JP5652008B2 - Method for producing o-tolidine sulfone - Google Patents
Method for producing o-tolidine sulfone Download PDFInfo
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本発明は、ポリアミド、ポリイミドなどの原料として好適に用いることができる高純度ｏ−トリジンスルホンの製造方法に関する。この製造方法によれば、ｏ−トリジンスルホンを安全で効率よく経済的に得ることができる。 The present invention relates to a method for producing high-purity o-tolidine sulfone that can be suitably used as a raw material for polyamide, polyimide, and the like. According to this production method, o-tolidine sulfone can be obtained safely, efficiently and economically.
特許文献１には、ｏ−トリジンスルホンをコポリアミド繊維のジアミン成分として使用することが記載されている。この文献には、使用するｏ−トリジンスルホンについて、ｏ−トリジンを硫酸塩にしたのち、発煙硫酸中でスルホン化することによってｏ−トリジンスルホンを合成することができる旨記載があり、参考例でｏ−トリジン硫酸塩を発煙硫酸中で８０〜８５℃に加温してスルホン化したことが記載されている。そして、参考例では、スルホン化した反応混合液を氷水中に注ぎ、析出した沈殿物を濾取し、この沈殿物を水に加えてアルカリ性にして処理した後で沈殿物を濾取し、更にこの沈殿物を水に加え濃塩酸を加えた後で６０〜７０℃に加温して溶解させ、その溶液に活性炭とハイドロサルファイトを加えて攪拌処理した後で活性炭を濾過で分離し、その濾液を水酸化ナトリウムで弱アルカリ性にして沈殿物としてｏ−トリジンスルホンを分離することによって、ｏ−トリジンスルホンを得ている。 Patent Document 1 describes the use of o-tolidine sulfone as a diamine component of a copolyamide fiber. In this document, there is a description that o-tolidine sulfone can be synthesized by converting o-tolidine into sulfate and then sulfonating in fuming sulfuric acid. It is described that o-tolidine sulfate was heated to 80 to 85 ° C. in fuming sulfuric acid to be sulfonated. In the reference example, the sulfonated reaction mixture was poured into ice water, the deposited precipitate was collected by filtration, the precipitate was added to water to make it alkaline, and then the precipitate was collected by filtration. This precipitate is added to water, concentrated hydrochloric acid is added, heated to 60 to 70 ° C. to dissolve, and activated carbon and hydrosulfite are added to the solution and stirred, and then the activated carbon is separated by filtration. The filtrate is weakly alkaline with sodium hydroxide to separate o-tolidine sulfone as a precipitate to obtain o-tolidine sulfone.
前記参考例の方法は、反応に発煙硫酸を使用し、後処理では多量の水や酸やアルカリなどを用いて煩雑な操作を行っているが、その製造方法の詳細について検討されていなかった。この為、高純度のｏ−トリジンスルホンをより安全で効率よく経済的に得ることができる製造方法が求められていた。 In the method of the reference example, fuming sulfuric acid is used for the reaction, and a complicated operation is performed using a large amount of water, acid, alkali, or the like in the post-treatment, but details of the production method have not been studied. For this reason, the manufacturing method which can obtain highly purified o-tolidine sulfone more safely, efficiently and economically was calculated | required.
本発明の目的は、ｏ−トリジンと発煙硫酸とを反応させて、高純度のｏ−トリジンスルホンをより安全で効率よく経済的に得ることができる製造方法を提供することである。 An object of the present invention is to provide a production method in which o-tolidine and fuming sulfuric acid are reacted to obtain high-purity o-tolidine sulfone more safely, efficiently and economically.
本発明は、以下の各項に関する。
１． 少なくとも、
（工程１）ｏ−トリジンと発煙硫酸とを反応させる工程、
（工程２）反応混合液を水と混合し、析出したｏ−トリジンスルホンの硫酸塩を分離する工程、
（工程３）ｏ−トリジンスルホンの硫酸塩を水に溶解又は懸濁した状態でアルカリ性にして処理してｏ−トリジンスルホンとし、粗ｏ−トリジンスルホンとして分離する工程、
（工程４）粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程、
を含んで構成されたことを特徴とするｏ−トリジンスルホンの製造方法。
The present invention relates to the following items.
1. at least,
(Step 1) a step of reacting o-tolidine and fuming sulfuric acid,
(Step 2) A step of mixing the reaction mixture with water and separating the precipitated o-tolidinesulfone sulfate,
(Step 3) A step of converting o-tolidine sulfone sulfate into an alkaline solution in a state of being dissolved or suspended in water to obtain o-tolidine sulfone and separating it as crude o-tolidine sulfone,
(Step 4) A step of acidifying the crude o-tolidine sulfone in a state suspended in water, followed by purification by adjusting the pH,
A process for producing o-tolidine sulfone, comprising:
２． 工程１のｏ−トリジンとして含水物を用いることを特徴とする前記項１に記載のｏ−トリジンスルホンの製造方法。 2. Item 2. The method for producing o-tolidine sulfone according to item 1, wherein a hydrous material is used as the o-tolidine in step 1.
３． 工程１において、ｏ−トリジン１モルに対して、反応する三酸化硫黄（ＳＯ３）が４モル以上になるように発煙硫酸を用いて反応させることを特徴とする前記項１〜２のいずれかに記載のｏ−トリジンスルホンの製造方法。 3. Any one of Items 1 and 2 above, wherein in Step 1, fuming sulfuric acid is used to react with 1 mol of o-tolidine so that the reacting sulfur trioxide (SO 3 ) is 4 mol or more. A method for producing o-tolidine sulfone according to 1.
４． 工程２において、反応混合液に混合する水の量は、ｏ−トリジンスルホンの硫酸塩を分離した、残りの混合液（濾液）中の硫酸濃度が１５〜３５質量％になるような量にすることを特徴とする前記項１〜３のいずれかに記載のｏ−トリジンスルホンの製造方法。 4). In step 2, the amount of water mixed in the reaction mixture is set such that the sulfuric acid concentration in the remaining mixture (filtrate) from which o-tolidinesulfone sulfate is separated is 15 to 35% by mass. Item 4. The method for producing o-tolidine sulfone according to any one of Items 1 to 3 above.
本発明の製造方法によれば、ｏ−トリジンと発煙硫酸とを反応させて高純度のｏ−トリジンスルホンをより安全で効率よく経済的に得ることができる。 According to the production method of the present invention, o-tolidine and fuming sulfuric acid can be reacted to obtain highly pure o-tolidine sulfone more safely, efficiently and economically.
本発明のｏ−トリジンスルホンの製造方法は、少なくとも、
（工程１）ｏ−トリジンと発煙硫酸とを反応させる工程、
（工程２）反応混合液を水と混合し、析出したｏ−トリジンスルホンの硫酸塩を分離する工程、
（工程３）ｏ−トリジンスルホンの硫酸塩を水に溶解又は懸濁した状態でアルカリ性にして処理してｏ−トリジンスルホンとし、粗ｏ−トリジンスルホンとして分離する工程、
（工程４）粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程、
を含んで構成されたことを特徴とする。
The method for producing o-tolidine sulfone of the present invention includes at least
(Step 1) a step of reacting o-tolidine and fuming sulfuric acid,
(Step 2) A step of mixing the reaction mixture with water and separating the precipitated o-tolidinesulfone sulfate,
(Step 3) A step of converting o-tolidine sulfone sulfate into an alkaline solution in a state of being dissolved or suspended in water to obtain o-tolidine sulfone and separating it as crude o-tolidine sulfone,
(Step 4) A step of acidifying the crude o-tolidine sulfone in a state suspended in water, followed by purification by adjusting the pH,
It is characterized by including.
