JP2004018500A - Method for producing chlorosulfonyl isocyanate - Google Patents
Method for producing chlorosulfonyl isocyanate Download PDFInfo
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- JP2004018500A JP2004018500A JP2002179363A JP2002179363A JP2004018500A JP 2004018500 A JP2004018500 A JP 2004018500A JP 2002179363 A JP2002179363 A JP 2002179363A JP 2002179363 A JP2002179363 A JP 2002179363A JP 2004018500 A JP2004018500 A JP 2004018500A
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- Prior art keywords
- chlorosulfonyl isocyanate
- liquid
- reaction
- sulfuric anhydride
- reaction system
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Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、クロロスルホニルイソシアネートの製造法であり、医薬品、農薬の中間原料として工業的に重要な化合物である。
【0002】
【従来の技術】
クロロスルホニルイソシアネートは、従来から無水硫酸とクロロイソシアネートとの反応で合成できることが知られており、その製造条件が種々報告されている。
例えば、特開2000−53630号特許公報には−10〜17℃で、特開平1−228955号特許公報及び特開平4−164064号特許公報には10〜50℃で、特開昭63−77855号特許公報には20〜50℃で反応させる方法が記載されている。
また、100〜200℃の高温で反応させる方法が西独特許928896号及び欧州特許294613B1号に記載されている。
【0003】
これらの方法は、収率、副生物の生成、原料のガス化等プロセス制御の観点からまだ十分な方法とはいえない。
【0004】
【発明が解決しようとする課題】
したがって、本発明は、無水硫酸とクロロシアンとの反応により高純度のクロロスルホニルイソシアネートを高収率で経済的に製造する方法を提供する。
【0005】
【課題を解決するための手段】
無水硫酸とクロロシアンとを反応させてクロロスルホニルイソシアネートを製造する方法において、液体の無水硫酸と液体のクロロシアンを反応系中へ連続的に供給し、50〜110℃に保って反応させるクロロスルホニルイソシアネートの製造方法であり、クロロシアンを無水硫酸1モルに対して0.9乃至1.1モルの割合で連続的に供給する製造方法であり、クロロスルホニルイソシアネートを反応系に50%以上存在させる製造方法であり、30分以上の無水硫酸とクロロシアンの供給量に相当する反応液が滞留するように、液体の無水硫酸と液体のクロロシアンを反応系中へ連続的に供給し反応系の反応液を連続的に引き出す製造方法である。
【0006】
【発明の実施の形態】
本発明において使用される無水硫酸は、液状のものであればいずれも使用出来るが、γ型が望ましく重合防止した安定化無水硫酸が好ましい。
クロロシアンは、青酸と塩素から工業的に製造されており、本発明方法においては液体状態で使用され、脱水剤あるいは蒸留により脱水されたものが望ましい。
本発明においては、反応系内を50〜110℃に保持して液体の無水硫酸と液体のクロロシアンを連続的に供給し、反応させる。
反応は発熱反応であり、反応に当たっては反応熱を除去する必要があり、反応系の反応槽を冷却して、更に、充填剤を充填した塔と還流冷却器を付けた攪拌機付きの反応槽を使用し所望の反応温度に保持すると有利である。
充填塔の塔頂からの排ガスは、コンデンサーで冷却し凝縮した液を全量充填塔に戻し、コンデンサーで凝縮しないガスを更にコンデンサーでブライン冷却しクロロシアンを回収し、反応槽に戻すのが望ましい。
【0007】
クロロシアンの使用量は無水硫酸1モルに対して0.8〜1.3モル、好ましくは0.9〜1.1モルの割合である。すなわち、0.8モル倍未満または1.3モル倍を超えると副生物の形成が多くなり、収率及び品位がともに低下する。
得られた反応液からのクロロスルホニルイソシアネートの精製は、蒸留により行うことができる。例えば、反応系から反応液を連続的に抜き出すか又回分式に全量取り出して、常圧下で副生物を分解しながら蒸留することができる。得られた粗クロロスルホニルイソシアネートを所望によりさらに、精製蒸留して高品位のクロロスルホニルイソシアネートを得ることができる。
【0008】
本発明の方法では、無水硫酸とクロロシアンとを、液相の反応系で反応させ、更に、液相の反応系から気化したものを気相部で反応させる。
無水硫酸とクロロシアンは反応系中で当モルづつ存在させるのが不純物の生成を防止するのに望ましく、更に、無水硫酸とクロロシアンを出来るだけ希釈した状態で反応させるのが望ましい。したがって、30分間以上の生成量のクロロスルホニルイソシアネートを溶媒として予め存在させて無水硫酸とクロロシアンの連続供給を開始するか、或いは、連続的に反応を行う場合には、30分以上の好ましくは1時間以上更に好ましく1時間30分以上の無水硫酸とクロロシアンの供給量に相当する反応液を常に反応系に滞留させて、無水硫酸とクロロシアンを連続供給し同時に連続的に供給量に相当する反応液を反応系から排出するのが便利である。
