JPS5810534A - Preparation of benzophenone derivative - Google Patents
Preparation of benzophenone derivativeInfo
- Publication number
- JPS5810534A JPS5810534A JP56107596A JP10759681A JPS5810534A JP S5810534 A JPS5810534 A JP S5810534A JP 56107596 A JP56107596 A JP 56107596A JP 10759681 A JP10759681 A JP 10759681A JP S5810534 A JPS5810534 A JP S5810534A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- heteropolyacid
- catalyst
- acid halide
- 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.)
- Granted
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はベンゾフェノン誘導体を効率良く製造する方法
忙関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for efficiently producing benzophenone derivatives.
ベンゾフェノン誘導体は医薬原料、プラスチック添加剤
(紫外線吸収剤)、農薬原料、各種合成用中間体などと
して、有用である。このベンゾフェノン誘導体の製造法
として従来一般的には塩化アルミニウム触媒を用いるフ
リーデル−クラ7ツ型反応による方法が採用されている
。このような例としては、2−クロロベンゾイルクロラ
イドとクロロベンゼンとを塩化アルミニウムの存在下で
反応させて2.4′−ジクロロベンゾフェノンを製造す
る方法がある。Benzophenone derivatives are useful as pharmaceutical raw materials, plastic additives (ultraviolet absorbers), agricultural chemical raw materials, various synthetic intermediates, and the like. Conventionally, as a method for producing this benzophenone derivative, a Friedel-Kraz type reaction using an aluminum chloride catalyst has been generally adopted. An example of this is the production of 2,4'-dichlorobenzophenone by reacting 2-chlorobenzoyl chloride and chlorobenzene in the presence of aluminum chloride.
しかしながら、この塩化アルミニウムを触媒として用い
るフリーデル−クラ7ツ型反応においては、所定の収率
を得るためには、原料基質に対して当量以上の塩化アル
ミニウムを必要とし、そのため多量の塩化アルミニウム
を使用して行うので反応の操作が困難となシ好ましくな
かった。また、使用された多量の塩化アルミニウム触媒
が回収されず、水溶液として廃水中に流出することがあ
り、それが加水分解により塩酸を生成するので、廃水公
害を拡げる一因となっていた。However, in this Friedel-Kraz type reaction using aluminum chloride as a catalyst, in order to obtain a predetermined yield, aluminum chloride is required in an amount equal to or more than the raw material substrate, and therefore a large amount of aluminum chloride is required. This was not preferable because it was difficult to operate the reaction. In addition, a large amount of the aluminum chloride catalyst used is not recovered and sometimes flows out into wastewater as an aqueous solution, which generates hydrochloric acid through hydrolysis, contributing to the spread of wastewater pollution.
本発明者らは、このような塩化アルミニウム触媒を用い
るフリーデル−クラフッ型反応によるベンゾフェノン誘
導体の製造法の欠点を克服するため種々検討を重ねた結
果、安息香酸類の酸ハロゲン化物とベンゼン誘導体を反
応させてベンゾフェノン誘導体を製造するに当り、塩化
アルミニウムの代りに特定のへテロポリ酸化合物を所定
量用いることにより、好収率でベンゾフェノン誘導体を
製造することができ、上記の目的を満足し得ることを見
出した。本発明はこの知見に基づき完成されるに至った
ものである。The present inventors have conducted various studies to overcome the drawbacks of the method for producing benzophenone derivatives by the Friedel-Krach type reaction using an aluminum chloride catalyst, and as a result, we have developed a method for reacting acid halides of benzoic acids with benzene derivatives. By using a specific amount of a specific heteropolyacid compound in place of aluminum chloride in producing benzophenone derivatives, benzophenone derivatives can be produced in good yields and the above objectives can be satisfied. I found it. The present invention has been completed based on this knowledge.
すなわち本発明は、安息香酸類の酸ハロゲン化物とベン
ゼン誘導体とを反応させるに当り、一般式
%式%(1)
(式中、XはOもしくは1〜12の整数を示す)で表わ
されるヘテロポリ酸の存在下で反応を行うことを特徴と
するベンゾフェノン誘導体の装造方法を提供するもので
ある。That is, in the present invention, when reacting an acid halide of benzoic acids with a benzene derivative, a heteropolyacid represented by the general formula % (1) (wherein X represents O or an integer from 1 to 12) is used. The present invention provides a method for preparing benzophenone derivatives, characterized in that the reaction is carried out in the presence of.
本発明の方法に用いられる上記一般式(I)で表わされ
るヘテロポリ酸触媒の中でH3PMo1204g。Among the heteropolyacid catalysts represented by the above general formula (I) used in the method of the present invention, 1204 g of H3PMo.