本発明の製造方法で用いる原料のｏ−トリジン類は、下記化学式（１）で表されるようなジメチルベンジジン骨格を有する化合物である。 The raw material o-tolidine used in the production method of the present invention is a compound having a dimethylbenzidine skeleton as represented by the following chemical formula (1).
原料のｏ−トリジン類は、発がん性の疑いがあり慎重な取り扱いが要求される。このため、無水物を用いてもよいが、含水物を用いるのが好ましい。ｏ−トリジンの含水物は１０〜３０質量％程度の水を含有しており、粉末になって飛散し難いので比較的安全に取り扱うことができる。また、原料のｏ−トリジン類として、ｏ−トリジンの硫酸塩などの塩を用いても構わない。 The raw material o-tolidine is suspected to be carcinogenic and requires careful handling. For this reason, although an anhydride may be used, it is preferable to use a hydrate. The hydrous material of o-tolidine contains about 10 to 30% by mass of water and can be handled relatively safely because it is powdered and hardly scattered. In addition, as the raw o-tolidine, a salt such as o-tolidine sulfate may be used.
発煙硫酸は、硫酸に三酸化硫黄（ＳＯ３）を溶解させたものであり、硫酸に三酸化硫黄が付加した化合物である。発煙硫酸中の三酸化硫黄は、遊離の三酸化硫黄として反応する。本発明において、発煙硫酸は三酸化硫黄を１０〜５０質量％、好ましくは２０〜３０質量％含有するものを好適に用いることができる。
三酸化硫黄は水と反応して直ちに硫酸になる。
Fuming sulfuric acid is a compound in which sulfur trioxide (SO 3 ) is dissolved in sulfuric acid, and sulfur trioxide is added to sulfuric acid. Sulfur trioxide in fuming sulfuric acid reacts as free sulfur trioxide. In the present invention, fuming sulfuric acid containing 10 to 50% by mass, preferably 20 to 30% by mass of sulfur trioxide can be suitably used.
Sulfur trioxide reacts with water and immediately becomes sulfuric acid.
本発明のｏ−トリジンスルホンの製造方法では、先ずｏ−トリジンと発煙硫酸とを反応する工程（工程１）を行う。この反応においては、ｏ−トリジン１モルに対して三酸化硫黄１モルが反応してｏ−トリジンのベンゼン環に１個のスルホキシル基が導入され、もう１モルの三酸化硫黄により脱水されて環状スルホンが形成されるので、理論的にはｏ−トリジン類１モルに対して２モルの三酸化硫黄があれば、ｏ−トリジンスルホンを製造することができる。 In the method for producing o-tolidine sulfone of the present invention, first, a step (step 1) of reacting o-tolidine and fuming sulfuric acid is performed. In this reaction, 1 mol of sulfur trioxide reacts with 1 mol of o-tolidine to introduce one sulfoxyl group into the benzene ring of o-tolidine, which is dehydrated by another mol of sulfur trioxide and cyclic. Since sulfone is formed, theoretically, if there is 2 moles of sulfur trioxide per mole of o-tolidine, o-tolidine sulfone can be produced.
しかしながら、本発明においては、ｏ−トリジン１モルに対して、三酸化硫黄が４モル以上、好ましくは５モル以上、更に好ましくは５．５モル以上になるように発煙硫酸を用いて反応させるのが好適である。三酸化硫黄が４モル未満では環状スルホン化反応が効率的に行われず、得られるｏ−トリジンスルホンの収率が低くなりやすい。
なお、原料としてｏ−トリジンの含水物を用いる場合には、それに含有される水１モルと三酸化硫黄１モルとは直ちに反応して硫酸になるため、ｏ−トリジン類に含まれる水と反応して消費される三酸化硫黄の量（水と等モル量）を除いた三酸化硫黄が、ｏ−トリジン類１モルに対して、４モル以上、好ましくは５モル以上、更に好ましくは５．５モル以上になるように発煙硫酸を用いて反応させるのが好適である。
However, in the present invention, the reaction is carried out using fuming sulfuric acid so that sulfur trioxide is 4 mol or more, preferably 5 mol or more, more preferably 5.5 mol or more per mol of o-tolidine. Is preferred. If the sulfur trioxide is less than 4 mol, the cyclic sulfonation reaction is not efficiently performed, and the yield of the obtained o-tolidine sulfone tends to be low.
In addition, when using the hydrous material of o-tolidine as a raw material, since 1 mol of water and 1 mol of sulfur trioxide react immediately and become sulfuric acid, it reacts with the water contained in o-tolidines. The amount of sulfur trioxide excluding the amount of sulfur trioxide consumed (equal molar amount to water) is 4 mol or more, preferably 5 mol or more, more preferably 5. It is preferable to react with fuming sulfuric acid so as to be 5 mol or more.
また、発煙硫酸を大過剰に用いると、反応後の後処理が困難になるので、ｏ−トリジン１モルに対して、三酸化硫黄が、好ましくは１０モル以下、より好ましくは８モル以下、更に好ましくは６．５モル以下、特に好ましくは６．１モル以下になるような量の発煙硫酸を用いて反応させるのが好適である。 In addition, if fuming sulfuric acid is used in a large excess, post-treatment after the reaction becomes difficult, so sulfur trioxide is preferably 10 moles or less, more preferably 8 moles or less, and more preferably 8 moles or less, per mole of o-tolidine. It is preferable to carry out the reaction using fuming sulfuric acid in such an amount that it is preferably 6.5 mol or less, particularly preferably 6.1 mol or less.
ｏ−トリジンと発煙硫酸との反応は、好適には次の工程で行うことができる。
まず、所定量の発煙硫酸中に所定量のｏ−トリジンを加えて均一に溶解する。この時に発熱が起こるので、高温にならないように必要なら冷却しながら攪拌下に少量ずつｏ−トリジンを加え、５０℃以下、好ましくは１０〜３０℃程度で、０．５〜２０時間、好ましくは１〜１０時間程度攪拌して均一に溶解させるのが好ましい。
次いで、この溶液を徐々に昇温し、最高温度を１００℃以下、好ましくは７０℃以下、より好ましくは６５℃以下、更に好ましくは６０℃以下の温度で、０．１〜２０時間、好ましくは１〜１０時間程度反応を行う。ここでは反応混合物の温度管理が重要である。最高温度が高くなると、発煙硫酸によるスルホン化が更に進行してスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）が副生し易くなるので好ましくない。通常、最高温度は１０℃以上、好ましくは３０℃以上である。
The reaction between o-tolidine and fuming sulfuric acid can be preferably carried out in the following step.
