CN106316915A - Method for preparing indole through dehydrocyclizing o-ethylaniline - Google Patents

Method for preparing indole through dehydrocyclizing o-ethylaniline Download PDF

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Publication number
CN106316915A
CN106316915A CN201510347011.1A CN201510347011A CN106316915A CN 106316915 A CN106316915 A CN 106316915A CN 201510347011 A CN201510347011 A CN 201510347011A CN 106316915 A CN106316915 A CN 106316915A
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indole
catalyst
ethyl aniline
dehydrocyclization
ethyl
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CN201510347011.1A
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CN106316915B (en
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赵思远
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China Petroleum and Chemical Corp
Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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China Petroleum and Chemical Corp
Research Institute of Nanjing Chemical Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Indole Compounds (AREA)

Abstract

The invention relates to a method for preparing indole through dehydrocyclizing o-ethylaniline. The method is characterized in that an RU-Al2O3 used as a catalyst boric acid adopted as a cocatalyst are added to a slurry bed reactor, nitrogen is introduced before a reaction to displace air, and o-ethylaniline is dehydrocyclized under a oxygen-free condition in order to synthesize indole. The method has the characteristics of low reaction temperature, easiness in operation and high indole selectivity.

Description

A kind of method of o ethyl aniline dehydrocyclization indole
Technical field
The present invention relates to a kind of indole production technology, belong to field of fine chemical.
Background technology
Indole is the intermediate producing tryptophan, is also the raw material of a series of pharmaceuticals, spice, dyestuff and other organic intermediate, and the preparation method of domestic and international indole is few, and the method for large-scale production indole mainly has ethylene glycol-aniline process and o-nitroethylbenzene method.
Ethylene glycol-aniline process needs substantial amounts of aniline as diluent, and aniline recovery energy consumption is high, and product purity is low, the shortcoming such as need to repeatedly purify, production cost is high.
O-nitroethylbenzene method first passes through o-nitroethylbenzene reduction and obtains o ethyl aniline, then o ethyl aniline adds dehydrocyclization in fixed bed reactors and prepares indole, and o ethyl aniline dehydrocyclization uses Al mostly2O3、SiO2-Al2O3, but it is high to there is reaction temperature, and typically more than 600 DEG C, indole yield relatively low (less than 30%), the later stage, interpolation copper and boron prepared CuO-Al by improving catalyst2O3-B2O3Three-way catalyst, for the dehydrocyclization of o ethyl aniline, is greatly improved yield and conversion ratio, but it is high (about 700 DEG C) to there is also reaction temperature, B in catalyst2O3Due to high temperature, easily running off in course of reaction, catalyst performance also can be gradually reduced, and the B run off2O3Reactor outlet inwall can be condensed upon, cause reactor plugs, there is also the shortcomings such as energy consumption is high, equipment investment is big simultaneously.
Catalyst of a CN1597111A indole using o-ethyl aniline catalytic dehydrocyclization and preparation method thereof, the present invention relates to o ethyl aniline dehydrocyclization catalyst preparing indole and preparation method thereof, this catalyst is with ZSM-5 as carrier, and at least a part of which contains one or more in copper, chromium, zinc, ferrum, nickel, palladium and platinum and oxide thereof.And use under the effect of this catalyst, by o ethyl aniline together with steam, dehydrocyclization aromatisation generates indole in the absence of oxygen, then through the higher indole product of rectification isolated purity.
Document " copper aluminum borate for indole synthesis prepares and catalytic performance is studied ", mainly describes preparation Cu-Al-B ternary system catalyst and prepares indole, in fixed bed reactors, reaction temperature 873～923K, air speed 0.1h for o ethyl aniline dehydrocyclization-1, when adding the steam of 10 times of materials, indole yield reaches 78.5%, o ethyl aniline conversion ratio more than 95%, indole selectivity more than 90%.
Document " technical study of o-nitroethylbenzene synthesis of indole ", mainly introduces with Pt-Al2O3For catalyst, in fixed bed reactors, ortho-nitraniline catalytic cyclization prepares indole, and optimum process condition is: reaction temperature is 400 DEG C；Response time is 3h；Catalyst amount 3% ；Proportioning raw materials n (o-nitroethylbenzene): n (hydrogen)=1:5 (mol:mo1).
