JPH07580B2 - Quinone production method - Google Patents
Quinone production methodInfo
- Publication number
- JPH07580B2 JPH07580B2 JP5085397A JP8539793A JPH07580B2 JP H07580 B2 JPH07580 B2 JP H07580B2 JP 5085397 A JP5085397 A JP 5085397A JP 8539793 A JP8539793 A JP 8539793A JP H07580 B2 JPH07580 B2 JP H07580B2
- Authority
- JP
- Japan
- Prior art keywords
- quinone
- hydroquinone
- exchange resin
- type
- cation exchange
- 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.)
- Expired - Lifetime
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)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ナトリウム型陽イオン
交換体によるヒドロキノンのキノンへの酸化反応を利用
したキノンの製造方法に関するものである。さらに詳し
くいえば、本発明は陽イオン交換体を用いて簡単なプロ
セスで収率よくキノンを製造する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing quinone utilizing the oxidation reaction of hydroquinone to quinone by a sodium type cation exchanger. More specifically, the present invention relates to a method for producing quinone in high yield by a simple process using a cation exchanger.
【０００２】[0002]
【従来の技術】キノンは、各種有機合成工業分野におけ
る原料として用いられ、これまで、ジフェノール、アミ
ノフェノール、ジアミノベンゼンを酸化するか、あるい
はベンゼンを酸化することにより製造されている。2. Description of the Related Art Quinone is used as a raw material in various fields of organic synthesis industry, and has been produced by oxidizing diphenol, aminophenol, diaminobenzene or benzene.
【０００３】しかしながら、多くの副反応を伴うことに
より、収率が低い上に、副生物の分離に手間がかかるな
どの欠点があり、工業的に実施する上に、多くの課題を
抱えていた。[0003] However, since many side reactions are involved, there are drawbacks such as low yield and time-consuming separation of by-products, and there are many problems in industrial implementation. .
【０００４】[0004]
【発明が解決しようとする課題】本発明は、従来方法の
欠点を克服し、ヒドロキノンから、副生物を伴わずに高
収率でキノンを得ることができる工業的に実施可能な製
造方法を提供することを目的としてなされたものであ
る。DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of conventional methods and provides an industrially practicable production method capable of obtaining quinone from hydroquinone in high yield without by-products. It was made for the purpose of doing.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記の目
的を達成するために、種々研究を重ねた結果、ナトリウ
ム型陽イオン交換樹脂が有する酸化作用に着目し、これ
を用いればヒドロキノンからキノンを効率よく製造しう
ることを見出し、この知見に基づいて本発明をなすに至
った。Means for Solving the Problems As a result of various studies to achieve the above-mentioned object, the present inventors have paid attention to the oxidative action of a sodium cation exchange resin. Based on this finding, it was found that quinone can be produced efficiently, and the present invention has been completed based on this finding.
【０００６】すなわち、本発明はナトリウム型又は中性
塩型の陽イオン交換樹脂を充填したカラムあるいは中空
型の陽イオン交換樹脂膜中に水あるいは水‐有機溶媒か
らなる溶離液を連続的に流入させ、その上部にヒドロキ
ノンの一定量を注入してナトリウム型あるいは中性塩型
の陽イオン交換樹脂中の固定陽イオンによりヒドロキノ
ンを酸化させ、下部よりキノンを回収することを特徴と
するキノンの製造方法を提供するものである。That is, according to the present invention, water or an eluent composed of a water-organic solvent is continuously flowed into a column or a hollow type cation exchange resin membrane packed with a sodium type or neutral salt type cation exchange resin. The quinone is characterized by injecting a certain amount of hydroquinone into the upper part of the quinone and oxidizing the hydroquinone with a fixed cation in a sodium-type or neutral salt-type cation exchange resin, and recovering the quinone from the lower part. It provides a method.
【０００７】本発明方法で用いる陽イオン交換体は、ナ
トリウム型や中性塩型の陽イオン交換樹脂又はそのイオ
ン交換膜であるがこれらはいずれも通常市販されている
ものでよい。The cation exchanger used in the method of the present invention is a sodium type or neutral salt type cation exchange resin or an ion exchange membrane thereof, and any of these may be commercially available.
【０００８】本発明において陽イオン交換樹脂を用いた
場合には回分式操作により交換反応が行われるが、イオ
ン交換膜を用いると再生液により再生操作を同時に行い
得るので連続変換操作が可能になる。When a cation exchange resin is used in the present invention, the exchange reaction is carried out by a batch operation, but when an ion exchange membrane is used, the regeneration operation can be carried out at the same time by a regenerant, so that a continuous conversion operation becomes possible. .
