Acta, XLI 1816-1823 (1958)]. However, this method using resorcinol as a raw material is a short process for DAR.
However, the concentration of resorcinol is 0.1% by weight, which is a practical problem in terms of productivity.
【０００６】また、特開平７−２４２６０４号によれ
ば、ｐＨ１０〜１２にコントロールし、レゾルシノール
と塩化（置換）ベンゼンジアゾニウムからカップリング
反応させ４，６−ビス（置換）フェニルアゾレゾルシノ
ールを比較的収率良く合成している。しかしこの方法に
おいても、希薄溶液を使用しており、これは大きな反応
容積を必要とするので工業経済的に実施が困難である。
（置換）ベンゼンジアゾニウム塩としてアニリンから誘
導される塩化ベンゼンジアゾニウムに変えて、ｐ−メト
キシアニリンから誘導される塩化ｐ−メトキシベンゼン
ジアゾニウムを用いると濃度、収率とも改善されるが、
レゾルシノールとして２重量％を越えると収率は非常に
悪くなっている。アニリンに比較して高価なｐ−メトキ
シアニリンを用い、この濃度では、工業的に実施困難で
ある。According to Japanese Patent Laid-Open No. 7-242604, the pH is controlled to 10 to 12, and a coupling reaction of resorcinol and benzenediazonium chloride (substituted) is carried out to relatively collect 4,6-bis (substituted) phenylazoresorcinol. I am synthesizing efficiently. However, even in this method, a dilute solution is used, which requires a large reaction volume, which is difficult to carry out industrially and economically.
When p-methoxybenzenediazonium chloride derived from p-methoxyaniline is used instead of benzenediazonium chloride derived from aniline as the (substituted) benzenediazonium salt, both concentration and yield are improved.
If the amount of resorcinol exceeds 2% by weight, the yield is very poor. P-methoxyaniline, which is more expensive than aniline, is used, and at this concentration, industrial implementation is difficult.
【０００７】[0007]
【発明が解決しようとする課題】上記したように、既知
の反応は、工業経済的に実施困難な希薄溶液（レゾルシ
ノールの濃度が１重量％以下）でのみ収率が良い。本発
明の目的は工業的に実施可能な濃度での、収率の良い
４，６−ビス（置換）フェニルアゾレゾルシノールの製
造法を提供するところにある。As described above, the known reaction has a good yield only in a dilute solution (concentration of resorcinol of 1% by weight or less) which is industrially difficult to carry out. It is an object of the present invention to provide a method for producing 4,6-bis (substituted) phenylazoresorcinol in good yield at a concentration that is industrially practicable.
【０００８】[0008]
【課題を解決するための手段】本発明者等は、（置換）
ベンゼンジアゾニウム塩の溶液をアルカリ性にした後
に、レゾルシノール及び／又はそのアルカリ金属塩若し
くはアルカリ土類金属塩と反応させると、工業的に実施
可能な濃度で、収率良く４，６−ビス（置換）フェニル
アゾレゾルシノールを得られる事を見いだした。[Means for Solving the Problems]
When the solution of the benzenediazonium salt is made alkaline and then reacted with resorcinol and / or its alkali metal salt or alkaline earth metal salt, the concentration of 4,6-bis (substituted) 4,6-bis (substituted) is high at an industrially practicable concentration. It was found that phenylazoresorcinol can be obtained.
【０００９】即ち、本発明は、 式［１］That is, the present invention provides the formula [1]
【化４】 （式中、Ｒはハロゲン原子、炭素原子数１〜５のアルキ
ル基、ヒドロキシカルボニル基又は炭素原子数１〜５の
アルコキシ基を表し、ｎは零又は１〜５のいずれかの整
数を表し、２個以上のＲは互いに同一又は異なっていて
もよく、そしてＸはＣｌ、Ｂｒ、ＯＳＯ3Ｈ又はＯＰＯ3
Ｈ2を表す。）で表される（置換）ベンゼンジアゾニウ
ム塩の溶液とアルカリ金属又はアルカリ土類金属の水酸
化物の溶液又は懸濁液とを混合し、アルカリ性とした混
合液を得、この混合液とレゾルシノール及び／又はその
アルカリ金属塩若しくはアルカリ土類金属塩を混合し反
応させることを特徴とする式［２］Embedded image (In the formula, R represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxycarbonyl group or an alkoxy group having 1 to 5 carbon atoms, and n represents zero or an integer of 1 to 5, Two or more R may be the same or different from each other, and X is Cl, Br, OSO 3 H or OPO 3
Representing the H 2. ) A solution of a (substituted) benzenediazonium salt represented by the formula (4) and a solution or suspension of a hydroxide of an alkali metal or an alkaline earth metal are mixed to obtain an alkaline mixed solution, and the mixed solution is mixed with resorcinol and / Or a formula [2] characterized by mixing and reacting an alkali metal salt or an alkaline earth metal salt thereof
【化５】 （式中、Ｒ及びｎは上記式［１］中と同じに定義され
る。）で表される４，６−ビス（置換）フェニルアゾレ
ゾルシノールの製造法に関する。Embedded image (In the formula, R and n are the same as those in the above formula [1].) The present invention relates to a method for producing 4,6-bis (substituted) phenylazoresorcinol.
【００１０】[0010]
【発明の実施の形態】以下、本発明を更に詳細に説明す
る。本発明は、（置換）ベンゼンジアゾニウム塩とアル
カリ金属又はアルカリ土類金属の水酸化物の溶液又は懸
濁液を混合し、アルカリ性とした混合液を得、この混合
液とレゾルシノール及び／又はそのアルカリ金属塩若し
くはアルカリ土類金属塩、例えばナトリウム塩若しくは
カルシウム塩を混合する事により、４，６−ビス（置
換）フェニルアゾレゾルシノールを製造する方法であ
る。この方法により、レゾルシノールの従来にない高い
濃度２〜１０重量％が可能になり、高収率と従来より極
めて高い容積効率が達成された。The present invention will be described in more detail below. In the present invention, a (substituted) benzenediazonium salt and a solution or suspension of a hydroxide of an alkali metal or an alkaline earth metal are mixed to obtain an alkaline mixed liquid, and the mixed liquid is mixed with resorcinol and / or its alkali. This is a method for producing 4,6-bis (substituted) phenylazoresorcinol by mixing a metal salt or an alkaline earth metal salt such as a sodium salt or a calcium salt. This method enables an unprecedented high concentration of resorcinol of 2 to 10% by weight, and achieves a high yield and an extremely higher volumetric efficiency than ever before.
【００１１】本発明の製造法の反応は、下記のスキーム
で進行する：The reaction of the production method of the present invention proceeds according to the following scheme:
【化６】 （スキーム中の置換基の定義は、式［１］中と同じであ
る。）。[Chemical 6] (Definition of the substituents in the scheme is the same as in formula [1].).