First, a predetermined amount of o-tolidine is added to a predetermined amount of fuming sulfuric acid and dissolved uniformly. Since heat is generated at this time, o-tolidine is added little by little with stirring while cooling, if necessary so as not to reach a high temperature, and is 50 ° C. or less, preferably about 10 to 30 ° C. for 0.5 to 20 hours, preferably It is preferable to stir for about 1 to 10 hours to dissolve uniformly.
Then, the temperature of the solution is gradually raised, and the maximum temperature is 100 ° C. or lower, preferably 70 ° C. or lower, more preferably 65 ° C. or lower, and still more preferably 60 ° C. or lower, preferably 0.1 to 20 hours, preferably The reaction is carried out for about 1 to 10 hours. Here, temperature control of the reaction mixture is important. A higher maximum temperature is not preferable because sulfonation with fuming sulfuric acid further proceeds and a sulfonic acid compound (o-tolidine sulfonesulfonic acid) is easily produced as a by-product. Usually, the maximum temperature is 10 ° C or higher, preferably 30 ° C or higher.
この反応では、前述のとおり発煙硫酸によってスルホン化が更に進行してベンゼン環の水素の位置がスルホン酸に置換したスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）が、目的物のｏ−トリジンスルホンと共に副生する。この副生成物のスルホン酸化合物は、化学的性質が目的物のｏ−トリジンスルホンと非常に類似しているために分離除去することが容易ではない。さらに、このスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）は、後工程で使用するアルカリに起因するアルカリ金属やアルカリ土類金属などの金属成分と容易に塩を形成してスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）の塩になる。スルホン酸化合物（ｏ−トリジンスルホンスルホン酸）の塩も容易に分離除去することはできない。これらが残存すると、得られたｏ−トリジンスルホンの純度が下がり、不純物として金属成分が含有されることになる。 In this reaction, as described above, sulfonation further proceeds with fuming sulfuric acid, and a sulfonic acid compound in which the hydrogen position of the benzene ring is substituted with sulfonic acid (o-tolidine sulfone sulfonic acid) is combined with the target o-tolidine sulfone. By-product. The by-product sulfonic acid compound is not easy to separate and remove because its chemical properties are very similar to the target o-tolidine sulfone. Furthermore, this sulfonic acid compound (o-tolidine sulfonesulfonic acid) easily forms a salt with a metal component such as an alkali metal or alkaline earth metal resulting from the alkali used in the subsequent step to form a sulfonic acid compound (o- Tolysine sulfonesulfonic acid). The salt of the sulfonic acid compound (o-tolidine sulfonesulfonic acid) cannot be easily separated and removed. If these remain, the purity of the obtained o-tolidine sulfone is lowered, and a metal component is contained as an impurity.
ｏ−トリジンスルホンに、副生成物のスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）やその金属塩が残存すると、ポリアミドやポリイミドを得るための重合反応に影響が及ぶことがあり好ましくない。 If a by-product sulfonic acid compound (o-tolidine sulfone sulfonic acid) or a metal salt thereof remains in o-tolidine sulfone, the polymerization reaction for obtaining polyamide or polyimide may be affected, which is not preferable.
反応終了後の後処理は、次の工程２〜４によって好適に行うことができる。
先ず、反応混合液を水と混合し、析出したｏ−トリジンスルホンの硫酸塩を分離する工程（工程２）を行う。具体的には、反応混合液を好ましくは４０℃程度以下の温度まで冷却する。反応混合液には三酸化硫黄が残存しているので、反応混合液を大量の水（好ましくは氷水）に投入して三酸化硫黄を水と反応させて硫酸にする。この結果、目的物であるｏ−トリジンスルホンは、硫酸塩になって析出する。
析出したｏ−トリジンスルホンの硫酸塩を濾取する。この操作によって、溶解成分である硫酸などの溶解性の不純物を除くことができる。
Post-treatment after completion of the reaction can be suitably performed by the following steps 2 to 4.
First, the reaction mixture is mixed with water to separate the precipitated o-tolidinesulfone sulfate (step 2). Specifically, the reaction mixture is preferably cooled to a temperature of about 40 ° C. or lower. Since sulfur trioxide remains in the reaction mixture, the reaction mixture is poured into a large amount of water (preferably ice water) to react the sulfur trioxide with water to make sulfuric acid. As a result, the target product, o-tolidine sulfone, is precipitated as sulfate.
The precipitated o-tolidinesulfone sulfate is collected by filtration. By this operation, soluble impurities such as sulfuric acid as a dissolving component can be removed.
ここで使用する水の量は、大量であるほど濾液の硫酸濃度が薄くなり、取り扱いは容易になるかも知れないが、本発明では比較的多くの発煙硫酸を用いているため極めて大きな装置が必要になり、目的物の量に比べて過大な装置が必要になるから実際的ではない。この工程で使用する水の量は、結果として、濾液の硫酸の濃度が１５〜３５質量％、好ましくは２０〜２６質量％程度になるように決めるのが、反応工程や精製工程も含めた工程全体の装置の大きさのバランスや濾液の後処理の容易性を勘案すると好適である。濾液の硫酸濃度が３５質量％以上の場合は安全性の面で取り扱いが難しく、１５質量％以下では取り扱う全体の液量が過大になって装置の大型化や生産性の悪化を招くので好ましくない。
すなわち、使用する水の量は、前記条件を満たすように決めるのが好ましい。原料のｏ−トリジンの量、発煙硫酸の濃度や量などに依存するので一義的に決められないが、通常用いる水の量は、原料のｏ−トリジン１００質量部当たり３０００〜４５００質量部、好ましくは３０００〜４０００質量部、より好ましくは３０００〜３５００質量部程度が好適である。
The larger the amount of water used here, the thinner the sulfuric acid concentration of the filtrate may be and the easier it may be to handle. However, in the present invention, since a relatively large amount of fuming sulfuric acid is used, a very large apparatus is required. This is not practical because an excessively large device is required as compared with the amount of the object. The amount of water used in this step is determined so that the concentration of sulfuric acid in the filtrate is 15 to 35% by mass, preferably about 20 to 26% by mass, including the reaction step and the purification step. Considering the balance of the overall apparatus size and the ease of post-treatment of the filtrate, it is preferable. When the sulfuric acid concentration of the filtrate is 35% by mass or more, it is difficult to handle in terms of safety, and when it is 15% by mass or less, the total amount of the liquid handled becomes excessive, which leads to an increase in the size of the apparatus and deterioration of productivity. .
That is, the amount of water to be used is preferably determined so as to satisfy the above conditions. Since it depends on the amount of raw material o-tolidine and the concentration and amount of fuming sulfuric acid, it is not uniquely determined. The amount of water usually used is 3000 to 4500 parts by weight, preferably 100 parts by weight of raw material o-tolidine. Is preferably about 3000 to 4000 parts by mass, more preferably about 3000 to 3500 parts by mass.
