JPH0718033B2 - Process for producing 3-hydroxybenzyl alcohol - Google Patents
Process for producing 3-hydroxybenzyl alcoholInfo
- Publication number
- JPH0718033B2 JPH0718033B2 JP61226134A JP22613486A JPH0718033B2 JP H0718033 B2 JPH0718033 B2 JP H0718033B2 JP 61226134 A JP61226134 A JP 61226134A JP 22613486 A JP22613486 A JP 22613486A JP H0718033 B2 JPH0718033 B2 JP H0718033B2
- Authority
- JP
- Japan
- Prior art keywords
- hboh
- reaction
- aqueous solution
- yield
- producing
- 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
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、m-ヒドロキシベンジルアルコール（以下、m-
HBOHと略記する）の製造方法に関するものである。TECHNICAL FIELD The present invention relates to m-hydroxybenzyl alcohol (hereinafter, m-hydroxybenzyl alcohol).
HBOH).
m-HBOHは、工薬、あるいは農薬の中間体として有用な化
合物であるが、現状ではこれの安価な製造方法による工
業的供給には至っていない。m-HBOH is a compound useful as an intermediate for industrial drugs or agricultural chemicals, but at present, it has not been industrially supplied by an inexpensive manufacturing method thereof.
従来の技術 m-HBOHの合成法として、m-クレゾールを原料とする発酵
法、m-ヒドロキシベンズアルデヒドを原料とするナトリ
ウム・アマルガム、NaBH4、LiAlH4等による還元及び水
素添加反応等があるが、収率的に不十分であったりし
て、実用化には至っていない。また水素添加反応は高
温、高圧下の反応であり工業的製造法には種々問題があ
る。As a conventional method for synthesizing m-HBOH, there are a fermentation method using m-cresol as a raw material, a sodium amalgam using m-hydroxybenzaldehyde as a raw material, reduction with NaBH 4 , LiAlH 4, etc., and a hydrogenation reaction, It has not been put to practical use due to insufficient yield. Further, the hydrogenation reaction is a reaction under high temperature and high pressure, and there are various problems in the industrial production method.
またm-ヒドロキシ安息香酸（以下、m-HBAと略記する）
を原料とする方法については、ナトリウム・アマルガム
による還元法及び電解還元法（Berichte 38 1752（190
5））が提案されているが収率的にも低く工業的方法に
はなり得なかった。In addition, m-hydroxybenzoic acid (hereinafter abbreviated as m-HBA)
For the method of using as a raw material, the reduction method using sodium amalgam and the electrolytic reduction method (Berichte 38 1752 (190
5)) has been proposed, but the yield is too low to be an industrial method.
本発明者らは、先にm-HBOHの製造方法について検討し、
m-HBAの電解還元を水溶液、あるいは水可溶性有機溶媒
中で行う方法、更に陰極液中に支持電解質を添加する方
法で高収率でm-HBOHを得る方法も既に見出している（特
開昭60-234987、特開昭60-243293）。The present inventors previously studied a method for producing m-HBOH,
A method of electrolytically reducing m-HBA in an aqueous solution or a water-soluble organic solvent, and a method of adding a supporting electrolyte to a catholyte to obtain m-HBOH in a high yield have already been found (Japanese Patent Laid-Open Publication No. S60-18753). 60-234987, JP-A-60-243293).
発明が解決しようとする問題点 本発明者らは、更にm-HBOHの工業的製法について鋭意検
討を行い、m-HBAを酸性水溶液中で電解還元を行い高収
率で高純度のm-HBOHを得る方法を先に提案した（特願昭
60-263858、特願昭60-272467）。Problems to be Solved by the Invention The present inventors further diligently studied the industrial production method of m-HBOH, and electrolytically reduced m-HBA in an acidic aqueous solution to perform high-yield and high-purity m-HBOH. First proposed a method of obtaining
60-263858, Japanese Patent Application No. 60-272467).