【００１２】異性体である２，４−ビス（置換）フェニ
ルアゾレゾルシノール（以下、２，４−ジ体という）の
競争反応による生成と、モノ体及びトリ体の逐次反応に
よる生成が４，６−ビス（置換）フェニルアゾレゾルシ
ノール（以下、４，６−ジ体という）の収率を下げてお
り、４，６−ジ体の収率を上げることが難しい反応であ
る。特に濃度が高い場合収率低下が著しい。The production of the isomer 2,4-bis (substituted) phenylazoresorcinol (hereinafter referred to as the 2,4-di-form) by the competitive reaction and the sequential reaction of the mono-form and the tri-form are 4,6. The yield of -bis (substituted) phenylazoresorcinol (hereinafter referred to as 4,6-di form) is lowered, and it is difficult to increase the yield of 4,6-di form. Especially when the concentration is high, the yield is significantly reduced.
【００１３】本発明で用いる（置換）ベンゼンジアゾニ
ウム塩の溶液をアルカリ性とした混合液は，例えば、ア
ニリン類を塩酸、硫酸、リン酸等の無機酸との混合溶液
とした後、亜硝酸ナトリウム水溶液を加えて（置換）ベ
ンゼンジアゾニウム塩を得、この置換ベンゼンジアゾニ
ウム塩を含む溶液とアルカリ金属又はアルカリ土類金属
の水酸化物の溶液又は懸濁液とを混合し、アルカリ性に
することにより得られる。ここで、好ましくは前記（置
換）ベンゼンジアゾニウム塩を含む前記アルカリ金属又
はアルカリ土類金属の水酸化物を含む溶液又は懸濁液に
滴下するか、あるいは前記（置換）ベンゼンジアゾニウ
ム塩を含む溶液と前記アルカリ金属又はアルカリ土類金
属の水酸化物を含む溶液又は懸濁液とを、例えばライン
上で同時的に混合することである。The mixed solution in which the solution of the (substituted) benzenediazonium salt used in the present invention is made alkaline is, for example, a mixed solution of aniline with an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, and then an aqueous sodium nitrite solution. To obtain a (substituted) benzenediazonium salt, which is obtained by mixing a solution containing the substituted benzenediazonium salt with a solution or suspension of an alkali metal or alkaline earth metal hydroxide to make the mixture alkaline. . Here, preferably, a solution or suspension containing the hydroxide of the alkali metal or alkaline earth metal containing the (substituted) benzenediazonium salt is added dropwise, or a solution containing the (substituted) benzenediazonium salt is added. Simultaneously mixing, for example, on a line with the solution or suspension containing the alkali metal or alkaline earth metal hydroxide.
【００１４】より具体的には、式［３］More specifically, the formula [3]
【化７】 （式中、Ｒとｎは式［１］中と同じに定義される。）で
表される（置換）アニリンとその（置換）アニリンに対
し５〜１０倍重量の水との混合物中に、（置換）アニリ
ンに対し２．５〜１０倍当量の無機酸を冷却下滴下し、
この混合液中へ、（置換）アニリンに対し２〜３倍重量
の水に溶解した（置換）アニリンに対し１〜１．５倍当
量の亜硝酸アルカリ塩例えば亜硝酸ナトリウム又は亜硝
酸カリウムを１０℃以下で滴下することにより、（置
換）ベンゼンジアゾニウム塩を得る。無機酸としては塩
酸、臭化水素酸、硫酸及び燐酸の中から選ばれた少なく
とも１種の無機酸が用いられる。これらの無機酸の中で
は塩酸が工業経済的に好ましい。Embedded image (In the formula, R and n are defined the same as in formula [1].) In a mixture of (substituted) aniline and 5 to 10 times by weight of water relative to the (substituted) aniline, 2.5-10 times equivalent amount of an inorganic acid is added dropwise to the (substituted) aniline under cooling,
Into this mixed solution, 1 to 1.5 times equivalent amount of an alkali nitrite such as sodium nitrite or potassium nitrite dissolved in 2 to 3 times the weight of (substituted) aniline with respect to (substituted) aniline is added at 10 ° C. The (substituted) benzenediazonium salt is obtained by dropping below. As the inorganic acid, at least one inorganic acid selected from hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid is used. Among these inorganic acids, hydrochloric acid is industrially preferable.
【００１５】本反応で用いる（置換）アニリンは、具体
的に例えばアニリン、２−クロルアニリン、４−クロル
アニリン、２，６−ジクロルアニリン、ｏ−トルイジ
ン、ｍ−トルイジン、ｐ−トルイジン、アントラニル
酸、ｏ−アニシジン、ｍ−アニシジン及びｐ−アニシジ
ン等を挙げることができる。経済性、化合物の安定性な
どを考慮するとアニリンが最も好ましい。The (substituted) aniline used in this reaction is, for example, aniline, 2-chloroaniline, 4-chloroaniline, 2,6-dichloroaniline, o-toluidine, m-toluidine, p-toluidine, anthranil. An acid, o-anisidine, m-anisidine, p-anisidine, etc. can be mentioned. Aniline is most preferable in consideration of economical efficiency and stability of the compound.
【００１６】ジアゾニウム塩生成後、過剰使用した亜硝
酸ナトリウムにより生成した亜硝酸を、尿素やスルファ
ミン酸で処理しても良い。この処理によりジアゾニウム
塩の分解が抑えられる。After the formation of the diazonium salt, the nitrous acid produced by the excess sodium nitrite may be treated with urea or sulfamic acid. This treatment suppresses the decomposition of the diazonium salt.
【００１７】このようにして得た（置換）ベンゼンジア
ゾニウム塩の溶液と、アルカリ金属又はアルカリ土類金
属の水酸化物の溶液又は懸濁液を混合し、混合液をアル
カリ性とする。The solution of the (substituted) benzenediazonium salt thus obtained is mixed with a solution or suspension of a hydroxide of an alkali metal or an alkaline earth metal, and the mixture is made alkaline.
【００１８】本反応に用いるアルカリ金属又はアルカリ
土類金属の水酸化物としては、ＮａＯＨ、ＫＯＨ、Ｌｉ
ＯＨ、Ｃａ（ＯＨ）2、Ｍｇ（ＯＨ）2 及びＢａ（Ｏ
Ｈ）2等が用いられるが、その経済性及び扱いやすさか
らＮａＯＨが好ましい。Examples of the alkali metal or alkaline earth metal hydroxide used in this reaction include NaOH, KOH, and Li.
