CN105111101B - Method for preparing N-cyanoethyl-N-ethoxylaniline by using ionic liquid - Google Patents

Method for preparing N-cyanoethyl-N-ethoxylaniline by using ionic liquid Download PDF

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CN105111101B
CN105111101B CN201510565536.2A CN201510565536A CN105111101B CN 105111101 B CN105111101 B CN 105111101B CN 201510565536 A CN201510565536 A CN 201510565536A CN 105111101 B CN105111101 B CN 105111101B
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cyanoethyl
hso
hydroxyethylaniline
ionic liquid
aniline
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CN105111101A (en
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郭辉
庄玉伟
褚艳红
张国宝
曹健
赵根锁
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High and New Technology Research Center of Henan Academy of Sciences
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High and New Technology Research Center of Henan Academy of Sciences
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

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Abstract

The invention discloses a method for preparing N-cyanoethyl-N-ethoxylaniline by using an ionic liquid, belonging to the field of organic chemical synthesis. According to the method, aniline, chloroethanol and acrylonitrile used as raw materials are subjected to a one-pot process by using a high-heat-stability low-volatility recyclable ionic liquid as a catalyst and solvent to prepare the N-cyanoethyl-N-ethoxylaniline. The method does not use any toxic or harmful catalyst, is simple to operate, has the advantages of simple after-treatment, mild reaction conditions, favorable selectivity and high yield, and is a green novel method for efficiently synthesizing N-cyanoethyl-N-ethoxylaniline.