【0009】
【実施例】
実施例1
300mlの四つ口フラスコに攪拌器、温度計、1.5cmφの充填塔に3.0mmφのガラス製ラシヒリングを20cm充填した充填塔及び還流冷却器を取りつけた。
この四つ口フラスコ内にクロロスルホニルイソシアネート141.5gを入れ、約90℃に加熱した。
反応系を90〜105℃に保持しながらこの中に定量ポンプでクロロシアンを2.05g/min、無水硫酸を2.67g/min の速度で1時間滴下した。クロロシアンの総供給量は123g、無水硫酸の総供給量は160gだった。滴下終了してから100〜105℃で0.5時間攪拌し反応を完結させた。
【0010】
反応終了後、取りつけた充填塔を使用して常圧で蒸留し、沸点105〜107℃/760mmHgの留分として421gの粗製のクロロスルホニルイソシアネートを得た。
さらに高純度のクロロスルホニルイソシアネートを得る為に、300mlのフラスコに1.5cmφの充填塔に3.0mmφのガラス製ラシヒリングを20cm充填した充填塔及び還流分配器をつけ、常圧で蒸留し、沸点106〜107℃/760mmHgの留分で410g(収率95.0%)の精製クロロスルホニルイソシアネートを得た。純度は99.0%であった。
【0011】
実施例2
300mlの四つ口フラスコに攪拌器、温度計、1.5cmφの充填塔に3.0mmφのガラス製ラシヒリングを20cm充填した充填塔及び還流冷却器を取りつけた。
この四つ口フラスコ内にクロロスルホニルイソシアネート141.5gを入れ、約90℃に加熱した。
反応系を90〜105℃に保持しながらこの中に定量ポンプでクロロシアンを2.05g/min、無水硫酸を2.67g/min(クロロシアンと無水硫酸の供給量は1時間当たり2モルに相当)で、1.5時間滴下した。その後、滴下を続けながら供給量とほぼ同量の反応液を連続的に抜き出し8時間反応を続けた。
【0012】
反応終了後、排出した反応液を常圧で蒸留し、沸点105〜107℃/760mmHgの留分として粗製のクロロスルホニルイソシアネートを得た。
さらに高純度のクロロスルホニルイソシアネートを得る為に、実施例1に準じて常圧で蒸留し、沸点106〜107℃/760mmHgの留分で精製クロロスルホニルイソシアネートを得た。純度は99.0%であり、クロロシアンからの収率は95.0%だった。
【0013】
【発明の効果】
原料を液体で供給するので流量制御が正確であり、よって、反応副生物が少なくクロロスルホニルイソシアネートの純度が高く、高収率であり、更に、原料のガス化工程を必要とせず、工業的にも極めて簡単な方法で製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is a method for producing chlorosulfonyl isocyanate, which is an industrially important compound as an intermediate material for pharmaceuticals and agricultural chemicals.
[0002]
[Prior art]
It has been known that chlorosulfonyl isocyanate can be synthesized by a reaction between sulfuric anhydride and chloroisocyanate, and various production conditions have been reported.
For example, Japanese Patent Application Laid-Open No. 2000-53630 discloses a temperature of -10 to 17 ° C., and Japanese Patent Application Laid-Open Nos. 1-228955 and 4-16464 discloses a temperature of 10-50 ° C .; The patent publication discloses a method of reacting at 20 to 50 ° C.
Further, a method of reacting at a high temperature of 100 to 200 ° C. is described in West German Patent 922896 and European Patent 294613B1.
[0003]
These methods are not yet satisfactory from the viewpoint of process control such as yield, generation of by-products, and gasification of raw materials.
[0004]
[Problems to be solved by the invention]
Accordingly, the present invention provides a method for economically producing high-purity chlorosulfonyl isocyanate in a high yield by reacting sulfuric anhydride with chlorocyan.
