JPS5837394B2 - Method for producing 2-methyl-1,4-naphthoquinone - Google Patents
Method for producing 2-methyl-1,4-naphthoquinoneInfo
- Publication number
- JPS5837394B2 JPS5837394B2 JP56076101A JP7610181A JPS5837394B2 JP S5837394 B2 JPS5837394 B2 JP S5837394B2 JP 56076101 A JP56076101 A JP 56076101A JP 7610181 A JP7610181 A JP 7610181A JP S5837394 B2 JPS5837394 B2 JP S5837394B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- naphthoquinone
- producing
- present
- methylnaphthalene
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- MJVAVZPDRWSRRC-UHFFFAOYSA-N Menadione Chemical compound C1=CC=C2C(=O)C(C)=CC(=O)C2=C1 MJVAVZPDRWSRRC-UHFFFAOYSA-N 0.000 title description 17
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 2
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 chromium Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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、２−メチルナフタレンの電解酸化により２−
メチル−１，４−ナフトキノンを好収率で製造する方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 2-methylnaphthalene by electrolytic oxidation.
The present invention relates to a method for producing methyl-1,4-naphthoquinone in good yield.
，２−メチル−１，４−ナフトキノンは医薬あるいはそ
の中間体として重要な化合物であり、従来２−メチルナ
フタレンの試薬酸化により合成されている。, 2-methyl-1,4-naphthoquinone is an important compound as a drug or an intermediate thereof, and has conventionally been synthesized by reagent oxidation of 2-methylnaphthalene.
しかし、この方法によると廃液にクロムなどの有害な金
属塩が含まれるのでその除去に煩雑な操作を必要とする
という欠点がある。However, this method has the disadvantage that the waste liquid contains harmful metal salts such as chromium, and its removal requires complicated operations.
本発明者らは、こうした従来法に代わる新しい２−メチ
ル−１，４−ナフトキノンの製造方法を開発するため鋭
意研究を重ねた結果、２−メチルナフタレンを特定の溶
媒中で、硫酸を支持電解質として、所定の電極材料を用
いて電解酸化することにより、好収率で目的の２−メチ
ル−１，４ナフトキノンを合成できることを見出した。The present inventors have conducted intensive research to develop a new method for producing 2-methyl-1,4-naphthoquinone to replace such conventional methods. We have found that the desired 2-methyl-1,4 naphthoquinone can be synthesized in good yield by electrolytic oxidation using a predetermined electrode material.
本発明は、この知見に基づいてなされるに至ったもので
ある。The present invention has been made based on this knowledge.
すなわち本発明は、２−メチルナフタレンを、含水アセ
トン中で硫酸を支持電解質とし、炭素電極を用いて電解
酸化することを特徴とする２−メチル−１，４−ナフト
キノンの製造方法を提供するものである。That is, the present invention provides a method for producing 2-methyl-1,4-naphthoquinone, which comprises electrolytically oxidizing 2-methylnaphthalene in aqueous acetone using sulfuric acid as a supporting electrolyte and using a carbon electrode. It is.
本発明方法は、隔膜を有する電解槽に支持電解・質とし
ての硫酸を含む含水アセトンを媒体として装入し、陽極
室に原料の２−メチルナフタレンを加える以外は常法に
より電位あるいは電流を規制しながら電解酸化を行うこ
とにより実施できる。In the method of the present invention, hydrous acetone containing sulfuric acid as a supporting electrolyte is charged as a medium into an electrolytic cell having a diaphragm, and the potential or current is regulated by a conventional method except for adding the raw material 2-methylnaphthalene to the anode chamber. This can be carried out by performing electrolytic oxidation while
支持電解質の硫酸濃度は、媒体に対して通常０．０５〜
０．２ ｍａｉｌ／ｌである。The sulfuric acid concentration of the supporting electrolyte is usually 0.05 to 0.05 to the medium.
It is 0.2 mail/l.
溶媒の含水アセトン中の水含量は４０〜５０容積％がよ
いが、これに限定されない。The water content in the aqueous acetone solvent is preferably 40 to 50% by volume, but is not limited thereto.
電極としては陽極には、炭素電極を用いる。As an electrode, a carbon electrode is used as an anode.
また陰極には、白金板あるいは炭素板を用いる。Further, a platinum plate or a carbon plate is used for the cathode.
陽極室における２−メチルナフタレンの濃度は、通常０
． ０ １〜０． １ ０ ｍｏｌ／ｌであり、好まし
くは０．０２〜０．０５ｍｏｌ／ｌである。The concentration of 2-methylnaphthalene in the anode chamber is usually 0.
．． 0 1~0. 10 mol/l, preferably 0.02 to 0.05 mol/l.