H5PMo 1 oV204os H4PMo 1 、
VO46s H6PMogV3040が特に好ましいも
のとしてあげられる。H5PMo 1 oV204os H4PMo 1 ,
VO46s H6PMogV3040 is particularly preferred.
ヘテロポリ酸の合成法は一般に公知であり、水溶液中で
原料オキシ酸を縮合させることにより合成できる(例え
ば「触媒J 23 (2)、昭和56年5月11日 p
178〜179参照)。本発明方法に用いられる触媒は
、この方法に準じて製造することができる。The method for synthesizing heteropolyacids is generally known, and can be synthesized by condensing raw oxyacids in an aqueous solution (for example, "Catalyst J 23 (2), May 11, 1980, p.
178-179). The catalyst used in the method of the present invention can be produced according to this method.
しかし、このようにして合成されたヘテロポリ酸は通常
、1分子中VC20〜30分子の結晶水を有しているの
で、本発明方法においてはこれを除く必要がある。この
結晶水の除去はへテロポリ酸の室温での真空排気及び、
700℃までの温度範囲での焼成により行うことができ
る。好ましい焼成条件は250〜500℃で2〜4時間
の範囲である。この結晶水の除去が十分でないと原料の
酸ハロゲン化物が容易に加水分解を受けて安息香酸とな
り、収率低下の原因となる。However, since the heteropolyacid synthesized in this manner usually has water of crystallization with a VC of 20 to 30 molecules per molecule, it is necessary to remove this water in the method of the present invention. This water of crystallization is removed by evacuation of the heteropolyacid at room temperature and
This can be done by firing at a temperature range up to 700°C. Preferred firing conditions range from 250 to 500°C for 2 to 4 hours. If this water of crystallization is not removed sufficiently, the acid halide as a raw material is easily hydrolyzed to benzoic acid, causing a decrease in yield.
なお、このヘテロポリ酸触媒は、必要に応じ、通常の触
媒担体、例えば活性炭、シリカ、ケイソウ土などに担持
させて用いることができる。Note that this heteropolyacid catalyst can be used by being supported on a common catalyst carrier such as activated carbon, silica, diatomaceous earth, etc., if necessary.
本発明方法は、このヘテロポリ酸触媒の存在下で安息香
酸類の酸ハロゲン化物とベンゼン誘導体とを反応させる
ことにより行われる。The method of the present invention is carried out by reacting an acid halide of benzoic acids with a benzene derivative in the presence of this heteropolyacid catalyst.
安息香酸類の酸ハロゲン化物としては、一般式(式中、
Yはハロゲン原子又は低級アルキル基を示し、Xはハロ
ゲン原子を示す)
で表わされるものが用いられる。その例としては、ベン
ゾイルクロライド、2−クロロベンゾイルクロライド、
4−クロロベンゾイルクロライド、p−トルオイルクロ
ライドなどがあげられるがこれに限定されない。As acid halides of benzoic acids, the general formula (in the formula,
Y represents a halogen atom or a lower alkyl group, and X represents a halogen atom). Examples include benzoyl chloride, 2-chlorobenzoyl chloride,
Examples include, but are not limited to, 4-chlorobenzoyl chloride and p-toluoyl chloride.
一方、ベンゼン誘導体としては、一般式(式中、2は水
素原子又はハロゲン原子を示す)で表わされるものが用
いられる。On the other hand, as the benzene derivative, those represented by the general formula (in the formula, 2 represents a hydrogen atom or a halogen atom) are used.
この安息香酸類の酸ハロゲン化物とベンゼン誘導体のモ
ル比/fi1:2〜3の範囲が好ましい。この範囲を外
れてベンゼン誘導体の量が少なすぎると生成物が着色す
る傾向を示し、また多すぎると反応速度が低下する、容
積効率が低下するなどの支障があられれる。The molar ratio of the acid halide of benzoic acids to the benzene derivative/fi1: is preferably in the range of 2 to 3. If the amount of the benzene derivative is too small outside this range, the product tends to be colored, and if it is too large, problems such as a decrease in reaction rate and a decrease in volumetric efficiency may occur.
本発明方法において、上記のへテロポリ酸触媒の使用量
は安息香酸類の酸ハロゲン化物に対して、通常1〜20
重量%、好ましくは5〜10重量%の範囲である。触媒
の量が上記範囲の上限を越えると触媒の脱水が不完全の
場合、酸ハロゲン化物が加水分解を受けるため収率が低
下し、下限より少量では、反応速度が遅くなる。In the method of the present invention, the amount of the heteropolyacid catalyst used is usually 1 to 20% based on the acid halide of benzoic acids.