OH, Ca (OH) 2 , Mg (OH) 2 and Ba (O
H) 2 and the like are used, but NaOH is preferable because of its economical efficiency and easy handling.
【００１９】アルカリ金属又はアルカリ土類金属の水酸
化物の量は、（置換）ベンゼンジアゾニウム塩溶液中の
酸を中和し、更にアルカリ性にするための過剰量とし
て、（置換）ベンゼンジアゾニウム塩の１．１〜２０倍
当量、好ましくは１．５〜１０倍当量の範囲である。ア
ルカリ金属又はアルカリ土類金属の水酸化物の過剰量が
１．１倍当量未満であると目的物の４，６−ジ体の収率
が向上しない。アルカリ金属又はアルカリ土類金属の水
酸化物の過剰量を２０倍当量越えて多くしてもアルカリ
金属又はアルカリ土類金属の水酸化物を多くした効果が
ない。The amount of the alkali metal or alkaline earth metal hydroxide is an excess amount of the (substituted) benzenediazonium salt as an excess amount for neutralizing the acid in the (substituted) benzenediazonium salt solution and further making it alkaline. It is in the range of 1.1 to 20 times equivalent, preferably 1.5 to 10 times equivalent. If the excess amount of the alkali metal or alkaline earth metal hydroxide is less than 1.1 times equivalent, the yield of the desired 4,6-di-form is not improved. Increasing the excess amount of the alkali metal or alkaline earth metal hydroxide in excess of 20 times the equivalent does not have the effect of increasing the alkali metal or alkaline earth metal hydroxide.
【００２０】（置換）ベンゼンジアゾニウム塩とアルカ
リ金属又はアルカリ土類金属の水酸化物を混合し、反応
させる際の温度は−５０〜５０℃、好ましくは−５０〜
１５℃である。溶媒が水だけの場合は、固化するので−
５〜１０℃が好ましい。−５０〜１０℃の範囲内では、
原料の（置換）ベンゼンジアゾニウム塩と生成する反応
中間体（水酸化（置換）ベンゼンジアゾニウムと推定さ
れる）が安定に存在し得るからである。−５０℃より低
い温度に冷却する事は、困難であり、１５℃を越えての
温度では、前記反応中間体が安定に存在し得ない。The temperature at which the (substituted) benzenediazonium salt and the hydroxide of alkali metal or alkaline earth metal are mixed and reacted is -50 to 50 ° C, preferably -50 to 50 ° C.
15 ° C. If water is the only solvent, it solidifies.
5-10 degreeC is preferable. Within the range of -50 to 10 ° C,
This is because the (substituted) benzenediazonium salt as a raw material and a reaction intermediate (presumed to be (substituted) benzenediazonium hydroxide) that is formed can be stably present. Cooling to temperatures below -50 ° C is difficult and at temperatures above 15 ° C the reaction intermediates may not be stable.
【００２１】（置換）ベンゼンジアゾニウム塩の溶液と
アルカリ金属又はアルカリ土類金属の水酸化物の溶液又
は懸濁液の混合は、普通、反応容器内で行われる。そし
て、その反応容器が混合液の貯蔵槽として機能する場合
もある。しかし、この混合は、該混合液とレゾルシノー
ル及び／又はそのアルカリ金属塩若しくはアルカリ土類
金属塩との反応を行う反応容器へ連結しているラインの
中で行っても良い。これにより、反応容器の数を節約す
ることができる。又、生成した反応中間体の経時変化の
時間を短くできる。The mixing of the solution of the (substituted) benzenediazonium salt with the solution or suspension of the alkali metal or alkaline earth metal hydroxide is usually carried out in a reaction vessel. Then, the reaction container may function as a storage tank for the mixed liquid. However, this mixing may be carried out in a line connected to a reaction vessel in which the mixed solution is reacted with resorcinol and / or its alkali metal salt or alkaline earth metal salt. As a result, the number of reaction vessels can be saved. In addition, the time of aging of the produced reaction intermediate can be shortened.
【００２２】次に、得られた（置換）ベンゼンジアゾニ
ウム塩の溶液とアルカリ金属又はアルカリ土類金属の水
酸化物の溶液又は懸濁液の混合液とレゾルシノール及び
／又はそのアルカリ金属塩若しくはアルカリ土類金属塩
と混合してカップリング反応で目的物を得る。通常は、
レゾルシノール及び／又はそのアルカリ金属塩若しくは
アルカリ土類金属塩の溶液に、攪拌下、上記混合液を滴
下又は流下する。攪拌により、局部的過剰反応進行を回
避でき、トリ体の生成を少なくすることができる。Next, a mixture of the obtained (substituted) benzenediazonium salt solution and an alkali metal or alkaline earth metal hydroxide solution or suspension and resorcinol and / or its alkali metal salt or alkaline earth. The target compound is obtained by a coupling reaction by mixing with a metal salt. Normally,
To the solution of resorcinol and / or its alkali metal salt or alkaline earth metal salt, the above mixed solution is added dropwise or allowed to flow under stirring. By stirring, the progress of local excess reaction can be avoided, and the formation of avian body can be reduced.
【００２３】レゾルシノールの塩としては、ナトリウ
ム、カリウム等のアルカリ金属塩又はマグネシウム、バ
リウム等のアルカリ土類金属塩が使用できる。（置換）
ベンゼンジアゾニウム塩と水酸化物の混合液がアルカリ
性になっているので、レゾルシノールの前記塩の製造の
ために、使用されるアルカリ金属又はアルカリ土類金属
の水酸化物の量は、レゾルシノールのみでも反応系で塩
を生成するので、０〜２０倍当量を使用できるが、好ま
しくは０〜５倍当量である。（置換）ベンゼンジアゾニ
ウム塩と水酸化物の混合液中に水酸化物の過剰量が（置
換）ベンゼンジアゾニウム塩に対して５〜２０倍当量で
ある場合は、通常レゾルシノールのみに、（置換）ベン
ゼンジアゾニウム塩とアルカリ金属又はアルカリ土類金
属の水酸化物の混合液とを反応させる。As the resorcinol salt, an alkali metal salt such as sodium or potassium or an alkaline earth metal salt such as magnesium or barium can be used. (Replacement)
Since the mixed solution of the benzenediazonium salt and the hydroxide is alkaline, the amount of the alkali metal or alkaline earth metal hydroxide used for the production of the salt of resorcinol is the same as that of resorcinol alone. Since the system produces a salt, 0 to 20 times equivalents can be used, but preferably 0 to 5 times equivalents. When the excess amount of the hydroxide in the mixed solution of the (substituted) benzenediazonium salt and the hydroxide is 5 to 20 times the equivalent amount of the (substituted) benzenediazonium salt, the (substituted) benzene is usually added only to the resorcinol. The diazonium salt is reacted with a mixed solution of an alkali metal or alkaline earth metal hydroxide.
