JPH0116916B2 - - Google Patents
Info
- Publication number
- JPH0116916B2 JPH0116916B2 JP56212976A JP21297681A JPH0116916B2 JP H0116916 B2 JPH0116916 B2 JP H0116916B2 JP 56212976 A JP56212976 A JP 56212976A JP 21297681 A JP21297681 A JP 21297681A JP H0116916 B2 JPH0116916 B2 JP H0116916B2
- Authority
- JP
- Japan
- Prior art keywords
- substituted phenylacetic
- general formula
- tetramethylammonium
- anode
- cathode
- 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
- -1 4-substituted phenylacetic acid Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- FHVCZJGBXWNGIZ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetramethylazanium Chemical group C[N+](C)(C)C.CC1=CC=C(S([O-])(=O)=O)C=C1 FHVCZJGBXWNGIZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- YHXHKYRQLYQUIH-UHFFFAOYSA-N 4-hydroxymandelic acid Chemical compound OC(=O)C(O)C1=CC=C(O)C=C1 YHXHKYRQLYQUIH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229940073735 4-hydroxy acetophenone Drugs 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 description 2
- ZQYLDVNTWDEAJI-UHFFFAOYSA-N methyl 2-(4-methoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C=C1 ZQYLDVNTWDEAJI-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ITECRQOOEQWFPE-UHFFFAOYSA-N 2-hydroxy-2-(4-methoxyphenyl)acetic acid Chemical compound COC1=CC=C(C(O)C(O)=O)C=C1 ITECRQOOEQWFPE-UHFFFAOYSA-N 0.000 description 1
- REAVCZWUMGIGSW-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetrabutylazanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CCCC[N+](CCCC)(CCCC)CCCC REAVCZWUMGIGSW-UHFFFAOYSA-M 0.000 description 1
- QKFFSWPNFCXGIQ-UHFFFAOYSA-M 4-methylbenzenesulfonate;tetraethylazanium Chemical compound CC[N+](CC)(CC)CC.CC1=CC=C(S([O-])(=O)=O)C=C1 QKFFSWPNFCXGIQ-UHFFFAOYSA-M 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004275 glycolic acid Drugs 0.000 description 1
- XGDZEDRBLVIUMX-UHFFFAOYSA-N methyl 2-(4-hydroxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(O)C=C1 XGDZEDRBLVIUMX-UHFFFAOYSA-N 0.000 description 1
- DHPYYPJMQRYNLX-UHFFFAOYSA-N methyl 2-hydroxy-2-(4-hydroxyphenyl)acetate Chemical compound COC(=O)C(O)C1=CC=C(O)C=C1 DHPYYPJMQRYNLX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、４―置換フエニル酢酸類の製造法に
関する。更に詳しくは本発明は、一般式
〔式中R1は水酸基又は低級アルコキシ基を、R2
は水素原子又は低級アルキル基をそれぞれ示す。〕
で表わされる４―置換フエニル酢酸類の新規な製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 4-substituted phenylacetic acids. More specifically, the present invention relates to the general formula [In the formula, R 1 is a hydroxyl group or a lower alkoxy group, R 2
represents a hydrogen atom or a lower alkyl group, respectively. ] This invention relates to a novel method for producing 4-substituted phenylacetic acids represented by:
上記一般式(2)で表わされる４―置換フエニル酢
酸類は、反応性に富み生理活性物質の原料として
有用であり、医薬や農薬の原料として広く使用さ
れている。例えば一般式(2)で表わされる４―置換
フエニル酢酸類から気管支拡張作用を有する２―
（４―ヒドロキシフエニル）―３―アミノ―１―
プロパノールに容易に誘導することができる（西
独特許公報第2621090号参照）。 The 4-substituted phenylacetic acids represented by the above general formula (2) are highly reactive and useful as raw materials for physiologically active substances, and are widely used as raw materials for medicines and agricultural chemicals. For example, from 4-substituted phenylacetic acids represented by general formula (2), 2-
(4-hydroxyphenyl)-3-amino-1-
It can be easily derived into propanol (see West German Patent Publication No. 2621090).