% by weight, preferably in the range 5-10% by weight. If the amount of the catalyst exceeds the upper limit of the above range, the acid halide will undergo hydrolysis if the catalyst is incompletely dehydrated, resulting in a decrease in yield, and if the amount is less than the lower limit, the reaction rate will slow down.
本発明方法において、反応温度は130〜190℃が好
ましい。この範囲を外れると高温では異性体の副生量お
よび酸ハロゲン化物の分解量がともに増加し、低温では
反応速度が著しく遅くなる。In the method of the present invention, the reaction temperature is preferably 130 to 190°C. Outside this range, at high temperatures both the amount of by-products of isomers and the amount of decomposed acid halides increase, and at low temperatures the reaction rate becomes significantly slow.
また、反応圧力は通常常圧から加圧条件下まで任意に選
ぶことができるが、常圧〜50 Kg/all Gの範
囲が好ましい。あまり圧力が高すぎると装置の建設費が
高くなシ実際的でない。圧力が低すぎると反応速度が遅
くなる。Further, the reaction pressure can be arbitrarily selected from normal pressure to pressurized conditions, but is preferably in the range of normal pressure to 50 Kg/all G. If the pressure is too high, the construction cost of the device will be high and it is not practical. If the pressure is too low, the reaction rate will be slow.
本発明方法は、工業的には前記のように、ベンゼン誘導
体を過剰として無溶媒で行ってもよく、また、実験室的
にはヘキサン、二硫化炭素及び、ニトロベンゼンのよう
な溶媒中で行ってもよい。Industrially, the method of the present invention may be carried out without a solvent using an excess of the benzene derivative as described above, and in the laboratory, it may be carried out in a solvent such as hexane, carbon disulfide, or nitrobenzene. Good too.
本発明方法においては、安息香酸の酸・・ロゲン化物と
ベンゼン誘導体が反応して目的のベンゾフェノン誘導体
が得られる。このものは、主に、ベンゼン誘導体の前記
一般式の2に対し、p−位にベンゾイル基が結合したも
のからなる。In the method of the present invention, the acid chloride of benzoic acid reacts with a benzene derivative to obtain the desired benzophenone derivative. This product mainly consists of a benzene derivative having a benzoyl group bonded to the p-position of 2 in the above general formula.
この反応生成物の分離精製は、未反応の原料を減圧留去
したのち、触媒をろ過、水洗などにより適宜分離し、次
いでアルコールで再結晶を行うことにより容易に達成で
きる。Separation and purification of this reaction product can be easily achieved by distilling off unreacted raw materials under reduced pressure, separating the catalyst as appropriate by filtration, washing with water, etc., and then recrystallizing it with alcohol.
本発明方法によれば、塩化アルミニウムのように多量を
用いなくても、ヘテロポリ酸触媒を少量用いることKよ
り、好収率でベンゾフェノン誘導体を得ることができる
という優れた利点を有する。The method of the present invention has the excellent advantage that a benzophenone derivative can be obtained in a better yield without using a large amount of aluminum chloride than by using a small amount of a heteropolyacid catalyst.
しかも、本発明の場合、触媒は、水で分解するようなこ
とがなく、回収、再利用が極めて容易である。本発明方
法は工業的に実施するのに好適である0
次に本発明方法を実施例に基づきさらに詳細に説明する
。Furthermore, in the case of the present invention, the catalyst does not decompose with water and is extremely easy to recover and reuse. The method of the present invention is suitable for industrial implementation. Next, the method of the present invention will be explained in more detail based on Examples.
実施例1
300mt容のオートクレーブに2−クロロベンゾイル
クロライド50.0 g (286mmot)、りoo
ベンゼン100.0 g (888mmot)及び触媒
として空気中で350℃にて3時間焼成したH3PMO
120400,5〜5 gを仕込み、オートクレーブ内
を窒素で置換後、170℃まで加熱しこの温度で5時間
反応させた。反応終了後オートクレーブ内の圧力は第1
表に示すように9〜25に9/cdGまで昇圧していた
。Example 1 50.0 g (286 mmot) of 2-chlorobenzoyl chloride was placed in a 300 mt autoclave.
100.0 g (888 mmot) of benzene and H3PMO calcined in air at 350 °C for 3 hours as catalyst
After charging 5 to 5 g of 120400, the inside of the autoclave was purged with nitrogen, heated to 170°C, and reacted at this temperature for 5 hours. After the reaction is complete, the pressure inside the autoclave is
As shown in the table, the pressure was increased to 9/cdG from 9 to 25.
