JPS6342712B2 - - Google Patents
Info
- Publication number
- JPS6342712B2 JPS6342712B2 JP59090887A JP9088784A JPS6342712B2 JP S6342712 B2 JPS6342712 B2 JP S6342712B2 JP 59090887 A JP59090887 A JP 59090887A JP 9088784 A JP9088784 A JP 9088784A JP S6342712 B2 JPS6342712 B2 JP S6342712B2
- Authority
- JP
- Japan
- Prior art keywords
- mhbzoh
- cathode
- water
- alcohol
- mhba
- 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
Links
- 238000000034 method Methods 0.000 claims description 16
- OKVJCVWFVRATSG-UHFFFAOYSA-N 3-hydroxybenzyl alcohol Chemical compound OCC1=CC=CC(O)=C1 OKVJCVWFVRATSG-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- 239000007769 metal material Substances 0.000 claims 1
- 239000003021 water soluble solvent Substances 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 229910001023 sodium amalgam Inorganic materials 0.000 description 2
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- -1 NaBH 4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Description
【発明の詳細な説明】
本発明は、ｍ−ハイドロオキシベンジルアルコ
ール（以下mHBzOHと略記する）の製造方法に
関する。さらに詳しくは、ｍ−ハイドロオキシ安
息香酸（以下mHBAと略記する）、またはこの
mHBAのエステルを、電解還元してmHBzOHを
製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing m-hydroxybenzyl alcohol (hereinafter abbreviated as mHBzOH). More specifically, m-hydroxybenzoic acid (hereinafter abbreviated as mHBA) or this
This invention relates to a method for producing mHBzOH by electrolytically reducing an ester of mHBA.
mHBzOHは工薬あるいは農薬の中間体として
種々の利用開発が考えられるが、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つていな
い。 mHBzOH can be developed for various uses as an intermediate for pharmaceuticals or agricultural chemicals, but at present it has not been commercially supplied using an inexpensive manufacturing method.
従来、提案されているmHBzOHの合成法とし
ては、ｍ−クレゾールを原料とする発酵法、ｍ−
ハイドロオキシベンズアルデヒトを原料とする、
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
十分であつたり高価な還元剤を使用せねばならぬ
欠点があり、実用化には至つていない。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。 Conventionally proposed synthesis methods for mHBzOH include fermentation using m-cresol as a raw material, m-
Made from hydroxybenzaldehyde,
Reduction and hydrogenation reactions using sodium amalgam, NaBH 4 , LiAlH 4 , etc. are available, but they have drawbacks such as insufficient yields and the need to use expensive reducing agents, so they have not been put into practical use. do not have. Further, the hydrogenation reaction is a reaction under high temperature and high pressure, and there are various problems with industrial production methods.
一方、mHBAを原料とする方法についてはナ
トリウムアマルガム及び電解還元法も提案〔ベル
ヒテ（Bericht）38、1752（1905）〕されているが
収率も低く工業的方法にはなり得ない。 On the other hand, regarding methods using mHBA as a raw material, sodium amalgam and electrolytic reduction methods have been proposed [Bericht 38, 1752 (1905)], but the yields are low and cannot be used as industrial methods.
本発明者らはmHBzOHの製造方法について鋭
意検討を行ない、mHBAの電解還元により高収
率で高純度のmHBzOHを得る方法を見い出し
た。 The present inventors have conducted intensive studies on the method for producing mHBzOH, and have discovered a method for obtaining high-yield, high-purity mHBzOH by electrolytic reduction of mHBA.
本発明方法によれば電解溶液の酸性度及び陰極
材料を適当に選択することにより、電流効率を高
め、かつ高収率でmHBzOHを得ることが出来
る。さらに本発明は選択率も高く、また電解液の
酸性度を保持する為の酸以外の反応保進材は添加
する必要はないので、電解マスからの取り出しも
容易で、高純度のmHBzOHが得られる。 According to the method of the present invention, by appropriately selecting the acidity of the electrolytic solution and the cathode material, it is possible to increase the current efficiency and obtain mHBzOH in high yield. Furthermore, the present invention has a high selectivity, and since there is no need to add reaction promoters other than acid to maintain the acidity of the electrolytic solution, it is easy to take out from the electrolytic mass, and high purity mHBzOH can be obtained. It will be done.