しかし、本電解反応は酸性水溶液中で行なわれるため、
反応中に酸に不安定なm-HBAとm-HBOHの分解が避けられ
ずタール状の分解物が副生する。However, since this electrolysis reaction is carried out in an acidic aqueous solution,
During the reaction, decomposition of acid-labile m-HBA and m-HBOH is unavoidable, and tar-like decomposition products are by-produced.
これらのタール状の分解物は水に不溶であり、反応を重
ねていくうちに電解槽内に蓄積し、一部は電極表面に付
着して、電極の活性を低下させ、そのため反応の電流効
率を悪化させる。These tar-like decomposition products are insoluble in water and accumulate in the electrolytic cell as the reaction is repeated, and some of them adhere to the electrode surface, reducing the activity of the electrode, and thus the current efficiency of the reaction. Aggravate.
電解還元反応を安定して長期間運転を行うには、副生す
る分解物が電極面に付着し活性を低下させるのを防止す
ることが重要である。In order to stably carry out the electrolytic reduction reaction for a long period of time, it is important to prevent the decomposition products produced as by-products from adhering to the electrode surface and lowering the activity.
本発明の課題は、m-HBAを酸性水溶液中で電解還元を行
い高収率で高純度のm-HBOHを得る方法において、副生す
るタール状分解物の電極表面への付着を防止できる改善
された製造方法を提供することである。An object of the present invention is to improve the method of preventing the deposition of a tar-like decomposed product as a by-product on the electrode surface in the method of electrolytically reducing m-HBA in an acidic aqueous solution to obtain high-purity m-HBOH in high yield. It is to provide the manufacturing method.
問題点を解決するための手段 本発明者らは、上記の課題を解決するために鋭意検討
し、反応系中に第４級アンモニウム塩系カチオン性界面
活性剤を触媒量加えることで、副生するタール状の分解
物がエマルジョン化され、電極表面への付着が防止でき
ることを見出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and by adding a catalytic amount of a quaternary ammonium salt-based cationic surfactant to the reaction system, a by-product is obtained. The present inventors have completed the present invention by finding that the tar-like decomposed product that is formed into an emulsion can be prevented from adhering to the electrode surface.
即ち、本発明は3-ヒドロキシ安息香酸を酸性水溶液中で
電解還元するに際して、第４級アンモニウム塩系カチオ
ン性界面活性剤を、酸性水溶液に対して0.001〜１重量
％添加して、20〜70℃で電解を行うことを特徴とする3-
ヒドロキシベンジルアルコールの製造法である。That is, in the present invention, when electrolytically reducing 3-hydroxybenzoic acid in an acidic aqueous solution, 0.001 to 1% by weight of a quaternary ammonium salt-based cationic surfactant is added to the acidic aqueous solution to give 20 to 70%. Characterized by performing electrolysis at ℃ 3-
It is a method for producing hydroxybenzyl alcohol.
本発明において、酸性水溶液としては、陰極での電解反
応に不活性な酸性物質であれば、特に限定するものでは
ないが、コスト的に通常鉱酸を用いるのが望ましく、特
に材質及び収率の点から硫酸が好ましい鉱酸であり、通
常５〜30重量％の硫酸水溶液が用いられる。In the present invention, the acidic aqueous solution is not particularly limited as long as it is an acidic substance which is inactive in the electrolytic reaction at the cathode, but it is preferable to use a normal mineral acid in terms of cost, and particularly the material and the yield. From this point of view, sulfuric acid is a preferred mineral acid, and an aqueous 5-30 wt% sulfuric acid solution is usually used.
３−ヒドロキシ安息香酸の硫酸水溶液中の濃度は通常５
〜20重量％である。The concentration of 3-hydroxybenzoic acid in a sulfuric acid aqueous solution is usually 5
~ 20% by weight.
本発明方法で用いる第４級アンモニウム塩系カチオン性
界面活性剤としては、触媒量でタール状の副生物をエマ
ルジョン化できるものが良い。The quaternary ammonium salt-based cationic surfactant used in the method of the present invention is preferably one that can emulsify the tar-like by-product with a catalytic amount.
