JPH0627079B2 - Method for producing halogenated benzenes - Google Patents
Method for producing halogenated benzenesInfo
- Publication number
- JPH0627079B2 JPH0627079B2 JP59052953A JP5295384A JPH0627079B2 JP H0627079 B2 JPH0627079 B2 JP H0627079B2 JP 59052953 A JP59052953 A JP 59052953A JP 5295384 A JP5295384 A JP 5295384A JP H0627079 B2 JPH0627079 B2 JP H0627079B2
- Authority
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- Japan
- Prior art keywords
- substituted
- acid
- zeolite
- halogen
- catalyst
- 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.)
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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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 本発明は，ハロゲン化ベンゼン類の製造方法，さらに詳
しくいえば新規な触媒を用いて核置換ベンゼン類をハロ
ゲン化し，良好な選択率でＰ−ハロゲン化核置換ベンゼ
ン類を製造する方法に関するものである。The present invention relates to a method for producing halogenated benzenes, and more specifically, halogenation of nuclear-substituted benzenes using a novel catalyst, and P-halogenated nuclear-substituted benzenes with good selectivity. The present invention relates to a method of manufacturing.
ベンゼン類の核ハロゲン化物は，医薬，農薬などの製造
原料として使用されているが，その中で特に需要が多い
のは置換基に対してＰ位がハロゲン化された核置換ベン
ゼン類であるので，Ｐ−ハロゲン化の選択率を上げるた
めに種々の研究が行われている。Nuclear halides of benzenes are used as raw materials for the production of pharmaceuticals, agricultural chemicals, etc. Among them, the ones in particular demand are nuclear-substituted benzenes in which the P-position is halogenated with respect to the substituent. , Various studies have been conducted to increase the selectivity of P-halogenation.
従来，アルキルベンゼン類のハロゲン化方法としては，
塩化アンチモン，塩化第二鉄，塩化アルミニウムなどの
ルイス酸触媒の存在下で，塩素ガスのようなハロゲンを
用いてハロゲン化する方法が一般に行われているが，こ
の方法によると主としてＯ−クロロアルキルベンゼンが
生成し，さらにｍ−クロロ化物，多クロロ化物なども副
生するため，Ｐ−クロロアルキルベンゼンの収率を４０
％以上にすることは不可能であった。そのため，Ｐ−ク
ロロアルキルベンゼンの選択率を増大させるべく，種々
の触媒の開発研究が行われ，これまでにもいくつか提案
されている。Conventionally, as a method for halogenating alkylbenzenes,
A method of halogenating with a halogen such as chlorine gas in the presence of a Lewis acid catalyst such as antimony chloride, ferric chloride or aluminum chloride is generally performed. According to this method, mainly O-chloroalkylbenzene is used. Is produced, and m-chlorinated products and polychlorinated products are also produced as by-products, so the yield of P-chloroalkylbenzene is 40%.
It was impossible to make it more than%. Therefore, various catalysts have been developed and studied in order to increase the selectivity of P-chloroalkylbenzene, and some have been proposed so far.
例えばルイス酸と硫黄又はセレンから成る触媒を用いて
４５〜５２％の収率でＰ−クロロ化物を得る方法，ルイ
ス酸とチアンスレンから成る触媒を用いて５５〜６０％
の収率でＰ−クロロ化物を得る方法（特開昭52−19630
号公報），ルイス酸とフエノキサチン化合物から成る触
媒系を用いて５２〜６０％の収率でＰ−クロロ化物を得
る方法（特開昭57−175133号公報）などが知られてい
る。For example, a method of obtaining a P-chlorinated product in a yield of 45 to 52% using a catalyst composed of Lewis acid and sulfur or selenium, 55 to 60% using a catalyst composed of Lewis acid and thianthrene
Method for obtaining P-chlorinated product in a yield of
JP-A-57-175133) and the like, a method of obtaining a P-chloro compound in a yield of 52 to 60% using a catalyst system consisting of a Lewis acid and a phenoxatin compound is known.
他方，クロロベンゼンの塩素化に関しては，硫化鉄触媒
の存在下，塩素を作用させて６０〜７０％の収率でＰ−
ジクロロベンゼンを得る方法（特開昭50−64231号公
報），セレン又はセレン化合物を触媒として塩素を作用
させ，７２％の収率でＰ−ジクロロベンゼンを得る方法
（特公昭５０−34010 号公報）などが知られている。On the other hand, regarding chlorination of chlorobenzene, chlorine is allowed to act in the presence of an iron sulfide catalyst to give P- at a yield of 60 to 70%.