本発明方法において、mHBAは溶液状態で電
解に供することが、電流効率的にも、容積効率的
にも好ましい。水を溶媒に用いた場合、mHBA
の水に対する溶解度は20℃では0.1％弱でほとん
ど溶解しないが、60℃で３％、80℃で９％と、温
度の上昇とともに溶解性を増すので電解液を加温
することが効率的である。またmHBAの溶解性
を増す他の手段として、水に可溶性で、かつ反応
条件下で非還元性である有機溶媒を添加すること
が効果的である。これらの有機溶媒としては、メ
チルアルコール、エチルアルコール、イソプロピ
ルアルコール、ジオキサン、テトラヒドロフラ
ン、アセトニトリル、ジメチルホルムアミド、ジ
メチルスルホキシドなどであり、その添加量は特
に限定しないが、水に対して５〜80％、好ましく
は10〜60％である。この他mHBAの溶解性を増
す手段としてmHBAをエステル化することも好
ましい方法である。 In the method of the present invention, it is preferable to subject mHBA to electrolysis in a solution state in terms of current efficiency and volume efficiency. When water is used as a solvent, mHBA
Its solubility in water is a little less than 0.1% at 20°C, which means it hardly dissolves in water, but its solubility increases with increasing temperature, increasing to 3% at 60°C and 9% at 80°C, so it is efficient to heat the electrolyte. be. Furthermore, as another means of increasing the solubility of mHBA, it is effective to add an organic solvent that is soluble in water and non-reducible under the reaction conditions. Examples of these organic solvents include methyl alcohol, ethyl alcohol, isopropyl alcohol, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, and dimethyl sulfoxide, and the amount added is not particularly limited, but is preferably 5 to 80% based on water. is 10-60%. In addition, esterification of mHBA is also a preferred method as a means of increasing the solubility of mHBA.
本発明方法において、mHBAを溶液状態にし
て電解するに際して溶液のPHは重要な因子であ
る。アルカリ性ではカルボン酸はベンジルアルコ
ールには移行せず、酸性下で行なう必要がある。
詳細に検討した結果、PH４以下にならないと、反
応は進行しないことを見い出した。溶液を酸性に
保持する手段としては、電解反応に関与しない酸
性物質なら特に限定するものではないが、一般的
には鉱酸類、あるいはスルホン酸類が好ましい。
この中特に硫酸は安価でかつ反応系材質の腐蝕性
もなく使い易い。 In the method of the present invention, the pH of the solution is an important factor when electrolyzing mHBA in a solution state. Carboxylic acid does not transfer to benzyl alcohol under alkaline conditions, so it is necessary to carry out the process under acidic conditions.
As a result of detailed study, it was discovered that the reaction does not proceed unless the pH is below 4. The means for keeping the solution acidic is not particularly limited as long as it is an acidic substance that does not participate in the electrolytic reaction, but mineral acids or sulfonic acids are generally preferred.
Among these, sulfuric acid is particularly inexpensive and easy to use since it does not corrode the reaction material.
また本発明方法においては電極のうち特に陰極
材料は水素過電圧の低い白金、ステンレス等を用
いた場合はmHBzOHを生成せず、水素過電圧の
高いもの、具体的には亜鉛、鉛、カドミウム、水
銀が用いられる。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 addition, in the method of the present invention, mHBzOH will not be generated if the cathode material of the electrode is made of platinum, stainless steel, etc., which has a low hydrogen overvoltage; used. The anode, on the other hand, is not particularly limited as long as it is made of a normal electrode material.