次いで、ｏ−トリジンスルホンの硫酸塩を水に溶解又は懸濁した状態でアルカリ性にして処理してｏ−トリジンスルホンとし、粗ｏ−トリジンスルホンとして分離する工程（工程３）を行う。すなわち、濾取したｏ−トリジンスルホンの硫酸塩からなるウエット結晶は、特に乾燥する必要はなく、再び水に加えて懸濁させ、これに水酸化ナトリウム水溶液のようなアルカリを加えて液をアルカリ性にし、遊離のｏ−トリジンスルホンとする。水の量は、限定するものではないがｏ−トリジンスルホンの硫酸塩１００質量部に対して通常１０００〜３０００質量部好ましくは２０００〜３０００質量部程度であり、アルカリを加えることによってｐＨが７〜１０程度のアルカリ性にするのが好適である。この操作は、液を懸濁状態のままで好適に行うことができる。アルカリは、ｏ−トリジンスルホンの硫酸塩をアルカリ性の環境にするのが目的であるから、特に限定されるものではなく、水酸化ナトリウム、水酸化カルシウム、水酸化マグネシウム、水酸化カリウムなどの強アルカリがよく、それらは水溶液にして加えるのが好ましい。
この懸濁液を濾過して粗ｏ−トリジンスルホンを得ることができる。
Subsequently, the step of converting o-tolidine sulfone sulfate into alkali in a state of being dissolved or suspended in water to form o-tolidine sulfone and separating it as crude o-tolidine sulfone (step 3) is performed. That is, the wet crystals of o-tolidinesulfone sulfate collected by filtration do not need to be dried in particular, but are added again to water and suspended, and an alkali such as an aqueous sodium hydroxide solution is added thereto to make the solution alkaline. To free o-tolidine sulfone. Although the amount of water is not limited, it is usually 1000 to 3000 parts by mass, preferably about 2000 to 3000 parts by mass with respect to 100 parts by mass of the sulfate of o-tolidine sulfone. It is preferable that the alkalinity is about 10. This operation can be suitably performed while the liquid remains in a suspended state. The alkali is not particularly limited because it is intended to make o-tolidinesulfone sulfate into an alkaline environment, and strong alkali such as sodium hydroxide, calcium hydroxide, magnesium hydroxide, potassium hydroxide, etc. They are preferably added in the form of an aqueous solution.
This suspension can be filtered to obtain crude o-tolidine sulfone.
この濾取した粗ｏ−トリジンスルホン中には、加えたアルカリ成分に起因した例えば硫酸ナトリウムのような塩が多量に残存している。
また、反応混合液には副生成物であるスルホン酸化合物類（ｏ−トリジンスルホンスルホン酸）の硫酸塩が含まれ、前記処理によっても分離除去できず残存しているので、この副生成物もスルホン酸化合物（ｏ−トリジンスルホンスルホン酸）のナトリウム塩のような塩になって、粗ｏ−トリジンスルホン中に残存している。
In the crude o-tolidine sulfone collected by filtration, a large amount of salt such as sodium sulfate remaining due to the added alkali component remains.
In addition, the reaction mixture contains a sulfate of sulfonic acid compounds (o-tolidine sulfonesulfonic acid) as a by-product, and cannot be separated and removed by the above treatment. It becomes a salt such as a sodium salt of a sulfonic acid compound (o-tolidine sulfone sulfonic acid) and remains in the crude o-tolidine sulfone.
このため、粗ｏ−トリジンスルホンはさらに精製する必要があり、粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程（工程４）を行う。
すなわち、粗ｏ−トリジンスルホン類の精製は、酸性水溶液で処理して、前工程で加えたアルカリと反応して生じた塩を取り除く方法によって好適に行われる。
具体的には、特許文献１に記載されているように、大量の水と塩酸でｏ−トリジンスルホンを塩酸塩にして溶解し、更に活性炭やハイドロサルファイトで不純物を除去した後で、水酸化ナトリウム水溶液を加えて弱アルカリ性にｐＨ調整することによってｏ−トリジンスルホンを沈殿させ、濾過して回収する方法でも可能かも知れない。しかし、この方法では、ｏ−トリジンスルホンの塩酸塩は水への溶解度が非常に低いために液量が多くなるので、非常に大きな装置が必要になり、生産性も良くない。
本発明のｏ−トリジンスルホンの製造方法においては、粗ｏ−トリジンスルホンを塩酸塩として完全に溶解させず、酸性水溶液中で懸濁させた状態のままで処理し、その後水酸化ナトリウム水溶液などのアルカリ成分を加えてｐＨを調製することによって、必要な品質のｏ−トリジンスルホンを得る。この方法によれば、取り扱う液量が比較的少なくて済み、従って過大な装置を必要とせず、生産性は良好である。
For this reason, the crude o-tolidine sulfone needs to be further purified, and the step of purifying the crude o-tolidine sulfone by acidifying it in a state suspended in water and then adjusting the pH (step 4). Do.
That is, the purification of the crude o-tolidine sulfones is preferably performed by a method in which the salt generated by reacting with the alkali added in the previous step is treated with an acidic aqueous solution.
Specifically, as described in Patent Document 1, o-tolidine sulfone is dissolved in hydrochloride with a large amount of water and hydrochloric acid, and impurities are removed with activated carbon or hydrosulfite, followed by hydroxylation. A method may also be possible in which o-tolidine sulfone is precipitated by adding a sodium aqueous solution to adjust the pH to be weakly alkaline and then recovered by filtration. However, in this method, since the hydrochloride of o-tolidine sulfone has a very low solubility in water, the amount of liquid increases, so a very large apparatus is required and productivity is not good.
In the method for producing o-tolidine sulfone according to the present invention, the crude o-tolidine sulfone is not completely dissolved as a hydrochloride, but is treated in a state suspended in an acidic aqueous solution, and then a sodium hydroxide aqueous solution or the like is used. The required quality of o-tolidine sulfone is obtained by adjusting the pH by adding an alkaline component. According to this method, the amount of liquid to be handled is relatively small. Therefore, an excessive apparatus is not required and the productivity is good.
酸性水溶液中で懸濁させた状態のままで処理する方法において、洗浄の効果・効率を考えた場合、酸性にするために用いる酸は比較的溶解性が高い塩酸を用いるのが好ましい。硫酸や燐酸などの他の酸でも構わないが、洗浄の効果・効率が悪くなる。 In the method of treatment in a state of being suspended in an acidic aqueous solution, when considering the effect and efficiency of washing, it is preferable to use hydrochloric acid having a relatively high solubility as the acid used for acidification. Other acids such as sulfuric acid and phosphoric acid may be used, but the cleaning effect and efficiency are deteriorated.
また、得られるｏ−トリジンスルホンに含有されるナトリウムなどの金属成分の量を減少させるためには、粗ｏ−トリジンスルホンを酸性水溶液で処理した後のアルカリ成分によるｐＨ調整において、特許文献１に記載のような弱アルカリ性に調整するのではなく、ｐＨを好ましくは７以下、より好ましくは６以下、更に好ましくは５以下、特に好ましくは４以下、更に好ましくは３以下、特に好ましくは２．５以下であって、１．５以上の酸性領域に調整することが好適である。このような調整によって、濾過に要する期間を大幅に短縮できるので生産効率を改善することができる。また、ナトリウムなどの金属成分の含有量を好ましくは１５０ｐｐｍ以下好ましくは１００ｐｐｍ以下より好ましくは８０ｐｐｍ以下に抑制することができる。 Moreover, in order to reduce the amount of metal components such as sodium contained in the obtained o-tolidine sulfone, in pH adjustment with an alkali component after treating the crude o-tolidine sulfone with an acidic aqueous solution, Patent Document 1 discloses. Rather than adjusting to weak alkalinity as described, the pH is preferably 7 or less, more preferably 6 or less, even more preferably 5 or less, particularly preferably 4 or less, still more preferably 3 or less, particularly preferably 2.5. It is preferable to adjust to an acidic region of 1.5 or more. By such adjustment, the period required for filtration can be greatly shortened, so that production efficiency can be improved. Moreover, content of metal components, such as sodium, can be preferably suppressed to 150 ppm or less, preferably 100 ppm or less, more preferably 80 ppm or less.
