CN103539718A - Indole production method - Google Patents

Indole production method Download PDF

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Publication number
CN103539718A
CN103539718A CN201210239872.4A CN201210239872A CN103539718A CN 103539718 A CN103539718 A CN 103539718A CN 201210239872 A CN201210239872 A CN 201210239872A CN 103539718 A CN103539718 A CN 103539718A
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China
Prior art keywords
reaction
indoles
production method
catalyzer
ethylene glycol
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CN103539718B (en
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齐国祯
钟思青
王洪涛
王莉
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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 an indole production method and mainly aims to solve the problem of lower indole yield in the prior art. The problem is better solved through the technical scheme that the production method comprises the steps: enabling raw materials, i.e., phenylamine and ethylene glycol, to enter a pre-reaction region to be in contact with a pre-reaction catalyst to generate an anilinoethanol-containing mixture; then, enabling the mixture to enter a main reaction region to be in contact with a main reaction catalyst to generate an indole-containing product. The indole production method can be used for the industrial production of indole.

Description

The production method of indoles
Technical field
The present invention relates to a kind of production method of indoles.
Background technology
Indoles is the important source material of each medicine of system, agricultural chemicals, spices, dyestuff and fodder additives, is important heterocycle fine-chemical intermediate.The throughput in the whole world is 7000t/a at present.Along with the development of its applied research, by it, derive medicine and the agricultural chemicals of many important high added values, the current market requirement rapid development of indole derivatives tryptophane particularly, only this item whole world distant view demand is at 100000t/a.Therefore, the market outlook of indoles are very wide.
Current industrial main employing ortho-chlorotolu'ene multistep processes synthesis of indole.Ortho-chlorotolu'ene obtains dihydroindole through chlorination, cyaniding, ammonification, Dehydration, then dehydrogenation and indoles.Because synthesis step is various, sepn process is numerous and diverse, and energy consumption is large, and cost is high, and preparation process produces a large amount of wastes and causes environmental pollution.China at present method of this backwardness of main application produces indoles, and meanwhile, China successfully realizes the industrialization of fourth indoles combination colour propylhomoserin now, therefore, is badly in need of that alternative technique is simple, the new technology of environmental friendliness and the inexpensive synthesis of indole of cost.
Not only cost of material is cheap as raw material heterogeneous catalyst One Step Synthesis of Indole to take aniline and ethylene glycol, and production cost is low, and operating procedure is simple, and environmental friendliness has obvious advantage, is that synthesis of indole is the most promising a kind of.The eighties in 20th century, Japan carried out a large amount of correlative studys to this catalyzer.The catalyzer such as discovery Cd, Cu, Ag and Zn such as Matsuda all have certain activity (United States Patent (USP) 4436917) to the reaction of aniline and ethylene glycol One Step Synthesis of Indole.Under 350 ℃, normal pressure, in fixed bed reaction the yield of indoles all more than 20% (because of aniline excessive, in ethylene glycol).Ag/SiO wherein 2the indoles yield of-ZnO catalyst reaches more than 40%.But a main problem is also found in experiment: catalyzer is at a few hours inactivation, and yield straight line declines.This is mainly all to contain due to aniline and indoles the N atom that has lone-pair electron, and these materials are strong especially at chemisorbed on catalyst, is difficult to desorption, is easy to cause catalyst carbon deposition inactivation.
T.Honda etc. have developed Ag-Co/SiO 2-ZnO catalyst (European patent 0427287).First he prepare specific surface by water glass and zinc nitrate coprecipitation method is 240m 2the SiO of/g 2-ZnO carrier, then uses the first back loading 0.6%Co of sub-dip method and 11%Ag, makes Ag-Co/SiO 2-ZnO catalyst.Result shows, under 1.0MPa, 375 ℃ of conditions, and in fixed-bed reactor, Ag-Co/SiO 2on-ZnO catalyst, the yield of aniline and ethylene glycol One Step Synthesis of Indole reaches 78%, and the stability of catalyzer is relatively good simultaneously.And this catalyzer of order can pass through charcoal regeneration, the performance of regeneration rear catalyst is substantially constant.
