JPS6259234A - Production of catechol derivative - Google Patents
Production of catechol derivativeInfo
- Publication number
- JPS6259234A JPS6259234A JP19968185A JP19968185A JPS6259234A JP S6259234 A JPS6259234 A JP S6259234A JP 19968185 A JP19968185 A JP 19968185A JP 19968185 A JP19968185 A JP 19968185A JP S6259234 A JPS6259234 A JP S6259234A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- hydrogen peroxide
- solution
- alkali
- formula
- 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は医薬・農薬等の製造中間体として有用な化合物
であるカテコール類の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing catechols, which are compounds useful as intermediates in the production of pharmaceuticals, agricultural chemicals, and the like.
（従来の技術）
ン
○−ヒドロキシベｊズアルデヒドを塩基性条件下で過酸
化水素で処理することによりカテコール誘導体を得る反
応は、Ｄａｋｉｎ反応として知られている。(Prior Art) The reaction of obtaining a catechol derivative by treating n-hydroxybenzaldehyde with hydrogen peroxide under basic conditions is known as the Dakin reaction.
（Ｈ，Ｄ、 Ｄａｋｉｎ、 Ａｍ、 Ｏｈｅｍ、
Ｊ、、 ｌＡ２，１１７７、／り０り年）近年、λ−
ヒドロキシー３−メトキシベンズアルデヒド（０−バニ
リン）のＤａｋｉｎ反応によるカテコールの合成例が下
記のとおシ報告されている。(H, D, Dakin, Am, Ohem,
In recent years, λ-
An example of the synthesis of catechol by the Dakin reaction of hydroxy-3-methoxybenzaldehyde (0-vanillin) has been reported as follows.
／） Ｃｂｅｍ、Ｂｅｒ、、１０２，２１６３．／り
６り年では０−バニリン−ＮａＯＨ水−Ｈ２Ｏ２水 の
懸濁恐址溶液を４１００−、ｙｊＯ℃で攪拌下反応させ
ｒ♂チの収率で０−メトキシカテコールを得ている。/) Cbem, Ber,, 102, 2163. In 2007, a suspended solution of 0-vanillin-NaOH water-H2O2 water was reacted at 4100°C with stirring to obtain 0-methoxycatechol in a yield of r♂.
コ） Ｔｅｔｒａｈｅｄｒｏｎ ＩＩｏ、 ２１２り
、／９ｒμ年ではＮ３下、Ｏ−バニリン−アルカリ水の
懸濁溶液に過酸化水素水を滴下したのち、μ０−４！
７℃で反応させて７ｔ％の収率で目的の０−メトキシカ
テコールを得ている。j) Tetrahedron IIo, 212 years, /9rμ years, after dropping hydrogen peroxide solution into a suspension of O-vanillin-alkaline water under N3, μ0-4!
The reaction was carried out at 7°C to obtain the desired 0-methoxycatechol with a yield of 7t%.
できるものではなく、さらに、再現性に乏しいという欠
点を有している。この主たる原因としては、生成したカ
テコールがアルカリに対して不安定であることが挙げら
れる。Moreover, it has the disadvantage of poor reproducibility. The main reason for this is that the produced catechol is unstable to alkalis.
および反応の安定性を自相して鋭意検討を行った結果、
本発明に到達したものである。After careful consideration of the stability of the reaction and the stability of the reaction, we found that
This has led to the present invention.
すなわち、本発明の要旨は、下記一般式（１）で示され
る２−ヒドロキシベンズアルデヒド誘〔式中、Ｒは水素
原子、低級アルキル基、また下、酸化するに際して、過
酸化水素を含有する反応系中にアルカリ水溶液を滴下す
るか、または、過酸化水素水とアルカリ水浴液を同時に
滴下することを特徴とするカテコール誘導体の製造方法
を存する。That is, the gist of the present invention is to provide a 2-hydroxybenzaldehyde derivative represented by the following general formula (1) [wherein R is a hydrogen atom, a lower alkyl group, and a reaction system containing hydrogen peroxide during oxidation]. There is a method for producing catechol derivatives, which is characterized by dropping an alkaline aqueous solution or simultaneously dropping a hydrogen peroxide solution and an alkaline water bath solution.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で用いられる２−ヒドロキシベンズアルデヒド誘
導体の例としては、２−ヒドロキシベンズアルデヒド、
コーヒドロキシー３−メトキシベンズアルデヒド、λ−
ヒドロキシーｔ −メトキシベンズアルデヒド、ノーヒ
ドロキシ−３−エトキシペ／ズアルデヒド、コーヒドロ
キシーよ一エトキシベ／ズアルデヒド、２−ヒドロキシ
−弘−メチルベンズアルデヒド、コーヒドロキシーｊ−
メチルベノズアルデヒド等が挙げられる。Examples of the 2-hydroxybenzaldehyde derivatives used in the present invention include 2-hydroxybenzaldehyde,
co-hydroxy-3-methoxybenzaldehyde, λ-
Hydroxy-t-methoxybenzaldehyde, no-hydroxy-3-ethoxybe/dualdehyde, co-hydroxy-ethoxybe/dualdehyde, 2-hydroxy-ethoxybenzaldehyde, co-hydroxy-j-
Examples include methylbenozaldehyde.