電解槽は無隔膜でもmHBzOHは生成するが、
陽極での酸化反応が生じる為、mHBAに対する
mHBzOHの収率は低下する。その為に隔膜によ
り、陽極室、陰極室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、セラミツク
ス、シンタードグラス等を使用する。 Although mHBzOH is produced even if the electrolytic cell does not have a diaphragm,
Due to the oxidation reaction at the anode,
The yield of mHBzOH decreases. For this reason, it is preferable to separate the anode chamber and the cathode chamber by a diaphragm.
Asbestos, ceramics, sintered glass, etc. are used as the material for the diaphragm.
本発明の電解還元において、電流密度は0.1〜
10A／ｄm2、好ましくは１〜5A／ｄm2である。
理論的には４電子還元であり4Fr／moleの通電量
であるが、電流効率は50〜70％である為反応を完
結させる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 0.1 to
10 A/dm 2 , preferably 1 to 5 A/dm 2 .
Theoretically, it is a four-electron reduction and the amount of electricity to be passed is 4 Fr/mole, but since the current efficiency is 50 to 70%, it is necessary to pass 5 to 8 Fr/mole of electricity to complete the reaction.
電流終了後の陰極液は、微量の不溶性タール物
質を除去後、有機溶剤にて抽出し、溶剤を留去し
て生成物を得る。生成物中には微量の原料の
mHBA未反応物、及びmHBAとmHBzOHの中
間物であるｍ−ハイドロオキシベンズアルデヒト
（mHBzCHO）などが含まれているので、精製に
付して目的生成物mHBzOHを単離する。 After the current is terminated, the catholyte is extracted with an organic solvent after removing a trace amount of insoluble tar material, and the solvent is distilled off to obtain a product. There are trace amounts of raw materials in the product.
Since unreacted mHBA and m-hydroxybenzaldehyde (mHBzCHO), which is an intermediate between mHBA and mHBzOH, are contained, the target product mHBzOH is isolated by purification.
次に、本発明を実施例によつてさらに具体的に
説明するが、本発明はこれらに限定されるもので
はない。 Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
なお％は重量％を意味する。 Note that % means weight %.
実施例 １
両極室とも300mlの容量を有し、隔膜としてＧ
−４のシンタードグラスで隔離されたＨ型の電解
セルを使用し、陰極室にはmHBAのメチルエス
テル5.0ｇ（0.0329モル）を50％メタノール水200
mlに溶解後、硫酸を添加してPH２とする。陽極室
は５％の硫酸水200mlを仕込む。陰極として陰極
室の底部（10cm2）に水銀を入れリード線でとり出
し、一方陽極は10cm2のグラフアイト電極を用い
た。両極液は室温で常に撹拌しつつ、1Aの直流
定電流電解を５時間行なつた（0.187Fr）。Example 1 Both polar chambers have a capacity of 300 ml, and G is used as a diaphragm.
An H-type electrolytic cell isolated with sintered glass No. 4 was used, and in the cathode chamber, 5.0 g (0.0329 mol) of mHBA methyl ester was added to 200 ml of 50% methanol water.
ml, add sulfuric acid to adjust the pH to 2. Fill the anode chamber with 200ml of 5% sulfuric acid water. Mercury was placed in the bottom (10 cm 2 ) of the cathode chamber as a cathode and taken out with a lead wire, while a 10 cm 2 graphite electrode was used as the anode. Both electrode solutions were subjected to 1A DC constant current electrolysis for 5 hours (0.187Fr) while constantly stirring at room temperature.
電解終了後、陰極液を5Aの紙で過後エー
テルで抽出し、エーテルを留去後3.8ｇの生成物
を得た。生成物の一部を液体クロマトグラフイー
（HLC）で分析した結果、mHBA0.5％、
mHBzOH95％、mHBzCHO3％、その他1.5％で
あつた。mHBzOHの収率88.5％。電流効率62.4
％。 After the electrolysis was completed, the catholyte was passed through 5A paper and extracted with ether, and after distilling off the ether, 3.8 g of product was obtained. As a result of analyzing a part of the product by liquid chromatography (HLC), mHBA0.5%,
95% mHBzOH, 3% mHBzCHO, and 1.5% others. Yield of mHBzOH 88.5%. Current efficiency 62.4
%.
