JP3680203B2 - Process for producing 4-acetylaminobenzenesulfonyl azide - Google Patents
Process for producing 4-acetylaminobenzenesulfonyl azide Download PDFInfo
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- JP3680203B2 JP3680203B2 JP19221899A JP19221899A JP3680203B2 JP 3680203 B2 JP3680203 B2 JP 3680203B2 JP 19221899 A JP19221899 A JP 19221899A JP 19221899 A JP19221899 A JP 19221899A JP 3680203 B2 JP3680203 B2 JP 3680203B2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Description
【０００１】
【発明の属する技術分野】
本発明は、４−アセチルアミノベンゼンスルホニルクロライドを原料とする、４−アセチルアミノベンゼンスルホニルアジドの新規な製造方法に関する。４−アセチルアミノベンゼンスルホニルアジドは、医薬品、光磁気記憶材料等の原料として有用なジアゾ化剤である。
【０００２】
【従来の技術】
従来、４−アセチルアミノベンゼンスルホニルアジドを製造する方法としては、４−アセチルアミノベンゼンスルホニルクロライドに無機アジ化塩を反応させる方法が一般的であり、数多くの文献に記載されている。
【０００３】
例えば、Ｊ．Ｏｒｇ．Ｃｈｅｍ．，６１，２５４０−２５４１（１９９６年）においては、アセトンを反応溶媒に用い、４−アセチルアミノベンゼンスルホニルクロライドに固形のアジ化ナトリウムを反応させて、収率９４％を得ている。
【０００４】
しかしながら、上記方法には以下の問題点がある。
（１）同一条件で反応を行っても、反応が速やかに完結する場合と、途中で全く転換反応が進まなくなる場合があり、反応の定量的安定性が得られていない。
（２）反応を完結させるためには、反応溶媒のアセトンに不溶なアジ化ナトリウムを過剰に使用することから、その過剰分のアジ化ナトリウムに汚染された反応副生物の塩化ナトリウムが発生し、その無害化処理を行うために多くの時間と費用が必要となる。
【０００５】
また、米国特許５，６１０，３１４号においては、４−アセチルアミノベンゼンスルホニルクロライドをアセトンに溶解し、アジ化ナトリウム水溶液を滴下して転換反応を行っている。この場合、 ４−アセチルアミノベンゼンスルホニルクロライドが水に不安定で加水分解を受けることから、収率は７９％と工業的には高い収率とは言い難い。
【０００６】
【発明が解決しようとする課題】
本発明は、上記の問題点を解決して高収率で高品質の４−アセチルアミノベンゼンスルホニルアジドを、容易かつ安全に製造することのできる方法を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために工業的に有利な方法を鋭意研究したところ、出発原料の４−アセチルアミノベンゼンスルホニルクロライドが加水分解を受けないように非水反応系とし、出発原料をアセトニトリル、アセトン、塩化メチレン等の有機溶媒に溶解させ、固形の無機アジ化塩との反応において、転換反応が定量的安定に進行し、且つ、反応完結に必要な無機アジ化塩の過剰分をできるだけ少なくするために、上記転換反応をアミン塩触媒の存在下で行うことで、上記課題を解決し、本発明を完成するに至った。
【０００８】
すなわち、本発明は、下記式（１）の４−アセチルアミノベンゼンスルホニルクロライドと一般式（２）で表される無機アジ化塩とを、触媒にアミン塩を用い、４−アセチルアミノベンゼンスルホニルクロライドを溶解する溶媒中に於いて反応させることを特徴とする下記式（３）で表される４−アセチルアミノベンゼンスルホニルアジドの製造方法である。
【化３】
【化４】
アミン塩触媒を用いたこの新規な方法は、定量的に安定して４−アセチルアミノベンゼンスルホニルアジドを製造することができ、更に、大過剰量の無機アジ化塩は不必要となったため、副生塩中に存在する無機アジ化塩の公害処理が容易となった。また、非水反応系であるため、４−アセチルアミノベンゼンスルホニルクロライドの加水分解反応が起こらないことから、高収率に４−アセチルアミノベンゼンスルホニルアジドを得ることができる。