前記精製後、濾過によって得られたｏ−トリジンスルホンは、好ましくはエタノールなどで洗浄した後で、好ましくは減圧下、１３０℃以下、特に１００〜１２０℃程度の温度範囲で加熱することによって好適に乾燥することができる。 After the purification, the o-tolidine sulfone obtained by filtration is preferably washed by heating with ethanol or the like, and then preferably heated by heating under a reduced pressure at a temperature of 130 ° C. or less, particularly about 100 to 120 ° C. Can be dried.
本発明において得られるｏ−トリジンスルホンは、下記化学式（２）（３）（４）で表される異性体の混合物である。 The o-tolidine sulfone obtained in the present invention is a mixture of isomers represented by the following chemical formulas (2), (3) and (4).
なお、本発明における副生成物のｏ−トリジンスルホンスルホン酸は、下記化学式（５）で表される化合物である。 The by-product o-tolidine sulfonesulfonic acid in the present invention is a compound represented by the following chemical formula (5).
本発明によれば、副生成物のｏ−トリジンスルホンスルホン酸の含有量が少ない高純度のｏ−トリジンスルホンをより安全で効率よく経済的に得ることができる。このような高純度のｏ−トリジンスルホンは、ポリアミドやポリイミドなどのポリマーのジアミン成分として好適に用いることができる。 According to the present invention, high-purity o-tolidine sulfone having a low content of by-product o-tolidine sulfonesulfonic acid can be obtained more safely, efficiently and economically. Such high-purity o-tolidine sulfone can be suitably used as a diamine component of polymers such as polyamide and polyimide.
以下、実施例を用いて本発明をより詳細に説明する。なお、本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to an Example.
以下の例で用いた測定方法は次のとおりである。
［ＨＰＬＣ分析］
ＨＰＬＣ分析条件は以下のとおり。
測定装置：高速液体クロマトグラフ Ｌ−７０００シリーズ 日立製作所製
カラム：ＯＤＳ−８０Tｓ ２５０ｍｍ×４．６ｍｍ
カラム温度：４０℃
溶離液：ＭｅＯＨ／Ｈ２Ｏ
流量：１ｍｌ／ｍｉｎ
グラジエント：５／９５（０−１０ｍｉｎ）→５０／５０（１９−４５ｍｉｎ）
検出器：紫外吸光検出器
検出波長：２５４ｎｍ
この分析条件で、リテンションタイム５〜４５分のピークをカウントした。例えばリテンションタイムが２２〜２４分付近にｏ−トリジンスルホンスルホン酸の異性体の複数のピーク、２４〜２８分付近にｏ−トリジンスルホンの異性体の複数のピークが得られた。
The measurement methods used in the following examples are as follows.
[HPLC analysis]
The HPLC analysis conditions are as follows.
Measuring apparatus: High-performance liquid chromatograph L-7000 series manufactured by Hitachi, Ltd. Column: ODS-80Ts 250 mm × 4.6 mm
Column temperature: 40 ° C
Eluent: MeOH / H 2 O
Flow rate: 1 ml / min
Gradient: 5/95 (0-10 min) → 50/50 (19-45 min)
Detector: UV absorption detector Detection wavelength: 254 nm
Under these analysis conditions, peaks with a retention time of 5 to 45 minutes were counted. For example, a plurality of peaks of isomers of o-tolidinesulfone sulfonic acid were obtained at a retention time of around 22 to 24 minutes, and a plurality of peaks of isomers of o-tolidine sulfone were obtained at around 24 to 28 minutes.
［純度の算出］
ｏ−トリジンスルホンの純度（％）とｏ−トリジンスルホンスルホン酸の含有量（％）は、ＨＰＬＣ分析結果（ピーク面積）から下式に従って計算した。
[Calculation of purity]
The purity (%) of o-tolidine sulfone and the content (%) of o-tolidine sulfonesulfonic acid were calculated from the HPLC analysis result (peak area) according to the following formula.
［硫酸塩からなるウエット結晶のＨＰＬＣ測定から収率（％）の算出］
前記の純度算出で純度が確認された高純度のｏ−トリジンスルホンを標準品として用い、標準品とｏ−トリジンスルホン硫酸塩のサンプルを、それぞれＨＰＬＣ測定を行い、得られる両者のｏ−トリジンスルホンのピーク面積から、下式に従ってｏ−トリジンスルホン硫酸塩サンプルのｏ−トリジンスルホン純度を求めた。
[Calculation of yield (%) from HPLC measurement of wet crystals of sulfate]
Using high-purity o-tolidine sulfone whose purity was confirmed by the above purity calculation as a standard product, each of the standard product and the o-tolidine sulfone sulfate sample was subjected to HPLC measurement, and both o-tolidine sulfones obtained were obtained. From the peak area, the o-tolidine sulfone purity of the o-tolidine sulfone sulfate sample was determined according to the following formula.
［収率の算出］
収率（％）は下式に従って算出した。
[Calculation of yield]
The yield (%) was calculated according to the following formula.
［金属の含有量］
金属成分の含有量（ｐｐｍ）は、試料を硫酸と硝酸で加熱分解後、超純水で定容して検液とし、ＩＣＰ−ＡＥＳ法により下記の測定装置を用いて分析を行った。単位は（μｇ／ｇ）＝（ｐｐｍ）である。
測定装置：ＩＣＰ−ＡＥＳ・エスアイアイ・ナノテクノロジー社製ＳＰＳ５１００型
[Metal content]
The content (ppm) of the metal component was analyzed using the following measuring device by the ICP-AES method after heat-decomposing the sample with sulfuric acid and nitric acid and then making a constant volume with ultrapure water to make a test solution. The unit is (μg / g) = (ppm).
