JPS58126830A - Preparation of 3-hydroxyacetophenone - Google Patents
Preparation of 3-hydroxyacetophenoneInfo
- Publication number
- JPS58126830A JPS58126830A JP57008264A JP826482A JPS58126830A JP S58126830 A JPS58126830 A JP S58126830A JP 57008264 A JP57008264 A JP 57008264A JP 826482 A JP826482 A JP 826482A JP S58126830 A JPS58126830 A JP S58126830A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- isopropylacetophenone
- hydroxyacetophenone
- present
- acetylcumyl
- 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
- Low-Molecular Organic Synthesis Reactions Using 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３−ヒドロキシアセトフェノンの新規な製造方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 3-hydroxyacetophenone.
本発明方法によって製造される３−ヒドロキシアセトフ
ェノンは、医薬、農薬、染料等の合成出発原料として極
めて重要な物質である。しかしながら、従来、３−ヒド
ロキシアセトフェノンは極めて複雑な多段階の反応によ
って製造され、その製造方法は工業的に有利な方法とは
云えなかった。3-Hydroxyacetophenone produced by the method of the present invention is an extremely important substance as a starting material for the synthesis of medicines, agricultural chemicals, dyes, and the like. However, 3-hydroxyacetophenone has conventionally been produced by an extremely complicated multi-step reaction, and the production method cannot be said to be industrially advantageous.
即ち、従来法は、
（１）アセトフェノンのニトロ化反応、（２）還元反応
によるアミノ化、
（３）ジアゾ化、
（４）酸性処理分解による３−ヒドロキシ化、という四
段階反応によるものであった。That is, the conventional method involves a four-step reaction: (1) nitration reaction of acetophenone, (2) amination by reduction reaction, (3) diazotization, and (4) 3-hydroxylation by acidic treatment and decomposition. Ta.
従って、本発明の目的は、このような従来の３−ヒドロ
キシアセトフェノンの複雑な製造方法の問題点を解決し
、極めて簡単で短い反応過程により３−ヒドロキシアセ
トフェノンを効果的に製造する方法を提供することにあ
る。Therefore, an object of the present invention is to solve the problems of the conventional complicated production method of 3-hydroxyacetophenone and to provide a method for effectively producing 3-hydroxyacetophenone through an extremely simple and short reaction process. There is a particular thing.
本発明に従った３−ヒドロキシアセトフェノンの製造方
法は、３−イソプロピルアセトフェノンを不活性溶媒中
又は無溶媒で、パーオキサイド触媒の存在下に酸化反応
させ、一旦３−アセチルクミルハイドロパーオキサイド
を生成させ、更に酸性処理分解することから成る。The method for producing 3-hydroxyacetophenone according to the present invention involves oxidizing 3-isopropylacetophenone in an inert solvent or without a solvent in the presence of a peroxide catalyst to once produce 3-acetylcumyl hydroperoxide. The process consists of decomposition and further decomposition by acid treatment.
本発明の出発原料である３−イソプロピルアセトフェノ
ンは、アセトフェノンとプロピレン又はイソプロピルハ
ライドをフリーデルタラット触媒、例えば塩化アルミ等
を使って反応させることにより、比較的容品に合成する
ことができる。この場合に、反応転化率を上げ過ぎると
、３．５−ジイソプロピルアセトフェノンの副生量が増
大スるが、これも反応系へ戻して循環使用することによ
って再び３−イソプロピルアセトフェノンに返すことが
できる。3-isopropylacetophenone, which is the starting material of the present invention, can be synthesized in a relatively simple manner by reacting acetophenone with propylene or isopropyl halide using a free delta rat catalyst such as aluminum chloride. In this case, if the reaction conversion rate is increased too much, the amount of by-product 3,5-diisopropylacetophenone will increase, but this can also be returned to 3-isopropylacetophenone by returning it to the reaction system and recycling it. .