Document " indole synthesis ", optimizes the production technology of indole.With o-nitroethylbenzene as raw material, through being catalyzed the adjacent aminoethylbenzene of oxidative synthesis；Again with aluminium oxide as catalyst, make adjacent aminoethylbenzene dehydrogenation closed loop synthesis of indole.
Summary of the invention
The present invention proposes a kind of method of o ethyl aniline catalytic dehydrogenation Cyclization indole, uses RU-Al2O3Catalyst, boric acid is promoter, in paste state bed reactor, logical nitrogen displacement before reaction, in the case of anaerobic, o ethyl aniline dehydrocyclization synthesis of indole.
Main technical schemes of the present invention: a kind of method of o ethyl aniline dehydrocyclization indole, is characterized in that with o ethyl aniline as raw material, in paste state bed reactor, with o ethyl aniline as raw material, with RU-Al2O3For catalyst, boric acid is promoter, and dehydrocyclization generates indole.
Usually, described catalyst RU-Al2O3, wherein the content of Ru is 3%～10%, and optimum add amount is 8%.
Described catalyst RU-Al2O3Addition (mass percent) is raw material o ethyl aniline 3%～6%, optimum add amount is 5%.
Addition is raw material o ethyl aniline 0.3%～the 0.7% of described promoter boric acid, optimum add amount is 0.5%.
Described dehydrocyclization temperature 280～400 DEG C, optimum temperature 380 DEG C.
One typical method of the present invention: equipped with in the autoclave of gas-liquid separator, add a certain amount of o ethyl aniline, RU-Al2O3 catalyst and promoter boric acid, after logical nitrogen displacement, it is warmed up to reaction temperature, slow release when pressure arrives 0.5MPa in still, release terminates to keep reaction temperature certain time, when in still, pressure continues slow release when reaching 0.3MPa, the most repeatedly until pressure is less than 0.1Mpa in still, reaction terminates discharging cooling discharge, and frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 90%, indole yield more than 80%, indole selectivity more than 92%.
The present invention has this technique, and to have reaction temperature low, easily operation, the selectivity high of indole.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail in.
Embodiment 1
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O38.64 gram, wherein the content of Ru is 3%, boric acid 0.86 gram, logical nitrogen displacement, it is warming up to 280 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 72%, indole yield more than 45%, indole selectivity more than 65%.
Embodiment 2
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O317.3 grams, wherein the content of Ru is 3%, boric acid 1.73 grams, logical nitrogen displacement, it is warming up to 300 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 75%, indole yield more than 50%, indole selectivity more than 70%.
Embodiment 3
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O314.4 grams, wherein the content of Ru is 8%, boric acid 1.44 grams, logical nitrogen displacement, it is warming up to 380 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 90%, indole yield more than 80%, indole selectivity more than 92%.
Embodiment 4
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O314.4 grams, wherein the content of Ru is 8%, boric acid 1.44 grams, logical nitrogen displacement, it is warming up to 400 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 87%, indole yield more than 75%, indole selectivity more than 90%.
Embodiment 5
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O38.64 gram, wherein the content of Ru is 10%, boric acid 0.86 gram, logical nitrogen displacement, it is warming up to 380 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 85%, indole yield more than 76%, indole selectivity more than 91%.
Embodiment 6
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O317.28 grams, wherein the content of Ru is 10%, boric acid 1.9 grams, logical nitrogen displacement, it is warming up to 380 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 80%, indole yield more than 70%, indole selectivity more than 90%.
Embodiment 7
Equipped with in the 0.5L autoclave of gas-liquid separator, add 300 milliliters of o ethyl anilines, catalyst RU-Al2O38.64 gram, wherein the content of Ru is 10%, boric acid 0.86 gram, logical nitrogen displacement, it is warming up to 280 DEG C, Deng in still during pressure 0.5Mpa, slow release, release terminates to keep reaction temperature, when in still, pressure reaches the 0.3Mpa slow release of continuation, the most repeatedly until pressure is less than 0.1Mpa in still, reaction end discharging cooling down, frozen water cooled product indole separates out from solution.O ethyl aniline conversion ratio more than 50%, indole yield more than 32%, indole selectivity more than 65%.

