JPS595132A - Preparation of 4-chloro-3,5-xylenol - Google Patents
Preparation of 4-chloro-3,5-xylenolInfo
- Publication number
- JPS595132A JPS595132A JP57111802A JP11180282A JPS595132A JP S595132 A JPS595132 A JP S595132A JP 57111802 A JP57111802 A JP 57111802A JP 11180282 A JP11180282 A JP 11180282A JP S595132 A JPS595132 A JP S595132A
- Authority
- JP
- Japan
- Prior art keywords
- xylenol
- catalyst
- copper salt
- chloro
- hydrochloric acid
- 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
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は4−クロル−3,5−キシレノールの製造法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 4-chloro-3,5-xylenol.
4−クロル−5,5−キシレノールは殺W剤、fi薬及
びそれらの中間体として工業的に重要な化合物である。4-Chloro-5,5-xylenol is an industrially important compound as a tungstenicide, a fi agent, and an intermediate thereof.
これは3.5−キシレノールの塩素化により製造される
が、塩素化に際しては高選択率で得ること及び安価な製
造法を確立することが工業的製造法の大きな課題となつ
【いる。It is produced by chlorination of 3,5-xylenol, but the major challenges for industrial production methods are obtaining high selectivity during chlorination and establishing an inexpensive production method.
本発明は5.5−キシレノールの塩素化物を製造するに
当り、目的物の選択率が高く原料費が安く、しかも簡単
な設備で製造が出来る工業的に有利な製造法を提供する
ことにある。The object of the present invention is to provide an industrially advantageous manufacturing method for producing a chlorinated product of 5,5-xylenol, which has a high selectivity for the target product, has low raw material costs, and can be produced using simple equipment. .
5.5−キシレノールの塩素化に関しては従来よりいく
つかの報告がなされており、例えば特公昭45−408
82号公報によれば3.5−キシレノールを熱塩酸溶液
中でCuCt!を塩素化剤とし″C填素化する方法が、
また特開昭49−55544号公報によれば、5.5−
キシレノールを同じく熱塩酸溶液中でCuCLzを触媒
としてα鵞ガスを導入して塩素化する方法が、また特公
昭55−5335号公報によればFectl 、AIC
Lz、TiCz4及び8b(z、からなる群より選ばれ
た少なくとも一種の金属塩化物塩化スルフリルによって
塩素化する方法及び回−〇、0.系を用いた方法として
特開昭56−1!11555号公報VCI%tct3ま
たはFeCj4を触媒としテH(J−HtO* !り塩
素化し、4−クロル−3,5−キシレノールを高選択率
で得る方法が報告されている。There have been several reports regarding the chlorination of 5.5-xylenol, for example, Japanese Patent Publication No. 45-408.
According to Publication No. 82, 3.5-xylenol was added to CuCt! in a hot hydrochloric acid solution. The method of chlorinating with C as a chlorinating agent is
According to Japanese Patent Application Laid-Open No. 49-55544, 5.5-
According to Japanese Patent Publication No. 55-5335, xylenol is similarly chlorinated in a hot hydrochloric acid solution using CuCLz as a catalyst by introducing alpha gas, and according to Japanese Patent Publication No. 55-5335,
A method of chlorinating with at least one metal chloride sulfuryl chloride selected from the group consisting of Lz, TiCz4 and 8b(z) and a method using the system JP-A-56-1!11555 A method has been reported in which 4-chloro-3,5-xylenol is obtained with high selectivity by chlorinating TeH(J-HtO*!) using VCI%tct3 or FeCj4 as a catalyst.
しかしながら、いづれの方法も工業的生産な実施するに
は種々改良すべき点を有する。すなわち、前記公開公報
忙係る技術では、熱塩酸を使用するための装置上の問題
、a!素を用いるための安全上の問題、塩素化剤を再生
するための工程上の複雑化に伴う経済的負担の増加、C
t2 ガスに起因するタール化によるトラブル等があり
、また特公昭55−5555号公報忙よル方法K ツイ
テli 3o、Ct=を用いることによる原料費高及び
発生SOfの吸収除去、そのための装置が必要となる等
がその主なものである。また特開昭56−13153号
公報については、本発明者等が実施例に記載のAt(1
3及びFe(J4触媒を用いて追試実験を実施したとこ
ろ4−クロル体(p−クロル体)の選択率h′−低く、
該公報実施例の結果を再現出来なかった。そこで、鋭意
触媒の探索研究を行った結果、以下詳述するように銅塩
触媒を用いること忙より、ジクロル体生成率が極めて低
り、シかも4−クロル体選択率が約80%台と極めて高
い選択率を示す触媒を見出すに至った。However, each method has various points that need to be improved for industrial production. That is, in the technique disclosed in the above-mentioned publication, there are problems with the equipment for using hot hydrochloric acid, a! safety issues when using chlorinating agents; increased economic burden due to the complexity of the process for regenerating chlorinating agents;
There are troubles due to tar formation caused by t2 gas, and the use of Japanese Patent Publication No. 55-5555 requires high raw material costs and absorption and removal of generated SOf, and equipment for that purpose. The main ones are necessary. Furthermore, regarding JP-A No. 56-13153, the present inventors described At(1
When a follow-up experiment was conducted using 3 and Fe (J4 catalyst), the selectivity of 4-chlor form (p-chlor form) h'- was low;
The results of the examples in the publication could not be reproduced. Therefore, as a result of intensive research on catalysts, we found that due to the use of copper salt catalysts, the dichlor formation rate was extremely low, and the 4-chlor formation selectivity was around 80%. We have now discovered a catalyst that exhibits extremely high selectivity.
