JPS5938948B2 - Manufacturing method of indoles - Google Patents
Manufacturing method of indolesInfo
- Publication number
- JPS5938948B2 JPS5938948B2 JP54112420A JP11242079A JPS5938948B2 JP S5938948 B2 JPS5938948 B2 JP S5938948B2 JP 54112420 A JP54112420 A JP 54112420A JP 11242079 A JP11242079 A JP 11242079A JP S5938948 B2 JPS5938948 B2 JP S5938948B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- anilines
- indoles
- ethylene glycol
- catalyst
- 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
Landscapes
- Indole Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、インドール類の新規製法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing indoles.
インドール類は、香料、染料、アルカロイド、あるいは
必須アミノ酸であるトリプトファンなどの原料として、
工業的に用途を種々有している。Indoles are used as raw materials for fragrances, dyes, alkaloids, and the essential amino acid tryptophan.
It has various industrial uses.
従来、アニリン類を出発原料とするインドール類の製法
は、種々知られているが、そのほとんど北”て）（Ｒ２
＋Ｃ１Ｈ。Conventionally, various methods for producing indoles using anilines as starting materials have been known, but most of them are
+C1H.
哀がアニリン類の分子内脱水素環化によるものである。This is due to intramolecular dehydrogenation of anilines.
従つて、原料アニリン類としては、Ｎ−（β−ヒドロキ
シ）アルキルアニリン、０−アルキルアニリンあるいは
Ｎ−ホルミルー ０−トルイジンなどの特殊なものに限
定され、その調製もはん雑である。本発明者らは、これ
ら公知法と異なるインドール類の製法を確立することを
目的とし、鋭意研究を行つた。Therefore, raw anilines are limited to special ones such as N-(β-hydroxy)alkylaniline, 0-alkylaniline or N-formyl-0-toluidine, and their preparation is complicated. The present inventors conducted extensive research with the aim of establishing a method for producing indoles that is different from these known methods.
その結果、アニリン類とエチレングリコールを脱水素触
媒下に気相接触させれば、インドール類を極めて工業的
に製造できることを知見し、本発明に到達した。本発明
は、公知法のようにアニリン類の分子内脱水素環化によ
る反応でなく、アニリン類とエチレングリコールの反応
によりインドール類を製造するものであるため、使用に
供される原料アニリン類は特殊なものに限定されない。As a result, the inventors discovered that indoles can be produced in an extremely industrial manner by bringing anilines and ethylene glycol into gas phase contact under a dehydrogenation catalyst, leading to the present invention. In the present invention, indoles are produced not by intramolecular dehydrocyclization of anilines as in known methods, but by a reaction between anilines and ethylene glycol. Not limited to special items.
すなわち本発明における原料アニリン類は、次の一般式
で示される化合物が有用である。That is, as the raw material anilines in the present invention, compounds represented by the following general formula are useful.
□ＮＨＲ２
（ただし、式中Ｒ１は水素原子、アルキル基、アルコキ
シ基、ハロゲン原子、ニトロ基、を示し、Ｒ２は水素原
子、アルキル基、を示す。□NHR2 (In the formula, R1 represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a nitro group, and R2 represents a hydrogen atom or an alkyl group.
）これらアニリン類とエチレングリコールの反応は次式
により進行する。) The reaction between these anilines and ethylene glycol proceeds according to the following formula.
”・ −Ｒ、□
（ただし、式中のＲ１およびＲ２は前記と同じ意味を有
する。"-R, □ (However, R1 and R2 in the formula have the same meanings as above.
）従つて、理論的には等モル反応であるが、工業的には
エチレングリコール１モルに対しアニリン類を１〜５０
モル、好ましくは２〜１５モルというアニリン類過剰で
行うのがよい。本発明の反応は、２００〜４００℃、好
ましくは２５０〜３５０℃と、公知法に比較し低温で行
われる。本発明の触媒は、通常アルコールの脱水素に用
いられる触媒で、これらは例えば「反応別触媒分類表」
（化学工業社発行、昭和４６年９月１日発行）の第７４
〜７６頁に開示されている。) Therefore, theoretically it is an equimolar reaction, but industrially 1 to 50% of aniline is added to 1 mole of ethylene glycol.
It is advisable to use a molar excess of aniline, preferably 2 to 15 molar excess. The reaction of the present invention is carried out at a lower temperature of 200 to 400°C, preferably 250 to 350°C, compared to known methods. The catalyst of the present invention is a catalyst normally used for the dehydrogenation of alcohol, and these are listed in the "Catalyst Classification Table by Reaction", for example.
(Published by Kagaku Kogyosha, September 1, 1971) No. 74
It is disclosed on pages 76 to 76.
次のものは、その例示である。ＣｕｓＣｒ，．ＣＯ，．
ＦｅｘＮｉｘＺｎ．ＭｎｓＡｌ．ＣａＳＰｄ，．ＰｔＳ
Ｒｈなどの金属、およびこれら金属の酸化物。The following are examples. CusCr,. CO,.
FexNixZn. MnsAl. CaSPd,. PtS
Metals such as Rh and oxides of these metals.