【００１０】
【発明の実施の形態】
本発明において、出発原料となる４−アセチルアミノベンゼンスルホニルクロライドは、どのような方法で製造されたものであってもよく、また、市販品を使用してもよい。
【００１１】
一般式（２）で表わされる無機アジ化塩としては、具体的にはナトリウム、カリウム、リチウム、カルシウム、マグネシウム等のアルカリ金属またはアルカリ土類金属のアジ化物が挙げられるが、アジ化ナトリウムが工業的に好適である。
【００１２】
無機アジ化塩の使用量は、４−アセチルアミノベンゼンスルホニルクロライド１モルに対し、アジ化水素換算で通常１．０〜１．１モルの範囲、好ましくは１．０１〜１．０５モルである。
【００１３】
本発明で使用するアミン塩は、アミンと塩から形成される。アミンとしては、第１級、第２級、第３級アミンのいずれでもよいが、特に脂肪族第３級アミンが好ましい。アミン塩としては、例えば、トリメチルアミン塩、トリエチルアミン塩、トリプロピルアミン塩、トリブチルアミン塩、トリアミルアミン塩、トリヘキシルアミン塩、トリアリルアミン塩、ヒリジン塩、トリエタノールアミン塩、Ｎ−メチルモルホリン塩、Ｎ，Ｎ−ジメチルシクロヘキシルアミン塩、Ｎ，Ｎ−ジメチルアニリン塩、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン塩、４−ジメチルアミノピリジン塩などの第３級アミン等が挙げられるが、これらに限定されるわけではない。また、これらのアミン塩の２種以上を併用してもよい。
【００１４】
塩を形成する酸としては、基本的にはアミンと塩を形成する酸であればよい。酸としては、例えば、塩酸、臭化水素、硫酸、硝酸、リン酸、ホウ酸、アジ化水素、塩素酸、炭酸、硫化水素等の無機酸等が挙げられるが、これらに限定されるわけではない。好ましい酸は、塩酸、臭化水素、硫酸等である。
【００１５】
好ましいアミン塩は、トリエチルアミン塩酸塩である。
【００１６】
アミン塩は、市販のものを使用してもよいし、または反応系内でアミンと酸を反応させて塩を合成して作用させてもよい。
【００１７】
アミン塩の使用量は、反応が進行するのに必要な最低限度量でよいが、４−アセチルアミノベンゼンスルホニルクロライド１モルに対し、通常０．００２〜０．０２モルの範囲、好ましくは０．００２〜０．００４モルの範囲である。アミン塩のモル比は、反応速度、反応生成率に影響する。
【００１８】
反応溶媒としては、４−アセチルアミノベンゼンスルホニルクロライドに対する溶解性の良いことから、アセトニトリル、Ｎ，Ｎ−ジメチルホルムアミド、アセトン、エチルメチルケトン、塩化メチレン、クロロホルム等が挙げられるが、これらに限定されるわけではない。好ましくは、アミン塩触媒の効果が最も高い非プロトン極性溶媒類であり、更に好ましくはアセトニトリルである。反応溶媒の使用量は、４−アセチルアミノベンゼンスルホニルクロライド１ｇに対し、通常１〜１０ｍｌの範囲、好ましくは３〜５ｍｌの範囲である。
【００１９】
反応温度は、原料の４−アセチルアミノベンゼンスルホニルクロライドが完全溶解し、生成した４−アセチルアミノベンゼンスルホニルアジドが熱分解しない程度の温度であればよく、特に限定されるものではない。通常２０〜６０℃の範囲、好ましくは３５〜５０℃の範囲である。
【００２０】
反応時間は、特に限定されないが、通常１〜１２０時間であり、好ましくは３〜５時間の範囲である。
【００２１】
反応後、副生する塩化物と少量過剰仕込した無機アジ化塩が混ざる固相を濾別した後、濾液を減圧下、溶媒と生成された４−アセチルアミノベンゼンスルホニルアジドが容積比で１対１になる程度まで濃縮する。留出溶媒はそのまま反応に再使用することも可能である。
【００２２】
晶析は、温度０〜２０℃の範囲で、晶析溶媒として水を加えて行う。その水量は生成した４−アセチルアミノベンゼンスルホニルアジド１容量に対し容積比が３〜５になる範囲で添加する。但し、塩化メチレン溶媒使用時のみ晶析溶媒としてトルエンを使用する。結晶を濾取し、温風乾燥後、４−アセチルアミノベンゼンスルホニルアジドを得ることができる。
【００２３】
【実施例】
以下の実施例により本発明を更に具体的に説明するが、本発明はこれらの実施例に何等限定されるものではない。
【００２４】
実施例１