Method for obtaining dichlorobenzene (JP-A-50-64231), method for reacting chlorine with selenium or a selenium compound as a catalyst to obtain P-dichlorobenzene with a yield of 72% (JP-B-50-34010) Are known.
しかしながら，これらの方法はいずれもＰ−ハロゲン化
物に対する選択率は低く，Ｐ−ハロゲン化ベンゼン類の
製造方法としては必ずしも満足し得るものとはいえなか
った。However, all of these methods have a low selectivity for P-halides, and are not necessarily satisfactory as methods for producing P-halogenated benzenes.
本発明者らは，このような従来方法の欠点を克服し，高
い選択率でＰ−ハロゲン化核置換ベンゼン類を製造し得
る方法を開発するために，鋭意研究を重ねた結果，ある
種のゼオライトをハロゲン置換又は無置換の低級脂肪族
カルボン酸で処理したものを触媒として用いることによ
りその目的を達成し得ることを見出し，その知見に基づ
いて本発明をなすに至った。The present inventors have conducted extensive studies in order to overcome such drawbacks of the conventional method and develop a method capable of producing P-halogenated nucleus-substituted benzenes with high selectivity. It has been found that the object can be achieved by using zeolite treated with halogen-substituted or unsubstituted lower aliphatic carboxylic acid as a catalyst, and the present invention has been completed based on the finding.
すなわち，本発明は，触媒の存在下，一般式 （式中のＲは低級アルキル基，低級アルコキシ基又はハ
ロゲン原子である） で表わされる核置換ベンゼン類を液相でハロゲン化し
て，一般式 （式中のＲは前記と同じ意味をもち，Ｘはハロゲン原子
である） で表わされるハロゲン化ベンゼン類を製造するに当り，
触媒としてハロゲン置換又は無置換の低級脂肪族カルボ
ン酸で処理した，SiO2／Al2O3 モル比３〜８，細孔径６
〜１０Åのゼオライトを用いることを特徴とするハロゲ
ン化核置換ベンゼン類の製造方法を提供するものであ
る。That is, the present invention is based on the general formula in the presence of a catalyst. (R in the formula is a lower alkyl group, a lower alkoxy group or a halogen atom), and a halogenated ring-substituted benzene is represented by the general formula (Wherein R has the same meaning as described above and X is a halogen atom), a halogenated benzene represented by
Treated with halogen-substituted or unsubstituted lower aliphatic carboxylic acid as a catalyst, SiO 2 / Al 2 O 3 molar ratio 3 to 8, pore size 6
The present invention provides a method for producing halogenated nucleus-substituted benzenes, which comprises using 10 to 10Å of zeolite.
本発明方法における一般式(1)で示される原料化合物中
の，核置換基Ｒの例としては，直鎖状及び分枝鎖状のア
ルキル基あるいはアルコキシ基又はフッ素原子，塩素原
子，臭素原子等のハロゲン原子を挙げることができる
が，特に炭素数１〜４のアルキル基，塩素原子が好まし
い。Examples of the nuclear substituent R in the raw material compound represented by the general formula (1) in the method of the present invention include linear and branched alkyl groups or alkoxy groups, fluorine atoms, chlorine atoms, bromine atoms, etc. The halogen atom can be mentioned, but an alkyl group having 1 to 4 carbon atoms and a chlorine atom are particularly preferable.
次に，本発明方法においては，触媒として，SiO2／Al2O
3 のモル比が３〜８の範囲にあり，細孔径が６〜１０Å
の範囲にあるゼオライトを，ハロゲン置換又は無置換の
低級脂肪族カルボン酸で処理したものを用いることが必
要である。SiO2／Al2O3 のモル比や細孔径が前記の範囲
外にあるゼオライトを用いた場合は，Ｐ−ハロゲン化物
の選択率が著しく低下する。Next, in the method of the present invention, SiO 2 / Al 2 O is used as a catalyst.
Molar ratio of 3 is in the range of 3-8, pore size 6~10Å
It is necessary to use a zeolite in the range of 1) treated with a halogen-substituted or unsubstituted lower aliphatic carboxylic acid. When a zeolite having a SiO 2 / Al 2 O 3 molar ratio or a pore diameter outside the above range is used, the selectivity of P-halide is significantly reduced.
