JPS5852032B2 - Method for producing 6-substituted-1,4-naphthoquinone - Google Patents
Method for producing 6-substituted-1,4-naphthoquinoneInfo
- Publication number
- JPS5852032B2 JPS5852032B2 JP57034955A JP3495582A JPS5852032B2 JP S5852032 B2 JPS5852032 B2 JP S5852032B2 JP 57034955 A JP57034955 A JP 57034955A JP 3495582 A JP3495582 A JP 3495582A JP S5852032 B2 JPS5852032 B2 JP S5852032B2
- Authority
- JP
- Japan
- Prior art keywords
- substituted
- naphthoquinone
- salt
- acid
- 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
Links
- -1 6-substituted-1,4-naphthoquinone Chemical class 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003115 supporting electrolyte Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 claims description 2
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002791 naphthoquinones Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- CGYGETOMCSJHJU-UHFFFAOYSA-N 2-chloronaphthalene Chemical compound C1=CC=CC2=CC(Cl)=CC=C21 CGYGETOMCSJHJU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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２一置換ナフタレンの電解酸化により６−置換
−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 relates to a process for producing 6-substituted-1,4-naphthoquinones in good yields by electrolytic oxidation of 2-monosubstituted naphthalenes.
６−置換−１，４ナフトキノンは医薬中間体として重要
な化合物であり、従来は２一置換ナフタレンあるいはナ
フトール誘導体の試薬酸化により合成されている。6-Substituted-1,4 naphthoquinones are important compounds as pharmaceutical intermediates, and have conventionally been synthesized by reagent oxidation of 2-substituted naphthalenes or naphthol derivatives.
しかしこの方法は量論的に多量の試薬を必要とし、その
結果として廃液にクロムなどの有害な重金属塩が含まれ
るので、その除去に煩雑な操作を必要とする欠点がある
。However, this method requires a stoichiometrically large amount of reagents, and as a result, the waste liquid contains harmful heavy metal salts such as chromium, which has the drawback of requiring complicated operations for removal.
本発明者らは、このような従来法に代る新しい６−置換
−１，４−ナフトキノンの製造法を開発するため鋭意研
究を重ねた結果、２一置換ナフタレンを特定の溶媒中で
所定の支持電解質の存在のもとに所定の電極材料を用い
て電解酸化することにより、目的の６−置換−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 6-substituted-1,4-naphthoquinone to replace the conventional method. The desired 6-substituted-1,4-
We discovered that naphthoquinone can be synthesized.
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、２一置換ナフタレンを含水アセトン
あるいは含水アセトニトリル中で、硫酸、トリフルオロ
メタンスルホン酸、ｐ−）ルエンスルホン酸あるいはそ
の塩、テトラフルオロ硼酸あるいはその塩、過塩素塩あ
るいはその塩を支持電解質とし、炭素あるいは二酸化鉛
電極を用いて電解酸化することを特徴とする６−置換−
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 supports 2-monosubstituted naphthalene in hydrous acetone or acetonitrile with sulfuric acid, trifluoromethanesulfonic acid, p-)luenesulfonic acid or its salt, tetrafluoroboric acid or its salt, perchlorate or its salt. 6-substitution, characterized by electrolytic oxidation using a carbon or lead dioxide electrode as an electrolyte
A method for producing 1,4-naphthoquinone is provided.
本発明方法は隔膜を有する電解槽に支持電解質として上
記の物質を含む含水アセトンあるいは含水アセトニトリ
ルを溶媒として装入し、陽極室に原料の２一置換ナフタ
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 or hydrous acetonitrile containing the above-mentioned substances is charged as a supporting electrolyte into an electrolytic cell having a diaphragm, and a potential or current is applied by a conventional method except for adding the raw material 2-substituted naphthalene to the anode chamber. This can be carried out by performing electrolytic oxidation under controlled conditions.
２一置換ナフタレンとしては、ナフタレンの２位に、塩
素、臭素などのハロゲン、アセトキシ、ベンゾイルオキ
シなどのアシルオキシの他、ニトロ基、シアノ基、カル
ボキシル基、Ｎ−置換又は未置換のアミド基などの不活
性基を有するものが挙げられる。2-Substituted naphthalene includes, at the 2-position of naphthalene, a halogen such as chlorine or bromine, an acyloxy such as acetoxy or benzoyloxy, a nitro group, a cyano group, a carboxyl group, an N-substituted or unsubstituted amide group, etc. Examples include those having an inert group.
支持電解質の濃度は媒体に対して通常０．０５〜０．２
ｍｏｌｌ／ ｌである。The concentration of supporting electrolyte is usually 0.05-0.2 relative to the medium.
mol/l.
溶媒中の水含量は１０〜２０容積％がよいがこれに限定
されない。The water content in the solvent is preferably 10 to 20% by volume, but is not limited thereto.
電極としては陽極には炭素あるいは二酸化鉛電極を用い
る。As an electrode, a carbon or lead dioxide electrode is used as an anode.
また陰極には炭素板あるいは白金板を用いる。Further, a carbon plate or a platinum plate is used for the cathode.