【００２４】（置換）ベンゼンジアゾニウム塩とアルカ
リ金属又はアルカリ土類金属の水酸化物の混合液と、レ
ゾルシノール又はそのアルカリ金属塩若しくはアルカリ
土類金属塩との混合における（置換）ジアゾニウム塩の
量は、レゾルシノール及び／又はその塩の合計量に対し
て２倍モル以上使用するのが目的物の収率上好ましい
が、当然多過ぎるとトリ体が生成するので、好ましくは
２．０５〜２．２０倍モルである。２．０５モル以下で
あると、レゾルシノール及び／又はモノ体が残り易く、
２．２０倍モル以上であるとトリ体が生成し易くなるか
らである。The amount of the (substituted) diazonium salt in the mixture of the (substituted) benzenediazonium salt and the alkali metal or alkaline earth metal hydroxide and resorcinol or its alkali metal salt or alkaline earth metal salt is It is preferable to use 2 times or more moles of resorcinol and / or its salt with respect to the total amount in terms of the yield of the target product, but if it is too much, a tri-form is formed, so it is preferably 2.05 to 2.20. It is twice the mole. When it is 2.05 mol or less, resorcinol and / or mono-forms are likely to remain,
This is because if it is 2.20 times or more moles, the tri-form is likely to be generated.
【００２５】（置換）ベンゼンジアゾニウム塩の溶液と
アルカリ金属又はアルカリ土類金属の水酸化物の混合の
際、及び、レゾルシノール及び／又はそのアルカリ金属
塩若しくはアルカリ土類金属塩と（置換）ベンゼンジア
ゾニウム塩と水酸化物の混合液を反応させる際の溶媒と
しては、水又は水と均一に混合する有機溶媒を使用でき
る。有機溶媒としては、メタノール、エタノール、プロ
パノール、ｔ−ブタノール、ジオキサン、テトラヒドロ
フラン、アセトン，ジメチルホルムアミド（ＤＭＦ）、
ジメチルスルホオキシド（ＤＭＳＯ）及びジメチルイミ
ダゾリジノン（ＤＭＩ）等が使用できるが、ＤＭＦ、Ｄ
ＭＳＯ及びアセトン等の強アルカリ性に対して不安定な
ものは好ましくない。最も好ましいものは水である。と
いうのは、有機溶媒回収の必要がないので後処理操作が
容易であり、収率が最も高いからである。Upon mixing a solution of the (substituted) benzenediazonium salt with a hydroxide of an alkali metal or an alkaline earth metal, and resorcinol and / or its alkali metal salt or alkaline earth metal salt and a (substituted) benzenediazonium salt. As the solvent for reacting the mixed liquid of the salt and the hydroxide, water or an organic solvent that is uniformly mixed with water can be used. As the organic solvent, methanol, ethanol, propanol, t-butanol, dioxane, tetrahydrofuran, acetone, dimethylformamide (DMF),
Dimethyl sulfoxide (DMSO) and dimethyl imidazolidinone (DMI) can be used, but DMF, D
Those unstable to strong alkalinity such as MSO and acetone are not preferable. Most preferred is water. This is because there is no need to recover the organic solvent, the post-treatment operation is easy, and the yield is highest.
【００２６】このレゾルシノール及び／又はレゾルシノ
ールアルカリ塩との反応は比較的速いが、反応に要する
時間は、反応温度に依存する。反応温度は通常は、−５
０〜５０℃である。反応温度上昇と共に、反応速度は高
まる。原料の反応中間体（水酸化（置換）ベンゼンジア
ゾニウムと推定される）と生成したジ体の分解を回避す
るためには、−５０〜２０℃の温度が好ましい。溶媒が
水だけの場合は、固化するので−５〜２０℃が好まし
い。反応時間は−５〜２０℃で通常０．１〜１０時間で
ある。The reaction with resorcinol and / or the alkali salt of resorcinol is relatively fast, but the time required for the reaction depends on the reaction temperature. The reaction temperature is usually -5.
0-50 ° C. The reaction rate increases as the reaction temperature increases. In order to avoid decomposition of the reaction intermediate of the raw material (presumed to be (substituted) benzenediazonium hydroxide) and the formed di-form, a temperature of −50 to 20 ° C. is preferable. When the solvent is only water, it solidifies, so that it is preferably -5 to 20 ° C. The reaction time is -5 to 20 ° C and is usually 0.1 to 10 hours.
【００２７】４，６ジ体のアルカリ溶液中での分解を抑
制するために、反応終了後、後処理を直ぐ行うのが好ま
しい。In order to suppress the decomposition of the 4,6 di-form in an alkaline solution, it is preferable to carry out a post-treatment immediately after the completion of the reaction.
【００２８】反応終了後の後処理は、反応液を濾過する
とトリ体の大半が除去される。反応時の水量が少ないと
４，６−ジ体も固体として分離されるので、水で固体を
洗浄し、４，６−ジ体を溶解回収する必要がある。濾液
と洗浄液を塩酸、酢酸、硫酸、燐酸等で酸性にすると４
−モノ体、４，６−ジ体、２，４−ジ体が析出する。こ
れを濾集して、乾燥し、還元工程に供する。４−モノ体
を分離する必要がある場合は、得られた固体を、Ｎａ2
ＣＯ3水溶液により洗浄すると、４−モノ体だけが溶解
し、除去できる。In the post-treatment after completion of the reaction, most of the avian form is removed by filtering the reaction solution. If the amount of water during the reaction is small, the 4,6-di form is also separated as a solid, so it is necessary to wash the solid with water to dissolve and recover the 4,6-di form. If the filtrate and washing solution are acidified with hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, etc., 4
-Mono body, 4,6-di body, and 2,4-di body are precipitated. This is collected by filtration, dried and subjected to the reduction step. When it is necessary to separate the 4-mono form, the solid obtained is treated with Na 2
When washed with a CO 3 aqueous solution, only the 4-mono body is dissolved and can be removed.