上記一般式(2)で表わされる４―置換フエニル酢
酸類のうち４―ヒドロキシフエニル酢酸の製造法
としては、例えばフエノールからフリーデル・ク
ラフツ反応により４―ヒドロキシアセトフエノン
を生成させ、次いで４―ヒドロキシアセトフエノ
ンをウイルゲロツト反応させて４―ヒドロキシフ
エニル酢酸を得る方法〔J.Sci.Ind.Hes.（New
Delhi）Sect.B.、21、284（1962）参照〕、４―ヒ
ドロキシマンデル酸及びそのエステルや３―ハロ
ゲノ―４―ヒドロキシマンデル酸及びそのエステ
ルを還元して４―ヒドロキシフエニル酢酸を得る
方法〔特開昭54−125635号公報、同54−148746号
公報等参照〕等が知られている。しかしながら、
前者の方法では目的とする４―ヒドロキシ酢酸が
せいぜい30％程度で得られるに過ぎず、工業的な
方法としては不充分である。また後者の方法にお
いても、還元反応を高温、高圧下の苛酷な条件下
に行なわねばならず、しかもそのような場合でも
目的化合物が低収率、低純度で得られるに過ぎな
い。また上記一般式(2)で表わされる４―置換フエ
ニル酢酸類のうち４―低級アルコキシフエニル酢
酸は、上記で得られる４―ヒドロキシフエニル酢
酸からジメチル硫酸等のアルキル化剤を用いてア
ルキル化して製造されているに止まる。 Among the 4-substituted phenylacetic acids represented by the above general formula (2), 4-hydroxyphenylacetic acid can be produced by, for example, producing 4-hydroxyacetophenone from phenol by a Friedel-Crafts reaction, and then producing 4-hydroxyacetophenone from phenol. - Method for obtaining 4-hydroxyphenylacetic acid by Willgerott reaction of hydroxyacetophenone [J.Sci.Ind.Hes. (New
Delhi) Sect.B., 21, 284 (1962)], a method for obtaining 4-hydroxyphenylacetic acid by reducing 4-hydroxymandelic acid and its esters and 3-halogeno-4-hydroxymandelic acid and its esters. [See Japanese Unexamined Patent Publication No. 54-125635, No. 54-148746, etc.] and the like are known. however,
The former method yields only about 30% of the desired 4-hydroxyacetic acid at most, and is insufficient as an industrial method. In the latter method as well, the reduction reaction must be carried out under harsh conditions at high temperature and high pressure, and even in such cases the target compound can only be obtained in low yield and purity. Among the 4-substituted phenylacetic acids represented by the above general formula (2), 4-lower alkoxyphenylacetic acid is obtained by alkylating the 4-hydroxyphenylacetic acid obtained above using an alkylating agent such as dimethyl sulfuric acid. It is manufactured only by the manufacturer.
本発明者らは一般式(2)で表わされる４―置換フ
エニル酢酸類を工業的に有利に製造する方法を開
発すべく鋭意研究を重ねた結果、ついに本発明を
完成するに至つた。 The present inventors have conducted extensive research to develop an industrially advantageous method for producing 4-substituted phenylacetic acids represented by general formula (2), and have finally completed the present invention.
即ち本発明は、一般式
〔式中R1は水酸基又は低級アルコキシ基を、R2
は水素原子又は低級アルキル基をそれぞれ示す。〕
で表わされる４―置換フエニル酢酸誘導体を電解
還元して一般式
〔式中R1及びR2は前記に同じ。〕
で表わされる４―置換フエニル酢酸類を得ること
を特徴とする４―置換フエニル酢酸類の製造法に
係る。 That is, the present invention is based on the general formula [In the formula, R 1 is a hydroxyl group or a lower alkoxy group, R 2
represents a hydrogen atom or a lower alkyl group, respectively. ] The 4-substituted phenylacetic acid derivative represented by is electrolytically reduced to form the general formula [In the formula, R 1 and R 2 are the same as above. ] This relates to a method for producing 4-substituted phenylacetic acids, characterized by obtaining 4-substituted phenylacetic acids represented by the following.
本発明の方法によれば、簡便な操作且つ緩和な
反応条件下で目的とする４―置換フエニル酢酸類
を高収率、高純度で製造し得る。 According to the method of the present invention, the desired 4-substituted phenylacetic acids can be produced in high yield and purity under simple operations and mild reaction conditions.
本発明の電解還元は、通常中央に隔膜を設けた
陽極室及び陰極室よりなる電解槽中にて行なわれ
る。隔膜としては、カチオン交換膜の他アスベス
ト、セラミツク等も使用可能であるが、カチオン
交換膜が好適である。また陽極室は通常硫酸溶液
及び陽極より構成されており、陰極室は通常一般
式(1)で表わされる４―置換フエニル酢酸誘導体、
有機溶媒、電解質及び陰極より構成されている。 The electrolytic reduction of the present invention is usually carried out in an electrolytic cell consisting of an anode chamber and a cathode chamber provided with a diaphragm in the center. As the diaphragm, in addition to the cation exchange membrane, asbestos, ceramic, etc. can also be used, but the cation exchange membrane is preferred. The anode chamber usually consists of a sulfuric acid solution and an anode, and the cathode chamber usually consists of a 4-substituted phenylacetic acid derivative represented by general formula (1),
It consists of an organic solvent, an electrolyte, and a cathode.