陽極質における２一置換ナフタレンの濃度は通常０．０
１〜０．１０ｍｏ １１／１！であり、好ましくは０．
０２〜０．０５ ｍｏ ｉｔ／１１である。The concentration of 2-monosubstituted naphthalene in the anolyte is usually 0.0
1~0.10mo 11/1! and preferably 0.
02-0.05 mo it/11.
酸化電位は参照電極に対して＋１．２〜１．８■の範囲
がよく、例えば、２−ブロモナフタレンに対しては＋１
．４Ｖ、そのほかの基質に対しては＋１．６ｖがより好
ましい。The oxidation potential is preferably in the range of +1.2 to 1.8 cm relative to the reference electrode, for example, +1 for 2-bromonaphthalene.
．． 4V, more preferably +1.6V for other substrates.
酸化電位の上昇とともに基質の転換率は向上するが、目
的とするナフトキノン誘導体の選択率は低下する。As the oxidation potential increases, the conversion rate of the substrate increases, but the selectivity for the desired naphthoquinone derivative decreases.
通電量は通常基質に対し６．０〜７．２Ｆ／ｍｏ仄ある
。The amount of current applied to the substrate is usually between 6.0 and 7.2 F/mo.
本発明の電解酸化は通常１５°Ｃ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 15°C, but is not limited thereto, and may be carried out at an appropriate temperature in the range 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６−置
換−１，４−ナフトキノンは陽極液を水に注ぎ、クロロ
ホルムで抽出し、クロロホルム層をいったん蒸発乾固し
、残渣をベンゼン−クロロホルム等容積混合物に溶解し
、シリカゲルを充てん剤とするカラムクロマトグラフィ
ーで処理して分離できる。The 6-substituted-1,4-naphthoquinone produced by the electrolytic oxidation reaction in the method of the present invention is obtained by pouring the anolyte into water, extracting with chloroform, evaporating the chloroform layer to dryness, and adding the residue to an equal volume mixture of benzene and chloroform. It can be dissolved and separated by column chromatography using silica gel as a packing material.
このように本発明方法によれば、比較的簡単な操作で６
−置換−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, 6
-Substituted-1,4-naphthoquinone can be obtained in good yield and purity.
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−アセトン溶媒又は水−ア
セトニトリル溶媒１００ＴＩＬｌを装入し、基質濃度約
０．０５ ｍａｌ／１１溶媒となるように２−クロロナ
フタレンをカロえた。Example 100 TIL of water-acetone solvent or water-acetonitrile solvent containing various supporting electrolytes was charged into a glass H-type electrolytic cell having a glass filter diaphragm so that the substrate concentration was approximately 0.05 mal/11 solvent. Added 2-chloronaphthalene.
次いで所定の電極材料を陽極、Ａ＆／Ａｇ＋（ＩＮＫＣ
７）を参照電極として電位を規制しながら、水浴で１５
℃に保ちながら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, A&/Ag+ (INKC
7) as a reference electrode while regulating the potential for 15 minutes in a water bath.
Electrolytic oxidation was performed by applying a predetermined amount of current while maintaining the temperature at °C.
反応終了後、反応混合物をクロロホルムで抽出し、クロ
ロホルム層中の反応生成物をガスクロマトグラフィー（
充填剤シリコン０Ｖ−１７，４ｍ。After the reaction was completed, the reaction mixture was extracted with chloroform, and the reaction products in the chloroform layer were analyzed by gas chromatography (
Filler silicone 0V-17.4m.
１６０°Ｃ）によって分析した。160°C).
Claims (1)
ル−水媒体中において硫酸、トリフルオロメタンスルホ
ン酸あるいはその塩、テトラフルオロ硼酸あるいはその
塩、過塩素酸あるいはその塩、ｐ−トルエンスルホン酸
あるいはその塩を支持電解質として、炭素あるいは二酸
化鉛電極を用いて電解酸化することを特徴とする６−置
換１゜４−ナフトキノンの製造方法。12 Monosubstituted naphthalene in an acetone-water or acetonitrile-water medium with sulfuric acid, trifluoromethanesulfonic acid or its salt, tetrafluoroboric acid or its salt, perchloric acid or its salt, p-toluenesulfonic acid or its salt as a supporting electrolyte. 1. A method for producing 6-substituted 1°4-naphthoquinone, which comprises electrolytic oxidation using a carbon or lead dioxide electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57034955A JPS5852032B2 (en) | 1982-03-05 | 1982-03-05 | Method for producing 6-substituted-1,4-naphthoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57034955A JPS5852032B2 (en) | 1982-03-05 | 1982-03-05 | Method for producing 6-substituted-1,4-naphthoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58153792A JPS58153792A (en) | 1983-09-12 |
| JPS5852032B2 true JPS5852032B2 (en) | 1983-11-19 |
Family
ID=12428577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57034955A Expired JPS5852032B2 (en) | 1982-03-05 | 1982-03-05 | Method for producing 6-substituted-1,4-naphthoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5852032B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4397730A (en) * | 1982-06-30 | 1983-08-09 | International Business Machines Corporation | Electrolytic cells with alkaline electrolytes containing trifluoromethylane sulfonic acid |
-
1982
- 1982-03-05 JP JP57034955A patent/JPS5852032B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58153792A (en) | 1983-09-12 |
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