メカニカルシール攪拌機を備え付けた５００Ｌガラスライニング製のオートクレーブにアセトニトリル２１９ｋｇ、４−アセチルアミノベンゼンスルホニルクロライド８０ｋｇ、アジ化ナトリウム２３．５ｋｇ、トリエチルアミン塩酸塩０．１６ｋｇを仕込み、強攪拌を開始した。缶内温度は反応熱の発生により２０℃から徐々に上昇し４２℃まで達した。反応物を攪拌している間、反応を高速液体クロマトグラフィーでモニターした。反応は強攪拌開始後約５時間で完結した。反応混合物をガラスライニング製の濾過器に通し、固相を濾別し、この固相をアセトニトリル３０ｋｇで洗浄した。反応溶液３２６ｋｇを得た。この反応溶液を別の５００Ｌガラスライニング製のオートクレーブに仕込み、内温３０〜４５℃で減圧濃縮を行いアセトニトリル約１８０ｋｇを系内から留去した。濃縮後、系内を１０℃まで冷却した後、水２８０ｋｇを滴下し晶析を行った。晶析スラリーを遠心分離し、湿結晶８２ｋｇを得た。この湿結晶を４０℃で温風乾燥し、４−アセチルアミノベンゼンスルホニルアジド７９ｋｇを得た。得られた４−アセチルアミノベンゼンスルホニルアジドの収率は９６．％（４−アセチルアミノベンゼンスルホニルクロライド）で、純度は９９．８％であった。
【００２５】
実施例２
メカニカルオーバーヘッド攪拌機を備え付けた５００ｍｌ四つ口フラスコにアセトン２１９ｇ、４−アセチルアミノベンゼンスルホニルクロライド８０ｇ、アジ化ナトリウム２３．５ｇ、トリエチルアミン塩酸塩０．２０ｇを仕込み、強攪拌を開始した。缶内温度は反応熱の発生により２０℃から徐々に上昇し４３℃まで達した。反応物を攪拌している間、反応を高速液体クロマトグラフィーでモニターした。反応は強攪拌開始後約５時間で完結した。ヌッチェを用い反応混合物中から固相を濾別し、この固相をアセトン３０ｇで洗浄した。反応溶液３２０ｇを得た。この反応溶液を別のメカニカルオーバーヘッド攪拌機を備え付けた５００ｍｌ四つ口フラスコに仕込み、内温３０〜４５℃で減圧濃縮を行いアセトン約１８０ｇを系内から留去した。濃縮後、系内を１０℃まで冷却した後、水２８０ｇを滴下し晶析を行った。晶析スラリーを濾取し、湿結晶８２ｇを得た。この湿結晶を４０℃で温風乾燥し、４−アセチルアミノベンゼンスルホニルアジド７６ｇを得た。得られた４−アセチルアミノベンゼンスルホニルアジドの収率は９２．４％（４−アセチルアミノベンゼンスルホニルクロライド）で、純度は９９．８％であった。
【００２６】
実施例３
メカニカルオーバーヘッド攪拌機を備え付けた５００ｍｌ四つ口フラスコに塩化メチレン３７０ｇ、４−アセチルアミノベンゼンスルホニルクロライド８０ｇ、アジ化ナトリウム２３．５ｇ、トリエチルアミン塩酸塩０．２０ｇを仕込み、強攪拌を開始した。缶内温度は反応熱の発生により２０℃から徐々に上昇し、冷却を行い４５℃を超えない範囲で攪拌を続けた。反応物を攪拌している間、反応を高速液体クロマトグラフィーでモニターした。反応は強攪拌開始後約５時間で完結した。ヌッチェを用い反応混合物中から固相を濾別し、この固相を塩化メチレン５０ｇで洗浄した。反応溶液４９０ｇを得た。この反応溶液を別のメカニカルオーバーヘッド攪拌機を備え付けた５００ｍｌ四つ口フラスコに仕込み、内温３０〜４５℃で減圧濃縮を行い塩化メチレン約３０５ｇを系内から留去した。濃縮後、系内を１０℃まで冷却した後、トルエン４００ｇを滴下し晶析を行った。晶析スラリーを濾取し、湿結晶８２ｇを得た。この湿結晶を４０℃で温風乾燥し、４−アセチルアミノベンゼンスルホニルアジド７５ｇを得た。得られた４−アセチルアミノベンゼンスルホニルアジドの収率は９１．２％（４−アセチルアミノベンゼンスルホニルクロライド）で、純度は９９．７％であった。
【００２７】
【発明の効果】
本発明によって、大過剰の無機アジ化塩を必要とせず、安全、安価に、安定して高品質の４−アセチルアミノベンゼンスルホニルアジドを製造することができる。従って、経済的、工業的価値が極めて大きい。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel method for producing 4-acetylaminobenzenesulfonyl azide using 4-acetylaminobenzenesulfonyl chloride as a raw material. 4-acetylaminobenzenesulfonyl azide is a diazotizing agent useful as a raw material for pharmaceuticals, magneto-optical storage materials and the like.