陽極室における硫酸溶液の濃度としては特に制
限されず広い範囲内から適宜選択できるが、通常
１〜20％、好ましくは５〜10％の硫酸水溶液又は
アルコール溶液を使用するのがよい。陽極として
は硫酸溶液により溶解されないものである限り公
知のものをいずれも使用でき、例えば鉛、鉛合
金、白金、ニツケル、ニツケル合金、亜鉛、亜鉛
合金、カドミウム等を挙げることができる。これ
らのうちでも鉛や白金を使用するのが好ましい。 The concentration of the sulfuric acid solution in the anode chamber is not particularly limited and can be appropriately selected within a wide range, but it is usually 1 to 20%, preferably 5 to 10% sulfuric acid aqueous solution or alcohol solution that is preferably used. Any known anode can be used as long as it is not dissolved by the sulfuric acid solution, and examples thereof include lead, lead alloy, platinum, nickel, nickel alloy, zinc, zinc alloy, cadmium, and the like. Among these, it is preferable to use lead or platinum.
陰極室における有機溶媒としては例えばメタノ
ール、エタノール、プロパノール等の低級脂肪族
アルコール、アセトニトリル等のニトリル類、テ
トラヒドロフラン、ジオキサン等の環状エーテル
等を挙げることができる。斯かる有機溶媒の使用
量としては特に制限されず広範囲から適宜選択使
用できるが、通常原料化合物１モル当り有機溶媒
を６〜20程度、好ましくは６〜10用いるのが
よい。また電解質としては通常の第４級アンモニ
ウム塩をいずれも使用でき、具体的にはテトラメ
チルアンモニウムトシレート、テトラメチルアン
モニウムクロライド、テトラメチルアンモニウム
ブロマイド、テトラエチルアンモニウムトシレー
ト、テトラエチルアンモニウムクロライド、テト
ラエチルアンモニウムブロマイド、テトラブチル
アンモニウムトシレート、テトラブチルアンモニ
ウムクロライド等を例示できる。これらのうちで
テトラメチルアンモニウムトシレート、テトラメ
チルアンモニウムクロライド及びテトラメチルア
ンモニウムブロマイドが好適である。斯かる電解
質の使用量としては特に限定がなく広い範囲内か
ら適宜選択されるが、通常原料化合物１モル当り
電解質を100〜300ｇ程度、好ましくは200〜250ｇ
使用するのがよい。また陰極としては鉛、亜鉛等
が好適である。 Examples of the organic solvent in the cathode chamber include lower aliphatic alcohols such as methanol, ethanol, and propanol, nitrites such as acetonitrile, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of such an organic solvent to be used is not particularly limited and can be appropriately selected from a wide range, but it is usually about 6 to 20, preferably 6 to 10, organic solvents used per mole of raw material compound. Further, as the electrolyte, any ordinary quaternary ammonium salt can be used, and specifically, tetramethylammonium tosylate, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium tosylate, tetraethylammonium chloride, tetraethylammonium bromide, Examples include tetrabutylammonium tosylate and tetrabutylammonium chloride. Among these, tetramethylammonium tosylate, tetramethylammonium chloride and tetramethylammonium bromide are preferred. The amount of such electrolyte to be used is not particularly limited and is appropriately selected within a wide range, but it is usually about 100 to 300 g, preferably 200 to 250 g, of electrolyte per 1 mole of raw material compound.
Good to use. Moreover, lead, zinc, etc. are suitable for the cathode.
本発明の電解還元において、電解方法としては
定電圧法及び定電流法のいずれでも可能である
が、定電流法によるのが好ましい。定電流法を採
用する場合、電流密度としては通常１〜
100mA／cm2程度、好ましくは30〜60mA／cm2であ
る。電解反応に必要な通電量としては、電解槽の
形状、電極の種類、基質濃度、基質反応性等によ
り一定しないが、通常約５〜６モル／Ｆ程度の電
気量を通電すればよい。該電解還元は通常０〜60
℃、好ましく30〜50℃にて行なわれる。 In the electrolytic reduction of the present invention, either a constant voltage method or a constant current method can be used as the electrolysis method, but a constant current method is preferable. When using the constant current method, the current density is usually 1~
It is about 100 mA/cm 2 , preferably 30 to 60 mA/cm 2 . The amount of electricity required for the electrolytic reaction varies depending on the shape of the electrolytic cell, the type of electrode, the substrate concentration, the substrate reactivity, etc., but it is usually sufficient to apply an amount of electricity of about 5 to 6 mol/F. The electrolytic reduction is usually 0 to 60
It is carried out at a temperature of preferably 30 to 50°C.