中でも、式（Ｉ） （式中、Ｒはアルキル基及び／又はアルキルポリオキシ
エチレン基、ＸはCl又はBr）の構造を有する界面活性剤
が有効である。具体的には、ラウリルトリメチルアンモ
ニウムクロライド（コータミン24P:商品名、花王石鹸
（株）製）、ステアリルトリメチルアンモニウムクロラ
イド（コータミン86Pコンク：商品名、花王石鹸（株）
製）、アルキルベンジルメチルアンモニウムクロライド
（サニゾールＣ、サニゾールB-50:商品名、花王石鹸
（株）社製）、モノアルキル第４級アンモニウム塩やジ
アルキル第４級アンモニウム塩（アカードやエソカー
ド：ライオンアグゾ（株）社製）等が例示される。Among them, the formula (I) (In the formula, R is an alkyl group and / or an alkyl polyoxyethylene group, and X is Cl or Br). A surfactant having a structure is effective. Specifically, lauryl trimethyl ammonium chloride (KOTAMIN 24P: trade name, manufactured by Kao Soap Co., Ltd.), stearyl trimethyl ammonium chloride (KOTAMIN 86P CONC: trade name, Kao Soap Co., Ltd.)
Alkylbenzylmethylammonium chloride (Sanizole C, Sanizol B-50: trade name, manufactured by Kao Soap Co., Ltd.), monoalkyl quaternary ammonium salt and dialkyl quaternary ammonium salt (Accard and Esocard: Lion Agzo ( Co., Ltd.) and the like.
その添加量は、溶媒である酸性水溶液に対して0.001〜
１重量％、好ましくは0.01〜0.5重量％の範囲である。
添加量が0.001重量％未満ではタール状副生物のエマル
ジョン化が不充分で副生物が電極表面に付着する。又、
１重量％を越えても更にエマルジョン化効果の向上はみ
られない。The addition amount is 0.001 to the acidic aqueous solution which is a solvent.
It is in the range of 1% by weight, preferably 0.01 to 0.5% by weight.
If the addition amount is less than 0.001% by weight, the tar-like by-product is not sufficiently emulsified and the by-product adheres to the electrode surface. or,
Even if it exceeds 1% by weight, the emulsifying effect is not further improved.
本発明方法において、電解還元反応は20〜70℃の温度範
囲で実施する。又、電解に用いる電極のうち特に陰極材
料は水素過電圧の高いもの、具体的には亜鉛、鉛、カド
ミウム、水銀を用いる。対する陽極については、通常の
電極材料であれば特に限定しない。In the method of the present invention, the electrolytic reduction reaction is carried out in the temperature range of 20 to 70 ° C. Among the electrodes used for electrolysis, the cathode material having a high hydrogen overvoltage, specifically zinc, lead, cadmium, or mercury is used. The opposite anode is not particularly limited as long as it is an ordinary electrode material.
陽イオン交換隔膜により、陽極質、陰極質を隔離するこ
とが好ましい。隔膜の材質としては、アスベスト、セラ
ミックス、シンタードグラス等が使用できる。It is preferable to separate the anolyte and the catholyte by a cation exchange membrane. As the material of the diaphragm, asbestos, ceramics, sintered glass or the like can be used.
本発明の電解還元において、電流密度は好ましくは５〜
30A/dm2である。理論的には４電子還元であり、4Fr/mol
eの通電量であるが、電流効率は50〜70％であるので、
反応を完結させるには５〜8FR/mole電気量を通す必要が
ある。In the electrolytic reduction of the present invention, the current density is preferably 5 to
It is 30 A / dm 2 . Theoretically 4-electron reduction, 4Fr / mol
Although it is the energizing amount of e, since the current efficiency is 50 to 70%,
To complete the reaction, it is necessary to pass 5-8 FR / mole of electricity.