Recently, domesticly also start to have carried out this research.(471-474) pickling process has been developed Ag/SiO to bibliographical information for catalysis journal .2003, V24 (6) 2and Cu/SiO 2catalyzer, and investigated the catalytic performance of aniline, ethylene glycol One Step Synthesis of Indole.The indoles yield of two kinds of catalyzer can reach 80% left and right, but the very fast inactivation of catalyzer, and the yield that reacts 3 hours rear catalysts declines a lot.
Still there is the shortcoming that indoles yield is lower in prior art, the present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the lower problem of indoles yield existing in prior art, and a kind of production method of new indoles is provided.The method, for the production of indoles, has advantages of that in product, indoles yield is higher.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of production method of indoles, the raw material that comprises aniline, ethylene glycol enters pre-reaction zone, contact with pre-reaction catalyzer, generation comprises the mixture of β-anilino-ethanol, then enter main reaction region, contact with main reaction catalyzer, generate the product that comprises indoles.
In technique scheme, described pre-reaction zone is fixed bed or fluidized-bed, and main reaction region is fixed bed or fluidized-bed; Described pre-reaction catalyzer is γ-Al 2o 3; Described main reaction catalyzer is that Ag or Cu are catalyst based; Described pre-reaction zone reaction conditions is: 300～400 ℃ of temperature of reaction, and reaction pressure is counted 0～0.3Mpa with gauge pressure, and aniline and ethylene glycol charging mass ratio are 1～10:1; Main reaction region reaction conditions is: 330～450 ℃ of temperature of reaction, and reaction pressure is counted 0～0.3Mpa with gauge pressure; In the charging of described main reaction region, add volume fraction and be 0.01～5% hydrogen; In described main reaction catalyzer, the load quality percentage ratio of Ag or Cu is 0.5～30%, and carrier is SiO 2, gac or Al 2o 3.
The pickling process preparation that the catalyst based employing of Ag of the present invention or Cu is conventional, selects commercially available carrier.Primary Catalysts needs hydrogen mixed gas reduction before use, and general hydrogen volume content is 5～100%, and gas mixture volume air speed was at 100～1000 hours -1, reduction temperature is between 100～500 ℃, and the recovery time was at 1～72 hour.
The general water vapour that adds massfraction 0.5～50% in the charging of main reaction region, to delay the inactivation of catalyzer, improves object product yield.After the catalyst deactivation of main reaction region, cut out after raw material, pass into nitrogen purging displacement clean after, pass into and contain nitrogen and the oxygen mixture that volume fraction is 0.1～10% oxygen and regenerate, after regenerate, reduce rear continuation use.
The inventor finds by research, and one of them hydroxyl of the amino on aniline and ethylene glycol dehydration reaction can occur and generates β-anilino-ethanol, and β-anilino-ethanol can continue reaction and generates indoles.Adopt method of the present invention, first in pre-reaction zone, aniline and ethylene glycol are converted into β-anilino-ethanol, and the β-anilino-ethanol then forming and unreacted aniline, ethylene glycol enter main reaction region and continues reaction, generate indoles.Ethylene glycol activity is high, easily becomes the side reactions such as ring, polymerization, causes catalyst deactivation rate to accelerate simultaneously.In pre-reaction zone, catalyzer is γ-Al 2o 3, can conversion portion ethylene glycol, thus the side reaction of ethylene glycol on Primary Catalysts reduced, improve indoles yield, slow down Primary Catalysts inactivation simultaneously.
Adopt technical scheme of the present invention: described pre-reaction zone is fixed bed or fluidized-bed, main reaction region is fixed bed or fluidized-bed; Described pre-reaction catalyzer is γ-Al 2o 3; Described main reaction catalyzer is that Ag or Cu are catalyst based; Described pre-reaction zone reaction conditions is: 300～400 ℃ of temperature of reaction, and reaction pressure is counted 0～0.3Mpa with gauge pressure, and aniline and ethylene glycol charging mass ratio are 1～10:1; Main reaction region reaction conditions is: 330～450 ℃ of temperature of reaction, and reaction pressure is counted 0～0.3Mpa with gauge pressure; In the charging of described main reaction region, add volume fraction and be 0.01～5% hydrogen; In described main reaction catalyzer, the load quality percentage ratio of Ag or Cu is 0.5～30%, and carrier is SiO 2, gac or Al 2o 3, indoles mass yield reaches 84.8%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
 