[0002]
[Prior art]
Conventionally, as a method for producing 4-acetylaminobenzenesulfonyl azide, a method of reacting 4-acetylaminobenzenesulfonyl chloride with an inorganic azide salt is generally used and described in many documents.
[0003]
For example, J. et al. Org. Chem. , 61, 2540-2541 (1996), acetone is used as a reaction solvent, and 4-acetylaminobenzenesulfonyl chloride is reacted with solid sodium azide to obtain a yield of 94%.
[0004]
However, the above method has the following problems.
(1) Even if the reaction is performed under the same conditions, the reaction may be completed quickly, or the conversion reaction may not proceed at all during the process, and the quantitative stability of the reaction is not obtained.
(2) In order to complete the reaction, an excessive amount of sodium azide insoluble in acetone as a reaction solvent is used, so that reaction by-product sodium chloride contaminated with the excess sodium azide is generated, It takes a lot of time and money to perform the detoxification process.
[0005]
In US Pat. No. 5,610,314, 4-acetylaminobenzenesulfonyl chloride is dissolved in acetone, and an aqueous sodium azide solution is added dropwise to carry out a conversion reaction. In this case, since 4-acetylaminobenzenesulfonyl chloride is unstable in water and undergoes hydrolysis, the yield is 79%, which is difficult to say industrially.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of easily and safely producing 4-acetylaminobenzenesulfonyl azide with high yield and high quality by solving the above-mentioned problems.
[0007]
[Means for Solving the Problems]
The present inventors diligently studied an industrially advantageous method for solving the above-mentioned problems. As a result, the starting material 4-acetylaminobenzenesulfonyl chloride was used as a non-aqueous reaction system so as not to be hydrolyzed. The raw material is dissolved in an organic solvent such as acetonitrile, acetone, methylene chloride, etc., and in the reaction with the solid inorganic azide salt, the conversion reaction proceeds quantitatively and stably, and the excess of inorganic azide salt necessary for the completion of the reaction In order to reduce the amount as much as possible, the above-described conversion reaction is performed in the presence of an amine salt catalyst, thereby solving the above-mentioned problems and completing the present invention.
[0008]
That is, the present invention uses 4-acetylaminobenzenesulfonyl chloride represented by the following formula (1) and an inorganic azide salt represented by the general formula (2), an amine salt as a catalyst, and 4-acetylaminobenzenesulfonyl chloride. Is a method for producing 4-acetylaminobenzenesulfonyl azide represented by the following formula (3).
[Chemical 3]
[Formula 4]
This new method using an amine salt catalyst can quantitatively and stably produce 4-acetylaminobenzenesulfonyl azide, and further, a large excess of inorganic azide salt is unnecessary. Pollution treatment of inorganic azide salt present in raw salt became easy. Moreover, since it is a non-aqueous reaction system, 4-acetylaminobenzenesulfonyl azide can be obtained in a high yield since hydrolysis reaction of 4-acetylaminobenzenesulfonyl chloride does not occur.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, 4-acetylaminobenzenesulfonyl chloride as a starting material may be produced by any method, and a commercially available product may be used.
[0011]
Specific examples of the inorganic azide salt represented by the general formula (2) include alkali metal or alkaline earth metal azides such as sodium, potassium, lithium, calcium and magnesium. It is particularly suitable.
[0012]
The amount of the inorganic azide salt used is usually in the range of 1.0 to 1.1 mol, preferably 1.01 to 1.05 mol in terms of hydrogen azide, with respect to 1 mol of 4-acetylaminobenzenesulfonyl chloride. .
[0013]
The amine salt used in the present invention is formed from an amine and a salt. The amine may be any of primary, secondary, and tertiary amines, but aliphatic tertiary amines are particularly preferable. Examples of the amine salt include trimethylamine salt, triethylamine salt, tripropylamine salt, tributylamine salt, triamylamine salt, trihexylamine salt, triallylamine salt, hydridine salt, triethanolamine salt, N-methylmorpholine salt, Tertiary amines such as N, N-dimethylcyclohexylamine salt, N, N-dimethylaniline salt, N, N, N ′, N′-tetramethylethylenediamine salt, 4-dimethylaminopyridine salt, etc. However, it is not limited to these. Two or more of these amine salts may be used in combination.