酸化電位は参照電極に対して＋１．２〜１．８■の範囲
がよく、特に＋１，４■がより好ましい。The oxidation potential is preferably in the range of +1.2 to 1.8 cm with respect to the reference electrode, and particularly preferably +1.4 cm.
酸化電位の上昇とともに基質の転換率は向上するが、目
的の２−メチル−１，４−ナフトキノンの選択率は＋１
．４Ｖで最大値を示す。As the oxidation potential increases, the conversion rate of the substrate increases, but the selectivity for the target 2-methyl-1,4-naphthoquinone increases by +1.
．． The maximum value is shown at 4V.
通電量は、通常、基質に対し、４．８〜６．ＯＦ／ｍｏ
ｂ である。The amount of current applied to the substrate is usually 4.8 to 6. OF/mo
b.
本発明の電解酸化は、通常室温で行われるが、これに限
定されず、適宜１０〜４０℃の範囲で行われる。The electrolytic oxidation of the present invention is usually carried out at room temperature, but is not limited thereto, and may be carried out at an appropriate temperature of 10 to 40°C.
本発明方法において、電解酸化反応により生成した２−
メチル−１，４−ナフトキノンは、陽極液を水に注ぎ、
ベンゼンあるいはクロロホルムで抽出し、有機層を例え
ばフロリシル（商品名、シリカゲル）を充てん剤とする
カラムクロマトグラフイーで処理して分離できる。In the method of the present invention, 2-
Methyl-1,4-naphthoquinone is prepared by pouring the anolyte into water,
The organic layer can be separated by extraction with benzene or chloroform and treatment with column chromatography using, for example, Florisil (trade name, silica gel) as a packing material.
このように、本発明方法によれば、比較的簡単ナ操作で
、２−メチル−１，４−ナフトキノンを好収率かつ好純
度で得ることができる。As described above, according to the method of the present invention, 2-methyl-1,4-naphthoquinone can be obtained in good yield and purity with relatively simple operations.
次に本発明を実施例に基づきさらに詳細に説明する。Next, the present invention will be explained in more detail based on examples.
実施例
グラスフィルターの隔膜を有するガラス製Ｈ型電解槽に
、各種の支持電解質を含む水一アセトン醍媒又は水一ア
セトニ１・リル溶媒１００ｍｌを装入し、基質濃度約０
．０５ｍｏｌ／ｌ溶媒となるように２−メチルナフクレ
ンを加えた。Example A glass H-type electrolytic cell having a glass filter diaphragm was charged with 100 ml of a water-acetone solvent or a water-acetonylic solvent containing various supporting electrolytes, and the substrate concentration was approximately 0.
．． 2-Methylnaphculene was added to give a solvent of 0.05 mol/l.
次いで、所定の電極材料を陽極、Ａｇ／Ａｇ＋＋（ＩＮ
ＫＣＪ！）を参照電極として電位を規制しながら、室
温下、所定量の電流を通電することにより電解酸化を行
った。Next, a predetermined electrode material is used as an anode, Ag/Ag++ (IN
KCJ! ) was used as a reference electrode, and electrolytic oxidation was performed by applying a predetermined amount of current at room temperature while regulating the potential.
反応終了後、反応混合物をクロロホルムで抽出し、有機
層中の反応生成物をＧｌｃ（シリコンＯ■一１ ０ １
．４ｍ，１ ５０’Ｃ）によって分析した。After the reaction is completed, the reaction mixture is extracted with chloroform, and the reaction product in the organic layer is extracted with Glc (silicon O 1 0 1
．． 4m, 150'C).
その結果を次表に示した。The results are shown in the table below.
Claims (1)
支持電解質とし、炭素電極を用いて電解酸化することを
特徴とする２−メチル−１，４−ナフ］・キノンの製造
方法。1. A method for producing 2-methyl-1,4-naph]quinone, which comprises electrolytically oxidizing 2-methylnaphthalene in aqueous acetone with sulfuric acid as a supporting electrolyte and a carbon electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56076101A JPS5837394B2 (en) | 1981-05-20 | 1981-05-20 | Method for producing 2-methyl-1,4-naphthoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56076101A JPS5837394B2 (en) | 1981-05-20 | 1981-05-20 | Method for producing 2-methyl-1,4-naphthoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57192277A JPS57192277A (en) | 1982-11-26 |
| JPS5837394B2 true JPS5837394B2 (en) | 1983-08-16 |
Family
ID=13595476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56076101A Expired JPS5837394B2 (en) | 1981-05-20 | 1981-05-20 | Method for producing 2-methyl-1,4-naphthoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5837394B2 (en) |
-
1981
- 1981-05-20 JP JP56076101A patent/JPS5837394B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57192277A (en) | 1982-11-26 |
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