反応終了後反応液をガスクロマトグラフィーで分析した
ところ、2.4’−ジクロロベンゾフェノンが高選択率
かつ好収率で生成していることがわかった。この結果を
第1表に示す。After the reaction was completed, the reaction solution was analyzed by gas chromatography, and it was found that 2,4'-dichlorobenzophenone was produced with high selectivity and good yield. The results are shown in Table 1.
実施例2
実施例1と同様のオートクレーブに2−クロロベンゾイ
ルクロライド50.0 g (286mmot)、クロ
ロベンゼン100.0 g (888mmot)及び実
施例1と同様の触媒5gを仕込み、オートクレ−プ内を
窒素で置換後反応圧力を2 s ”q/ct aまで昇
圧し、反応温度を130〜190℃の範囲で変えて反応
を開始し5時間反応を行った。反応終了後、反応液をガ
スクロマトグラフィーで分析した。その結果を第2表に
示す。Example 2 50.0 g (286 mmot) of 2-chlorobenzoyl chloride, 100.0 g (888 mmot) of chlorobenzene, and 5 g of the same catalyst as in Example 1 were placed in an autoclave similar to that in Example 1, and the inside of the autoclave was flushed with nitrogen. After the substitution, the reaction pressure was increased to 2 s"q/cta, and the reaction temperature was varied in the range of 130 to 190°C to start the reaction, and the reaction was carried out for 5 hours. After the reaction was completed, the reaction solution was subjected to gas chromatography. The results are shown in Table 2.
実施例3
攪拌機、温度計及び還流冷却器を備えた100mt容の
フラスコに2−クロロベンゾイルクロライド2 s、o
g (143mmot)、クロロベンゼン46.5
g (413mmot)及び空気中300℃で3時間焼
成したH3PMo 1(IV204 (12,5gを仕
込み135℃にて、10時間、還流下で反応させた。Example 3 In a 100 mt flask equipped with a stirrer, thermometer and reflux condenser was added 2 s, o of 2-chlorobenzoyl chloride.
g (143 mmot), chlorobenzene 46.5
g (413 mmot) and H3PMo 1 (IV204 (12.5 g) calcined in air at 300° C. for 3 hours were charged and reacted at 135° C. for 10 hours under reflux.
反応終了後、反応液をガスクロマトグラフィーで分析し
たところ、仕込んだ2−クロロベンゾイルクロライドに
対するジクロロベンゾフェノンの収率は45,9%であ
シ、その組成は、2.4’−ジクロロベンゾフェノン8
9.4 ess 2 + 2’ yクロロベンゾフ
ェノン10.6%、 4.4’−ジクロロベンゾフェノ
ン0.4%であった。After the reaction was completed, the reaction solution was analyzed by gas chromatography, and the yield of dichlorobenzophenone based on the charged 2-chlorobenzoyl chloride was 45.9%, and its composition was 2.4'-dichlorobenzophenone 8.
9.4 ess 2 + 2'ychlorobenzophenone 10.6%, 4.4'-dichlorobenzophenone 0.4%.
特許出願人 フクデイハラケミカル株式会社に!A *
fi¥ つ61ゴ・−・声、グPatent applicant: Fukudayhara Chemical Co., Ltd.! A*
fi¥ Tsu61 Go--Voice, Gu
Claims (1)
を反応させるに当り、一般式 %式%(1) (式中、Xは0もしくは1〜12の整数を示す) で表わされるヘテロポリ酸の存在下で反応を行うことを
特徴とするベンゾフェノン誘導体の製造方法。(1) When reacting acid halides of benzoic acids with benzene derivatives, the presence of a heteropolyacid represented by the general formula % (1) (wherein, X represents 0 or an integer from 1 to 12) 1. A method for producing a benzophenone derivative, comprising carrying out the reaction below.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56107596A JPS5810534A (en) | 1981-07-11 | 1981-07-11 | Preparation of benzophenone derivative |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP56107596A JPS5810534A (en) | 1981-07-11 | 1981-07-11 | Preparation of benzophenone derivative |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5810534A true JPS5810534A (en) | 1983-01-21 |
JPH021822B2 JPH021822B2 (en) | 1990-01-12 |
Family
ID=14463162
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP56107596A Granted JPS5810534A (en) | 1981-07-11 | 1981-07-11 | Preparation of benzophenone derivative |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5810534A (en) |
-
1981
- 1981-07-11 JP JP56107596A patent/JPS5810534A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH021822B2 (en) | 1990-01-12 |
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