本発明方法において使用することができるパーオキサイ
ド触媒は多数あるが、その代表的なものを、分解温度と
共に、以下の第１表にかかげる。There are many peroxide catalysts that can be used in the method of the present invention, and representative ones are listed in Table 1 below, along with their decomposition temperatures.
以下余白
本発明方法の反応過程は、次の通りであり、この反応式
から本発明方法が極めて簡単な反応であることが明らか
であろう。The reaction process of the method of the present invention is as follows, and it is clear from this reaction formula that the method of the present invention is an extremely simple reaction.
本発明方法における酸化反応温度は、使用するパーオキ
サイドの種類によって異なるが、第１表に示した分解温
度よりも若干低い温度を選んだ方が反応の選択率が高く
なるので好ましい。例えば、アゾビスイソブチロニトリ
ルの場合は６０’Ｃないし７０℃が適当であり、ジクミ
ルパーオキサイドを使用するばあいには９０℃前後の反
応温度が好、ましい。The oxidation reaction temperature in the method of the present invention varies depending on the type of peroxide used, but it is preferable to select a temperature slightly lower than the decomposition temperature shown in Table 1 because the selectivity of the reaction will be higher. For example, in the case of azobisisobutyronitrile, a reaction temperature of 60'C to 70°C is suitable, and when dicumyl peroxide is used, a reaction temperature of around 90°C is preferred.
一般的にいえば、本発明方法における酸化反応温度は５
０℃ないし２００℃の範囲内に選定するのが好ましい。Generally speaking, the oxidation reaction temperature in the method of the present invention is 5
It is preferable to select the temperature within the range of 0°C to 200°C.
換言すれば、この範囲内の温度で反応を進行させると、
反応転化率を５０％以内に制御することが容易になる。In other words, if the reaction proceeds at a temperature within this range,
It becomes easy to control the reaction conversion rate within 50%.
転化率が５０％を超えると、副反応の進行する割合が増
大し、特に原料アセトフェノンのアセチル基が攻撃を受
け、選択率が低下する傾向にある。When the conversion rate exceeds 50%, the rate at which side reactions proceed increases, and in particular, the acetyl group of the raw material acetophenone is attacked, and the selectivity tends to decrease.
本発明方法においては、温度を加えるだけでなく、紫外
線を照射することによっても反応を容易に促進させるこ
とができる。特に触媒としてジ−ｔ−ブチルパーオキサ
イド及びアゾビスイソブチロニトリル等を使用した場合
に、紫外線照射の効果が著しい。紫外線照射を併用した
場合には、触媒としてはパーオキサイド類だけでなく、
ベンゾフェノン等のケトン類も有効になってくる。In the method of the present invention, the reaction can be easily promoted not only by applying temperature but also by irradiating with ultraviolet rays. In particular, when di-t-butyl peroxide, azobisisobutyronitrile, or the like is used as a catalyst, the effect of ultraviolet irradiation is remarkable. When UV irradiation is used together, not only peroxides can be used as catalysts, but also
Ketones such as benzophenone are also effective.
本発明方法における酸化反応は不活性溶媒又は無溶媒で
実施できる。The oxidation reaction in the method of the present invention can be carried out in an inert solvent or without a solvent.
本発明方法において使用することができる不活性溶媒と
しては、例えばシクロヘキサン、シクロヘキセン、ベン
ゼン、クロロベンゼン、ニトロベンゼン、アセトニトリ
ル、トリエチルアミン、Ｎ。Inert solvents that can be used in the process of the invention include, for example, cyclohexane, cyclohexene, benzene, chlorobenzene, nitrobenzene, acetonitrile, triethylamine, N.
Ｎ−ジメチルアニリン、テトラヒドロフラン、ｔ−ブチ
ルアルコール、ｔ−アミルアルコール、安息香酸エチル
及び酢酸などが好ましい。Preferred are N-dimethylaniline, tetrahydrofuran, t-butyl alcohol, t-amyl alcohol, ethyl benzoate and acetic acid.