【０００９】溶離液としては、水あるいは水‐有機溶媒
が用いられる。この場合の有機溶媒としてはアセトニト
リル、メチルアルコール、エチルアルコールなどが用い
られる。Water or a water-organic solvent is used as the eluent. As the organic solvent in this case, acetonitrile, methyl alcohol, ethyl alcohol or the like is used.
【００１０】[0010]
【発明の効果】本発明によると、キノンが、簡単なプロ
セスで収率よく製造することができ、有機合成における
中間工業原料の製造方法として好適である。INDUSTRIAL APPLICABILITY According to the present invention, quinone can be produced in high yield by a simple process and is suitable as a method for producing an intermediate industrial raw material in organic synthesis.
【００１１】[0011]
【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。EXAMPLES The present invention will be described in more detail with reference to examples.
【００１２】実施例１ 粒径５ミクロンのナトリウム型強酸性陽イオン交換樹脂
が充填された長さ２０ｃｍ、内径８ｍｍのプラスチック
カラムに定流量ポンプによって１ｍｌ／ｍｉｎの流量で
水あるいは１０％アセトニトリル‐水を流しておく。次
に、このカラムの上部に０．５ｍＭのヒドロキノンの
０．１ｍｌを６方弁方式の試料注入器を用いて注入し、
ヒドロキノンを中性塩（ナトリウム）型イオン交換樹脂
と接触させる。カラムからの溶出物はその直後に配置し
たフォトダイオードアレーを用いた紫外吸光検出器によ
って検出し、紫外吸収スペクトルを得る。Example 1 A plastic column having a length of 20 cm and an inner diameter of 8 mm packed with a sodium-type strongly acidic cation exchange resin having a particle size of 5 μm and water or 10% acetonitrile-water at a flow rate of 1 ml / min by a constant flow pump. Discharge. Next, 0.1 ml of 0.5 mM hydroquinone was injected into the upper part of the column using a 6-way valve type sample injector,
The hydroquinone is contacted with a neutral salt (sodium) type ion exchange resin. The eluate from the column is detected by an ultraviolet absorption detector using a photodiode array arranged immediately after that to obtain an ultraviolet absorption spectrum.
【００１３】カラムに注入する前のヒドロキノンは、図
１に示すように２２０及び２８９ｎｍで最大吸収波長を
示した。図２に示すようにカラムからの溶出液の紫外吸
収スペクトルはヒドロキノンのそれと明らかに異なり、
２４７ｎｍに吸収ピークを示した。したがって、イオン
交換樹脂との接触により、ヒドロキノンは類似の構造を
有する別の化合物に変化したことが推定されたので、図
３のキノンの標準液のスペクトルと比較したところ、両
者のスペクトルは完全に一致し、ヒドロキノンがイオン
交換樹脂の作用によりキノンに酸化されていることが明
らかとなった。Prior to injection into the column, hydroquinone exhibited maximum absorption wavelengths at 220 and 289 nm as shown in FIG. As shown in Fig. 2, the ultraviolet absorption spectrum of the eluate from the column was clearly different from that of hydroquinone,
It showed an absorption peak at 247 nm. Therefore, it was estimated that hydroquinone was changed to another compound having a similar structure by contact with the ion-exchange resin. Therefore, when compared with the spectrum of the quinone standard solution in FIG. 3, both spectra were completely In agreement, it was revealed that hydroquinone was oxidized to quinone by the action of the ion exchange resin.
【００１４】この例ではナトリウム型陽イオン交換樹脂
を充填したカラムを用いて回分式操作により変換反応を
進行させ、一定時間ごとに再生液として塩化ナトリウム
水溶液を用い、再生操作を行ったが、再生液として塩化
ナトリウム水溶液を用いて連続操作が可能な中空型の陽
イオン交換樹脂膜で行った場合も同じ結果が得られた。In this example, a conversion reaction was carried out by a batch operation using a column packed with a sodium type cation exchange resin, and a regenerating operation was carried out using an aqueous sodium chloride solution as a regenerating solution at regular intervals. The same result was obtained when a hollow cation exchange resin membrane capable of continuous operation was used with an aqueous solution of sodium chloride as the liquid.