実施例 ２
実施例１と同様な電解セルを用いmHBA5.0ｇ
（0.0362モル）を200mlの水に添加後、硫酸を添加
してPHｌとする。Example 2 mHBA5.0g using the same electrolytic cell as Example 1
After adding (0.0362 mol) to 200 ml of water, sulfuric acid is added to make PHl.
陽極室には５％の硫酸水を仕込む。陰極として
10cm2の亜鉛板、陽極として10cm2の白金板を用い
た。電解セルを80℃の水浴中で加温しつつ、
0.5Aの直流定電流電解を12時間行なつた。
（0.224Fr）
電解終了後、実施例１と同様に処理し4.0ｇの
生成物を得た。HLCの分析結果はmHBA0.3％、
mHBzOH93％、mHBzCHO5％、その他1.7％で
あつた。mHBzOHの収率82.8％。電流効率53.6
％。 Fill the anode chamber with 5% sulfuric acid water. as a cathode
A 10 cm 2 zinc plate and a 10 cm 2 platinum plate were used as the anode. While heating the electrolytic cell in a water bath at 80℃,
Constant current electrolysis at 0.5A was performed for 12 hours.
(0.224Fr) After the electrolysis was completed, the same treatment as in Example 1 was carried out to obtain 4.0g of product. HLC analysis results are mHBA0.3%,
93% of mHBzOH, 5% of mHBzCHO, and 1.7% of others. Yield of mHBzOH 82.8%. Current efficiency 53.6
%.
実施例 ３
陰極として10cm2の鉛板を用いた以外は実施例２
と同様に電解を行なつた。Example 3 Example 2 except that a 10 cm 2 lead plate was used as the cathode.
Electrolysis was carried out in the same manner.
電解終了後、実施例１と同様に処理し、4.2ｇ
の生成物を得た。HLCの分析結果はmHBA0.4
％、mHBzOH94％、mHBzCHO4％、その他1.6
％であつた。mHBzOHの収率88.0％。電硫効率
56.9％。 After the electrolysis was completed, it was treated in the same manner as in Example 1, and 4.2g
of product was obtained. HLC analysis result is mHBA0.4
%, mHBzOH94%, mHBzCHO4%, others 1.6
It was %. Yield of mHBzOH 88.0%. electric sulfur efficiency
56.9%.
実施例 ４
溶媒として50％アセトニトリル水200mlを用い、
PH４として行なつた以外は実施例１と同様にして
mHBAのメチルエステルの電解を行なつた。Example 4 Using 200 ml of 50% acetonitrile water as a solvent,
Same as Example 1 except that it was carried out as PH4.
Electrolysis of mHBA methyl ester was carried out.
電解終了後、3.6ｇの生成物を得た。HLCの分
析結果はmHBA0.8％、mHBzOH93％、
mHBzCHO5％、その他1.2％であつた。収率74.6
％。電流効率57.8％。 After completion of electrolysis, 3.6 g of product was obtained. HLC analysis results are mHBA0.8%, mHBzOH93%,
mHBzCHO was 5% and others 1.2%. Yield 74.6
%. Current efficiency 57.8%.
比較例 １
陰極液のPHを６に調整した以外は実施例２と同
様にして、mHBAの電解を行なつた。Comparative Example 1 mHBA was electrolyzed in the same manner as in Example 2 except that the pH of the catholyte was adjusted to 6.
電解終了後は実施例１と同様に処理し4.9ｇの
生成物を得た。HLCの分析結果はmHBA99％、
mHBzOH不検出、mHBzCHO不検出、その他１
％であり、mHBzOHの収率０％、電流効率０％
で目的生成物は全く得られなかつた。 After the electrolysis was completed, the same procedure as in Example 1 was carried out to obtain 4.9 g of product. HLC analysis results are mHBA99%,
mHBzOH not detected, mHBzCHO not detected, other 1
%, mHBzOH yield 0%, current efficiency 0%
No desired product was obtained.