Description

A kind of method that utilization ionic liquid prepares n- cyanoethyl-n- hydroxyethylaniline
Technical field
The present invention relates to a kind of method preparing n- cyanoethyl-n- hydroxyethylaniline, more particularly to utilize ionic liquid The method preparing n- cyanoethyl-n- hydroxyethylaniline, belongs to organic chemical synthesis field.
Background technology
N- cyanoethyl-n- hydroxyethylaniline is as a kind of broad-spectrum dyestuff intermediate.It is mainly for the production of dispersion The disperse dyes of multiple coloured light such as red s-fl, disperse scarlet 3gfl, disperse yellow brown 2rfl.
Traditional synthetic method is to synthesize n- cyanoethyl-n- hydroxyethylaniline by two-step method: aniline is first and propylene Nitrile occurs cyanoethylation reaction to obtain cyanoethyl aniline, and then obtained cyanoethyl aniline occurs ethoxy with oxirane again Change reaction obtain target compound (referring to document: " study on the synthesis of cyanoethyl hydroxyethylaniline ", too change science and technology, 1996, 1,36).The method first step is used metal chloride as catalyst, and as promoter, catalyst is difficult to reclaim glacial acetic acid And unfriendly to environment, generate n, n- dicyanoethyl-aniline by-product with being difficult to avoid that in course of reaction, therefore terminate in reaction Also need to the reaction carrying out carrying out next step after purification afterwards；React second step generally using metal chloride as catalyst, Carry out under uniform temperature and pressure, operation is more complicated；And the oxirane being used belongs to inflammable explosive article, exists Certain danger.It is badly in need of at present the preparation method of n- cyanoethyl-n- hydroxyethylaniline is improved, meet commercial production need Ask.
Content of the invention
In order to solve severe reaction conditions present in prior art, complex operation, catalyst is difficult to reclaim and to environment Unfriendly the problems such as, it is an object of the present invention to provide a kind of new method preparing n- cyanoethyl-n- hydroxyethylaniline.
For realizing the object of the invention, the present invention with the ionic liquid sufficiently stable to water and air as catalysts and solvents, One pot reaction synthesis n- cyanoethyl-n- hydroxyethylaniline, particular technique side are carried out for raw material with aniline, 2-chloroethyl alcohol and acrylonitrile Case is as follows:
With imidazoles or lactams or quaternary ammonium cationoid and tetrafluoride boron or phosphorus hexafluoride or bisulfate ion or phosphoric acid The ionic liquid of two hydrogen radical or the formation of p-methyl benzenesulfonic acid root anion is catalysts and solvents, with aniline, 2-chloroethyl alcohol and acrylonitrile Carry out n- cyanoethyl-n- hydroxyethylaniline is synthesized for raw material；React through extraction after terminating, merge organic layer, rotary evaporation The crude product removing solvent obtains n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation again.Ionic liquid follows after treatment Ring is applied.Reaction equation is as follows:
Ionic liquid of the present invention includes: [nmph] h2po4、[nmph]hso4、[nmph]tsoh、[hmim]h2po4、 [hmim]hso4、[bmim]hso4、[emim]hso4、[me3nh]hso4、[et3nh] hso4、[pr3nh]hso4、[bu3nh] hso4、[me2nh]hso4、[et3nh]h2po4、[bmim]bf4、[bmim]pf6、[pr3nh]h2po4、[bu3nh]h2po4、 [me2nh]h2po4、[et2nh2]h2po4、[pr2nh2]h2po4、[bu2nh2]h2po4、[menh3]h2po4、[etnh3]h2po4、 [prnh3]h2po4Or [bu2nh2]h2po4.
Aniline of the present invention: 2-chloroethyl alcohol: the mol ratio of acrylonitrile is in 1:0.1～2:0.1～3.
Between aniline of the present invention and mol ratio 1:0.1～8 of ionic liquid.
Reaction temperature of the present invention is 15 DEG C～120 DEG C.
Response time of the present invention was at 1～24 hour.
The invention has the advantages that: with the ionic liquid sufficiently stable to water and air as catalysts and solvents, with aniline, chlorine Ethanol and acrylonitrile carry out one pot reaction synthesis n- cyanoethyl-n- hydroxyethylaniline for raw material.Compared with conventional two-step, should Method does not use poisonous and hazardous metallic catalyst and promoter, does not use the reaction examination that oxirane etc. is inflammable and explosive Agent, need not carry out purification and process to reaction intermediate, and course of reaction is simple, and easy and simple to handle, catalyst can also recycle； Additionally, three component reaction of aniline, 2-chloroethyl alcohol and acrylonitrile would generally obtain including n- cyanoethyl-n- hydroxyethylaniline, n- cyanogen MEA, n, n- dicyanoethyl-aniline, n- hydroxyethylaniline, n, n- dihydroxy ethyl aniline etc. in interior multi-products, and The generation of by-product can effectively be suppressed in ionic liquid, improve the selection of target product n- cyanoethyl-n- hydroxyethylaniline Property, the n- cyanoethyl-n- hydroxyethylaniline yield using this method synthesis can reach more than 80%.