Embodiment
[embodiment 1]
Aniline and ethylene glycol enter pre-reaction zone with mass ratio 7:1, with γ-Al 2o 3contact, 300 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates the mixture that comprises β-anilino-ethanol, then enters main reaction region, with Cu/SiO 2catalyzer contact, Cu load quality mark is 10%, 330 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates indoles product.Pre-reaction zone is fixed bed, and main reaction region is fixed bed, adds volume fraction and be 0.01% hydrogen in the charging of main reaction region.Product adopts gas chromatographic analysis, and indoles mass yield is 76.6% (based on ethylene glycol).
 
[embodiment 2]
According to the condition of embodiment 1 and step, aniline and ethylene glycol enter pre-reaction zone with mass ratio 10:1, with γ-Al 2o 3contact, 400 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates the mixture that comprises β-anilino-ethanol, then enters main reaction region, with Ag/SiO 2catalyzer contact, Ag load quality mark is 10%, 450 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates indoles product.Described pre-reaction zone is fixed bed, and main reaction region is fixed bed, adds volume fraction and be 5% hydrogen in the charging of main reaction region.Product adopts gas chromatographic analysis, and indoles mass yield is 81.5% (based on ethylene glycol).
 
[embodiment 3]
According to the condition of embodiment 1 and step, aniline and ethylene glycol enter pre-reaction zone with mass ratio 1:1, with γ-Al 2o 3contact, 330 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates the mixture that comprises β-anilino-ethanol, then enters main reaction region, with Ag/SiO 2catalyzer contact, Ag load quality mark is 0.5%, 375 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates indoles product.In the charging of main reaction region, add aniline liquid phase feeding, liquid phase feeding amount and pre-reaction zone combined feed total feed mass ratio are 0.6:1, add volume fraction and be 1% hydrogen in the charging of main reaction region.Product adopts gas chromatographic analysis, and indoles mass yield is 67.2% (based on ethylene glycol).
 
[embodiment 4]
According to the condition of embodiment 1 and step, aniline and ethylene glycol enter pre-reaction zone with mass ratio 5:1, with γ-Al 2o 3contact, 300 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates the mixture that comprises β-anilino-ethanol, then enters main reaction region, with Cu/SiO 2catalyzer contact, Cu load quality mark is 20%, 375 ℃ of temperature of reaction, reaction pressure is counted under 0Mpa with gauge pressure, generates indoles product.Pre-reaction zone is fluidized-bed, and main reaction region is fluidized-bed, adds volume fraction and be 3% hydrogen in the charging of main reaction region.Product adopts gas chromatographic analysis, and indoles mass yield is 83.7% (based on ethylene glycol).
 
[embodiment 5]
According to the condition of embodiment 4 and step, just main reaction catalyzer changes Cu/C into, and indoles mass yield is 72.1% (based on ethylene glycol).
 
[embodiment 6]
According to the condition of embodiment 4 and step, just main reaction catalyzer changes Cu/Al into 2o 3, indoles mass yield is 80.4% (based on ethylene glycol).
 
[embodiment 7]
According to the condition of embodiment 4 and step, just pre-reaction zone and main reaction region reaction pressure change 0.3Mpa in gauge pressure, and indoles mass yield is 79.4% (based on ethylene glycol).
 
[embodiment 8]
According to the condition of embodiment 4 and step, just main reaction catalyzer changes Cu/Al into 2o 3, indoles mass yield is 80.4% (based on ethylene glycol).
 
[embodiment 9]
According to the condition of embodiment 4 and step, just in the charging of main reaction region, also add the water vapour of massfraction 10%, indoles mass yield is 84.8% (based on ethylene glycol).
 