比較例 ２
陰極に10cm2の白金を用いて電解を行なつた以外
は実施例２と全く同様にして実施した。Comparative Example 2 Electrolysis was carried out in exactly the same manner as in Example 2, except that 10 cm 2 of platinum was used as the cathode for electrolysis.
電解終了後は実施例１と同様に処理し、4.9ｇ
の生成物を得た。HLCの分析結果はmHBA98
％、mHBzOH不検出、mHBzCHO不検出、その
他２％であり、mHBzOHの収率０％、電流効率
０％で、目的生成物は全く得られなかつた。 After the electrolysis was completed, the same process as in Example 1 was carried out, and 4.9g
of product was obtained. HLC analysis result is mHBA98
%, mHBzOH undetected, mHBzCHO undetected, and others 2%, the mHBzOH yield was 0%, the current efficiency was 0%, and no target product was obtained at all.
Claims (1)
イドロオキシ安息香酸のエステルを、水溶液中あ
るいは水可溶性有機溶媒の存在下で、PH４以下に
保持して、水素過電圧の高い金属材料を陰極に用
いて電解還元することを特徴とするｍ−ハイドロ
オキシベンジルアルコールの製造方法。 ２ 水可溶性溶媒が、メチルアルコール、エチル
アルコール、イソプロピルアルコール、ジオキサ
ン、テトラヒドロフラン、アセトニトリル、ジメ
チルホルムアミド、ジメチルスルホキシドのいず
れかである特許請求の範囲第１項記載の方法。 ３ 陰極材料が、亜鉛、鉛、カドミウム、水銀の
いずれかである特許請求の範囲第１項記載の方
法。 ４ 陰極室、陽極室を隔膜で分離して行う特許請
求の範囲第１項記載の方法。[Claims] 1. A metal material with a high hydrogen overvoltage by maintaining m-hydroxybenzoic acid or an ester of m-hydroxybenzoic acid at a pH of 4 or less in an aqueous solution or in the presence of a water-soluble organic solvent. 1. A method for producing m-hydroxybenzyl alcohol, the method comprising electrolytically reducing m-hydroxybenzyl alcohol using a cathode. 2. The method according to claim 1, wherein the water-soluble solvent is any one of methyl alcohol, ethyl alcohol, isopropyl alcohol, dioxane, tetrahydrofuran, acetonitrile, dimethylformamide, and dimethyl sulfoxide. 3. The method according to claim 1, wherein the cathode material is zinc, lead, cadmium, or mercury. 4. The method according to claim 1, wherein the cathode chamber and the anode chamber are separated by a diaphragm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59090887A JPS60234987A (en) | 1984-05-09 | 1984-05-09 | Manufacture of m-hydroxybenzyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59090887A JPS60234987A (en) | 1984-05-09 | 1984-05-09 | Manufacture of m-hydroxybenzyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60234987A JPS60234987A (en) | 1985-11-21 |
| JPS6342712B2 true JPS6342712B2 (en) | 1988-08-25 |
Family
ID=14010935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59090887A Granted JPS60234987A (en) | 1984-05-09 | 1984-05-09 | Manufacture of m-hydroxybenzyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60234987A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0384309U (en) * | 1989-12-19 | 1991-08-27 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63103093A (en) * | 1986-10-21 | 1988-05-07 | Mitsui Toatsu Chem Inc | Production of 3-hydroxybenzyl alcohol |
| JPS63162890A (en) * | 1986-12-26 | 1988-07-06 | Mitsui Toatsu Chem Inc | Electrolytic synthesis method of m-hydroxybenzyl alcohol |
| JP2632832B2 (en) * | 1987-02-24 | 1997-07-23 | 日本カーバイド工業株式会社 | Method for producing polyfluorobenzyl alcohol |
| JP2767703B2 (en) * | 1988-06-20 | 1998-06-18 | 三井化学株式会社 | Method for electrolytic reduction of aromatic carboxylic acids |
-
1984
- 1984-05-09 JP JP59090887A patent/JPS60234987A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0384309U (en) * | 1989-12-19 | 1991-08-27 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60234987A (en) | 1985-11-21 |
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