[0005]
[Means for Solving the Problems]
In a method for producing chlorosulfonyl isocyanate by reacting sulfuric anhydride and chlorocyanide, chlorosulfonyl is produced by continuously supplying liquid sulfuric anhydride and liquid chlorocyanide into a reaction system and maintaining the temperature at 50 to 110 ° C. This is a method for producing isocyanate, in which chlorocyanide is continuously supplied at a ratio of 0.9 to 1.1 mol per mol of sulfuric anhydride, and 50% or more of chlorosulfonyl isocyanate is present in the reaction system. This is a production method in which liquid sulfuric anhydride and liquid chlorocyanine are continuously supplied into the reaction system so that a reaction solution corresponding to the supply amounts of sulfuric anhydride and chlorocyanide for 30 minutes or more stays therein. This is a production method in which a reaction solution is continuously withdrawn.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
Any sulfuric anhydride used in the present invention can be used as long as it is a liquid. However, a stabilized sulphated anhydride which is preferably a γ-type and polymerization-prevented is preferred.
Chlorocyan is industrially produced from hydrocyanic acid and chlorine, and is preferably used in a liquid state in the method of the present invention, and is desirably dehydrated by a dehydrating agent or distillation.
In the present invention, while maintaining the inside of the reaction system at 50 to 110 ° C., liquid sulfuric anhydride and liquid chlorocyanine are continuously supplied and reacted.
The reaction is an exothermic reaction, and it is necessary to remove the heat of the reaction in the reaction.The reaction tank of the reaction system is cooled, and a reaction vessel equipped with a tower filled with a filler and a stirrer equipped with a reflux condenser is further provided. It is advantageous to use and maintain the desired reaction temperature.
It is preferable that the exhaust gas from the top of the packed tower is cooled by a condenser and the entire liquid condensed is returned to the packed tower, and the gas not condensed by the condenser is further cooled by a condenser to recover chlorocyan and returned to the reaction tank.
[0007]
The amount of chlorocyan used is 0.8 to 1.3 mol, preferably 0.9 to 1.1 mol, per 1 mol of sulfuric anhydride. That is, if it is less than 0.8 mole times or more than 1.3 mole times, the formation of by-products increases, and both the yield and the quality deteriorate.
Purification of chlorosulfonyl isocyanate from the obtained reaction solution can be performed by distillation. For example, the reaction solution can be continuously withdrawn from the reaction system or can be withdrawn in batches in a batch manner and distilled under normal pressure while decomposing by-products. The obtained crude chlorosulfonyl isocyanate can be further purified and distilled, if desired, to obtain high-quality chlorosulfonyl isocyanate.
[0008]
In the method of the present invention, sulfuric anhydride and chlorocyan are reacted in a reaction system in a liquid phase, and further, gaseous matter from the reaction system in a liquid phase is reacted in a gas phase.
It is desirable that sulfuric anhydride and chlorocyan be present in equimolar amounts in the reaction system in order to prevent the generation of impurities, and it is further desirable that sulfuric anhydride and chlorocyan be reacted in a state as diluted as possible. Therefore, the continuous supply of sulfuric anhydride and chlorocyanide is started in the presence of chlorosulfonyl isocyanate in a production amount of 30 minutes or more as a solvent in advance, or when the reaction is performed continuously, preferably 30 minutes or more, The reaction solution corresponding to the supply amount of sulfuric anhydride and chlorocyan for more than 1 hour and more preferably for 1 hour and 30 minutes is always kept in the reaction system, and sulfuric anhydride and chlorocyan are continuously supplied and simultaneously correspond to the supply amount. It is convenient to discharge the reaction solution from the reaction system.
[0009]
【Example】
Example 1
A 300 ml four-necked flask was equipped with a stirrer, a thermometer, a packed tower of 1.5 cmφ packed with 20 cm of a 3.0 mmφ glass Raschig ring, and a reflux condenser.
141.5 g of chlorosulfonyl isocyanate was put into the four-necked flask and heated to about 90 ° C.
While maintaining the reaction system at 90 to 105 ° C., chlorocyanide and sulfuric anhydride at a rate of 2.05 g / min and 2.67 g / min were added dropwise thereto at a rate of 1 hour by a metering pump. The total supply of chlorocyanide was 123 g and the total supply of sulfuric anhydride was 160 g. After completion of the dropwise addition, the mixture was stirred at 100 to 105 ° C. for 0.5 hour to complete the reaction.