Claims (9)

1. a method for o ethyl aniline dehydrocyclization indole, is characterized in that with o ethyl aniline as raw material, in paste state bed reactor, with o ethyl aniline as raw material, with RU-Al2O3For catalyst, boric acid is promoter, and dehydrocyclization generates indole.
Method the most according to claim 1, it is characterised in that catalyst RU-Al2O3, wherein the content of Ru is 3%～10%.
Method the most according to claim 2, it is characterised in that catalyst RU-Al2O3, wherein the content of Ru is 8%.
Method the most according to claim 1, it is characterised in that catalyst RU-Al2O3Addition (mass percent) is raw material o ethyl aniline 3%～6%.
Method the most according to claim 4, it is characterised in that catalyst RU-Al2O3Addition (mass percent) be the 5% of raw material o ethyl aniline.
Method the most according to claim 1, it is characterised in that the addition of promoter boric acid is the 0.3%～0.7% of raw material o ethyl aniline.
Method the most according to claim 6, it is characterised in that the addition of promoter boric acid is the 0.5% of raw material o ethyl aniline.
Method the most according to claim 1, it is characterised in that dehydrocyclization temperature 280～400 DEG C.
Method the most according to claim 8, it is characterised in that dehydrocyclization temperature 380 DEG C.
CN201510347011.1A 2015-06-23 2015-06-23 A kind of method of o ethyl aniline dehydrocyclization indoles Active CN106316915B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112047871A (en) * 2020-10-14 2020-12-08 南京大学 Preparation method of indole compound
CN112724067A (en) * 2021-01-13 2021-04-30 江苏普洛德化学科技有限公司 Preparation process of indigo and obtained intermediate indoline

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63196562A (en) * 1987-02-09 1988-08-15 Idemitsu Kosan Co Ltd Production of indoles
US5332838A (en) * 1988-03-29 1994-07-26 Amoco Corporation Cyclization process utilizing copper aluminum borate as a catalyst
JPH08176106A (en) * 1994-12-21 1996-07-09 Osaka Gas Co Ltd Production of indoline, production of indole, catalyst therefor and production of catalyst therefor
CN1597111A (en) * 2004-08-04 2005-03-23 南京工业大学 Catalyst for preparation indole using o-ethyl aniline catalytic dehydrocyclization and its preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63196562A (en) * 1987-02-09 1988-08-15 Idemitsu Kosan Co Ltd Production of indoles
US5332838A (en) * 1988-03-29 1994-07-26 Amoco Corporation Cyclization process utilizing copper aluminum borate as a catalyst
JPH08176106A (en) * 1994-12-21 1996-07-09 Osaka Gas Co Ltd Production of indoline, production of indole, catalyst therefor and production of catalyst therefor
CN1597111A (en) * 2004-08-04 2005-03-23 南京工业大学 Catalyst for preparation indole using o-ethyl aniline catalytic dehydrocyclization and its preparation method

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DARRELL DEAN，等: "The effect of temperature, catalyst and sterics on the rate of N-heterocycle dehydrogenation for hydrogen storage", 《NEW J. CHEM.》 *
朱优江,等: "铈修饰的硼铝酸铜催化邻乙基苯胺脱氢环化制备吲哚的催化性能", 《分子催化》 *
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112047871A (en) * 2020-10-14 2020-12-08 南京大学 Preparation method of indole compound
CN112047871B (en) * 2020-10-14 2022-06-21 南京大学 Preparation method of indole compound
CN112724067A (en) * 2021-01-13 2021-04-30 江苏普洛德化学科技有限公司 Preparation process of indigo and obtained intermediate indoline

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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee after: China Petroleum & Chemical Corp.

Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd.

Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699

Patentee before: China Petroleum & Chemical Corp.

Patentee before: Nanhua Group Research Institute