以下に実施例を挙げる。 Examples are given below.
実施例 １
４―ヒドロキシマンデル酸0.5ｇ及びテトラメ
チルアンモニウムトシレート0.75ｇをメタノール
20mgに溶解し、この溶液を隔膜〔カチオン交換
膜、セレミオンCMV、旭硝子製〕で隔てられた
電解槽の陰極室へ入れ、陽極室には10％硫酸メタ
ノール溶液20mlを入れる。陰極材料として亜鉛、
陽極材料として白金を用いて50℃で定電流電解
（30mA／cm2）を行ない、6F／mol通電し反応を
行なつた。反応終了後陰極液のメタノールを留去
し、水５mlを加え、10mlの酢酸エチルで５回抽出
を行ない、抽出液を無水硫酸マグネシウムで乾燥
する。溶媒を留去した後、残渣をシリカゲルカラ
ムで分離・精製すると４―ヒドロキシフエニル酢
酸0.40ｇを得る。Example 1 0.5 g of 4-hydroxymandelic acid and 0.75 g of tetramethylammonium tosylate were added to methanol.
Dissolve 20 mg of this solution and put this solution into the cathode chamber of an electrolytic cell separated by a diaphragm (cation exchange membrane, Selemion CMV, manufactured by Asahi Glass), and put 20 ml of 10% sulfuric acid methanol solution into the anode chamber. Zinc as cathode material,
Constant current electrolysis (30 mA/cm 2 ) was carried out at 50° C. using platinum as the anode material, and the reaction was carried out by applying a current of 6 F/mol. After the reaction is completed, methanol in the catholyte is distilled off, 5 ml of water is added, extraction is performed five times with 10 ml of ethyl acetate, and the extract is dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was separated and purified using a silica gel column to obtain 0.40 g of 4-hydroxyphenylacetic acid.
得られた化合物のNMRデーター（溶媒CDCl3）
を以下に示す。 NMR data of the obtained compound (solvent CDCl 3 )
is shown below.
σ（ppm）＝3.50（Ｓ、2H）
＝6.60〜7.18（ｍ、4H）
＝5.26（Ｓ、1H）
実施例 ２
４―ヒドロキシマンデル酸の代りに４―ヒドロ
キシマンデル酸メチル0.5ｇを用いる以外は実施
例１と同様の操作を行ない、４―ヒドロキシフエ
ニル酢酸メチル0.41ｇを得る。 σ (ppm) = 3.50 (S, 2H) = 6.60 to 7.18 (m, 4H) = 5.26 (S, 1H) Example 2 Except for using 0.5 g of methyl 4-hydroxymandelate instead of 4-hydroxymandelic acid. The same operation as in Example 1 was carried out to obtain 0.41 g of methyl 4-hydroxyphenylacetate.
得られた化合物のNMRデーター（溶媒CDCl3）
を以下に示す。 NMR data of the obtained compound (solvent CDCl 3 )
is shown below.
σ（ppm）＝3.54（Ｓ、2H）
＝3.68（Ｓ、3H）
＝6.60〜7.20（ｍ、4H）
＝7.80（Ｓ、1H）
実施例 ３
４―ヒドロキシマンデル酸の代りに４―メトキ
シマンデル酸メチル0.5ｇを用いて実施例１と同
様な操作を30℃の温度で行ない、４―メトキシフ
エニル酢酸メチル0.43ｇを得る。 σ (ppm) = 3.54 (S, 2H) = 3.68 (S, 3H) = 6.60-7.20 (m, 4H) = 7.80 (S, 1H) Example 3 4-Methoxymandelic acid instead of 4-hydroxymandelic acid The same operation as in Example 1 was carried out using 0.5 g of methyl at a temperature of 30°C to obtain 0.43 g of methyl 4-methoxyphenylacetate.
以下にNMRデーター（溶媒CDCl3）を示す。 NMR data (solvent CDCl 3 ) is shown below.