また、本発明で用いられるアルカリ水溶液中のアルカリ
としては、ＩＪａＯＨ，ＫＯＨ等が挙げられ、２−ヒド
ロキシベンズアルデヒド誘導体に対して０．ｊｔ −７
０倍モル、好ましくは、０・ｔ−コ倍モル用いられる。Further, examples of the alkali in the aqueous alkali solution used in the present invention include IJaOH, KOH, etc., and 0.0% to 2-hydroxybenzaldehyde derivative. jt −7
It is used in an amount of 0 times the mole, preferably 0.t-times the mole.
また、本発明で用いられる過酸化水素の量は、コーヒド
ロキシペンズアルデヒド誘導体に対して０．ｊｔ −７
０倍モル、好ましくは、ｏ、ｒ−コ倍モル
−である０反応源度は−ｉｏ℃〜／２０℃
、好ましくは２０℃〜１００℃である。Further, the amount of hydrogen peroxide used in the present invention is 0.00% relative to the co-hydroxypenzaldehyde derivative. jt −7
0 times molar, preferably o, r-co times molar
- 0 reaction source is -io℃~/20℃
, preferably 20°C to 100°C.
滴下方法としては、
１）−２−ヒドロキシベンズアルデヒド誘導体と過酸化
水素水溶液の懸濁溶液に、攪拌しながらアルカリ水溶液
を滴下する。The dropping method is as follows: 1) An alkaline aqueous solution is dropped into a suspension of a -2-hydroxybenzaldehyde derivative and a hydrogen peroxide aqueous solution while stirring.
又は、
コ）、２−ヒドロキシベンズアルデヒド誘導体の懸濁水
溶液に、アルカリ水溶液と過酸化水素水溶液の当量を同
時に滴下する。Or, c), equivalent amounts of an aqueous alkali solution and an aqueous hydrogen peroxide solution are simultaneously dropped into an aqueous suspension of a 2-hydroxybenzaldehyde derivative.
のいずれの方法をとってもよい。Either method may be used.
−番 − 水濃度には特に制限はない。-No.- There is no particular limit to the water concentration.
（実施例）
以下、実施例によυ本発明を更に詳細に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例１
Ｏ−バニリン／ ！、２ ／ ｔ （０，１モル）およ
び５％過酸化水素水７７．７ ｆ （０，１２５モル）
を混合し、室温にて攪拌した。Example 1 O-vanillin/! , 2 / t (0,1 mol) and 5% hydrogen peroxide 77.7 f (0,125 mol)
were mixed and stirred at room temperature.
この溶液に、２規定ＮａＯＨｊ ＯＨｌ （０，１モル
）を３０分かけて滴下し、さらに、２０分間攪拌して反
応を終了した。このとき内温は約≠θ℃まで上昇した。To this solution, 2N NaOHj OHl (0.1 mol) was added dropwise over 30 minutes, and the mixture was further stirred for 20 minutes to complete the reaction. At this time, the internal temperature rose to approximately ≠θ°C.