更に発明では、使用原料はHCt水* H2O2水及び
銅塩といずれも一般的なものであり、取扱上問題なく廉
価である。また反応は常温で十分に進行し。Furthermore, in the invention, the raw materials used are HCt water*H2O2 water and copper salt, which are all common materials, and are inexpensive and pose no problem in handling. In addition, the reaction proceeds satisfactorily at room temperature.
n、o、の自己分解もなく、過剰仕込の必要はない。There is no self-decomposition of n, o, and there is no need for excessive preparation.
精製、取り出しについても反応液のオイル層をそのまま
冷却、晶析することにより純度99%以上の高純度品を
簡単忙得ることができる等の利点がある。Regarding purification and extraction, there are advantages such as the ability to easily obtain a highly purified product with a purity of 99% or more by directly cooling and crystallizing the oil layer of the reaction solution.
本発明で使用する触媒としては銅塩が用いられるが、特
にCば−およびCuC1が望ましく、5.5−キシレノ
ールに対し0.01〜20%(重量)使用することが必
要であIJ、更に好ましくは1%〜10%である。Copper salts are used as catalysts used in the present invention, and CuCl and CuCl are particularly preferred, and it is necessary to use them in an amount of 0.01 to 20% (by weight) based on 5.5-xylenol. Preferably it is 1% to 10%.
また塩酸濃度は5〜35%の範囲で用いられるが、液量
等の関係から20〜55%と高濃度で行うことが望まし
く、又濃度による選択率への影譬は全くみられない。塙
酸量については、必要塩素化度に応じて適宜変えて行な
えばよく、3.5−キシレノールに対して目的塩素化度
の1.01〜2.0倍モル程度でよいが、少ないと反応
速度低下をきたすので、好ましくは1.5〜2.0倍モ
ルが適当である。また本発明で用いる過酸化水素水溶液
の濃度は5〜60%の範囲のものであるが、好ましくは
35〜60%のものである。過酸化水素水溶液の使用量
は、目的塩素化度の1.0〜1.2倍モルの範囲が適当
で、これ以上用いるとジクロル体の生成をまねき、4−
クロル体の減収となる。反応温度は出来るだけ低温がよ
いが1反応速度を考慮すると15〜55℃にするととK
よ?)発明の最良の効果が達せられる。The concentration of hydrochloric acid used is in the range of 5 to 35%, but it is desirable to use a high concentration of 20 to 55% in view of the liquid volume, and there is no effect on the selectivity due to the concentration. The amount of sulfuric acid may be changed as appropriate depending on the required degree of chlorination, and may be about 1.01 to 2.0 times the mole of the desired degree of chlorination relative to 3.5-xylenol, but if it is too small, the reaction may occur. Since this causes a decrease in speed, the appropriate amount is preferably 1.5 to 2.0 times the mole. Further, the concentration of the aqueous hydrogen peroxide solution used in the present invention is in the range of 5 to 60%, preferably 35 to 60%. The appropriate amount of hydrogen peroxide aqueous solution to be used is 1.0 to 1.2 times the mole of the desired degree of chlorination.
This will result in a decrease in the yield of chloride. It is best to keep the reaction temperature as low as possible, but considering the reaction rate, a temperature of 15 to 55°C is recommended.
Yo? ) the best effects of the invention are achieved.
本発明の塩素化法は、溶媒の存在下即ち5.5−キシレ
ノールをハロゲン化炭化水素、有機酸、ハロゲン置換芳
香族炭化水素等に溶解し反応するものでいずれを用いて
もよいが、後処理を考えると好ましくはジクロロエタン
、cHct、、 、CCl4等のI・ロゲン化低級脂肪
族炭化水素が好ましい。The chlorination method of the present invention involves dissolving 5,5-xylenol in a halogenated hydrocarbon, an organic acid, a halogen-substituted aromatic hydrocarbon, etc., and reacting in the presence of a solvent. Considering the treatment, I-logenated lower aliphatic hydrocarbons such as dichloroethane, cHct, , CCl4, etc. are preferred.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例1
撹拌器、温度計、滴下ロート及び還流冷却器を備えた四
ツロセパラプルフラスコにジクaルエタン50部、6.