【００１５】実施例２ 実施例１と同様の装置、溶離液及びカラムを用い、ヒド
ロキノンのキノンへの変換反応がカラム内で定量的に進
行していることを実証するために、０．０２から０．５
ｍＭのヒドロキノン水溶液をカラム内に注入して、その
濃度とカラムから溶出したキノンの吸収スペクトル（２
４７ｎｍ）の吸光度の間の関係（検量線）を作成した。
その結果、ヒドロキノンの注入濃度の増大に比例してキ
ノンの吸光度は増大し、カラム内での変換反応が化学量
論的に進行していることが明らかとなった。Example 2 Using the same apparatus, eluent and column as in Example 1, from 0.02 to demonstrate that the conversion reaction of hydroquinone to quinone is proceeding quantitatively in the column. 0.5
An aqueous solution of mM hydroquinone was injected into the column, and the concentration and absorption spectrum of quinone eluted from the column (2
A relationship (calibration curve) between the absorbance at 47 nm) was created.
As a result, it was clarified that the absorbance of quinone increased in proportion to the increase of the injection concentration of hydroquinone, and the conversion reaction in the column proceeded stoichiometrically.
【００１６】濃度既知のヒドロキノンとキノンの標準液
の吸収スペクトルの吸光度からヒドロキノンのキノンへ
の変換効率（収率）を計算したところ、その値は約９５
％であり、ほぼ完全に変換反応が進行していることを示
した。The conversion efficiency (yield) of hydroquinone to quinone was calculated from the absorbance of the absorption spectra of hydroquinone of a known concentration and a standard solution of quinone. The value was about 95.
%, Which indicated that the conversion reaction was almost complete.
【図１】 ヒドロキノンの標準溶液の紫外吸収スペクト
ル図。FIG. 1 is an ultraviolet absorption spectrum diagram of a standard solution of hydroquinone.
【図２】 実施例１で得た生成物の紫外吸収スペクトル
図。FIG. 2 is an ultraviolet absorption spectrum chart of the product obtained in Example 1.
【図３】 キノンの標準水溶液の紫外吸収スペクトル
図。FIG. 3 is an ultraviolet absorption spectrum diagram of a standard aqueous solution of quinone.
Claims (1)
換樹脂を充填したカラムあるいは中空型の陽イオン交換
樹脂膜中に水あるいは水‐有機溶媒からなる溶離液を連
続的に流入させ、その上部にヒドロキノンの一定量を注
入してナトリウム型あるいは中性塩型の陽イオン交換樹
脂中の固定陽イオンによりヒドロキノンを酸化させ、下
部よりキノンを回収することを特徴とするキノンの製造
方法。1. A column filled with a sodium-type or neutral salt-type cation exchange resin or a hollow cation exchange resin membrane is continuously flowed with an eluent consisting of water or a water-organic solvent, A process for producing a quinone, comprising injecting a certain amount of hydroquinone into the upper portion, oxidizing the hydroquinone with a fixed cation in a sodium-type or neutral salt-type cation exchange resin, and recovering the quinone from the lower portion.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63262603A JPH02108645A (en) | 1988-10-18 | 1988-10-18 | Production of hydroquinone from quinone or hydroquinone from quinone with cation exchange resin |
| JP5085397A JPH07580B2 (en) | 1988-10-18 | 1993-03-19 | Quinone production method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63262603A JPH02108645A (en) | 1988-10-18 | 1988-10-18 | Production of hydroquinone from quinone or hydroquinone from quinone with cation exchange resin |
| JP5085397A JPH07580B2 (en) | 1988-10-18 | 1993-03-19 | Quinone production method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63262603A Division JPH02108645A (en) | 1988-10-18 | 1988-10-18 | Production of hydroquinone from quinone or hydroquinone from quinone with cation exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0640997A JPH0640997A (en) | 1994-02-15 |
| JPH07580B2 true JPH07580B2 (en) | 1995-01-11 |
Family
ID=26426414
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63262603A Granted JPH02108645A (en) | 1988-10-18 | 1988-10-18 | Production of hydroquinone from quinone or hydroquinone from quinone with cation exchange resin |
| JP5085397A Expired - Lifetime JPH07580B2 (en) | 1988-10-18 | 1993-03-19 | Quinone production method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63262603A Granted JPH02108645A (en) | 1988-10-18 | 1988-10-18 | Production of hydroquinone from quinone or hydroquinone from quinone with cation exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JPH02108645A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09145099A (en) * | 1995-11-20 | 1997-06-06 | Burest Kogyo Kenkyusho Co Ltd | Foundation block for channel material frame base |
-
1988
- 1988-10-18 JP JP63262603A patent/JPH02108645A/en active Granted
-
1993
- 1993-03-19 JP JP5085397A patent/JPH07580B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02108645A (en) | 1990-04-20 |
| JPH0640997A (en) | 1994-02-15 |
| JPH0565496B2 (en) | 1993-09-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |