CN103539718B - The production method of indoles - Google Patents
The production method of indoles Download PDFInfo
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- CN103539718B CN103539718B CN201210239872.4A CN201210239872A CN103539718B CN 103539718 B CN103539718 B CN 103539718B CN 201210239872 A CN201210239872 A CN 201210239872A CN 103539718 B CN103539718 B CN 103539718B
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- reaction
- indoles
- ethylene glycol
- main reaction
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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 present invention relates to a kind of production method of indoles, mainly solve the problem that in prior art, indoles yield is lower.The present invention comprises aniline by adopting, the raw material of ethylene glycol enters pre-reaction zone, with pre-reaction catalyst exposure, generate the mixture comprising β-anilino-ethanol, then main reaction region is entered, with main reaction catalyst exposure, generate the technical scheme comprising the product of indoles, solve this problem preferably, can be used in the industrial production of indoles.
Description
Technical field
The present invention relates to a kind of production method of indoles.
Background technology
Indoles is the important source material of system each medicine, agricultural chemicals, spices, dyestuff and fodder additives, is important heterocycle fine-chemical intermediate.The throughput in the current whole world is 7000t/a.Along with the development of its applied research, derived medicine and the agricultural chemicals of many important high added values by it, particularly the market requirement rapid development of current indole derivatives tryptophane, 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.The method that China mainly applies this backwardness at present produces indoles, and meanwhile, China successfully realizes the industrialization of fourth indole synthesis tryptophane now, and therefore, the technique being badly in need of substituting is simple, the new technology of environmental friendliness and the inexpensive synthesis of indole of cost.
With aniline and ethylene glycol for raw material heterogeneous catalyst One Step Synthesis of Indole not only low in raw material price, production cost is low, and operating procedure is simple, and environmental friendliness, has obvious advantage, is the most promising one of synthesis of indole.The eighties in 20th century, Japan carried out a large amount of correlative studys to this catalyzer.Matsuda etc. find that the reactions of catalyzer to aniline and ethylene glycol One Step Synthesis of Indole such as Cd, Cu, Ag and Zn all have certain activity (United States Patent (USP) 4436917).350 DEG C, under normal pressure, in fixed bed reaction, the yield of indoles all more than 20% (because aniline is excessive, in ethylene glycol).Wherein Ag/SiO
2the indoles yield of-ZnO catalyst reaches more than 40%.But experiment also finds a main problem: catalyzer is at a few hours inactivation, and yield straight line declines.This is mainly because aniline and indoles are all containing the atom N having lone-pair electron, and these materials chemisorption is on a catalyst strong especially, 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 first back loading 0.6%Co and 11%Ag of sub-dip method, obtained Ag-Co/SiO
2-ZnO catalyst.Result shows, under 1.0MPa, 375 DEG C of conditions, in fixed-bed reactor, and 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 regenerated catalyst is substantially constant.
Recently, domestic also beginning has carried out this research.Bibliographical information (catalysis journal .2003, V24 (6), 471-474) pickling process have developed Ag/SiO
2and Cu/SiO
2catalyzer, and the catalytic performance having investigated aniline, ethylene glycol One Step Synthesis of Indole.The indoles yield of two kinds of catalyzer can reach about 80%, but the very fast inactivation of catalyzer, and the yield reacting 3 hours rear catalysts declines a lot.
Still there is the lower shortcoming of indoles yield in prior art, the present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the indoles yield that exists in prior art is lower, provides a kind of production method of new indoles.The method is used for, in the production of indoles, having the advantage that in product, indoles yield is higher.
For solving the problem, the technical solution used in the present invention is as follows: a kind of production method of indoles, comprise aniline, the raw material of ethylene glycol enters pre-reaction zone, with pre-reaction catalyst exposure, generate the mixture comprising β-anilino-ethanol, then enter main reaction region, with main reaction catalyst exposure, generate the product comprising 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 is catalyst based; Described pre-reaction zone reaction conditions is: temperature of reaction 300 ~ 400 DEG C, and reaction pressure counts 0 ~ 0.3Mpa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 1 ~ 10:1; Main reaction region reaction conditions is: temperature of reaction 330 ~ 450 DEG C, and reaction pressure counts 0 ~ 0.3Mpa with gauge pressure; The hydrogen that volume fraction is 0.01 ~ 5% is added in the charging of described main reaction region; 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.
Ag or Cu of the present invention is catalyst based adopts conventional pickling process preparation, selects commercially available carrier.Primary Catalysts needs hydrogen mixed gas to reduce before use, and general hydrogen volume content is 5 ~ 100%, and gas mixture volume space velocity was at 100 ~ 1000 hours
-1, reduction temperature is between 100 ~ 500 DEG C, and the recovery time was at 1 ~ 72 hour.
The general water vapour adding massfraction 0.5 ~ 50% in the charging of main reaction region, to delay the inactivation of catalyzer, improves object product yield.When after the catalyst deactivation of main reaction region, after cutting out raw material, pass into nitrogen purging displacement clean after, passing into containing volume fraction is that the nitrogen of 0.1 ~ 10% oxygen and oxygen mixture regenerate, and after regenerate, continues use after reducing.
The present inventor passes through research and finds, 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 generation indoles.Adopt method of the present invention, first in pre-reaction zone aniline and ethylene glycol reforming be β-anilino-ethanol, the β-anilino-ethanol then formed and unreacted aniline, ethylene glycol enter main reaction region and continue reaction, generate indoles.Ethylene glycol activity is high, easily becomes the side reaction 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 reduce the side reaction of ethylene glycol on Primary Catalysts, 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 is catalyst based; Described pre-reaction zone reaction conditions is: temperature of reaction 300 ~ 400 DEG C, and reaction pressure counts 0 ~ 0.3Mpa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 1 ~ 10:1; Main reaction region reaction conditions is: temperature of reaction 330 ~ 450 DEG C, and reaction pressure counts 0 ~ 0.3Mpa with gauge pressure; The hydrogen that volume fraction is 0.01 ~ 5% is added in the charging of described main reaction region; 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%, achieves 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, temperature of reaction 300 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates the mixture comprising β-anilino-ethanol, then enters main reaction region, with Cu/SiO
2catalyst exposure, Cu load quality mark is 10%, temperature of reaction 330 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates indoles product.Pre-reaction zone is fixed bed, and main reaction region is fixed bed, adds the hydrogen that volume fraction is 0.01% 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 condition and the step of embodiment 1, aniline and ethylene glycol enter pre-reaction zone with mass ratio 10:1, with γ-Al
2o
3contact, temperature of reaction 400 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates the mixture comprising β-anilino-ethanol, then enters main reaction region, with Ag/SiO
2catalyst exposure, Ag load quality mark is 10%, temperature of reaction 450 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates indoles product.Described pre-reaction zone is fixed bed, and main reaction region is fixed bed, adds the hydrogen that volume fraction is 5% 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 condition and the step of embodiment 1, aniline and ethylene glycol enter pre-reaction zone with mass ratio 1:1, with γ-Al
2o
3contact, temperature of reaction 330 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates the mixture comprising β-anilino-ethanol, then enters main reaction region, with Ag/SiO
2catalyst exposure, Ag load quality mark is 0.5%, temperature of reaction 375 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates indoles product.Add aniline liquid phase feeding in the charging of main reaction region, liquid phase feeding amount and pre-reaction zone combined feed total feed mass ratio are 0.6:1, add the hydrogen that volume fraction is 1% 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 condition and the step of embodiment 1, aniline and ethylene glycol enter pre-reaction zone with mass ratio 5:1, with γ-Al
2o
3contact, temperature of reaction 300 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates the mixture comprising β-anilino-ethanol, then enters main reaction region, with Cu/SiO
2catalyst exposure, Cu load quality mark is 20%, temperature of reaction 375 DEG C, under reaction pressure counts 0Mpa with gauge pressure, generates indoles product.Pre-reaction zone is fluidized-bed, and main reaction region is fluidized-bed, adds the hydrogen that volume fraction is 3% 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 condition and the step of embodiment 4, just main reaction catalyzer changes Cu/C into, and indoles mass yield is 72.1% (based on ethylene glycol).
[embodiment 6]
According to condition and the step of embodiment 4, just main reaction catalyzer changes Cu/Al into
2o
3, indoles mass yield is 80.4% (based on ethylene glycol).
[embodiment 7]
According to condition and the step of embodiment 4, 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 condition and the step of embodiment 4, just main reaction catalyzer changes Cu/Al into
2o
3, indoles mass yield is 80.4% (based on ethylene glycol).
[embodiment 9]
According to condition and the step of embodiment 4, just also add the water vapour of massfraction 10% in the charging of main reaction region, indoles mass yield is 84.8% (based on ethylene glycol).
[comparative example 1]
According to condition and the step of embodiment 9, just cancel pre-reaction zone, indoles mass yield is 80.3% (based on ethylene glycol).
Obviously, adopt method of the present invention, the object improving indoles yield can be reached, there is larger technical superiority, can be used in the industrial production of indoles.
Claims (5)
1. a production method for indoles, comprises aniline, the raw material of ethylene glycol enters pre-reaction zone, with pre-reaction catalyst exposure, generates the mixture comprising β-anilino-ethanol, then enters main reaction region, with main reaction catalyst exposure, generates the product comprising indoles; Wherein, described pre-reaction catalyzer is γ-Al
2o
3; Described main reaction catalyzer is that Ag or Cu is catalyst based.
2. the production method of indoles according to claim 1, it is characterized in that described pre-reaction zone is fixed bed or fluidized-bed, main reaction region is fixed bed or fluidized-bed.
3. the production method of indoles according to claim 1, it is characterized in that described pre-reaction zone reaction conditions is: temperature of reaction 300 ~ 400 DEG C, reaction pressure counts 0 ~ 0.3Mpa with gauge pressure, and aniline and ethylene glycol charge-mass ratio are 1 ~ 10:1; Main reaction region reaction conditions is: temperature of reaction 330 ~ 450 DEG C, reaction pressure counts 0 ~ 0.3Mpa with gauge pressure.
4. the production method of indoles according to claim 1, is characterized in that adding the hydrogen that volume fraction is 0.01 ~ 5% in the charging of described main reaction region.
5. the production method of indoles according to claim 1, it is characterized in that the load quality percentage ratio of Ag or Cu in described main reaction catalyzer is 0.5 ~ 30%, carrier is SiO
2, gac or Al
2o
3.
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| CN201210239872.4A CN103539718B (en) | 2012-07-12 | 2012-07-12 | The production method of indoles |
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| CN103539718B true CN103539718B (en) | 2015-09-09 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2644751B1 (en) * | 2016-05-31 | 2018-09-11 | Universitat De Valéncia | Procedure for obtaining B-Amino alcohols |
| 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 |
| CN114315613B (en) * | 2021-12-27 | 2024-03-19 | 江苏康恒化工有限公司 | Synthesis process of hydroxyethyl ethylenediamine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436917A (en) * | 1981-04-15 | 1984-03-13 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indoles |
| 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 |
-
2012
- 2012-07-12 CN CN201210239872.4A patent/CN103539718B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436917A (en) * | 1981-04-15 | 1984-03-13 | Mitsui Toatsu Chemicals, Inc. | Process for the preparation of indoles |
| 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 |
Non-Patent Citations (1)
| 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》.2008,第29卷(第2期),第159-162页. * |
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