JPS63313740A - Separation and purification of chlorotoluene - Google Patents
Separation and purification of chlorotolueneInfo
- Publication number
- JPS63313740A JPS63313740A JP1915388A JP1915388A JPS63313740A JP S63313740 A JPS63313740 A JP S63313740A JP 1915388 A JP1915388 A JP 1915388A JP 1915388 A JP1915388 A JP 1915388A JP S63313740 A JPS63313740 A JP S63313740A
- Authority
- JP
- Japan
- Prior art keywords
- chlorotoluene
- chlorination
- toluene
- purification
- distillation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000746 purification Methods 0.000 title abstract description 4
- 238000000926 separation method Methods 0.000 title abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 11
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 239000000047 product Substances 0.000 abstract description 8
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical class ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 abstract description 7
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical class CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- 229940073608 benzyl chloride Drugs 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 hydrogen halides Chemical class 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- FUNUTBJJKQIVSY-UHFFFAOYSA-N 2,4-Dichlorotoluene Chemical compound CC1=CC=C(Cl)C=C1Cl FUNUTBJJKQIVSY-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、医薬および農薬の製造中間体として有用なり
ロロトルエンの工業的な分離精製方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an industrial separation and purification method for lorotoluene, which is useful as an intermediate in the production of pharmaceuticals and agricultural chemicals.
（従来の技術および問題点）
トルエンを、塩化鉄および塩化アンチモン等の塩素化触
媒の存在下核塩素化することによりモノクロロトルエン
を製造することができるが、この際、クロロトルエン混
合物中には、副生物として２００ｐｐｍ前後のベンジル
クロライドおよびクロロベンジルクロライド等の側鎖塩
素化物が生成する。(Prior art and problems) Monochlorotoluene can be produced by nuclear chlorination of toluene in the presence of a chlorination catalyst such as iron chloride and antimony chloride, but at this time, in the chlorotoluene mixture, Around 200 ppm of side chain chlorinated products such as benzyl chloride and chlorobenzyl chloride are produced as by-products.
この側鎖塩素化物は、反応性が高いため、容易に分解２
重合を起こし、常温での保存中でさえも次第に分解し着
色や濁りを発生し、蒸留時のような高温で処理する場合
には、この傾向はさらに促進され不溶不融の化合物さえ
生成することが認められる。これらは側鎖塩素化物が容
易に分解し、脱ハロゲン化反応をおこしジフェニルアル
キル型槽金物を生成することによるものであり、脱ハロ
ゲン化水素反応の生成図としては、定説はないが空気中
の湿気、ちり、光、熱あるいは金属汚染さらには分解生
成したハロゲン化水素などによるとされている。This side chain chlorinated product has high reactivity and is easily decomposed.
Polymerization occurs and even during storage at room temperature, it gradually decomposes and produces color and turbidity, and when processed at high temperatures such as during distillation, this tendency is further accelerated and even insoluble and infusible compounds are produced. is recognized. These are caused by the fact that the side chain chloride easily decomposes and causes a dehalogenation reaction to produce diphenylalkyl-type metals.Although there is no established theory for the formation diagram of the dehydrohalogenation reaction, This is thought to be caused by moisture, dust, light, heat, metal contamination, and even hydrogen halides produced by decomposition.
また、例えば、トルエンの核塩素化により得られたモノ
クロロトルエンを蒸留して０−クロロトルエンおよびｐ
−クロロトルエンを分離精製しようとした場合、２化合
物の沸点が非常に近いことからその蒸留に要する蒸留塔
は約２００段もの段数を必要とし、必然的にその材質は
鉄またはニッケル等の金属を選択せざるをえない。For example, monochlorotoluene obtained by nuclear chlorination of toluene can be distilled to produce 0-chlorotoluene and p
- When attempting to separate and purify chlorotoluene, the distillation column required for distillation requires approximately 200 plates because the boiling points of the two compounds are very close, and the material of the distillation column is inevitably made of metals such as iron or nickel. I have no choice but to choose.