[0014]
The acid that forms a salt may be basically an acid that forms a salt with an amine. Examples of the acid include, but are not limited to, inorganic acids such as hydrochloric acid, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrogen azide, chloric acid, carbonic acid, and hydrogen sulfide. Absent. Preferred acids are hydrochloric acid, hydrogen bromide, sulfuric acid and the like.
[0015]
A preferred amine salt is triethylamine hydrochloride.
[0016]
A commercially available amine salt may be used, or a salt may be synthesized by reacting an amine and an acid in a reaction system.
[0017]
The amount of the amine salt used may be the minimum amount necessary for the reaction to proceed, but is usually in the range of 0.002 to 0.02 mol, preferably 0.000, per 1 mol of 4-acetylaminobenzenesulfonyl chloride. It is the range of 002-0.004 mol. The molar ratio of the amine salt affects the reaction rate and the reaction production rate.
[0018]
Examples of the reaction solvent include acetonitrile, N, N-dimethylformamide, acetone, ethyl methyl ketone, methylene chloride, chloroform and the like because of their good solubility in 4-acetylaminobenzenesulfonyl chloride, but are not limited thereto. Do not mean. Preferred are aprotic polar solvents having the highest effect of the amine salt catalyst, and more preferred is acetonitrile. The amount of the reaction solvent to be used is generally in the range of 1 to 10 ml, preferably in the range of 3 to 5 ml, with respect to 1 g of 4-acetylaminobenzenesulfonyl chloride.
[0019]
The reaction temperature is not particularly limited as long as the raw material 4-acetylaminobenzenesulfonyl chloride is completely dissolved and the produced 4-acetylaminobenzenesulfonyl azide is not thermally decomposed. Usually, it is in the range of 20-60 ° C, preferably in the range of 35-50 ° C.
[0020]
Although reaction time is not specifically limited, Usually, it is 1-120 hours, Preferably it is the range of 3-5 hours.
[0021]
After the reaction, the solid phase in which the by-produced chloride and the inorganic azide salt added in a small amount are mixed is filtered off, and the filtrate is reduced under reduced pressure, so that the solvent and the produced 4-acetylaminobenzenesulfonyl azide have a volume ratio of 1: Concentrate to 1 The distillate solvent can be reused in the reaction as it is.
[0022]
Crystallization is performed at a temperature in the range of 0 to 20 ° C. by adding water as a crystallization solvent. The amount of water is added in such a range that the volume ratio is 3 to 5 with respect to 1 volume of the produced 4-acetylaminobenzenesulfonyl azide. However, toluene is used as a crystallization solvent only when a methylene chloride solvent is used. Crystals are collected by filtration and dried with warm air to give 4-acetylaminobenzenesulfonyl azide.
[0023]
【Example】
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.
[0024]
Example 1
A 500 L glass-lined autoclave equipped with a mechanical seal stirrer was charged with 219 kg of acetonitrile, 80 kg of 4-acetylaminobenzenesulfonyl chloride, 23.5 kg of sodium azide, and 0.16 kg of triethylamine hydrochloride, and strong stirring was started. The inside temperature of the can gradually increased from 20 ° C. to 42 ° C. due to generation of reaction heat. While the reaction was stirred, the reaction was monitored by high performance liquid chromatography. The reaction was completed about 5 hours after the start of strong stirring. The reaction mixture was passed through a filter made of glass lining, the solid phase was filtered off, and this solid phase was washed with 30 kg of acetonitrile. 326 kg of reaction solution was obtained. This reaction solution was charged into another autoclave made of 500 L glass lining, concentrated under reduced pressure at an internal temperature of 30 to 45 ° C., and about 180 kg of acetonitrile was distilled off from the system. After concentration, the system was cooled to 10 ° C., and 280 kg of water was added dropwise for crystallization. The crystallization slurry was centrifuged to obtain 82 kg of wet crystals. This wet crystal was dried in warm air at 40 ° C. to obtain 79 kg of 4-acetylaminobenzenesulfonyl azide. The yield of the obtained 4-acetylaminobenzenesulfonyl azide was 96. % (4-acetylaminobenzenesulfonyl chloride) and the purity was 99.8%.