5−キシレノール40部、35%塩酸73部及び触媒と
してCuC1z 5部を仕込み、攪拌下20〜50℃に
保ちながら55%過酸化水素水溶液17部を60分かけ
て滴下ロートより仕込み、更に5部℃で2.一時間攪拌
し反応させる。反応終了後1分液し、さら忙ジクロルエ
タン層を水洗した後、一部をサンプリングし、ガスクロ
マトグラフィーにより分析した結果1次の組成を得た。Example 1 50 parts of dichloroethane was added to a four-piece parallel flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser.6.
40 parts of 5-xylenol, 73 parts of 35% hydrochloric acid, and 5 parts of CuC1z as a catalyst were charged, and while stirring and maintaining the temperature at 20 to 50°C, 17 parts of a 55% aqueous hydrogen peroxide solution was added from the dropping funnel over 60 minutes, followed by another 5 parts. 2 at °C. Stir for one hour to react. After the completion of the reaction, the mixture was separated for 1 minute, and the dichloroethane layer was washed with water. A portion of the mixture was sampled and analyzed by gas chromatography. As a result, the following composition was obtained.
5.5−キシレノール 59.9モル%p−ク
ロル−5,5−キシレノール 54.010−りa
ルー3.5−キシレノール 6.0#2.4−ジ
クロル−3,5−キシレノール 0.Ol”p+o比
、85.0%
注) pは、p−クロル−3,5−キシレノールを、0
は、O−クロル−3,5−キシレノールをyb−t−0
実施例2〜4
実施例1と同様な操作により、触媒Cu C14の代り
に他の銅塩な使用した場合に得られた分析結果を表IK
示した。5.5-xylenol 59.9 mol% p-chloro-5,5-xylenol 54.010-ria
3.5-xylenol 6.0#2.4-dichloro-3,5-xylenol 0. Ol”p+o ratio, 85.0% Note) p is p-chloro-3,5-xylenol, 0
is O-chloro-3,5-xylenol as yb-t-0
Examples 2 to 4 Table IK shows the analytical results obtained when other copper salts were used in place of the catalyst Cu C14 by the same operation as in Example 1.
Indicated.
また、無触媒及び本発明に係る銅塩の代りに他の金属塩
を用いた比較例1〜4の結果も併せて表1VC,示した
。Table 1VC also shows the results of Comparative Examples 1 to 4 in which no catalyst was used and in which other metal salts were used in place of the copper salt according to the present invention.
表1
コノ表記カラ明うカtt ヨ5 IC、AtCz4 、
FeC4オよび5bczsを触媒として用いた場合は
、触媒を用いない場合とp/p+。比においてあまり差
が生じなかった。Table 1 Kono notation Color light cut yo5 IC, AtCz4,
When FeC4O and 5bczs were used as catalysts, p/p+ was compared to when no catalyst was used. There was not much difference in the ratio.
実施例5
実施例1と同様の反応装置を用い、四塩化炭素96部、
5.5−キシレノール40部、35%塩酸75部及びC
uCty 5部を仕込み、攪拌しながら25〜30℃で
35%過酸化水素35部を60分で滴下ロートより仕込
み、更VC50℃で6時間攪拌し1反応させる。反応途
中よりp−クロル−3,5−キシレノールが析出してく
る。反応終了後、反応液の温度を60℃まで昇温し、反
応生成物を完全に溶解させる。分液して水洗し、四塩化
炭素反応液の一部をサンプリングし、ガスクロマトグラ
フィー圧より分析した結果、次の組成を得た。Example 5 Using the same reaction apparatus as in Example 1, 96 parts of carbon tetrachloride,
5.5-xylenol 40 parts, 35% hydrochloric acid 75 parts and C
5 parts of uCty were charged, and while stirring, 35 parts of 35% hydrogen peroxide was charged from the dropping funnel at 25 to 30°C over 60 minutes, and the mixture was further stirred at VC 50°C for 6 hours to carry out one reaction. p-chloro-3,5-xylenol begins to precipitate during the reaction. After the reaction is completed, the temperature of the reaction solution is raised to 60° C. to completely dissolve the reaction product. After separating and washing with water, a portion of the carbon tetrachloride reaction solution was sampled and analyzed by gas chromatography pressure, and as a result, the following composition was obtained.