Measuring device: SPS5100 manufactured by ICP-AES / SII Nanotechnology
〔実施例１〕
（工程１）温度計、還流冷却器、撹拌機を付けた内容量５００ｍｌの四つ口フラスコに、３０質量％発煙硫酸３５０ｇ（三酸化硫黄として１．３１ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、２０質量％含水ｏ−トリジン３８．７ｇ（ｏ−トリジンとして３１．０ｇ、０．１４６ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンとのモル比（三酸化硫黄／ｏ−トリジン）は６．０であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約１０００ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウエット結晶１６９．９ｇを得た。この硫酸塩結晶からなるウエット結晶をＨＰＬＣで分析したところｏ−トリジンスルホンの量は３８．４ｇ（０．１４０ｍｏｌ）であり、これは収率９５．９％に相当した。また、このときの濾液の硫酸濃度は２５．９質量％であった。
（工程３）得られた硫酸塩結晶からなるウエット結晶を水７５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてｐＨを９にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。
（工程４）この粗ｏ−トリジンスルホンを水６００ｍｌに投入し、３６質量％塩酸水溶液９５ｇを加えて懸濁した状態で酸性にして加温し８０℃で２時間撹拌した。この液を冷却し、室温で４０質量％水酸化ナトリウム水溶液を加えてｐＨを２に調整し析出した黄色結晶を濾取した。
（後処理）結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶３７．９ｇ（０．１３８ｍоｌ）を収率９４．５％で得た。得られた結晶のｏ−トリジンスルホン純度はＨＰＬＣ分析で９８．７％（三種類の異性体合計）であり、不純物ｏ−トリジンスルホンスルホン酸の含有量は１．２２％、ナトリウム含有量は８２ｐｐｍで品質上問題はなかった。
前記一連の操作において、操作容量が大きいのは、反応液を氷水に注いだ工程２で約１３００ｍｌであり、粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程４で約９００ｍｌであった。
[Example 1]
(Step 1) Into a 500 ml four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 350 g of 30% by mass fuming sulfuric acid (1.31 mol as sulfur trioxide) was added, and the internal temperature was changed from 30 ° C While maintaining the temperature at 40 ° C., 38.7 g of 20% by mass water-containing o-tolidine (31.0 g as o-tolidine, 0.146 mol) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed by water was 6.0. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) After the reaction solution was cooled to 40 ° C., it was poured into about 1000 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain 169.9 g of wet crystals. When the wet crystal comprising this sulfate crystal was analyzed by HPLC, the amount of o-tolidine sulfone was 38.4 g (0.140 mol), which corresponded to a yield of 95.9%. Moreover, the sulfuric acid concentration of the filtrate at this time was 25.9 mass%.
(Step 3) The obtained wet crystals of sulfate crystals are added to 750 ml of water, and further 40 mass% sodium hydroxide aqueous solution is added to adjust the pH to 9, and the mixture is heated to 90 ° C., and the resulting free o-tolidine Crude sulfone crystals were collected by filtration.
(Step 4) The crude o-tolidine sulfone was added to 600 ml of water, and was acidified in a suspended state by adding 95 g of a 36% by mass aqueous hydrochloric acid solution, followed by stirring at 80 ° C. for 2 hours. This liquid was cooled, a 40 mass% sodium hydroxide aqueous solution was added at room temperature to adjust the pH to 2, and the precipitated yellow crystals were collected by filtration.
(Post-treatment) The crystals were washed with water and ethanol and then dried at 110 ° C. under reduced pressure to obtain 37.9 g (0.138 mol) of o-tolidinesulfone yellow crystals in a yield of 94.5%. The o-tolidine sulfone purity of the obtained crystal was 98.7% (total of three isomers) by HPLC analysis, the content of impurity o-tolidine sulfonesulfonic acid was 1.22%, and the sodium content was 82 ppm. There were no quality problems.
In the series of operations, the operation volume is large in about 1300 ml in the step 2 in which the reaction solution is poured into ice water, and the crude o-tolidine sulfone is acidified in a state suspended in water, and then the pH is adjusted. It was about 900 ml in the process 4 which refine | purifies by adjusting.
〔比較例１〕
特許文献１の参考例に準じてｏ−トリジンスルホンの製造を試みた。
（工程１）温度計、還流冷却器、撹拌機を付けた内容量５００ｍｌの四つ口フラスコに、３０質量％発煙硫酸３５６ｇ（三酸化硫黄として１．３３ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、２０質量％含水ｏ−トリジン３８．７ｇ（ｏ−トリジンとして３１．０ｇ、０．１４６ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンのモル比（三酸化硫黄／ｏ−トリジン）は６．２であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約１８００ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウェット結晶を得た。濾液の硫酸濃度は１６．４質量％だった。
（工程３）得られた硫酸塩結晶を水７５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてアルカリ性にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。
（工程４）この粗結晶を水１８００ｍｌに投入し、３６質量％塩酸水溶液３６０ｇを加えて加温して８０℃とし、塩酸塩として溶解させ２時間撹拌した。この液の不溶物を濾別後、液を冷却し、室温で４０％水酸化ナトリウム水溶液を加えてｐＨを９に調整し析出した黄色結晶を濾取した。
（後処理）結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶３４．４ｇ（０．１２５ｍоｌ）を収率８５．６％で得た。得られた結晶のｏ−トリジンスルホン純度はＨＰＬＣ分析で９８．２％（三種類の異性体合計）であり、品質上問題なかった。
前記一連の操作において、操作容量が大きいのは、反応液を氷水に注いだ工程２で約２０００ｍｌであり、粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程４で約２６００ｍｌであったので、非常に大きな装置が必要になった。
[Comparative Example 1]
An attempt was made to produce o-tolidine sulfone according to the reference example of Patent Document 1.
(Step 1) In a 500 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer, 356 g of 30% by mass fuming sulfuric acid (1.33 mol as sulfur trioxide) was added, and the internal temperature was changed from 30 ° C. While maintaining the temperature at 40 ° C., 38.7 g of 20% by mass water-containing o-tolidine (31.0 g as o-tolidine, 0.146 mol) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed with water was 6.2. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) The reaction solution was cooled to 40 ° C., poured into about 1800 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain wet crystals. The sulfuric acid concentration of the filtrate was 16.4% by mass.
(Step 3) The obtained sulfate crystals are added to 750 ml of water, and 40% by mass aqueous sodium hydroxide solution is added to make alkaline, and the mixture is heated to 90 ° C. The resulting crude crystals of free o-tolidine sulfone are filtered. I took it.
(Step 4) The crude crystals were added to 1800 ml of water, and 360 g of a 36% by mass hydrochloric acid aqueous solution was added and heated to 80 ° C., dissolved as a hydrochloride, and stirred for 2 hours. The insoluble material in this solution was filtered off, and the solution was cooled. A 40% aqueous sodium hydroxide solution was added at room temperature to adjust the pH to 9, and the precipitated yellow crystals were collected by filtration.
(Post-treatment) The crystals were washed with water and ethanol, and then dried at 110 ° C. under reduced pressure to obtain 34.4 g (0.125 mole) of o-tolidinesulfone yellow crystals in a yield of 85.6%. The o-tolidine sulfone purity of the obtained crystal was 98.2% (total of three isomers) by HPLC analysis, and there was no problem in quality.
In the series of operations described above, the operation volume is large in about 2000 ml in the step 2 in which the reaction solution was poured into ice water. The crude o-tolidine sulfone was acidified while suspended in water, and then the pH was adjusted. Since it was about 2600 ml in the process 4 which refine | purifies by adjusting, the very big apparatus was needed.
