CN106316915B - A kind of method of o ethyl aniline dehydrocyclization indoles - Google Patents

A kind of method of o ethyl aniline dehydrocyclization indoles Download PDF

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CN106316915B
CN106316915B CN201510347011.1A CN201510347011A CN106316915B CN 106316915 B CN106316915 B CN 106316915B CN 201510347011 A CN201510347011 A CN 201510347011A CN 106316915 B CN106316915 B CN 106316915B
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indoles
catalyst
dehydrocyclization
aniline
ethyl
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CN106316915A (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 present invention relates to a kind of methods of o ethyl aniline catalytic dehydrogenation Cyclization indoles, using RU-Al2O3Catalyst, boric acid is co-catalyst, in paste state bed reactor, logical nitrogen displacement before reacting, in the case of anaerobic, the features such as o ethyl aniline dehydrocyclization synthesis of indole, the invention is low with reaction temperature with the technique, easy to operate, indoles high selectivity.

Description

A kind of method of o ethyl aniline dehydrocyclization indoles
Technical field
The present invention relates to a kind of indoles production technologies, belong to field of fine chemical.
Background technology
Indoles is the intermediate and a series of pharmaceuticals, fragrance, dyestuff and other organic intermediates for producing tryptophan Raw material, the preparation method of domestic and international indoles is few, and the method for mass producing indoles mainly has ethylene glycol-aniline process and adjacent nitre Base ethylbenzene method.
Ethylene glycol-aniline process needs a large amount of aniline as diluent, and aniline recovery high energy consumption, product purity is low, needs more Secondary purification, the shortcomings of production cost is high.
O-nitroethylbenzene method restores to obtain o ethyl aniline first by o-nitroethylbenzene, and then o ethyl aniline is added Dehydrocyclization prepares indoles in fixed bed reactors, and o ethyl aniline dehydrocyclization mostly uses greatly Al2O3、SiO2-Al2O3, but deposit In reaction temperature height, generally at 600 DEG C or more, indoles yield is relatively low（30% or less）, the later stage by improving catalyst, adds Copper and boron prepare CuO- Al2O3-B2O3Three-way catalyst is used for the dehydrocyclization of o ethyl aniline, yield is greatly improved And conversion ratio, but there is also reaction temperature height（700 DEG C or so）, B in catalyst2O3Due to high temperature, it is easy stream during the reaction It loses, catalyst performance can be also gradually reduced, and the B being lost in2O3Reactor outlet inner wall can be condensed upon, reactor plugs are caused, Simultaneously there is also high energy consumption, equipment investment is big the shortcomings of.
A kind of catalyst of indole using o-ethyl aniline catalytic dehydrocyclization of CN1597111A and preparation method thereof, this hair The bright o ethyl aniline that is related to prepares dehydrocyclization catalyst of indoles and preparation method thereof, the catalyst using ZSM-5 as carrier, In at least contain copper, chromium, zinc, iron, nickel, palladium and one or more of platinum and its oxide.And use the catalyst Under the action of, together by o ethyl aniline and vapor, dehydrocyclization aromatisation generates indoles in the absence of oxygen, then through essence Evaporate the higher indoles product of isolated purity.
Document《Copper aluminum borate for indole synthesis prepares and catalytic performance research》, mainly describe and prepare Cu-Al-B Ternary system catalyst prepares indoles for o ethyl aniline dehydrocyclization, in fixed bed reactors, reaction temperature 873~ 923K, air speed 0.1h-1, when adding the vapor of 10 times of substances, indoles yield reaches 78.5%, o ethyl aniline conversion ratio 95% More than, 90% or more indoles selectivity.
Document《The technical study of o-nitroethylbenzene synthesis of indole》, main to introduce with Pt-Al2O3For catalyst, in fixed bed In reactor, ortho-nitraniline catalytic cyclization prepares indoles, and optimum process condition is：Reaction temperature is 400 DEG C；Reaction time is 3h；Catalyst amount 3%；Raw material proportioning n (o-nitroethylbenzene)：N (hydrogen)=1：5(mol：mo1).
Document《Indole synthesis》, optimize the production technology of indoles.Using o-nitroethylbenzene as raw material, synthesized through catalysis oxidation Adjacent aminoethylbenzene；Again using aluminium oxide as catalyst, make adjacent aminoethylbenzene dehydrogenation and closed loop synthesis of indole.
Invention content
The present invention proposes a kind of method of o ethyl aniline catalytic dehydrogenation Cyclization indoles, using RU-Al2O3Catalyst, Boric acid is co-catalyst, and in paste state bed reactor, logical nitrogen displacement before reacting, in the case of anaerobic, o ethyl aniline is de- Hydrogen Cyclization indoles.
Main technical schemes of the present invention：A kind of method of o ethyl aniline dehydrocyclization indoles, it is characterized in that with adjacent second Base aniline is raw material, in paste state bed reactor, using o ethyl aniline as raw material, with RU-Al2O3For catalyst, boric acid is to help to urge Agent, dehydrocyclization generate indoles.
Usually, the catalyst RU- Al2O3, the wherein content of Ru is 3%~10%, optimum add amount 8%.
The catalyst RU- Al2O3Addition（Mass percent）It is the 3%~6% of raw material o ethyl aniline, it is best to add Amount is 5%.
The addition of the co-catalyst boric acid is the 0.3%~0.7% of raw material o ethyl aniline, optimum add amount 0.5%.
280~400 DEG C of the dehydrocyclization temperature, 380 DEG C of optimum temperature.
A kind of typical method of the present invention：In the autoclave equipped with gas-liquid separator, a certain amount of adjacent second is added Base aniline, RU-Al2O3 catalyst and co-catalyst boric acid after leading to nitrogen displacement, are warming up to reaction temperature, and pressure reaches in kettle Slow release when 0.5MPa, release terminate to be kept for reaction temperature certain time, continue when pressure reaches 0.3MPa in kettle slow Release, so repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling discharge, and ice water cooled product indoles is from molten It is precipitated in liquid.O ethyl aniline conversion ratio is 90% or more, and indoles yield is 80% or more, 92% or more indoles selectivity.
The features such as present invention is low with reaction temperature with the technique, easy to operate, indoles high selectivity.
Specific implementation mode
The present invention is described in detail with reference to embodiment.
Embodiment 1
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O38.64 grams, the wherein content of Ru is 3%, and 0.86 gram of boric acid leads to nitrogen displacement, is warming up to 280 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 72% or more, and indoles yield is 45% or more, 65% or more indoles selectivity.
Embodiment 2
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O317.3 grams, the wherein content of Ru is 3%, and 1.73 grams of boric acid leads to nitrogen displacement, is warming up to 300 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 75% or more, and indoles yield is 50% or more, 70% or more indoles selectivity.
Embodiment 3
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O314.4 grams, the wherein content of Ru is 8%, and 1.44 grams of boric acid leads to nitrogen displacement, is warming up to 380 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 90% or more, and indoles yield is 80% or more, 92% or more indoles selectivity.
Embodiment 4
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O314.4 grams, the wherein content of Ru is 8%, and 1.44 grams of boric acid leads to nitrogen displacement, is warming up to 400 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 87% or more, and indoles yield is 75% or more, 90% or more indoles selectivity.
Embodiment 5
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O38.64 grams, the wherein content of Ru is 10%, and 0.86 gram of boric acid leads to nitrogen displacement, is warming up to 380 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 85% or more, and indoles yield is 76% or more, 91% or more indoles selectivity.
Embodiment 6
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O317.28 grams, the wherein content of Ru is 10%, and 1.9 grams of boric acid leads to nitrogen displacement, is warming up to 380 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 80% or more, and indoles yield is 70% or more, 90% or more indoles selectivity.
Embodiment 7
In the 0.5L autoclaves equipped with gas-liquid separator, 300 milliliters of o ethyl anilines, catalyst RU- is added Al2O38.64 grams, the wherein content of Ru is 10%, and 0.86 gram of boric acid leads to nitrogen displacement, is warming up to 280 DEG C, waits pressure in kettles When 0.5Mpa, slow release, release terminates to keep reaction temperature, when pressure reaches 0.3Mpa and continues slow release in kettle, so Repeatedly until pressure is less than 0.1Mpa in kettle, reaction terminates discharging cooling down, and ice water cooled product indoles is precipitated from solution. O ethyl aniline conversion ratio is 50% or more, and indoles yield is 32% or more, 65% or more indoles selectivity.