【００２９】以下、本発明の方法の好ましい実施態様を
列記する。 （１）（置換）ベンゼンジアゾニウム塩及びアルカリ金
属又はアルカリ土類金属の水酸化物の溶液又は懸濁液の
溶媒が水である本発明の方法。水であると、反応収率、
容積効率が共に高く、有機溶媒回収という余分の操作を
必要としないので、後処理が容易であるからである。 （２）（置換）ベンゼンジアゾニウム塩の溶液とアルカ
リ金属又はアルカリ土類金属の水酸化物の溶液又は懸濁
液とを混合する際の、該水酸化物の量は、（置換）ベン
ゼンジアゾニウム塩の溶液中の酸を中和した後の過剰量
が、（置換）ベンゼンジアゾニウム塩に対して１．１〜
２０倍当量、好ましくは１．５〜１０倍当量である本発
明又は上記（１）の実施態様の方法。上述したように、
レゾルシノールの溶解度を高め、存在する（置換）ベン
ゼンジアゾニウム塩と生成した４，６−ジ体の安定性も
高めるからである。 （３）（置換）ベンゼンジアゾニウム塩とアルカリ金属
又はアルカリ土類金属の水酸化物の混合液と、レゾルシ
ノール又はそのアルカリ金属塩若しくはアルカリ土類金
属塩との混合における（置換）ジアゾニウム塩の量が、
レゾルシノール及び／又はその塩の合計量に対して２．
０５〜２．２０倍モルである本発明又は上記（１）又は
（２）の実施態様の方法。２．０５モル以下であると、
レゾルシノール及び／又はモノ体が残り易く、２．２０
倍モル以上であるとトリ体が生成し易くなるからであ
る。 （４）（置換）ベンゼンジアゾニウム塩がベンゼンジア
ゾニウム塩である本発明又は上記（１）、（２）と
（３）の実施態様の方法。ベンゼンジアゾニウムが最も
工業経済的だからである。 （５）アルカリ金属の水酸化物が水酸化ナトリウムであ
る本発明又は上記（１）、（２）、（３）と（４）の実
施態様の方法。水酸化ナトリウムが経済的で扱いやすい
からである。The preferred embodiments of the method of the present invention will be listed below. (1) The method of the present invention, wherein the solvent of the solution or suspension of the (substituted) benzenediazonium salt and the alkali metal or alkaline earth metal hydroxide is water. If it is water, the reaction yield,
This is because both volumetric efficiency is high and an extra operation of recovering an organic solvent is not required, so that post-treatment is easy. (2) When the solution of the (substituted) benzenediazonium salt is mixed with the solution or suspension of the alkali metal or alkaline earth metal hydroxide, the amount of the hydroxide is the (substituted) benzenediazonium salt. The amount of excess after neutralizing the acid in the solution of 1.1 to 1.1 to (substituted) benzenediazonium salt
20 times equivalent, preferably 1.5 to 10 times equivalent of the method of the present invention or the above embodiment (1). As mentioned above,
This is because the solubility of resorcinol is increased, and the stability of the existing (substituted) benzenediazonium salt and the 4,6-di product formed is also increased. (3) The amount of the (substituted) diazonium salt in the mixture of the (substituted) benzenediazonium salt and an alkali metal or alkaline earth metal hydroxide mixture and resorcinol or its alkali metal salt or alkaline earth metal salt is ,
2. Based on the total amount of resorcinol and / or its salt.
The method according to the embodiment of the present invention or the above (1) or (2), wherein the molar ratio is from 05 to 2.20. When it is 2.05 mol or less,
Resorcinol and / or mono are likely to remain 2.20
This is because a tri-form is likely to be formed when the amount is more than twice the molar amount. (4) The method of the present invention or the embodiment of the above (1), (2) and (3), wherein the (substituted) benzenediazonium salt is a benzenediazonium salt. This is because benzenediazonium is the most industrial economy. (5) The method of the present invention or the embodiment of the above (1), (2), (3) and (4), wherein the alkali metal hydroxide is sodium hydroxide. This is because sodium hydroxide is economical and easy to handle.
【００３０】又、（置換）ベンゼンジアゾニウム塩とア
ルカリ金属又はアルカリ土類金属の水酸化物とを混合し
アルカリ性とする操作は、該混合液とレゾルシノール及
び／又はそのアルカリ金属塩若しくはアルカリ土類金属
塩との反応を行う反応容器への連結ラインの中で行うこ
とが可能である。これにより、反応容器及び／又は混合
液の貯蔵槽の数を減少できる。Further, the operation of mixing the (substituted) benzenediazonium salt and the hydroxide of an alkali metal or an alkaline earth metal to make it alkaline is carried out by mixing the mixed solution with resorcinol and / or its alkali metal salt or alkaline earth metal. It can be done in a connecting line to the reaction vessel where the reaction with the salt takes place. This can reduce the number of reaction vessels and / or storage tanks for the mixed solution.
【００３１】４，６−ジ体の還元は、Ｐｄ−Ｃなどの金
属触媒を用いて行う。この際に水溶媒又は低級アルコー
ルを加えた水とアルコールの混合溶媒を用い、４，６−
ジ体の３〜５倍モルの塩酸、触媒を加えて、水素で常圧
又は加圧で還元を行う。The reduction of the 4,6-di form is carried out using a metal catalyst such as Pd-C. At this time, using a water solvent or a mixed solvent of water and alcohol to which a lower alcohol is added, 4,6-
Hydrochloric acid and a catalyst, which are 3 to 5 times the molar amount of the di-form, are added, and reduction is carried out with hydrogen at atmospheric pressure or pressure.
【００３２】還元後、触媒を濾別し、濾液に多量の塩酸
を加えると４，６−ジアミノレゾルシノール塩酸塩が析
出する。これを濾集することにより４，６−ジアミノレ
ゾルシノール塩酸塩を得る事ができる。この濾液は、酸
素を断ってアルカリ性にするとアニリンがオイル層とし
て分離してくるので、回収し再使用が可能である。After the reduction, the catalyst was filtered off and a large amount of hydrochloric acid was added to the filtrate to precipitate 4,6-diaminoresorcinol hydrochloride. By collecting this by filtration, 4,6-diaminoresorcinol hydrochloride can be obtained. This filtrate can be recovered and reused because aniline separates as an oil layer when oxygen is turned off to make it alkaline.