本発明方法の酸化反応の補助材料である酸素は、純粋な
酸素ガスとして供給してもよく、また空気そのままで使
用してもよい。反応の圧力は常圧ないし加圧下であって
もよいが、２０気圧以上に加圧しても特に反応選択率が
そのために向上することはない。Oxygen, which is an auxiliary material for the oxidation reaction in the method of the present invention, may be supplied as pure oxygen gas, or may be used as air. The reaction pressure may be normal pressure or elevated pressure, but even if the pressure is increased to 20 atmospheres or more, the reaction selectivity will not be particularly improved.
この酸化反応の特徴は、反応転化率を適正に制御すれば
、はとんど定量的に酸素を吸収することである。この事
実もまた本発明方法の反応選択性が極めて高いことを示
している。A feature of this oxidation reaction is that if the conversion rate of the reaction is properly controlled, oxygen can be absorbed almost quantitatively. This fact also shows that the reaction selectivity of the method of the present invention is extremely high.
本発明方法における酸化反応によって生成した純度の高
い３−アセチルクミルハイドロパーオキサイドは、酸性
雰囲気下において極めて容易に分解し、目的とする３−
ヒドロキシアセトフェノン及びアセトンを生成する。The highly pure 3-acetylcumyl hydroperoxide produced by the oxidation reaction in the method of the present invention is extremely easily decomposed in an acidic atmosphere, and the desired 3-acetyl cumyl hydroperoxide is
Produces hydroxyacetophenone and acetone.
この酸性処理に使用する酸は、例えば塩酸、硫酸、硝酸
及びリン酸等の一般的な無機酸でよい。The acids used in this acidic treatment may be common inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
このような酸性水溶液の中に酸化反応系全体を投入し攪
拌することによって３−アセチルクミルハイドロパーオ
キサイドは分解反応を行なうが、その際反応系の親水性
を増すために、アルコールを添加してもよく、また適切
な乳化剤を使用してもよい。By pouring the entire oxidation reaction system into such an acidic aqueous solution and stirring, 3-acetylcumyl hydroperoxide undergoes a decomposition reaction. At this time, alcohol is added to increase the hydrophilicity of the reaction system. Also, suitable emulsifiers may be used.
酸性の程度、即ちｐＨは、３ないしｌの範囲が好ましい
、高い温度のもとであまり強い酸性にすると、生成した
３−ヒドロキシアセトフェノンの一部がアルドール縮合
により、三量化することがあるので注意が必要である。The degree of acidity, that is, the pH, is preferably in the range of 3 to 1. Be careful, if the acidity is too strong at high temperatures, a part of the generated 3-hydroxyacetophenone may be trimerized by aldol condensation. is necessary.
上記、酸性処理分解反応はほとんど定量的に進行する。The above acidic treatment decomposition reaction proceeds almost quantitatively.
以上、本発明の内容を詳細に説明して来たが、更に本発
明の特徴を明確にするために、以下に実層側を示し、本
発明の製造方法を更に具体的に説明する。しかしながら
、本発明の範囲をこれらの実施例に限定するもの−でな
いことはいうまでもない。The contents of the present invention have been explained in detail above, but in order to further clarify the features of the present invention, the actual layer side will be shown below and the manufacturing method of the present invention will be explained in more detail. However, it goes without saying that the scope of the present invention is not limited to these examples.