従ってこのような鉄またはニッケル等の金属の材質から
なる蒸留塔で、前記のような側鎖塩素化物をわずかにで
も含有するクロロトルエン混合物の蒸留を繰り返し行っ
た場合、側鎖塩素化物の分解に起因して生成する塩化水
素による蒸留塔の腐食が起こるという問題が起き、さら
に生成する分解物および重合物の蒸留塔内への付着によ
る蒸留効率の低下等の問題が生ずる。Therefore, if a chlorotoluene mixture containing even a small amount of side chain chloride is repeatedly distilled in a distillation column made of metal such as iron or nickel, the decomposition of the side chain chloride will occur. As a result, a problem arises in that the distillation column is corroded by the generated hydrogen chloride, and further problems occur such as a reduction in distillation efficiency due to the adhesion of the generated decomposition products and polymers in the distillation column.
また、蒸留塔の腐食を防ぐための方法として、蒸留工程
の前に、側鎖塩素化物を含有するクロロトルエン混合物
を水酸化ナトリウムと共にオートクレーブ中で加熱する
ことにより、生成した側鎖塩素化物の除去を行うという
方法が知られているが、この方法は有機物を含んだ排水
が出るためその処理が困難であるなどの問題点があった
。In addition, as a method to prevent corrosion of the distillation column, by heating a chlorotoluene mixture containing side chain chlorides with sodium hydroxide in an autoclave before the distillation process, the generated side chain chlorides are removed. However, this method has problems such as the production of wastewater containing organic matter, which is difficult to treat.
（問題点を解決するための手段）
このような現状に鑑み、本発明者らは、側鎖塩素化物の
分解２重合を抑制し、工業的にクロロトルエンを分離精
製する方法を得るべく鋭意研究を重ねた結果、側鎖塩素
化物を含むクロロトルエン混合物にジメチルスルホキシ
ドを加え蒸留することにより側鎖塩素化物の分解９重合
を抑制し、塩化水素の生成も起こらずにクロロトルエン
の分離精製を行うことができることを見出し、この見知
に基づき本発明を完成するに至った。(Means for Solving the Problems) In view of the current situation, the present inventors have conducted intensive research in order to obtain a method for industrially separating and purifying chlorotoluene by suppressing the decomposition double polymerization of side chain chlorinated products. As a result of repeated steps, by adding dimethyl sulfoxide to a chlorotoluene mixture containing chlorinated side chains and distilling them, the decomposition9 polymerization of chlorinated side chains was suppressed, and chlorotoluene was separated and purified without generating hydrogen chloride. Based on this finding, the present invention was completed.
すなわち本発明は、トルエンの核塩素化反応により得ら
れた反応混合物にジメチルスルホキシドを加え、蒸留す
ることを特徴とするクロロトルエンの分離精製方法であ
る。That is, the present invention is a method for separating and purifying chlorotoluene, which is characterized by adding dimethyl sulfoxide to a reaction mixture obtained by a nuclear chlorination reaction of toluene and distilling the mixture.
本発明で分離精製することができるクロロトルエンとし
ては、トルエンのモノ塩素化により得られるＯ−クロロ
トルエン、ｐ−クロロトルエン等のモノクロロトルエン
、さらに塩素化を続けることにより得られる２、４−ジ
クロロトルエン、３゜４−ジクロロトルエン等のジクロ
ロトルエンが挙げられる。The chlorotoluenes that can be separated and purified in the present invention include monochlorotoluenes such as O-chlorotoluene and p-chlorotoluene obtained by monochlorination of toluene, and 2,4-dichlorotoluene obtained by further chlorination. Examples include toluene and dichlorotoluene such as 3°4-dichlorotoluene.
本発明に従い、クロロトルエンを製造するには、例えば
、塩化鉄及び塩化アンチモン等の塩素化触媒の存在ある
いは非存在下、トルエンに０＝沸点以下の温度で塩素ガ
ス等の通常使用されている塩−４＝
素化剤を導入することにより得られたＯ Ｉ ｐ−
クロロトルエン、ジクロロトルエンおよび微量のベンジ
ルクロライド等の側鎖塩素化物を含有するクロロトルエ
ン混合物に、これら混合物に対して０．０００１〜１０
重量％好ましくは０．０００１〜１重量％の範囲でジメ
チルスルホキシドを添加し、常法に従い蒸留分離するこ
とにより側鎖塩素化物の分解１重合を抑制し、蒸留塔の
腐食もなくｏ−、ｐ−クロロトルエンを得ることができ
る。To produce chlorotoluene according to the invention, a commonly used salt, such as chlorine gas, is added to toluene at a temperature below the boiling point, with or without a chlorination catalyst, such as iron chloride and antimony chloride. −4= O I p− obtained by introducing the oxidizing agent
For chlorotoluene mixtures containing side chain chlorides such as chlorotoluene, dichlorotoluene and trace amounts of benzyl chloride, 0.0001 to 10
By adding dimethyl sulfoxide preferably in a range of 0.0001 to 1% by weight and separating it by distillation according to a conventional method, decomposition and polymerization of side chain chlorinated products can be suppressed, and o-, p- -Chlorotoluene can be obtained.