【００３３】[0033]
【実施例】以下、実施例によってさらに具体的に説明す
るが、これらによって本発明は、なんら限定されるもの
ではない。 実施例１：アニリン４．１ｇ、３５％塩酸９．８ｇ及び
水１０ｇの混合溶液中に、０〜５℃で亜硝酸ナトリウム
３．０４ｇを水５．５ｇに溶解させた溶液を滴下し、塩
化ベンゼンジアゾニウム水溶液を合成した。この塩化ベ
ンゼンジアゾニウム水溶液とＮａＯＨ４．９ｇと水１
２．３ｇからなる溶液を同じモル比率でポンプにより送
液し、１０℃に冷却しながらライン上で混合し、この混
合液をレゾルシノール２．２ｇ、ＮａＯＨ２．４ｇ及び
水１１ｇよりなる混合液に１０℃で４０分間にわたり加
えた。滴下終了後１０℃で３時間攪拌した。反応混合物
に塩酸を加えて酸性とし、析出した固体を濾集し、水洗
後、乾燥して暗赤色固体を得た。液体クロマトグラフィ
ーで定量したところ生成した４，６−ジ体の量は５．８
ｇで収率は９１％であった。EXAMPLES Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto. Example 1: In a mixed solution of 4.1 g of aniline, 9.8 g of 35% hydrochloric acid and 10 g of water, a solution of 3.04 g of sodium nitrite in 5.5 g of water was added dropwise at 0 to 5 ° C, and chlorination was performed. A benzenediazonium aqueous solution was synthesized. This benzenediazonium chloride aqueous solution, 4.9 g of NaOH and 1 part of water
A solution composed of 2.3 g was pumped at the same molar ratio and mixed on a line while being cooled to 10 ° C., and this mixed solution was mixed with a mixed solution composed of 2.2 g of resorcinol, 2.4 g of NaOH and 11 g of water to form a mixture. Add at 40 ° C. over 40 minutes. After the completion of dropping, the mixture was stirred at 10 ° C for 3 hours. Hydrochloric acid was added to the reaction mixture to make it acidic, and the precipitated solid was collected by filtration, washed with water and dried to obtain a dark red solid. The amount of 4,6-di-form produced by quantification by liquid chromatography was 5.8.
The yield was 91% in g.
【００３４】実施例２：アニリン４．１ｇ、３５％塩酸
９．８ｇ及び水１０ｇの混合溶液中に、０〜５℃で亜硝
酸ナトリウム３．０４ｇを水５．５ｇに溶解させた溶液
を滴下し、塩化ベンゼンジアゾニウム水溶液を合成し
た。この塩化ベンゼンジアゾニウム水溶液をＮａＯＨ
５．５ｇ、水１３．８ｇよりなる溶液に１０℃以下で滴
下し混合溶液を調製した。この混合溶液をレゾルシノー
ル２．２ｇ、ＮａＯＨ２．４ｇ、水１１ｇよりなる混合
液に１０℃で４０分間かけて滴下した。滴下終了後１０
℃で３時間攪拌した。反応終了後、反応混合物に塩酸を
加え酸性とし、析出した固体を濾集し、水洗後、乾燥し
て暗赤色固体を得た。液体クロマトグラフィーで定量し
たところ生成した４，６−ジ体の量は５．６ｇで収率は
８８％であった。Example 2: In a mixed solution of 4.1 g of aniline, 9.8 g of 35% hydrochloric acid and 10 g of water, a solution prepared by dissolving 3.04 g of sodium nitrite in 5.5 g of water was added dropwise at 0 to 5 ° C. Then, a benzenediazonium chloride aqueous solution was synthesized. This benzenediazonium chloride aqueous solution is treated with NaOH.
A mixed solution was prepared by adding dropwise to a solution composed of 5.5 g and 13.8 g of water at 10 ° C. or lower. This mixed solution was added dropwise to a mixed solution composed of 2.2 g of resorcinol, 2.4 g of NaOH and 11 g of water at 10 ° C. over 40 minutes. 10 after dropping
Stirred at C for 3 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture to make it acidic, and the precipitated solid was collected by filtration, washed with water and dried to obtain a dark red solid. As a result of quantification by liquid chromatography, the amount of 4,6-di product produced was 5.6 g and the yield was 88%.
【００３５】実施例３：アニリン４．１ｇ、３５％塩酸
９．８ｇ及び水１０ｇの混合溶液中に、０〜５℃で亜硝
酸ナトリウム３．０４ｇを水５．５ｇに溶解させた溶液
を滴下し、塩化ベンゼンジアゾニウム水溶液を合成し
た。この塩化ベンゼンジアゾニウム水溶液をＮａＯＨ
５．５ｇ、水１３．８ｇよりなる溶液に１０℃以下で滴
下し混合溶液を調製した。この混合溶液をレゾルシノー
ル２．２ｇ、水１１ｇよりなる混合液に１０℃で４０分
間かけて滴下した。滴下終了後１０℃で３時間攪拌し
た。反応終了後、反応混合物に塩酸を加え酸性とし、析
出した固体を濾集し、水洗後、乾燥して暗赤色固体を得
た。液体クロマトグラフィーで定量したところ４，６−
ジ体の量は５．８ｇで収率は９１％であった。Example 3: In a mixed solution of 4.1 g of aniline, 9.8 g of 35% hydrochloric acid and 10 g of water, a solution prepared by dissolving 3.04 g of sodium nitrite in 5.5 g of water was added dropwise at 0 to 5 ° C. Then, a benzenediazonium chloride aqueous solution was synthesized. This benzenediazonium chloride aqueous solution is treated with NaOH.
A mixed solution was prepared by adding dropwise to a solution composed of 5.5 g and 13.8 g of water at 10 ° C. or lower. This mixed solution was added dropwise to a mixed solution of 2.2 g of resorcinol and 11 g of water at 10 ° C. over 40 minutes. After the completion of dropping, the mixture was stirred at 10 ° C for 3 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture to make it acidic, and the precipitated solid was collected by filtration, washed with water and dried to obtain a dark red solid. Quantitative analysis by liquid chromatography 4,6-
The amount of di-form was 5.8 g, and the yield was 91%.
【００３６】実施例４：アニリン４．１ｇ、３５％塩酸
９．８ｇ及び水５ｇの混合溶液中に、０〜５℃で亜硝酸
ナトリウム３．０４ｇを水５．５ｇに溶解させた溶液を
滴下し、塩化ベンゼンジアゾニウム水溶液を合成した。
この塩化ベンゼンジアゾニウム水溶液をＮａＯＨ５．５
ｇ、水１３．８ｇよりなる溶液に１０℃以下で滴下し混
合溶液を調製した。この混合溶液をレゾルシノール２．
２ｇ、水５ｇよりなる混合液に１０℃で４０分間かけて
滴下した。滴下終了後１０℃で３時間攪拌した。反応終
了後、反応混合物に塩酸を加え酸性とし、析出した固体
を濾集し、水洗後、乾燥して暗赤色固体を得た。液体ク
ロマトグラフィーで定量したところ４，６−ジ体の量は
５．７ｇで収率は９０％であった。Example 4 In a mixed solution of 4.1 g of aniline, 9.8 g of 35% hydrochloric acid and 5 g of water, a solution prepared by dissolving 3.04 g of sodium nitrite in 5.5 g of water was added dropwise at 0 to 5 ° C. Then, a benzenediazonium chloride aqueous solution was synthesized.
This benzenediazonium chloride aqueous solution was treated with NaOH 5.5.
g, and 13.8 g of water were added dropwise at 10 ° C. or lower to prepare a mixed solution. This mixed solution was mixed with resorcinol 2.