このような条件に適合したゼオライトの代表的なものと
してはＬ型ゼオライトがあるが，これは酸化ケイ素(SiO
2)：酸化アルミニウム(Al2O3 )のモル比が４：１ないし
８：１の組成を有し，細孔径約７〜１０Åの結晶性アル
ミナシリケートである。前記の条件に適合したゼオライ
トの他の例としては，SiO2：Al2O3 のモル比が３：１な
いし７：１の組成を有し，細孔径約６〜９ÅのＹ型ゼオ
ライトを挙げることができる。A typical type of zeolite that meets these requirements is L-type zeolite, which is silicon oxide (SiO 2).
2 ): aluminum oxide (Al 2 O 3 ) having a molar ratio of 4: 1 to 8: 1 and a crystalline alumina silicate having a pore size of about 7 to 10Å. Another example of the zeolite satisfying the above conditions is a Y-type zeolite having a composition of SiO 2 : Al 2 O 3 in a molar ratio of 3: 1 to 7: 1 and having a pore size of about 6 to 9Å. be able to.
本発明における触媒としては，これらと同一のＸ線回折
スペクトルを有する合成ゼオライト，天然ゼオライトも
用いることができる。また，これらのゼオライト中に含
まれるイオン交換可能なカチオンは，通常ナトリウム又
はカリウムであるが，それ以外のカチオンを含むもので
もよい。このようなカチオンとしては，例えば周期表Ｉ
Ａ族，IIＡ族，IIIＡ族，IVＡ族，ＶＡ族の金属のイオ
ン又はプロトンを挙げることができる。これらのカチオ
ンは１種含まれていてもよいし，また２種以上含まれて
いてもよい。As the catalyst in the present invention, synthetic zeolite and natural zeolite having the same X-ray diffraction spectrum as these can also be used. The ion-exchangeable cation contained in these zeolites is usually sodium or potassium, but may contain other cations. Such cations include, for example, Periodic Table I.
Mention may be made of metal ions or protons of group A, group IIA, group IIIA, group IVA, and group VA. One kind of these cations may be contained, or two or more kinds thereof may be contained.
本発明方法においては，このゼオライトをハロゲン置換
又は無置換の低級脂肪族カルボン酸で処理したものが用
いられるが，この処理はハロゲン化での使用に先立って
あらかじめ施してもよいし，またハロゲン化反応時に反
応系内にハロゲン置換又は無置換の低級脂肪族カルボン
酸とゼオライトを同時に添加して行ってもよい。In the method of the present invention, this zeolite is treated with a halogen-substituted or unsubstituted lower aliphatic carboxylic acid, and this treatment may be carried out prior to use in halogenation, or it may be halogenated. At the time of the reaction, a halogen-substituted or unsubstituted lower aliphatic carboxylic acid and zeolite may be simultaneously added to the reaction system.
あらかじめ処理する場合には，例えばゼオライトを溶媒
に懸濁させハロゲン置換又は無置換の低級脂肪族カルボ
ン酸を加えたのち，溶媒及び過剰のハロゲン置換又は無
置換の低級脂肪族カルボン酸を留去し，減圧乾燥するこ
とによって行われる。この際，溶媒を用いずにハロゲン
置換又は無置換の低級脂肪族カルボン酸の中に直接ゼオ
ライトを加え，過剰分を留去してもよい。In the case of pretreatment, for example, zeolite is suspended in a solvent, halogen-substituted or unsubstituted lower aliphatic carboxylic acid is added, and then the solvent and excess halogen-substituted or unsubstituted lower aliphatic carboxylic acid are distilled off. , Dried under reduced pressure. At this time, the zeolite may be directly added to the halogen-substituted or unsubstituted lower aliphatic carboxylic acid without using a solvent, and the excess amount may be distilled off.
他方，反応時に処理する場合には，ハロゲン化装置内に
装入した原料の核置換ベンゼン類にゼオライトを懸濁さ
せ，これにハロゲン置換又は無置換の低級脂肪族カルボ
ン酸を加えて，沸点以下の温度，好ましくは室温から10
0℃までの温度でかきまぜたのち，そのまま後続のハロ
ゲン化を行う。On the other hand, when treating during the reaction, the zeolite is suspended in the nucleus-substituted benzenes, which are the raw material charged in the halogenation device, and halogen-substituted or unsubstituted lower aliphatic carboxylic acid is added to the suspension, and the temperature is kept below the boiling point. Temperature, preferably from room temperature to 10
After stirring at a temperature of up to 0 ° C, the subsequent halogenation is carried out.