3.5−キシレノール 2.5モ
ル%p−クロル−へ5−キシレノール 7c13
0−クロル # 16.7ジ
クロル 11.4
p/p+。比は82.6%
この反応液な徐々に冷却し、析出した結晶を炉別し、1
5℃の四塩化炭素24部で洗浄して34.7部の結晶(
収率68%)を得る。結晶は針状の純白結晶でガスクロ
マトグラフィー分析の結果は次の通りである。3.5-xylenol 2.5 mol% p-chloro-5-xylenol 7c13
0-Chlor # 16.7 Dichlor 11.4 p/p+. The ratio was 82.6%. This reaction solution was gradually cooled, the precipitated crystals were separated in a furnace, and 1
Washing with 24 parts of carbon tetrachloride at 5°C gave 34.7 parts of crystals (
yield of 68%). The crystals were needle-shaped pure white crystals, and the results of gas chromatography analysis were as follows.
へ5−キシレノール a5重量%p−ク
ロル−へ5−キシレノール 99.5#実施例6
実施例5と同様な操作により、触媒なCuCtlの代り
にCu(215部を用いた。反応終了液の一部をサンプ
リングし、分析した結果は以下である。5-xylenol a5% by weight p-chloro-5-xylenol 99.5 #Example 6 In the same manner as in Example 5, 215 parts of Cu (215 parts) was used instead of the catalytic CuCtl. The results of sampling and analyzing the area are as follows.
45−キシレノール 59モル%p−ク
ロル−45−キシレノール 75.9#0−クロル−#
1a6#ジクロル−#
1.6#p/p+。出御8α5%
又、得られた結晶は5部7部(収率66%)で、そのガ
スクロマトグラフィー分析の結果は次の通りである。45-xylenol 59 mol%p-chloro-45-xylenol 75.9#0-chloro-#
1a6#dichlor-#
1.6#p/p+. The amount of crystals obtained was 5 parts and 7 parts (yield 66%), and the results of gas chromatography analysis were as follows.
へ5−キシレノール 0.4重量%p−
クロル−45−キシレノール 99.6#保土谷化学工
業株式会社He5-xylenol 0.4% by weight p-
Chlor-45-xylenol 99.6#Hodogaya Chemical Industry Co., Ltd.
Claims (1)
液中に過酸化水素水溶液を滴下し、HCiL −H10
2液相オキシクロリネーションにより塩素化するにあた
り、触媒として銅塩を用いることを特徴とする4−クロ
ル−3,5−キシレノールの製造法。6. Drop an aqueous hydrogen peroxide solution into a mixture of 5-xylenol, an organic solvent, a catalyst, and hydrochloric acid, and add HCiL-H10.
A method for producing 4-chloro-3,5-xylenol, characterized in that a copper salt is used as a catalyst in chlorination by two-liquid phase oxychlorination.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57111802A JPS595132A (en) | 1982-06-30 | 1982-06-30 | Preparation of 4-chloro-3,5-xylenol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP57111802A JPS595132A (en) | 1982-06-30 | 1982-06-30 | Preparation of 4-chloro-3,5-xylenol |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS595132A true JPS595132A (en) | 1984-01-12 |
Family
ID=14570521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP57111802A Pending JPS595132A (en) | 1982-06-30 | 1982-06-30 | Preparation of 4-chloro-3,5-xylenol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS595132A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62223140A (en) * | 1986-03-26 | 1987-10-01 | Nippon Kayaku Co Ltd | Production of 2-chloro-4-fluorophenol |
CN102199075A (en) * | 2011-04-02 | 2011-09-28 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
DE102017216170A1 (en) | 2016-09-15 | 2018-03-15 | Yazaki Corporation | Seal and shield connection device |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5132616A (en) * | 1974-10-24 | 1976-03-19 | Beltek Corp | JIKIROKUON SAISEIKI |
-
1982
- 1982-06-30 JP JP57111802A patent/JPS595132A/en active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5132616A (en) * | 1974-10-24 | 1976-03-19 | Beltek Corp | JIKIROKUON SAISEIKI |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62223140A (en) * | 1986-03-26 | 1987-10-01 | Nippon Kayaku Co Ltd | Production of 2-chloro-4-fluorophenol |
CN102199075A (en) * | 2011-04-02 | 2011-09-28 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxy-3, 5-dimethyl-4-chlorobenzene |
WO2012136108A1 (en) * | 2011-04-02 | 2012-10-11 | 湖南利洁生物化工有限公司 | Method for preparing 1-hydroxyl-3,5-dimethyl-4-chlorobenzene |
DE102017216170A1 (en) | 2016-09-15 | 2018-03-15 | Yazaki Corporation | Seal and shield connection device |
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