It was added dropwise to a mixed solution of 2 g and 5 g of water at 10 ° C. over 40 minutes. After the completion of dropping, the mixture was stirred at 10 ° C for 3 hours. After completion of the reaction, hydrochloric acid was added to the reaction mixture to make it acidic, and the precipitated solid was collected by filtration, washed with water and dried to obtain a dark red solid. As a result of quantification by liquid chromatography, the amount of 4,6-di form was 5.7 g and the yield was 90%.
【００３７】比較例１：アニリン３．７６ｇ、３５％塩
酸９．４ｇ及び水１０ｇの混合溶液中に、０〜５℃で亜
硝酸ナトリウム２．７６ｇを水５．５ｇに溶解させた溶
液を滴下し、塩化ベンゼンジアゾニウム水溶液を合成し
た。レゾルシノール２．２ｇ、ＮａＯＨ８ｇ、水２２ｇ
を仕込み１０℃で良く攪拌した後、別途合成した上記の
塩化ベンゼンジアゾニウム水溶液を１０℃を保ちながら
３０分間かけて滴下した。滴下終了後１０℃で２時間攪
拌した後、不溶物を濾別し、その濾集物を水３０ｇで洗
浄し、濾液と洗浄液を合わせ塩酸により酸性とした。析
出した固体を濾集し、水洗後、乾燥して暗赤色固体を得
た。液体クロマトグラフィーで定量したところ４，６−
ジ体の量は２．２２ｇで収率は３５％であった。 Comparative Example 1: A solution prepared by dissolving 2.76 g of sodium nitrite in 5.5 g of water at 0-5 ° C. was dropped into a mixed solution of 3.76 g of aniline, 9.4 g of 35% hydrochloric acid and 10 g of water. Then, a benzenediazonium chloride aqueous solution was synthesized. Resorcinol 2.2g, NaOH 8g, water 22g
After stirring well at 10 ° C., the above separately synthesized benzenediazonium chloride aqueous solution was added dropwise over 30 minutes while maintaining 10 ° C. After the dropwise addition was completed, the mixture was stirred at 10 ° C. for 2 hours, the insoluble matter was filtered off, the filtered matter was washed with 30 g of water, and the filtrate and the washing solution were combined and acidified with hydrochloric acid. The precipitated solid was collected by filtration, washed with water and dried to obtain a dark red solid. Quantitative analysis by liquid chromatography 4,6-
The amount of di-form was 2.22 g and the yield was 35%.
【００３８】[0038]
【発明の効果】（置換）ベンゼンジアゾニウム塩の溶液
とアルカリ金属又はアルカリ土類金属の水酸化物の溶液
又は懸濁液を混合し、アルカリ性とした混合液を得、こ
の混合液とレゾルシノール及び／又はそのアルカリ金属
塩又はアルカリ土類金属塩を混合し反応させることによ
り、レゾルシノールの濃度を低くしなくても、高い収率
を維持することができる。これにより、反応容積を従来
法の約１／５ないし１／１５に下げること（換言すれ
ば、容積効率を５ないし１５倍に上げること）が可能に
なった。The solution of (substituted) benzenediazonium salt and the solution or suspension of the hydroxide of alkali metal or alkaline earth metal are mixed to obtain an alkaline mixed solution, which is mixed with resorcinol and / or Alternatively, by mixing and reacting the alkali metal salt or alkaline earth metal salt thereof, a high yield can be maintained without lowering the resorcinol concentration. This made it possible to reduce the reaction volume to about 1/5 to 1/15 of the conventional method (in other words, to increase the volumetric efficiency 5 to 15 times).
フロントページの続き (72)発明者 橋場 功 千葉県船橋市坪井町722番地１ 日産化学 工業株式会社中央研究所内 (72)発明者 鈴木 秀雄 千葉県船橋市坪井町722番地１ 日産化学 工業株式会社中央研究所内 (72)発明者 川下 英夫 大阪市淀川区西三国４丁目２番11号 田岡 化学工業株式会社内 (72)発明者 大崎 一雄 大阪市淀川区西三国４丁目２番11号 田岡 化学工業株式会社内 (72)発明者 山崎 智司 大阪市淀川区西三国４丁目２番11号 田岡 化学工業株式会社内Front page continuation (72) Inventor Isao Hashiba 722, Tsuboi-cho, Funabashi-shi, Chiba Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor Hideo Suzuki, 722, Tsuboi-cho, Funabashi, Chiba Pref. (72) Inventor Hideo Kawashita 4-2-11 Nishimikuni, Yodogawa-ku, Osaka City Taoka Chemical Industry Co., Ltd. (72) Inventor Kazuo Osaki 4-2-1-11 Nishimikuni, Yodogawa-ku, Osaka City Taoka Chemical Industry Co., Ltd. (72) Inventor Satoshi Yamazaki 4-2-11 Nishimikuni, Yodogawa-ku, Osaka City Taoka Chemical Industry Co., Ltd.
Claims (7)
ル基、ヒドロキシカルボニル基又は炭素原子数１〜５の
アルコキシ基を表し、ｎは零又は１〜５のいずれかの整
数を表し、２個以上のＲは互いに同一又は異なっていて
もよく、そしてＸはＣｌ、Ｂｒ、ＯＳＯ3Ｈ又はＯＰＯ3
Ｈ2を表す。）で表される（置換）ベンゼンジアゾニウ
ム塩の溶液とアルカリ金属又はアルカリ土類金属の水酸
化物の溶液又は懸濁液とを混合し、アルカリ性とした混
合液を得、この混合液とレゾルシノール及び／又はその
アルカリ金属塩若しくはアルカリ土類金属塩を混合し反
応させることを特徴とする式［２］ 【化２】 （式中、Ｒ及びｎは上記式［１］中と同じに定義され
る。）で表される４，６−ビス（置換）フェニルアゾレ
ゾルシノールの製造法。1. A formula [1] (In the formula, R represents a halogen atom, an alkyl group having 1 to 5 carbon atoms, a hydroxycarbonyl group or an alkoxy group having 1 to 5 carbon atoms, and n represents zero or an integer of 1 to 5, Two or more R may be the same or different from each other, and X is Cl, Br, OSO 3 H or OPO 3
Representing the H 2. ) A solution of a (substituted) benzenediazonium salt represented by the formula (4) and a solution or suspension of a hydroxide of an alkali metal or an alkaline earth metal are mixed to obtain an alkaline mixed solution, and the mixed solution is mixed with resorcinol and / Or an alkali metal salt or an alkaline earth metal salt thereof is mixed and reacted, and the formula [2] (In the formula, R and n are defined as in the above formula [1].) A method for producing 4,6-bis (substituted) phenylazoresorcinol.