σ（ppm）＝3.50（Ｓ、2H）
＝3.60（Ｓ、3H）
＝3.75（Ｓ、3H）
＝6.70〜7.25（ｍ、4H）
実施例 ４
硫酸メタノール溶液の代りに硫酸水溶液、白金
の代りに鉛、亜鉛の代りに鉛、テトラメチルアン
モニウムトシレート0.75ｇの代りにテトラメチル
アンモニウムクロライドを用い、実施例１と同様
の操作を行ない、４―ヒドロキシフエニル酢酸
0.38ｇを得る。 σ (ppm) = 3.50 (S, 2H) = 3.60 (S, 3H) = 3.75 (S, 3H) = 6.70 ~ 7.25 (m, 4H) Example 4 Sulfuric acid aqueous solution instead of sulfuric acid methanol solution, and instead of platinum 4-Hydroxyphenylacetic acid
Obtain 0.38g.
得られる化合物のNMRデータは実施例１のそ
れと一致する。 The NMR data of the compound obtained is consistent with that of Example 1.
実施例 ５
陰極液のメタノールの代りにアセトニトリル、
テトラメチルアンモニウムトシレート0.75ｇの代
りにテトラメチルアンモニウムブロマイド0.45ｇ
を用い、実施例１と同様の操作を行ない、４―ヒ
ドロキシフエニル酢酸0.37ｇを得る。Example 5 Acetonitrile instead of methanol in the catholyte,
0.45g of tetramethylammonium bromide instead of 0.75g of tetramethylammonium tosylate
The same operation as in Example 1 was carried out using 4-hydroxyphenylacetic acid to obtain 0.37 g of 4-hydroxyphenylacetic acid.
得られる化合物のNMRデータは実施例１のそ
れと一致する。 The NMR data of the compound obtained is consistent with that of Example 1.
Claims (1)
は水素原子又は低級アルキル基をそれぞれ示す。〕 で表わされる４―置換フエニル酢酸誘導体を電解
還元して 一般式 〔式中R1及びR2は前記に同じ。〕 で表わされる４―置換フエニル酢酸類を得ること
を特徴とする４―置換フエニル酢酸類の製造法。 ２ 陰極室が一般式(1)で表わされる４―置換フエ
ニル酢酸誘導体、有機溶媒、電解質及び陰極より
構成され且つ陽極室が硫酸溶液及び陽極より構成
される隔膜式電解槽を用いて電解還元を行なう特
許請求の範囲第１項記載の方法。 ３ 陽極として鉛又は白金を、陰極として亜鉛又
は鉛を用いる特許請求の範囲第１項又は第２項記
載の方法。 ４ 隔膜がカチオン交換膜である特許請求の範囲
第１項乃至第３項のいずれかに記載の方法。 ５ 電解質がテトラメチルアンモニウムトシレー
ト、テトラメチルアンモニウムクロライド又はテ
トラメチルアンモニウムブロマイドである特許請
求の範囲第１項乃至第４項のいずれかに記載の方
法。[Claims] 1. General formula [In the formula, R 1 is a hydroxyl group or a lower alkoxy group, R 2
represents a hydrogen atom or a lower alkyl group, respectively. ] The 4-substituted phenylacetic acid derivative represented by is electrolytically reduced to give the general formula [In the formula, R 1 and R 2 are the same as above. ] A method for producing 4-substituted phenylacetic acids, which comprises obtaining 4-substituted phenylacetic acids represented by: 2 Electrolytic reduction is carried out using a diaphragm electrolytic cell in which the cathode chamber is composed of a 4-substituted phenylacetic acid derivative represented by general formula (1), an organic solvent, an electrolyte, and a cathode, and the anode chamber is composed of a sulfuric acid solution and an anode. The method according to claim 1, which is carried out. 3. The method according to claim 1 or 2, wherein lead or platinum is used as the anode and zinc or lead is used as the cathode. 4. The method according to any one of claims 1 to 3, wherein the diaphragm is a cation exchange membrane. 5. The method according to any one of claims 1 to 4, wherein the electrolyte is tetramethylammonium tosylate, tetramethylammonium chloride, or tetramethylammonium bromide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212976A JPS58117886A (en) | 1981-12-29 | 1981-12-29 | Manufacture of 4-substituted phenylacetic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212976A JPS58117886A (en) | 1981-12-29 | 1981-12-29 | Manufacture of 4-substituted phenylacetic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58117886A JPS58117886A (en) | 1983-07-13 |
| JPH0116916B2 true JPH0116916B2 (en) | 1989-03-28 |
Family
ID=16631407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56212976A Granted JPS58117886A (en) | 1981-12-29 | 1981-12-29 | Manufacture of 4-substituted phenylacetic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58117886A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979714A (en) * | 2010-11-22 | 2011-02-23 | 天津市职业大学 | Electrolytic synthesis method for hydroxyphenylacetic acid |
-
1981
- 1981-12-29 JP JP56212976A patent/JPS58117886A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58117886A (en) | 1983-07-13 |
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