これらは単独あるいは組合せて使用に供され、またケイ
ソウ土、活性白土、ゼオライト、シリカアルミナなどの
担体に担持して使用してもよい。These may be used alone or in combination, or may be supported on a carrier such as diatomaceous earth, activated clay, zeolite, or silica alumina.
これらのうち、Ｃｕ−Ｃｒ．Ｃｕ−ＣＯ、およびこれら
を上記担体に担持したもの、Ｐｄ−ＳｉＯ２、Ｐｔ−Ｓ
ｉＯ２などが特に高い触媒作用を有している。本発明の
方法を実施するに際し、アニリン類とエチレングリコー
ルの所定モル比の混合液を調製し、これを完全に気化さ
せて窒素ガス、水素ガス、アンモニアガス、炭酸ガス、
空気、窒素酸化物などのキャリャーガスとともに触媒層
に送入する方法が便利である。Among these, Cu-Cr. Cu-CO and those supported on the above carrier, Pd-SiO2, Pt-S
iO2 and the like have particularly high catalytic activity. When carrying out the method of the present invention, a mixed solution of anilines and ethylene glycol at a predetermined molar ratio is prepared, and this is completely vaporized to produce nitrogen gas, hydrogen gas, ammonia gas, carbon dioxide gas, etc.
It is convenient to introduce the catalyst into the catalyst layer together with a carrier gas such as air or nitrogen oxide.
この場合の前記混合液の送入速度はＬ．Ｈ．Ｓ．Ｖ．（
液空間速度）が０．１〜２ｈｒ−１、好ましくは０．４
〜１５ｈＩ−一１がよい。その他、アニリン類およびエ
チレングリコールのそれぞれを加熱気化させて触媒層に
送入する方法、あるいはキャリャーガス中に気化同伴さ
せて触媒層に送入する方法等が採用される。反応後、常
法、例えば沢過、蒸留、抽出などの手段によつて、反応
系から目的物のインドール類を単離、取得することがで
きる。In this case, the feeding speed of the mixed liquid is L. H. S. V. (
liquid space velocity) is 0.1 to 2 hr-1, preferably 0.4
~15hI-1 is good. Other methods that can be employed include heating and vaporizing each of the anilines and ethylene glycol and feeding the latter into the catalyst layer, or vaporizing and entraining them in a carrier gas and feeding them into the catalyst layer. After the reaction, the target indoles can be isolated and obtained from the reaction system by conventional methods such as filtration, distillation, and extraction.
なお本発明で得られるインドール類は、上記原料アニリ
ン類に対応するもので、すなわち次の一般式で示される
。（ただし、式中Ｒ１およびＲ２は前記と同じ意味を有
す。）本発明は、新規反応によるインドール類の製法を
提供するもので、公知法に比較し、原料アニリン類を特
殊なものに選定、調製する必要がなく、しかも反応条件
も温和である、などの利点を有している。Note that the indoles obtained in the present invention correspond to the above-mentioned raw material anilines, that is, they are represented by the following general formula. (However, R1 and R2 in the formula have the same meanings as above.) The present invention provides a method for producing indoles by a new reaction, and the raw material anilines are specially selected compared to known methods. It has the advantages that it does not require preparation and the reaction conditions are mild.
次に、本発明の実施例を挙げる。Next, examples of the present invention will be given.
なお、各例で用いた反応管は、内径２５ＴｆＬＴ！Ｌ、
長さ４００ｍｍのパイレツクスガラス製の反応管である
。また、各例のインドールの収率は、いずれもエチレン
グリコール基準の単通収率である。実施例 １
反応管に、Ｃｕ−Ｃｒ触媒（日揮化学社製、Ｎ２Ｏｌ）
を１５ｍ１充填した後、アニリンとエチレングリコール
の混合液（モル比１０：１）を、Ｌ．Ｈ．Ｓ．Ｖ．（液
空間速度）０．４１ｈｒ−１の速度で予熱器に通して完
全に気化させて、水素ガス（１０ｍ１／Ｍｍ）とともに
２９０℃で送入し、５時間連続して反応を行つた。The reaction tube used in each example had an inner diameter of 25TfLT! L,
This is a Pyrex glass reaction tube with a length of 400 mm. Further, the yield of indole in each example is a single yield based on ethylene glycol. Example 1 Cu-Cr catalyst (manufactured by JGC Chemical Co., Ltd., N2Ol) was placed in the reaction tube.
After filling 15 ml of L. H. S. V. (Liquid hourly space velocity) The mixture was completely vaporized by passing through a preheater at a rate of 0.41 hr-1, and then fed together with hydrogen gas (10 ml/Mm) at 290° C., and the reaction was continued for 5 hours.
反応後、得られた油状生成物をガスクロマトグラフイ一
で分析した結果、インドールの収率は４４．６％であつ
た。After the reaction, the resulting oily product was analyzed by gas chromatography, and the yield of indole was 44.6%.