これらのハロゲン置換又は無置換の低級脂肪族カルボン
酸による処理は，いずれか一方を行うだけで十分である
が，所望ならばその両方を行うこともできる。It is sufficient to carry out either treatment with these halogen-substituted or unsubstituted lower aliphatic carboxylic acids, but it is also possible to carry out both if desired.
この際に用いるハロゲン置換又は無置換の低級脂肪族カ
ルボン酸としては，酢酸，プロピオン酸，イソバレリア
ン酸，モノクロロ酢酸，モノブロモ酢酸，ジクロロ酢
酸，トリクロロ酢酸，α−クロロプロピオン酸，β−ク
ロロプロピオン酸，ジフルオロ酢酸，トリフルオロ酢
酸，ペンタフルオロプロピオン酸，β−クロロ−テトラ
フルオロプロピオン酸等を挙げることができる。カルボ
ン酸として安息香酸のような芳香族カルボン酸を用いた
場合には目的とするＰ−ハロゲン化物の選択率の向上は
得られない。このハロゲン置換又は無置換の低級脂肪族
カルボン酸の使用量としては，ゼオライトに基づき１重
量％以上あれば十分である。Examples of the halogen-substituted or unsubstituted lower aliphatic carboxylic acid used at this time include acetic acid, propionic acid, isovaleric acid, monochloroacetic acid, monobromoacetic acid, dichloroacetic acid, trichloroacetic acid, α-chloropropionic acid, β-chloropropionic acid. , Difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, β-chloro-tetrafluoropropionic acid and the like. When an aromatic carboxylic acid such as benzoic acid is used as the carboxylic acid, the target selectivity of the P-halide cannot be improved. The amount of the halogen-substituted or unsubstituted lower aliphatic carboxylic acid to be used is sufficient if it is 1% by weight or more based on the zeolite.
本発明方法に従って核置換ベンゼンのハロゲン化を行う
には，例えばハロゲン置換又は無置換の低級脂肪族カル
ボン酸で処理したゼオライトを原料化合物１モル当り0.
01〜10ｇ，好ましくは０．１〜７ｇの割合で混合し，沸
点以下の温度でかきまぜながら液相でハロゲン化剤を導
入する。この際，所望に応じ反応溶媒を使用することも
できる。ハロゲン化剤としては，芳香環のハロゲン化に
慣用されているものが用いられるが，好ましいのは塩
素，臭素，スルフリルクロリドなどである。これらは、
所望に応じ窒素のような不活性ガスで希釈して用いるこ
ともできる。また，ハロゲン化の反応温度は０℃以上，
反応混合物の沸点以下の温度であり実用的には室温〜９
０℃である。この反応は減圧下，加圧下のいずれで行っ
てもよいが通常は常圧下で行われる。To carry out the halogenation of the nucleus-substituted benzene according to the method of the present invention, for example, zeolite treated with a halogen-substituted or unsubstituted lower aliphatic carboxylic acid is added in an amount of 0.
The mixture is mixed at a ratio of 01 to 10 g, preferably 0.1 to 7 g, and the halogenating agent is introduced in the liquid phase while stirring at a temperature below the boiling point. At this time, a reaction solvent may be used if desired. As the halogenating agent, those which are commonly used for halogenating aromatic rings are used, and preferred are chlorine, bromine, sulfuryl chloride and the like. They are,
If desired, it may be diluted with an inert gas such as nitrogen before use. Also, the reaction temperature for halogenation is 0 ° C or higher,
The temperature is not higher than the boiling point of the reaction mixture and practically room temperature to 9
It is 0 ° C. This reaction may be carried out under reduced pressure or increased pressure, but is usually carried out under normal pressure.
本発明方法によれば，核置換ベンゼン類のハロゲン化に
おいて，Ｏ−位のハロゲン化を抑制し，Ｐ−位のハロゲ
ン化を選択的かつ効率よく行うことができる上に，側鎖
ハロゲン化物や多核ハロゲン化物のような副生物の生成
を極めて少量に抑えることができ，利用度の高いＰ−ハ
ロゲン化核置換ベンゼン類を高い収率で得ることができ
るという利点がある。According to the method of the present invention, in the halogenation of the nucleus-substituted benzenes, the halogenation at the O-position can be suppressed, the halogenation at the P-position can be selectively and efficiently performed, and the halogenated side chain or The production of by-products such as polynuclear halides can be suppressed to an extremely small amount, and there is an advantage that highly utilized P-halogenated nucleus-substituted benzenes can be obtained in a high yield.