[0025]
Example 2
A 500 ml four-necked flask equipped with a mechanical overhead stirrer was charged with 219 g of acetone, 80 g of 4-acetylaminobenzenesulfonyl chloride, 23.5 g of sodium azide, and 0.20 g of triethylamine hydrochloride, and intense stirring was started. The inside temperature of the can gradually increased from 20 ° C. to 43 ° C. due to generation of reaction heat. While the reaction was stirred, the reaction was monitored by high performance liquid chromatography. The reaction was completed in about 5 hours after the start of strong stirring. The solid phase was filtered off from the reaction mixture using Nutsche, and this solid phase was washed with 30 g of acetone. 320 g of reaction solution was obtained. This reaction solution was charged into a 500 ml four-necked flask equipped with another mechanical overhead stirrer, concentrated under reduced pressure at an internal temperature of 30 to 45 ° C., and about 180 g of acetone was distilled off from the system. After concentration, the system was cooled to 10 ° C., and 280 g of water was added dropwise for crystallization. The crystallization slurry was collected by filtration to obtain 82 g of wet crystals. This wet crystal was dried in warm air at 40 ° C. to obtain 76 g of 4-acetylaminobenzenesulfonyl azide. The yield of the obtained 4-acetylaminobenzenesulfonyl azide was 92.4% (4-acetylaminobenzenesulfonyl chloride), and the purity was 99.8%.
[0026]
Example 3
A 500 ml four-necked flask equipped with a mechanical overhead stirrer was charged with 370 g of methylene chloride, 80 g of 4-acetylaminobenzenesulfonyl chloride, 23.5 g of sodium azide, and 0.20 g of triethylamine hydrochloride, and strong stirring was started. The internal temperature of the can gradually increased from 20 ° C. due to the generation of heat of reaction. While the reaction was stirred, the reaction was monitored by high performance liquid chromatography. The reaction was completed in about 5 hours after the start of strong stirring. The solid phase was filtered off from the reaction mixture using Nutsche, and this solid phase was washed with 50 g of methylene chloride. 490 g of reaction solution was obtained. This reaction solution was charged into a 500 ml four-necked flask equipped with another mechanical overhead stirrer, and concentrated under reduced pressure at an internal temperature of 30 to 45 ° C. to distill off about 305 g of methylene chloride from the system. After concentration, the system was cooled to 10 ° C., and 400 g of toluene was added dropwise for crystallization. The crystallization slurry was collected by filtration to obtain 82 g of wet crystals. This wet crystal was dried in warm air at 40 ° C. to obtain 75 g of 4-acetylaminobenzenesulfonyl azide. The yield of the obtained 4-acetylaminobenzenesulfonyl azide was 91.2% (4-acetylaminobenzenesulfonyl chloride), and the purity was 99.7%.
[0027]
【The invention's effect】
According to the present invention, high-quality 4-acetylaminobenzenesulfonyl azide can be produced stably and inexpensively without requiring a large excess of inorganic azide salt. Therefore, the economic and industrial value is extremely large.
Claims (5)
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| JP19221899A JP3680203B2 (en) | 1999-06-01 | 1999-06-01 | Process for producing 4-acetylaminobenzenesulfonyl azide |
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| JP19221899A JP3680203B2 (en) | 1999-06-01 | 1999-06-01 | Process for producing 4-acetylaminobenzenesulfonyl azide |
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| RU2464271C1 (en) | 2008-12-17 | 2012-10-20 | Дайити Санкио Компани, Лимитед | Method of producing diamine derivative |
| EP2383272A4 (en) | 2009-01-13 | 2012-07-25 | Daiichi Sankyo Co Ltd | Active blood coagulation factor inhibitor |
| CN102348688B (en) | 2009-03-10 | 2014-07-09 | 第一三共株式会社 | Process for producing diamine derivative |
| CN102348680B (en) * | 2009-03-13 | 2014-11-05 | 第一三共株式会社 | Method for producing optically active diamine derivative |
| WO2010147169A1 (en) | 2009-06-18 | 2010-12-23 | 第一三共株式会社 | Pharmaceutical composition having improved solubility |
| WO2011115066A1 (en) | 2010-03-19 | 2011-09-22 | 第一三共株式会社 | Crystal of diamine derivative and method of producing same |
| HUE031961T2 (en) | 2010-07-02 | 2017-09-28 | Daiichi Sankyo Co Ltd | Process for preparation of optically active diamine derivative salt |
| CN114940657B (en) * | 2022-05-09 | 2023-10-27 | 三峡大学 | Amidine compound synthesized from N, N, N ', N' -tetramethyl ethylenediamine |
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