作用および効果 本発明方法は、m-HBAを酸性水溶液中で電解還元反応を
行いm-HBOHを製造する際に、酸性水溶液中に第４級アン
モニウム塩系カチオン性界面活性剤を添加することによ
り、タール状の副生物の電極表面への付着を防止でき、
電解還元反応が長期に安定して運転が可能で、工業的に
極めて価値ある発明である。Action and Effect The method of the present invention comprises adding a quaternary ammonium salt-based cationic surfactant to an acidic aqueous solution when producing m-HBOH by electrolytically reducing m-HBA in the acidic aqueous solution. Can prevent tar-like by-products from adhering to the electrode surface,
This is an industrially valuable invention because the electrolytic reduction reaction can be stably operated for a long period of time.
実施例 以下、実施例により本発明の方法を詳しく説明する。Examples Hereinafter, the method of the present invention will be described in detail with reference to Examples.
実施例１ 両極室とも300mlの容量を有し、隔膜としてセレミオCMY
（旭硝子（株）の商品名の陽イオン交換膜）で隔離され
たＨ型の電解セルを使用して、両極室に10％の硫酸水溶
液を200mlづつ仕込む。陰極として50cm2の鉛板、陽極と
して50cm2白金板を用いた。Example 1 Both electrode chambers had a capacity of 300 ml, and selemio CMY was used as a diaphragm.
Using an H-type electrolytic cell isolated by (a cation exchange membrane under the trade name of Asahi Glass Co., Ltd.), 200 ml of a 10% sulfuric acid aqueous solution is charged in each of the bipolar chambers. A 50 cm 2 lead plate was used as the cathode, and a 50 cm 2 platinum plate was used as the anode.
さらに陰極室に界面活性剤としてジステアリルジメチル
アンモニウムクロリド（コータミン24P:花王石鹸）0.2g
を加えた。電解セルを60℃に保ちつつ、6Aの直流定電流
を通電しつつ、m-HBA25gをマイクロフィーダーを用いて
6g/時間の割合で陰極液中に添加し、4.2時間でm-HBAを
全量添加した。この後更に電解を0.8時間継続した（7Fr
/mol）。電解終了後、陰極液は抜き取った後、再び10％
硫酸水溶液200mlおよびジステアリルジメチルアンモニ
ウムクロリド0.2gを仕込んで、引き続き第２バッチ目の
反応を第１回目と同様に行った。抜き取った陰極液は液
体クロマトグラフィー（HLC）で分析を行った。0.2 g of distearyldimethylammonium chloride (coatamine 24P: Kao soap) as a surfactant in the cathode chamber
Was added. While maintaining the electrolysis cell at 60 ℃, while applying a DC constant current of 6A, m-HBA 25g using a micro feeder
It was added to the catholyte at a rate of 6 g / hour, and the entire amount of m-HBA was added in 4.2 hours. After this, electrolysis was continued for 0.8 hours (7Fr
/ mol). After completion of electrolysis, the catholyte is drained and then 10% again
200 ml of a sulfuric acid aqueous solution and 0.2 g of distearyldimethylammonium chloride were charged, and then the reaction of the second batch was carried out in the same manner as the first batch. The extracted catholyte was analyzed by liquid chromatography (HLC).
その後、同様な操作を20バッチ続けて、各バッチ毎の電
流効率、ｍ−HBOH収率を測定した。Then, the same operation was continued for 20 batches, and the current efficiency and m-HBOH yield of each batch were measured.
平均電流効率55.3％、平均m-HBOH収率90.2重量％であ
り、長時間の電解還元反応による電流効率、m-HBOH収率
の顕著な低下はみられなかった。The average current efficiency was 55.3% and the average m-HBOH yield was 90.2% by weight. No significant decrease in current efficiency or m-HBOH yield due to a long-term electrolytic reduction reaction was observed.
表‐１に各バッチ毎の電流効率、m-HBOH収率を示す。Table 1 shows the current efficiency and m-HBOH yield for each batch.