〔実施例２〕
（工程１）温度計、還流冷却器、撹拌機を付けた内容量１００ｍｌの四つ口フラスコに、３０質量％発煙硫酸７０ｇ（三酸化硫黄として０．２６ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、３６質量％含水ｏ−トリジン８．７１ｇ（ｏ−トリジンとして５．５７ｇ、０．０２６２ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンとのモル比（三酸化硫黄／ｏ−トリジン）は３．３であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約１８５ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウエット結晶を得た。このウエット結晶をＨＰＬＣで分析したところｏ−トリジンスルホンの量は５．７７ｇ（０．０２１０ｍｏｌ）であり、これは収率８０．２％に相当した。また、このときの濾液の硫酸濃度は２６．９質量％であった。
（工程３〜後処理）得られた硫酸塩結晶からなるウエット結晶を水１５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてｐＨを９にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。この粗ｏ−トリジンスルホンを水１２０ｍｌに投入し、３６質量％塩酸水溶液１９ｇを加えて懸濁した状態で酸性にして加温し８０℃で２時間撹拌した。この液を冷却し、室温で４０質量％水酸化ナトリウム水溶液を加えてｐＨを２に調整し析出した黄色結晶を濾取した。結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶５．７０ｇ（０．０２０８ｍоｌ）を収率７９．１％で得た。
[Example 2]
(Step 1) A 100 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer is charged with 70 g of 30% by weight fuming sulfuric acid (0.26 mole as sulfur trioxide), and the internal temperature is from 30 ° C. While maintaining the temperature at 40 ° C., 8.71 g of 36% by mass water-containing o-tolidine (5.57 g, 0.0262 mol as o-tolidine) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed with water was 3.3. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) The reaction solution was cooled to 40 ° C., poured into about 185 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain wet crystals. When the wet crystals were analyzed by HPLC, the amount of o-tolidine sulfone was 5.77 g (0.0210 mol), which corresponded to a yield of 80.2%. Moreover, the sulfuric acid concentration of the filtrate at this time was 26.9 mass%.
(Step 3-Post-treatment) The obtained wet crystals consisting of sulfate crystals are added to 150 ml of water, and further 40% by mass aqueous sodium hydroxide solution is added to adjust the pH to 9, followed by heating to 90 ° C. Crude crystals of o-tolidine sulfone were collected by filtration. This crude o-tolidine sulfone was added to 120 ml of water, and 19 g of a 36% by mass aqueous hydrochloric acid solution was added thereto to make it acidic in a suspended state, followed by heating at 80 ° C. for 2 hours. This liquid was cooled, a 40 mass% sodium hydroxide aqueous solution was added at room temperature to adjust the pH to 2, and the precipitated yellow crystals were collected by filtration. The crystals were washed with water and ethanol and then dried at 110 ° C. under reduced pressure to obtain 5.70 g (0.0208 mol) of o-tolidine sulfone yellow crystals in a yield of 79.1%.
〔実施例３〕
（工程１）温度計、還流冷却器、撹拌機を付けた内容量１００ｍｌの四つ口フラスコに、３０質量％発煙硫酸７８ｇ（三酸化硫黄として０．２９ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、３６質量％含水ｏ−トリジン８．７４ｇ（ｏ−トリジンとして５．５９ｇ、０．０２６３ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンとのモル比（三酸化硫黄／ｏ−トリジン）は４．５であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約２１０ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウエット結晶を得た。このウエット結晶をＨＰＬＣで分析したところｏ−トリジンスルホンの量は６．４９ｇ（０．０２３６ｍｏｌ）であり、これは収率８９．７％に相当した。また、このときの濾液の硫酸濃度は２６．６質量％であった。
（工程３〜後処理）得られた硫酸塩結晶からなるウエット結晶を水１５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてｐＨを９にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。この粗ｏ−トリジンスルホンを水１２０ｍｌに投入し、３６質量％塩酸水溶液１９ｇを加えて懸濁した状態で酸性にして加温し８０℃で２時間撹拌した。この液を冷却し、室温で４０質量％水酸化ナトリウム水溶液を加えてｐＨを２に調整し析出した黄色結晶を濾取した。結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶６．４２ｇ（０．０２３４ｍоｌ）を収率８８．８％で得た。
Example 3
(Step 1) In a 100 ml four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, 78 g of 30% by mass fuming sulfuric acid (0.29 mol as sulfur trioxide) was added, and the internal temperature was changed from 30 ° C. While maintaining the temperature at 40 ° C., 8.74 g of hydrous o-tolidine containing 36% by mass (5.59 g, 0.0263 mol as o-tolidine) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed with water was 4.5. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) After cooling this reaction solution to 40 ° C., it was poured into about 210 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain wet crystals. When the wet crystals were analyzed by HPLC, the amount of o-tolidine sulfone was 6.49 g (0.0236 mol), which corresponded to a yield of 89.7%. Moreover, the sulfuric acid concentration of the filtrate at this time was 26.6 mass%.
(Step 3-Post-treatment) The obtained wet crystals consisting of sulfate crystals are added to 150 ml of water, and further 40% by mass aqueous sodium hydroxide solution is added to adjust the pH to 9, followed by heating to 90 ° C. Crude crystals of o-tolidine sulfone were collected by filtration. This crude o-tolidine sulfone was added to 120 ml of water, and 19 g of a 36% by mass aqueous hydrochloric acid solution was added thereto to make it acidic in a suspended state, followed by heating at 80 ° C. for 2 hours. This liquid was cooled, a 40 mass% sodium hydroxide aqueous solution was added at room temperature to adjust the pH to 2, and the precipitated yellow crystals were collected by filtration. The crystals were washed with water and ethanol and then dried at 110 ° C. under reduced pressure to obtain 6.42 g (0.0234 mole) of o-tolidinesulfone yellow crystals in a yield of 88.8%.
〔実施例４〕
（工程１）温度計、還流冷却器、撹拌機を付けた内容量１００ｍｌの四つ口フラスコに、３０質量％発煙硫酸８５ｇ（三酸化硫黄として０．３２ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、３６質量％含水ｏ−トリジン８．７３ｇ（ｏ−トリジンとして５．５９ｇ、０．０２６３ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンとのモル比（三酸化硫黄／ｏ−トリジン）は５．５であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約２２０ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウエット結晶を得た。このウエット結晶をＨＰＬＣで分析したところｏ−トリジンスルホンの量は６．８２ｇ（０．０２４９ｍｏｌ）であり、これは収率９４．７％に相当した。また、このときの濾液の硫酸濃度は２７．４質量％であった。
（工程３〜後処理）得られた硫酸塩結晶からなるウエット結晶を水１５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてｐＨを９にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。この粗ｏ−トリジンスルホンを水１２０ｍｌに投入し、３６質量％塩酸水溶液１９ｇを加えて懸濁した状態で酸性にして加温し８０℃で２時間撹拌した。この液を冷却し、室温で４０質量％水酸化ナトリウム水溶液を加えてｐＨを２に調整し析出した黄色結晶を濾取した。結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶６．７３ｇ（０．０２４５ｍоｌ）を収率９３．２％で得た。
Example 4
(Step 1) Into a 100 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer, 85 g of 30% by mass fuming sulfuric acid (0.32 mol as sulfur trioxide) was added, and the internal temperature was changed from 30 ° C. While maintaining the temperature at 40 ° C., 8.73 g of 36% by mass water-containing o-tolidine (5.59 g, 0.0263 mol as o-tolidine) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed with water was 5.5. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) The reaction solution was cooled to 40 ° C., poured into about 220 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain wet crystals. When the wet crystals were analyzed by HPLC, the amount of o-tolidine sulfone was 6.82 g (0.0249 mol), which corresponded to a yield of 94.7%. Moreover, the sulfuric acid concentration of the filtrate at this time was 27.4 mass%.