実施例１
容１２５０ ｍ ｌのフラスコに攪拌機を取り付け、内
部を完全に酸素置換しシールする。このフラスコ中に０
．１８モルの３−イソプロピルアセトフェノンと１００
ｍ１のクロルベンゼンを装入し、０、００７５モルのア
ゾビスイソブチロニトリルを添加し、十分に攪拌しなが
ら、反応を６５℃に保ち５時間反応させた。この間に０
．０４７モルの酸素を吸収した。反応終了後、塩酸でρ
旧、５に調整したＩＡの酸性水溶液中に、上で得られた
反応液を投入し、乳化状態になるまで激しく攪拌し、約
１時間分解させた。Example 1 A flask with a volume of 1250 ml is equipped with a stirrer, the inside of the flask is completely replaced with oxygen, and the flask is sealed. 0 in this flask
．． 18 moles of 3-isopropylacetophenone and 100
ml of chlorobenzene was charged, 0,0075 mol of azobisisobutyronitrile was added, and the reaction was maintained at 65° C. for 5 hours with thorough stirring. During this time 0
．． 047 moles of oxygen were absorbed. After the reaction is complete, remove ρ with hydrochloric acid.
The reaction solution obtained above was poured into an acidic aqueous solution of IA that had been adjusted to a concentration of 5, and was vigorously stirred until it became an emulsified state, and was allowed to decompose for about 1 hour.
分解終了後静置して二層分離させ、有機層をガスクロ分
析したところ、反応転化率は２６．１％であり、３−ヒ
ドロキシアセトフェノンの生成選択率は９５．７％であ
った。After the decomposition was completed, the mixture was allowed to stand to separate into two layers, and the organic layer was analyzed by gas chromatography. The reaction conversion rate was 26.1%, and the selectivity for 3-hydroxyacetophenone production was 95.7%.
実施例２〜５
パーオキサイド触媒及びその使用量、溶媒、反応温度並
びに反応時間を下記第２表に示すように変化させて実施
例１と同様の反応を実施した。Examples 2 to 5 Reactions similar to those in Example 1 were carried out by changing the peroxide catalyst, its usage amount, solvent, reaction temperature, and reaction time as shown in Table 2 below.
得られた結果を第２表に示す。The results obtained are shown in Table 2.
以下余白 声Margin below voice
Claims (2)
１ま無溶媒で、パーオキサイド触媒の存在下に酸化反応
させ、一旦３−アセチルクミルノ＼イドロバ−オキサイ
ドを生成させ、更に酸性処理分解することを特徴とする
３−ヒドロキシアセトフェノンを製造する方法。1. 3-isopropylacetophenone is subjected to an oxidation reaction in an inert solvent or without a solvent in the presence of a peroxide catalyst to once generate 3-acetylcumylhydrobar oxide, which is then further decomposed by acid treatment. A method for producing characterized 3-hydroxyacetophenone.
パーオキサイド触媒を０．０１モルないし０．５モルの
範囲で使用する特許請求の範囲第１項記載の製造方法。 ３、酸化反応の転化率を５０％以下に制御する特許請求
の範囲第１項記載の製造方法。2. For 1 mole of 3-isopropylacetophenone,
The manufacturing method according to claim 1, wherein the peroxide catalyst is used in an amount of 0.01 mol to 0.5 mol. 3. The manufacturing method according to claim 1, wherein the conversion rate of the oxidation reaction is controlled to 50% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57008264A JPS58126830A (en) | 1982-01-23 | 1982-01-23 | Preparation of 3-hydroxyacetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57008264A JPS58126830A (en) | 1982-01-23 | 1982-01-23 | Preparation of 3-hydroxyacetophenone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58126830A true JPS58126830A (en) | 1983-07-28 |
Family
ID=11688288
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57008264A Pending JPS58126830A (en) | 1982-01-23 | 1982-01-23 | Preparation of 3-hydroxyacetophenone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58126830A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0149176A2 (en) * | 1983-12-20 | 1985-07-24 | Sumitomo Chemical Company, Limited | Process for producing m-hydroxyacetophenone |
-
1982
- 1982-01-23 JP JP57008264A patent/JPS58126830A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0149176A2 (en) * | 1983-12-20 | 1985-07-24 | Sumitomo Chemical Company, Limited | Process for producing m-hydroxyacetophenone |
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