実施例２ 界面活性剤として、ジステアリルジメチルアンモニウム
クロリドに替えて、塩化ベンゼトニウムを0.1g加えた以
外は実施例１と同様の実験を行った。反応は20バッチ連
続して行ったが電流効率、m-HBOH収率に顕著な低下はみ
られなかった。（平均電流効率55.5％、平均m-HBOH収率
90.0％） 比較例１ 界面活性剤を添加しなかった以外は実施例１と同様の実
験を12バッチ連続で行った。 Example 2 The same experiment as in Example 1 was conducted except that 0.1 g of benzethonium chloride was added instead of distearyldimethylammonium chloride as the surfactant. The reaction was carried out continuously for 20 batches, but no significant decrease in current efficiency or m-HBOH yield was observed. (Average current efficiency 55.5%, average m-HBOH yield
Comparative Example 1 The same experiment as in Example 1 was carried out for 12 batches in succession except that no surfactant was added.
電流効率は徐々に低下してゆき、12バッチ目においては
11％、m-HBOH収率18％に低下した。表‐２に各バッチ毎
の電流効率、及びm-HBOHの収率を示す。The current efficiency gradually decreases, and in the 12th batch,
11%, m-HBOH yield decreased to 18%. Table 2 shows the current efficiency and the yield of m-HBOH for each batch.
発明の効果 実施例と比較例の結果から明らかな通り、m-HBAの電解
還元によるm-HBOHの製造において、反応系に界面活性剤
を添加しない比較例の方法にくらべ、界面活性剤を添加
した場合には反応の繰り返しによっても電流効率および
m-HBOH収率とも殆ど低下することがない。 Effects of the invention As is clear from the results of Examples and Comparative Examples, in the production of m-HBOH by electrolytic reduction of m-HBA, compared with the method of Comparative Example in which no surfactant is added to the reaction system, the addition of surfactant Current efficiency and
Almost no decrease in m-HBOH yield occurs.
すなわち、界面活性剤を添加しないで反応を続けた場
合、電流効率が低下し、反応の再現性を失い、工業的な
m-HBAの電解還元プロセスとしては成り立たなくなる。
しかし、界面活性剤を反応系に仕込むことで、本電解反
応が長期に安定して運転が可能となった。That is, when the reaction is continued without adding the surfactant, the current efficiency is lowered, the reproducibility of the reaction is lost, and
It becomes impossible as an electrolytic reduction process of m-HBA.
However, by charging a surfactant into the reaction system, this electrolysis reaction could be stably operated for a long period of time.
Claims (1)
電解還元するに際して、第４級アンモニウム塩系カチオ
ン性界面活性剤を、酸性水溶液に対して0.001〜１重量
％添加して、20〜70℃で電解を行うことを特徴とする３
−ヒドロキシベンジルアルコールの製造法。1. When electrolytically reducing 3-hydroxybenzoic acid in an acidic aqueous solution, 0.001 to 1% by weight of a quaternary ammonium salt-based cationic surfactant is added to the acidic aqueous solution to give 20 to 70. Characterized by electrolysis at 3 ℃
-Method for producing hydroxybenzyl alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226134A JPH0718033B2 (en) | 1986-09-26 | 1986-09-26 | Process for producing 3-hydroxybenzyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61226134A JPH0718033B2 (en) | 1986-09-26 | 1986-09-26 | Process for producing 3-hydroxybenzyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6383289A JPS6383289A (en) | 1988-04-13 |
| JPH0718033B2 true JPH0718033B2 (en) | 1995-03-01 |
Family
ID=16840382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61226134A Expired - Lifetime JPH0718033B2 (en) | 1986-09-26 | 1986-09-26 | Process for producing 3-hydroxybenzyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0718033B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH028386A (en) * | 1988-06-27 | 1990-01-11 | Mitsui Toatsu Chem Inc | Method for electrolytically reducing m-hydroxybenzoic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60243293A (en) * | 1984-05-16 | 1985-12-03 | Mitsui Toatsu Chem Inc | Manufacture of m-hydroxybenzyl alcohol |
-
1986
- 1986-09-26 JP JP61226134A patent/JPH0718033B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6383289A (en) | 1988-04-13 |
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