(Step 3-Post-treatment) The obtained wet crystals consisting of sulfate crystals are added to 150 ml of water, and further 40% by mass aqueous sodium hydroxide solution is added to adjust the pH to 9, followed by heating to 90 ° C. Crude crystals of o-tolidine sulfone were collected by filtration. This crude o-tolidine sulfone was added to 120 ml of water, and 19 g of a 36% by mass aqueous hydrochloric acid solution was added thereto to make it acidic in a suspended state, followed by heating at 80 ° C. for 2 hours. This liquid was cooled, a 40 mass% sodium hydroxide aqueous solution was added at room temperature to adjust the pH to 2, and the precipitated yellow crystals were collected by filtration. The crystals were washed with water and ethanol and then dried at 110 ° C. under reduced pressure to obtain 6.73 g (0.0245 mol) of o-tolidinesulfone yellow crystals in a yield of 93.2%.
〔実施例５〕
（工程１）温度計、還流冷却器、撹拌機を付けた内容量１００ｍｌの四つ口フラスコに、３０質量％発煙硫酸１０３ｇ（三酸化硫黄として０．３９ｍоｌ）を入れ、内温を３０℃から４０℃に保ちながら、３６質量％含水ｏ−トリジン８．７８ｇ（ｏ−トリジンとして５．６２ｇ、０．０２６５ｍｏｌ）を発熱に注意しながら少しずつ添加した。水で分解する分を除いた三酸化硫黄とｏ−トリジンとのモル比（三酸化硫黄／ｏ−トリジン）は８．０であった。その後、内温３０℃で３０分撹拌し、更に３０分掛けて６０℃に昇温し、同温度で１時間撹拌、更に３０分掛けて８０℃に昇温し、同温度で１．５時間撹拌した。
（工程２）この反応液を４０℃まで冷却した後、約３００ｍｌの氷水に注ぎ、析出したｏ−トリジンスルホン硫酸塩の薄い褐色の結晶を濾過してウエット結晶を得た。このウエット結晶をＨＰＬＣで分析したところｏ−トリジンスルホンの量は７．０９ｇ（０．０２５８ｍｏｌ）であり、これは収率９７．４％に相当した。また、このときの濾液の硫酸濃度は２５．２質量％であった。
（工程３〜後処理）得られた硫酸塩結晶からなるウエット結晶を水１５０ｍｌに加え、更に４０質量％水酸化ナトリウム水溶液を加えてｐＨを９にし、９０℃に加温し、生じた遊離のｏ−トリジンスルホンの粗結晶を濾取した。この粗ｏ−トリジンスルホンを水１２０ｍｌに投入し、３６質量％塩酸水溶液１９ｇを加えて懸濁した状態で酸性にして加温し８０℃で２時間撹拌した。この液を冷却し、室温で４０質量％水酸化ナトリウム水溶液を加えてｐＨを２に調整し析出した黄色結晶を濾取した。結晶を水及びエタノールで洗浄した後、減圧下１１０℃で乾燥して、ｏ−トリジンスルホンの黄色結晶６．９８ｇ（０．０２５４ｍоｌ）を収率９６．１％で得た。
Example 5
(Step 1) In a 100 ml four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 103 g of 30% by weight fuming sulfuric acid (0.39 mol as sulfur trioxide) was added, and the internal temperature was changed from 30 ° C. While maintaining the temperature at 40 ° C., 8.78 g of 36% by mass water-containing o-tolidine (5.62 g, 0.0265 mol as o-tolidine) was added little by little while paying attention to heat generation. The molar ratio of sulfur trioxide to o-tolidine (sulfur trioxide / o-tolidine) excluding the amount decomposed with water was 8.0. Thereafter, the mixture was stirred at an internal temperature of 30 ° C. for 30 minutes, further heated for 30 minutes to 60 ° C., stirred at the same temperature for 1 hour, further heated for 30 minutes to 80 ° C., and heated at the same temperature for 1.5 hours. Stir.
(Step 2) The reaction solution was cooled to 40 ° C. and then poured into about 300 ml of ice water, and the precipitated brown crystals of o-tolidinesulfone sulfate were filtered to obtain wet crystals. When the wet crystals were analyzed by HPLC, the amount of o-tolidine sulfone was 7.09 g (0.0258 mol), corresponding to a yield of 97.4%. Moreover, the sulfuric acid concentration of the filtrate at this time was 25.2 mass%.
(Step 3-Post-treatment) The obtained wet crystals consisting of sulfate crystals are added to 150 ml of water, and further 40% by mass aqueous sodium hydroxide solution is added to adjust the pH to 9, followed by heating to 90 ° C. Crude crystals of o-tolidine sulfone were collected by filtration. This crude o-tolidine sulfone was added to 120 ml of water, and 19 g of a 36% by mass aqueous hydrochloric acid solution was added thereto to make it acidic in a suspended state, followed by heating at 80 ° C. for 2 hours. This liquid was cooled, a 40 mass% sodium hydroxide aqueous solution was added at room temperature to adjust the pH to 2, and the precipitated yellow crystals were collected by filtration. The crystals were washed with water and ethanol and then dried at 110 ° C. under reduced pressure to obtain 6.98 g (0.0254 mol) of o-tolidinesulfone yellow crystals in a yield of 96.1%.
本発明の製造方法によれば、ｏ−トリジンと発煙硫酸とを反応させて高純度のｏ−トリジンスルホンをより安全で効率よく経済的に得ることができる。 According to the production method of the present invention, o-tolidine and fuming sulfuric acid can be reacted to obtain highly pure o-tolidine sulfone more safely, efficiently and economically.
Claims (3)
（工程１）ｏ−トリジンの含水物と発煙硫酸とを反応させる工程、
（工程２）反応混合液を水と混合し、析出したｏ−トリジンスルホンの硫酸塩を分離する工程、
（工程３）ｏ−トリジンスルホンの硫酸塩を水に溶解又は懸濁した状態でアルカリ性にして処理してｏ−トリジンスルホンとし、粗ｏ−トリジンスルホンとして分離する工程、
（工程４）粗ｏ−トリジンスルホンを水に懸濁した状態で酸性にして処理し、次いでｐＨを調整することで精製する工程、
を含んで構成されたことを特徴とするｏ−トリジンスルホンの製造方法。 at least,
(Step 1) a step of reacting a hydrous material of o-tolidine with fuming sulfuric acid,
(Step 2) A step of mixing the reaction mixture with water and separating the precipitated o-tolidinesulfone sulfate,
(Step 3) A step of converting o-tolidine sulfone sulfate into an alkaline solution in a state of being dissolved or suspended in water to obtain o-tolidine sulfone and separating it as crude o-tolidine sulfone,
(Step 4) A step of acidifying the crude o-tolidine sulfone in a state suspended in water, followed by purification by adjusting the pH,
A process for producing o-tolidine sulfone, comprising:
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