また，本発明方法によれば，モノハロゲン化ベンゼンを
原料としてＰ−ジハロゲン化ベンゼンを製造する場合
に，ベンゼンからモノハロゲン化ベンゼンを製造し，こ
れをさらにハロゲン化してＰ−ジハロゲン化ベンゼンと
する工程を同一反応装置内で連続して行うことができる
ので有利である。Further, according to the method of the present invention, when P-dihalogenated benzene is produced from monohalogenated benzene, monohalogenated benzene is produced from benzene and further halogenated to obtain P-dihalogenated benzene. Advantageously, the steps can be carried out continuously in the same reactor.
さらに，本発明方法は，反応及びその後に行う後処理操
作が簡単であり，触媒の再使用も可能であるなどＰ−ハ
ロゲン化核置換ベンゼン類の工業的製法として好適であ
る。Furthermore, the method of the present invention is suitable as an industrial production method of P-halogenated nucleus-substituted benzenes, since the reaction and the post-treatment operation to be performed thereafter are simple and the catalyst can be reused.
次に実施例によって本発明をさらに詳細に説明する。Next, the present invention will be described in more detail with reference to examples.
実施例１ 冷却管，温度計，かきまぜ機及び吹込み管を備えた200m
l容量の反応フラスコに，Ｌ型ゼオライト（東洋曹達
(株)製，商品名TSZ-506）５ｇとトルエン92.1ｇ（１モ
ル）を入れ，モノクロロ酢酸１．０ｇを加えて，７０℃
に維持し，窒素ガスを導入しながら３０分間かきまぜ
る。続いて，反応温度を７０℃に保ち，塩素ガスを毎時
0.25モルの割合で４時間吹き込んで反応させる。反応終
了後，得られた反応生成物を，ガスクロマトグラフィー
により分析したところ，トルエンの反応率98.3％，Ｏ−
クロロトルエン／Ｐ−クロロトルエン生成比（以下o/p
と略す）0.262であった。Example 1 200 m equipped with a cooling pipe, a thermometer, an agitator and a blowing pipe
L type zeolite (Toyo Soda Co., Ltd.)
Co., Ltd., trade name TSZ-506) 5g and toluene 92.1g (1mol) put, monochloroacetic acid 1.0g added, 70 ℃
Stir for 30 minutes while introducing nitrogen gas. Then, keep the reaction temperature at 70 ° C and add chlorine gas every hour.
Blow for 4 hours at a rate of 0.25 mol to react. After completion of the reaction, the obtained reaction product was analyzed by gas chromatography to find that the reaction rate of toluene was 98.3%, O-
Chlorotoluene / P-chlorotoluene production ratio (hereinafter o / p
It was 0.262.
実施例２ モノクロロ酢酸の添加量を0.25ｇとする以外は実施例１
と同様の実験を繰り返したところ，トルエンの反応率は
95.3％，o/p比は0.269であった。Example 2 Example 1 except that the addition amount of monochloroacetic acid was 0.25 g.
When the same experiment was repeated, the reaction rate of toluene was
The ratio was 95.3% and the o / p ratio was 0.269.
実施例３ モノクロロ酢酸の代りに種々の異なったハロゲン置換又
は無置換の低級脂肪族カルボン酸を用い，ゼオライトの
処理温度及び反応時間を50℃又は70℃にした以外は実施
例１と同様にしてハロゲン化を行った。その結果を第１
表に示す。Example 3 Similar to Example 1, except that various different halogen-substituted or unsubstituted lower aliphatic carboxylic acids were used instead of monochloroacetic acid, and the treatment temperature and reaction time of the zeolite were 50 ° C. or 70 ° C. Halogenated. The result is first
Shown in the table.
なお，比較のために，無処理ゼオライト及び安息香酸で
処理したゼオライトを用いた場合の結果も併記した。For comparison, the results of using untreated zeolite and zeolite treated with benzoic acid are also shown.