及びアルカリ金属又はアルカリ土類金属の水酸化物の溶
液又は懸濁液の溶媒が水である請求項１に記載の４，６
−ビス（置換）フェニルアゾレゾルシノールの製造法。2. The solvent according to claim 1, wherein the (substituted) benzenediazonium salt solution and the alkali metal or alkaline earth metal hydroxide solution or suspension are water.
-Method for producing bis (substituted) phenylazoresorcinol.
とアルカリ金属又はアルカリ土類金属の水酸化物の溶液
又は懸濁液とを混合する際の該水酸化物の量は、前記
（置換）ベンゼンジアゾニウム塩溶液中の酸を中和した
後、更にアルカリ性にするための過剰量として、（置
換）ベンゼンジアゾニウム塩に対して１．１倍当量から
２０倍当量である請求項１又は２に記載の４，６−ビス
（置換）フェニルアゾレゾルシノールの製造法。3. The amount of the (substituted) benzene diazonium salt solution and the alkali metal or alkaline earth metal hydroxide solution or suspension when the solution is mixed with the (substituted) benzene The excess amount for neutralizing the acid in the diazonium salt solution and then making it alkaline is 1.1 times equivalent to 20 times equivalent with respect to the (substituted) benzenediazonium salt. Process for producing 4,6-bis (substituted) phenylazoresorcinol.
リ金属又はアルカリ土類金属の水酸化物の混合液と、レ
ゾルシノール又はそのアルカリ金属塩若しくはアルカリ
土類金属塩との混合における（置換）ジアゾニウム塩の
量が、レゾルシノール及び／又はそのアルカリ金属塩若
しくはアルカリ土類金属塩の合計量に対して２．０５〜
２．２０倍モルである請求項１乃至３のいずれかに記載
の４，６−ビス（置換）フェニルアゾレゾルシノールの
製造法。4. A (substituted) diazonium salt in a mixture of a (substituted) benzenediazonium salt and an alkali metal or alkaline earth metal hydroxide and resorcinol or its alkali metal salt or alkaline earth metal salt. The amount is 2.05 to the total amount of resorcinol and / or its alkali metal salt or alkaline earth metal salt.
The method for producing 4,6-bis (substituted) phenylazoresorcinol according to any one of claims 1 to 3, wherein the molar ratio is 2.20 times.
ンジアゾニウム塩である請求項１乃至４のいずれかに記
載の４，６−ビス（置換）フェニルアゾレゾルシノール
の製造法。5. The method for producing 4,6-bis (substituted) phenylazoresorcinol according to any one of claims 1 to 4, wherein the (substituted) benzenediazonium salt is a benzenediazonium salt.
項１乃至５のいずれかに記載の４，６−ビス（置換）フ
ェニルアゾレゾルシノールの製造法。6. The method for producing 4,6-bis (substituted) phenylazoresorcinol according to claim 1, wherein the hydroxide is sodium hydroxide.
とアルカリ金属又はアルカリ土類金属の水酸化物の溶液
又は懸濁液の混合を、該混合液とレゾルシノール及び／
又はそのアルカリ金属塩若しくはアルカリ土類金属塩と
の反応を行う反応容器へのラインの中で行う請求項１乃
至６のいずれかに記載の４，６−ビス（置換）フェニル
アゾレゾルシノールの製造法。7. A (substituted) benzenediazonium salt solution and an alkali metal or alkaline earth metal hydroxide solution or suspension are mixed, and the mixture is mixed with resorcinol and / or
Alternatively, the method for producing 4,6-bis (substituted) phenylazoresorcinol according to any one of claims 1 to 6, which is carried out in a line to a reaction vessel for carrying out a reaction with the alkali metal salt or alkaline earth metal salt thereof. .
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34648395A JP3790934B2 (en) | 1995-12-12 | 1995-12-12 | Process for producing 4,6-bis (substituted) phenylazoresorcinol |
| US09/066,335 US5962740A (en) | 1995-11-02 | 1996-10-31 | Processes for producing 4,6-bis (substituted)phenylazoresorcinols |
| DE69637797T DE69637797D1 (en) | 1995-11-02 | 1996-10-31 | Ten)phenylazoresorcinolen |
| CA002236101A CA2236101C (en) | 1995-11-02 | 1996-10-31 | Processes for producing 4,6-bis(substituted)phenylazoresorcinols |
| KR1020047014065A KR100633672B1 (en) | 1995-11-02 | 1996-10-31 | Processes for producing 4,6-bis(substituted)phenylazoresorcinols |
| KR1019980703272A KR100721220B1 (en) | 1995-11-02 | 1996-10-31 | Manufacturing method of 4,6-bis (substituted) phenyl azo resorcinol |
| PCT/JP1996/003199 WO1997016411A1 (en) | 1995-11-02 | 1996-10-31 | Processes for producing 4,6-bis(substituted)phenylazoresorcinols |
| EP96935515A EP0974577B1 (en) | 1995-11-02 | 1996-10-31 | Processes for producing 4,6-bis(substituted)phenylazoresorcinols |
| CN96198665A CN1073986C (en) | 1995-11-02 | 1996-10-31 | Process for producing 4,6-bis(substituted)phenylazoresorcinols |
| TW085113300A TW347382B (en) | 1995-11-02 | 1996-11-01 | Process for producing 4,6-bis(substituted)phenylazoresorcinols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34648395A JP3790934B2 (en) | 1995-12-12 | 1995-12-12 | Process for producing 4,6-bis (substituted) phenylazoresorcinol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09157239A true JPH09157239A (en) | 1997-06-17 |
| JP3790934B2 JP3790934B2 (en) | 2006-06-28 |
Family
ID=18383739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34648395A Expired - Fee Related JP3790934B2 (en) | 1995-11-02 | 1995-12-12 | Process for producing 4,6-bis (substituted) phenylazoresorcinol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3790934B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6222074B1 (en) | 1998-01-27 | 2001-04-24 | Nissan Chemical Industries, Ltd. | Process for preparation of 4,6-diaminoresorcinol or salts thereof |
| JP2001131134A (en) * | 1999-08-25 | 2001-05-15 | Nissan Chem Ind Ltd | Method for producing 4,6-bis(substituted)phenylazo- resorcinol and 4,6-diaminoresorcinol |
-
1995
- 1995-12-12 JP JP34648395A patent/JP3790934B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6222074B1 (en) | 1998-01-27 | 2001-04-24 | Nissan Chemical Industries, Ltd. | Process for preparation of 4,6-diaminoresorcinol or salts thereof |
| JP2001131134A (en) * | 1999-08-25 | 2001-05-15 | Nissan Chem Ind Ltd | Method for producing 4,6-bis(substituted)phenylazo- resorcinol and 4,6-diaminoresorcinol |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3790934B2 (en) | 2006-06-28 |
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