実施例 ２
反応管に、Ｃｕ−ＣＯ−ケイソウ土（日揮化学社製、Ｘ
−３２１）を２０ｍ１充填した後、アニリンとエチレン
グリコールの混合液（モル比２：１）をＬ．Ｈ．Ｓ．．
（液空間速度）０．２８ｈｒ−１の速度で予熱器に通し
て完全に気化させて、水素ガス（２０ｍ１／ＭＯととも
に３２０℃で送入し、５時間連続して反応を行つた。Example 2 Cu-CO-diatomaceous earth (manufactured by JGC Chemical Co., Ltd.,
-321), and then a mixture of aniline and ethylene glycol (molar ratio 2:1) was added to L. H. S. ．．
The mixture was completely vaporized by passing it through a preheater at a rate of (liquid hourly space velocity) 0.28 hr-1, and hydrogen gas (20 ml/MO) was fed at 320° C. to carry out the reaction continuously for 5 hours.
反応後、得られた油状生成物をガスクロマトグラフイ一
で分析した結果、インドールの収率は１１．８％であつ
た。After the reaction, the resulting oily product was analyzed by gas chromatography, and the yield of indole was 11.8%.
実施例 ３
触媒として、２％Ｐｄ−シリカ球を２０ｍ１用いた他は
、実施例２と同様の方法で実験を行つた。Example 3 An experiment was conducted in the same manner as in Example 2, except that 20 ml of 2% Pd-silica spheres were used as a catalyst.
その結果、インドールの収率は１０．３％であつた。実
施例４〜８反応管にＣｕ−Ｃｒ触媒（日揮化学社製、Ｎ
２Ｏｌ）を１５ｍ１充填した後、アニリン類とエチレン
グリコールの混合液（モル比２：１）を、Ｌ．Ｈ．Ｓ．
Ｖ．（液空間速度）０．４３ｈｒ−１の速度ミくで予熱
器に通して完全に気化させて、水素ガス（２０ｍ１／７
ｗｔ）とともに３２０℃で送入し、６時間連続して反応
を行つた。As a result, the yield of indole was 10.3%. Examples 4 to 8 A Cu-Cr catalyst (manufactured by JGC Chemical Co., Ltd., N
After filling 15 ml of L.2Ol), a mixed solution of anilines and ethylene glycol (molar ratio 2:1) was added. H. S.
V. (Liquid space velocity) Pass through a preheater at a speed of 0.43 hr-1 to completely vaporize hydrogen gas (20 m1/7
wt) at 320°C, and the reaction was continued for 6 hours.
反応後、得られた油状生成物をガスクロマトグラフイ一
で分析した。After the reaction, the obtained oily product was analyzed by gas chromatography.
Claims (1)
に気相接触させることを特徴とするインドール類の製法
。1. A method for producing indoles, which comprises bringing anilines and ethylene glycol into gas phase contact under a dehydrogenation catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54112420A JPS5938948B2 (en) | 1979-09-04 | 1979-09-04 | Manufacturing method of indoles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP54112420A JPS5938948B2 (en) | 1979-09-04 | 1979-09-04 | Manufacturing method of indoles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5636451A JPS5636451A (en) | 1981-04-09 |
| JPS5938948B2 true JPS5938948B2 (en) | 1984-09-20 |
Family
ID=14586196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP54112420A Expired JPS5938948B2 (en) | 1979-09-04 | 1979-09-04 | Manufacturing method of indoles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5938948B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655366A (en) * | 1979-10-15 | 1981-05-15 | Mitsui Toatsu Chem Inc | Preparation of indoles |
| JPS5663958A (en) * | 1979-10-29 | 1981-05-30 | Mitsui Toatsu Chem Inc | Preparation of indole or its derivative |
| JPS56150062A (en) * | 1980-04-22 | 1981-11-20 | Mitsui Toatsu Chem Inc | Production of indole or indole derivative |
| US4456760A (en) * | 1981-04-15 | 1984-06-26 | Mitsui Toatsu Chemicals, Incorporated | Process for the preparation of indoles |
| US4376205A (en) * | 1981-04-15 | 1983-03-08 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indoles from anilines and ethanolamines |
| JPS57206656A (en) * | 1981-06-12 | 1982-12-18 | Mitsui Toatsu Chem Inc | Preparation of indole compound |
| JPS5835171A (en) * | 1981-08-25 | 1983-03-01 | Mitsui Toatsu Chem Inc | Improved method for preparation of indole |
| CH652392A5 (en) * | 1982-02-10 | 1985-11-15 | Ciba Geigy Ag | METHOD FOR PRODUCING INDOLES SUBSTITUTED IN THE 2,3 POSITION. |
| JPS58225061A (en) * | 1982-06-24 | 1983-12-27 | Mitsui Toatsu Chem Inc | Preparation of indole compound |
| JPS63196561A (en) * | 1987-02-07 | 1988-08-15 | Idemitsu Kosan Co Ltd | Production of indoles |
| CN111054326B (en) * | 2019-12-26 | 2022-12-27 | 太原理工大学 | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline |
-
1979
- 1979-09-04 JP JP54112420A patent/JPS5938948B2/en not_active Expired
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS=1963 * |
| JKRAINSKII HIMICHYESKII JURNAL=1962 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5636451A (en) | 1981-04-09 |
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