Claims (9)

1. a kind of method of o ethyl aniline dehydrocyclization indoles, it is characterized in that using o ethyl aniline as raw material, in slurry bed system In reactor, using o ethyl aniline as raw material, with Ru-Al2O3For catalyst, boric acid is co-catalyst, and dehydrocyclization generates Yin Diindyl.
2. according to the method described in claim 1, it is characterized in that catalyst RU- Al2O3, the wherein mass percentage of Ru is 3%~10%.
3. according to the method described in claim 2, it is characterized in that catalyst RU- Al2O3, the wherein mass percentage of Ru is 8%。
4. according to the method described in claim 1, it is characterized in that catalyst RU- Al2O3Mass percent be raw material neighbour's second The 3%~6% of base aniline.
5. according to the method described in claim 4, it is characterized in that catalyst RU- Al2O3Mass percent be raw material neighbour's second The 5% of base aniline.
6. according to the method described in claim 1, it is characterized in that the mass percent of co-catalyst boric acid is raw material neighbour's ethyl The 0.3%~0.7% of aniline.
7. according to the method described in claim 6, it is characterized in that the mass percent of co-catalyst boric acid is raw material neighbour's ethyl The 0.5% of aniline.
8. according to the method described in claim 1, it is characterized in that 280~400 DEG C of dehydrocyclization temperature.
9. according to the method described in claim 8, it is characterized in that 380 DEG C of dehydrocyclization temperature.
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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

Citations (2)

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Publication number Priority date Publication date Assignee Title
US5332838A (en) * 1988-03-29 1994-07-26 Amoco Corporation Cyclization process utilizing copper aluminum borate as a catalyst
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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Publication number Priority date Publication date Assignee Title
JPH0813800B2 (en) * 1987-02-09 1996-02-14 出光興産株式会社 Indole manufacturing method
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

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Publication number Priority date Publication date Assignee Title
US5332838A (en) * 1988-03-29 1994-07-26 Amoco Corporation Cyclization process utilizing copper aluminum borate as a catalyst
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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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