反応液はＮａ４ＢＯ３で過剰のＨ２Ｏ３を消失させたの
ち、液体クロマトグラフィーで定量した。その結果、目
的のカテコール体の収量は／ Ｊ、ｊ ／ ｆであった
。（収率りｊ％）実施例コ
０−バニリン／ ｓ、２ｔ ｔ （０−１モル）を島Ｏ
ｊａｍに懸濁させ室温にて攪拌した。この懸濁溶液に２
規定ＩＪａＯＨｊ０−とＡ ％ ）！、０． ７７．７
ｆを、若干Ｈ，Ｏ，溶液を先行させ約３０分かけて同
時滴下した。滴下終了後、約２０分攪拌し反応を終了し
た。反応液はＮ ａｚ Ｓ ０３で過剰のＨ８０２を消
失させたのち、液体クロマトグラフィーで定量した。そ
の結果、目的のカテコール体の収量は／３．≠！Ｖであ
った。（収率？ｔ％）比較例
０−バニリンとアルカリ水を敷液にして、こミ１−Ｈ，
ｏ、水を滴下すること以外は実施例１と全く同様にして
反応を行ったところ、カテコール体の収率は♂タチであ
った。After eliminating excess H2O3 from the reaction solution with Na4BO3, it was quantified by liquid chromatography. As a result, the yield of the desired catechol body was /J,j/f. (Yield j%) Example 0-vanillin/s, 2t t (0-1 mol)
jam and stirred at room temperature. Add 2 to this suspension.
Regulation IJaOHj0- and A%)! ,0. 77.7
f was simultaneously added dropwise over about 30 minutes with some H, O, and solution added in advance. After the dropwise addition was completed, the mixture was stirred for about 20 minutes to complete the reaction. After eliminating excess H802 from the reaction solution with N az S 03, it was quantified using liquid chromatography. As a result, the yield of the desired catechol body was /3. ≠! It was V. (Yield? t%) Comparative Example 0- Vanillin and alkaline water were used as a bedding liquid, and rice 1-H,
o. When the reaction was carried out in exactly the same manner as in Example 1 except that water was added dropwise, the yield of the catechol compound was ♂.
（発明の効果）
本発明方法によれば、医薬、農薬等の製造中間体として
有用なカテコール誘導体を高収率で得ることができる。(Effects of the Invention) According to the method of the present invention, catechol derivatives useful as intermediates for producing pharmaceuticals, agricultural chemicals, etc. can be obtained in high yield.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士 長谷用 −ほか１名Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person
Claims (1)
ンズアルデヒド誘導体 ▲数式、化学式、表等があります▼・・・・・・・・（
I ） 〔式中、Ｒは水素原子、低級アルキル基、または低級ア
ルコキシ基を示し、３、４、５、または６位のどこに位
置していてもよい。〕 を水溶液中でアルカリおよび過酸化水素の存在下、酸化
するに際して、過酸化水素を含有する反応系中にアルカ
リ水溶後を滴下するか、または、過酸化水素とアルカリ
水溶液を同時に滴下することを特徴とするカテコール誘
導体の製造方法。(1) 2-Hydroxybenzaldehyde derivative represented by the general formula (I) below ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・・・・(
I) [In the formula, R represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and may be located at any of the 3, 4, 5, or 6 positions. ] When oxidizing in the presence of an alkali and hydrogen peroxide in an aqueous solution, it is recommended to drop the aqueous alkali solution into the reaction system containing hydrogen peroxide, or drop the hydrogen peroxide and aqueous alkali solution simultaneously. Characteristic method for producing catechol derivatives.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19968185A JPS6259234A (en) | 1985-09-10 | 1985-09-10 | Production of catechol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19968185A JPS6259234A (en) | 1985-09-10 | 1985-09-10 | Production of catechol derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6259234A true JPS6259234A (en) | 1987-03-14 |
Family
ID=16411840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19968185A Pending JPS6259234A (en) | 1985-09-10 | 1985-09-10 | Production of catechol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6259234A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5364983A (en) * | 1992-10-09 | 1994-11-15 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic polyhydroxy compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS514128A (en) * | 1974-06-27 | 1976-01-14 | Nippon Oils & Fats Co Ltd | KATEKOORU JUDOTAINOSEIZOHOHO |
| JPS56147737A (en) * | 1980-04-15 | 1981-11-16 | Sumitomo Chem Co Ltd | Preparation of dihydroxybenzene derivative |
-
1985
- 1985-09-10 JP JP19968185A patent/JPS6259234A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS514128A (en) * | 1974-06-27 | 1976-01-14 | Nippon Oils & Fats Co Ltd | KATEKOORU JUDOTAINOSEIZOHOHO |
| JPS56147737A (en) * | 1980-04-15 | 1981-11-16 | Sumitomo Chem Co Ltd | Preparation of dihydroxybenzene derivative |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5364983A (en) * | 1992-10-09 | 1994-11-15 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic polyhydroxy compounds |
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