（発明の効果）
本発明によりジメチルスルホキシドの存在下、クロロト
ルエンを分離精製することにより、トルエンの核塩素化
により副生じた側鎖塩素化物をわずかに含有するクロロ
トルエン混合物から、鉄およびニッケル等の金属材質か
らなる蒸留塔を腐食することなく、さらに側鎖塩素化物
の分解２重合物の付着による蒸留効率の低下を生ずるこ
ともなく、ｏ−クロロトルエン、ｐ−クロロトルエンと
等のモノロロトルエン及び種々のジクロロトルエンを分
離精製することができることを可能にしたものであり、
工業的に優れた方法である。(Effect of the invention) By separating and purifying chlorotoluene in the presence of dimethyl sulfoxide according to the present invention, iron, nickel, etc. It does not corrode the distillation column made of metal materials, and it also does not reduce the distillation efficiency due to the adhesion of decomposed bipolymers of side chain chlorinated products. It makes it possible to separate and purify toluene and various dichlorotoluenes,
This is an industrially excellent method.
（実施例） 次に、実施例により本発明をさらに詳細に説明する。(Example) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
トルエンの核塩素化により得られた、クロロトルエン９
９．１６６％、ジクロロトルエン０．８２８％およびベ
ンジルクロライド０．００６％の組成からなるクロロト
ルエン混合物２１４ｇにジメチルスルホキシド１．１ｇ
を添加し蒸留した。Example 1 Chlorotoluene 9 obtained by nuclear chlorination of toluene
9.166% dichlorotoluene, 0.828% dichlorotoluene and 0.006% benzyl chloride to 214 g chlorotoluene mixture and 1.1 g dimethyl sulfoxide.
was added and distilled.
その結果、塩化水素の生成およびベンジルクロリドの分
解９重合物の生成もなく、沸点５５〜６２”Ｃ／ ２０
ｍｍＨｇの留分２１０ｇを得た。蒸留収率は９８％で
あった。As a result, there is no generation of hydrogen chloride or decomposition of benzyl chloride, and the boiling point is 55-62"C/20.
210 g of a mmHg fraction was obtained. Distillation yield was 98%.
Claims (1)
メチルスルホキシドを加え、蒸留することを特徴とする
クロロトルエンの分離精製方法。A method for separating and purifying chlorotoluene, which comprises adding dimethyl sulfoxide to a reaction mixture obtained by a nuclear chlorination reaction of toluene and distilling the mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1915388A JPS63313740A (en) | 1988-01-29 | 1988-01-29 | Separation and purification of chlorotoluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1915388A JPS63313740A (en) | 1988-01-29 | 1988-01-29 | Separation and purification of chlorotoluene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8760780A Division JPS5714540A (en) | 1980-06-27 | 1980-06-27 | Stabilization of aromatic compound bearing halogenated side chains |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63313740A true JPS63313740A (en) | 1988-12-21 |
Family
ID=11991479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1915388A Pending JPS63313740A (en) | 1988-01-29 | 1988-01-29 | Separation and purification of chlorotoluene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63313740A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174217A (en) * | 2014-06-20 | 2015-12-23 | 唐慧建 | Method for purifying chlorotoluene byproduct hydrogen chloride gas and regenerating absorbent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4087335A (en) * | 1975-09-19 | 1978-05-02 | Rohm And Haas Company | Inhibitors for vinylbenzyl chloride and vinyltoluene decomposition |
-
1988
- 1988-01-29 JP JP1915388A patent/JPS63313740A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4087335A (en) * | 1975-09-19 | 1978-05-02 | Rohm And Haas Company | Inhibitors for vinylbenzyl chloride and vinyltoluene decomposition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105174217A (en) * | 2014-06-20 | 2015-12-23 | 唐慧建 | Method for purifying chlorotoluene byproduct hydrogen chloride gas and regenerating absorbent |
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