[0010]
After the completion of the reaction, distillation was carried out at normal pressure using the attached packed tower to obtain 421 g of crude chlorosulfonyl isocyanate as a fraction having a boiling point of 105 to 107 ° C./760 mmHg.
Further, in order to obtain a high-purity chlorosulfonyl isocyanate, a 300 ml flask was equipped with a 1.5 cmφ packed tower, a packed tower filled with 20 cm of a 3.0 mmφ glass Raschig ring, and a reflux distributor. 410 g (yield 95.0%) of purified chlorosulfonyl isocyanate was obtained with a fraction of 106 to 107 ° C./760 mmHg. Purity was 99.0%.
[0011]
Example 2
A 300 ml four-necked flask was equipped with a stirrer, a thermometer, a packed tower of 1.5 cmφ packed with 20 cm of a 3.0 mmφ glass Raschig ring, and a reflux condenser.
141.5 g of chlorosulfonyl isocyanate was put into the four-necked flask and heated to about 90 ° C.
While maintaining the reaction system at 90 to 105 ° C., a metering pump was used to supply 2.05 g / min of chlorocyan and 2.67 g / min of sulfuric anhydride (the supply amount of chlorocyanide and sulfuric anhydride was 2 mol / hour). For 1.5 hours. Thereafter, while continuing the dropping, the same amount of the reaction solution as the supplied amount was continuously withdrawn, and the reaction was continued for 8 hours.
[0012]
After completion of the reaction, the discharged reaction solution was distilled under normal pressure to obtain crude chlorosulfonyl isocyanate as a fraction having a boiling point of 105 to 107 ° C / 760 mmHg.
Furthermore, in order to obtain chlorosulfonyl isocyanate of high purity, distillation was performed at normal pressure according to Example 1, and purified chlorosulfonyl isocyanate was obtained by a fraction having a boiling point of 106 to 107 ° C / 760 mmHg. Purity was 99.0% and yield from chlorocyanine was 95.0%.
[0013]
【The invention's effect】
Since the raw material is supplied as a liquid, the flow rate control is accurate, and therefore, there are few reaction by-products, the purity of chlorosulfonyl isocyanate is high, the yield is high, and the gasification process of the raw material is not required. Can also be manufactured in a very simple manner.
Claims (4)
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JP2002179363A JP4004867B2 (en) | 2002-06-20 | 2002-06-20 | Method for producing chlorosulfonyl isocyanate |
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JP2002179363A JP4004867B2 (en) | 2002-06-20 | 2002-06-20 | Method for producing chlorosulfonyl isocyanate |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1695958A4 (en) * | 2003-12-16 | 2007-01-10 | Nippon Soda Co | Method for producing chlorosulfonyl isocyanate |
JP2008031116A (en) * | 2006-07-31 | 2008-02-14 | Nippon Soda Co Ltd | Method for subjecting chlorosulfonyl isocyanate to decomposition treatment |
CN109400506A (en) * | 2018-11-14 | 2019-03-01 | 四平市精细化学品有限公司 | A kind of synthetic method of high-purity chlorosulphonyl isocyanate |
CN112321462A (en) * | 2020-11-02 | 2021-02-05 | 四平市精细化学品有限公司 | Method for synthesizing chlorosulfonyl isocyanate by continuous method |
-
2002
- 2002-06-20 JP JP2002179363A patent/JP4004867B2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1695958A4 (en) * | 2003-12-16 | 2007-01-10 | Nippon Soda Co | Method for producing chlorosulfonyl isocyanate |
US7468174B2 (en) | 2003-12-16 | 2008-12-23 | Nippon Soda Co., Ltd. | Method for producing chlorosulfonyl isocyanate |
JP2008031116A (en) * | 2006-07-31 | 2008-02-14 | Nippon Soda Co Ltd | Method for subjecting chlorosulfonyl isocyanate to decomposition treatment |
CN109400506A (en) * | 2018-11-14 | 2019-03-01 | 四平市精细化学品有限公司 | A kind of synthetic method of high-purity chlorosulphonyl isocyanate |
CN112321462A (en) * | 2020-11-02 | 2021-02-05 | 四平市精细化学品有限公司 | Method for synthesizing chlorosulfonyl isocyanate by continuous method |
CN112321462B (en) * | 2020-11-02 | 2023-02-24 | 四平市精细化学品有限公司 | Method for synthesizing chlorosulfonyl isocyanate by continuous method |
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