[comparative example 1]
According to the condition of embodiment 9 and step, just cancel pre-reaction zone, indoles mass yield is 80.3% (based on ethylene glycol).
 
Obviously, adopt method of the present invention, can reach the object that improves indoles yield, there is larger technical superiority, can be used in the industrial production of indoles.

Claims (6)

1. a production method for indoles, comprises that the raw material of aniline, ethylene glycol enters pre-reaction zone, contacts with pre-reaction catalyzer, generates the mixture that comprises β-anilino-ethanol, then enters main reaction region, contacts with main reaction catalyzer, generates the product that comprises indoles.
2. the production method of indoles according to claim 1, is characterized in that described pre-reaction zone is fixed bed or fluidized-bed, and main reaction region is fixed bed or fluidized-bed.
3. the production method of indoles according to claim 1, is characterized in that described pre-reaction catalyzer is γ-Al 2o 3; Described main reaction catalyzer is that Ag or Cu are catalyst based.
4. the production method of indoles according to claim 1, is characterized in that described pre-reaction zone reaction conditions is: 300～400 ℃ of temperature of reaction, and reaction pressure is counted 0～0.3Mpa with gauge pressure, and aniline and ethylene glycol charging mass ratio are 1～10:1; Main reaction region reaction conditions is: 330～450 ℃ of temperature of reaction, reaction pressure is counted 0～0.3Mpa with gauge pressure.
5. the production method of indoles according to claim 1, is characterized in that adding in the charging of described main reaction region volume fraction and is 0.01～5% hydrogen.
6. the production method of indoles according to claim 3, is characterized in that the load quality percentage ratio of Ag in described main reaction catalyzer or Cu is 0.5～30%, and carrier is SiO 2, gac or Al 2o 3.
CN201210239872.4A 2012-07-12 2012-07-12 The production method of indoles Active CN103539718B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2644751A1 (en) * 2016-05-31 2017-11-30 Universitat De Valéncia Procedure for obtaining B-Amino alcohols
CN112279799A (en) * 2019-07-26 2021-01-29 中石化南京化工研究院有限公司 Method for preparing spice-grade indole by extraction crystallization
CN114315613A (en) * 2021-12-27 2022-04-12 江苏康恒化工有限公司 Synthesis process of hydroxyethyl ethylenediamine

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US4436917A (en) * 1981-04-15 1984-03-13 Mitsui Toatsu Chemicals, Inc. Process for the preparation of indoles
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Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
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EP0427287A1 (en) * 1989-11-10 1991-05-15 MITSUI TOATSU CHEMICALS, Inc. Preparation process of indoles
CN101007779A (en) * 2006-01-26 2007-08-01 中国科学院大连化学物理研究所 Method and device for making indole
CN101007277A (en) * 2006-01-26 2007-08-01 中国科学院大连化学物理研究所 Catalyst for synthesis of indole and its preparation method

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Title
刘静，等: "《吲哚的直接气相合成: MgO助剂对Cu/SiO2催化剂性能的影响》", 《催化学报》, vol. 29, no. 2, 29 February 2008 (2008-02-29), pages 159 - 162 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2644751A1 (en) * 2016-05-31 2017-11-30 Universitat De Valéncia Procedure for obtaining B-Amino alcohols
WO2017207839A1 (en) * 2016-05-31 2017-12-07 Universitat De València Method for obtaining β-amino alcohols
CN112279799A (en) * 2019-07-26 2021-01-29 中石化南京化工研究院有限公司 Method for preparing spice-grade indole by extraction crystallization
CN112279799B (en) * 2019-07-26 2022-02-22 中石化南京化工研究院有限公司 Method for preparing spice-grade indole by extraction crystallization
CN114315613A (en) * 2021-12-27 2022-04-12 江苏康恒化工有限公司 Synthesis process of hydroxyethyl ethylenediamine
CN114315613B (en) * 2021-12-27 2024-03-19 江苏康恒化工有限公司 Synthesis process of hydroxyethyl ethylenediamine

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