実施例４ 原料としてトルエンの代りにクロロベンゼン112.6ｇ
（１モル）を用い，モノクロロ酢酸の代りにジクロロ酢
酸を用い反応時間を５時間に代えた以外は実施例１と同
様にハロゲン化を行った。その結果，クロロベンゼンの
反応率90.5％，Ｏ−ジクロロベンゼン／Ｐ−ジクロロベ
ンゼン生成比は0.071であった。 Example 4 Chlorobenzene 112.6 g instead of toluene as a raw material
Halogenation was carried out in the same manner as in Example 1 except that (1 mol) was used and dichloroacetic acid was used instead of monochloroacetic acid and the reaction time was changed to 5 hours. As a result, the reaction rate of chlorobenzene was 90.5% and the O-dichlorobenzene / P-dichlorobenzene production ratio was 0.071.
実施例５ Ｌ型ゼオライトの代りにＹ型ゼオライト（米国ユニオン
カーバイド社製，商品名LZ-Y82）を用い，原料としてト
ルエンの代りにアニソール108.1ｇ（１モル）を用い，
モノクロロ酢酸の代りにジフルオロ酢酸を用いた以外は
実施例１と同様にハロゲン化を行った。その結果，アニ
ソールの反応率91.5％，Ｏ−クロロアニソール／Ｐ−ク
ロロアニソール生成比0.218であった。Example 5 Y-type zeolite (manufactured by Union Carbide, USA, trade name LZ-Y82) was used in place of L-type zeolite, and 108.1 g (1 mol) of anisole was used as a raw material in place of toluene.
Halogenation was carried out in the same manner as in Example 1 except that difluoroacetic acid was used instead of monochloroacetic acid. As a result, the reaction rate of anisole was 91.5% and the O-chloroanisole / P-chloroanisole production ratio was 0.218.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 43/225 Ｂ 8619−4Ｈ // Ｂ０１Ｊ 29/06 Ｘ 9343−4Ｇ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI technical display location C07C 43/225 B 8619-4H // B01J 29/06 X 9343-4G C07B 61/00 300
Claims (1)
ロゲン原子である。） で表わされる核置換ベンゼン類を液相でハロゲン化し
て，一般式 （式中のＲは前記と同じ意味を持ち，Ｘはハロゲン原子
である。） で表わされるハロゲン化ベンゼン類を製造するに当り，
触媒としてハロゲン置換又は無置換の低級脂肪族カルボ
ン酸で処理した，ＳｉＯ2／Ａｌ2Ｏ3モル比３〜８，細
孔径６〜１０Åのゼオライトを用いることを特徴とする
ハロゲン化核置換ベンゼン類の製造方法。1. A general formula in the presence of a catalyst (R in the formula is a lower alkyl group, a lower alkoxy group or a halogen atom.) A halogenated nucleus-substituted benzene represented by the general formula: (Wherein R has the same meaning as described above, and X is a halogen atom.)
Halogenated nucleus-substituted benzenes characterized by using a zeolite having a SiO 2 / Al 2 O 3 molar ratio of 3 to 8 and a pore diameter of 6 to 10 Å treated with a halogen-substituted or unsubstituted lower aliphatic carboxylic acid as a catalyst Manufacturing method.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59052953A JPH0627079B2 (en) | 1984-03-19 | 1984-03-19 | Method for producing halogenated benzenes |
| EP85101707A EP0154236B1 (en) | 1984-03-07 | 1985-02-15 | Process for producing a halobenzene |
| DE8585101707T DE3561389D1 (en) | 1984-03-07 | 1985-02-15 | Process for producing a halobenzene |
| CA000474550A CA1262920A (en) | 1984-03-07 | 1985-02-18 | Process for producing a halobenzene |
| KR1019850001359A KR900003295B1 (en) | 1984-03-07 | 1985-03-05 | Process for producing a halobenzene |
| US07/057,650 US4831199A (en) | 1984-03-07 | 1987-06-09 | Process for producing a halobenzene |
| US07/323,845 US4942268A (en) | 1984-03-07 | 1989-03-15 | Process for producing a halobenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59052953A JPH0627079B2 (en) | 1984-03-19 | 1984-03-19 | Method for producing halogenated benzenes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60197632A JPS60197632A (en) | 1985-10-07 |
| JPH0627079B2 true JPH0627079B2 (en) | 1994-04-13 |
Family
ID=12929238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59052953A Expired - Lifetime JPH0627079B2 (en) | 1984-03-07 | 1984-03-19 | Method for producing halogenated benzenes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0627079B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2598581B2 (en) * | 1991-06-17 | 1997-04-09 | 株式会社トクヤマ | Method for producing aromatic halide |
-
1984
- 1984-03-19 JP JP59052953A patent/JPH0627079B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60197632A (en) | 1985-10-07 |
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