Specific embodiment
Following case study on implementation more comprehensively will be described to the present invention.
Embodiment 1
0.1 mole aniline is put in reaction vessel, 0.15 mole of 2-chloroethyl alcohol, 0.15 mol propylene nitrile and 0.3 mole [nmph]hso4Ionic liquid, 30 DEG C of stirring reactions 20 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 80%；Ionic liquid Body after simple process, for testing next time.
ir (neat) ν: 3398, 3060, 3023, 2958, 2923, 2847, 2245, 1720, 1601, 1508, 1433, 1419, 1364, 1312, 1261, 1179, 1151, 1103, 1070, 1019, 991, 873, 801, 748, 749, 692, 504 cm-1;1h nmr (400mhz, cdcl3): δ=2.64 (t, 2h), 3.55 (t, 2h), 3.73 (t, 2h), 3.81 (t, 2h),6.75-6.83(m, 3h), 7.23-7.29 (m, 2h).
Embodiment 2
0.5 mole aniline is put in reaction vessel, 0.5 mole of 2-chloroethyl alcohol, 0.75 mol propylene nitrile and 0.8 mole [me3nh]hso4Ionic liquid, 40 DEG C of stirring reactions 18 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 87%；Ionic liquid Body after simple process, for testing next time.
Embodiment 3
1.5 mole aniline are put in reaction vessel, 1.5 moles of 2-chloroethyl alcohols, 1.75 mol propylene nitriles and 1 mole [et3nh]hso4Ionic liquid, 100 DEG C of stirring reactions 6 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 85%；Ionic liquid Body after simple process, for testing next time.
Embodiment 4
0.4 mole aniline is put in reaction vessel, 0.4 mole of 2-chloroethyl alcohol, 0.8 mol propylene nitrile and 0.6 mole [bmim]hso4Ionic liquid, 90 DEG C of stirring reactions 10 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 80%；Ionic liquid Body after simple process, for testing next time.
Embodiment 5
0.4 mole aniline is put in reaction vessel, 0.5 mole of 2-chloroethyl alcohol, 0.5 mol propylene nitrile and 0.4 mole [hmim]hso4Ionic liquid, 70 DEG C of stirring reactions 10 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 85%；Ionic liquid Body after simple process, for testing next time.
Embodiment 6
0.6 mole aniline is put in reaction vessel, 0.3 mole of 2-chloroethyl alcohol, 0.3 mol propylene nitrile and 0.6 mole [hmim]h2po4Ionic liquid, 120 DEG C of stirring reactions 12 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 82%；Ionic liquid Body after simple process, for testing next time.
Embodiment 7
0.7 mole aniline is put in reaction vessel, 0.7 mole of 2-chloroethyl alcohol, 0.7 mol propylene nitrile and 0.7 mole [emim]hso4Ionic liquid, 50 DEG C of stirring reactions 24 hours.Add ethyl acetate extraction, merge organic layer, rotary evaporation removes Go solvent to obtain crude product, then obtain n- cyanoethyl-n- hydroxyethylaniline through column chromatography for separation, the yield of reaction is 88%；Ionic liquid Body after simple process, for testing next time.
Embodiment 8-20
Similar to embodiment 1, use [bmim] bf respectively4、[bmim] pf6、[pr3nh]hso4、
[bu3nh]hso4、[me2nh]hso4、[et3nh]h2po4、[pr3nh]h2po4、[bu3nh]h2po4、[me2nh] h2po4、[et2nh2]h2po4、[pr2nh2]h2po4、[bu2nh2]h2po4、[menh3]h2po4、[etnh3]h2po4、[prnh3] h2po4、[bu2nh2]h2po4Make catalyst, reacted under similarity condition, react and after terminating, obtain following result (table one):
Table one
Embodiment Ionic liquid Yield (%)
8 [bmim]bf4 80
9 [bmim]pf6 85
10 [pr3nh]hso4 82
11 [bu3nh]hso4 85
12 [me2nh]hso4 80
13 [et3nh]h2po4 85
14 [pr3nh]h2po4 87
15 [bu3nh]h2po4 83
16 [me2nh]h2po4 88
17 [et2nh2]h2po4 84
18 [pr2nh2]h2po4 87
19 [bu2nh2]h2po4 85
20 [menh3]h2po4 82

Claims (5)

1. a kind of utilization ionic liquid prepares the method for n- cyanoethyl-n- hydroxyethylaniline it is characterised in that in the following way Realize: with imidazoles or lactams or quaternary ammonium cationoid and tetrafluoride boron or phosphorus hexafluoride or bisulfate ion or biphosphate Under conditions of the ionic liquid of root or the formation of p-methyl benzenesulfonic acid root anion is catalysts and solvents, with aniline, 2-chloroethyl alcohol, propylene Nitrile synthesizes n- cyanoethyl-n- hydroxyethylaniline for raw material by one pot reaction.
2. preparation n- cyanoethyl-n- hydroxyethylaniline method according to claim 1 is it is characterised in that described ionic liquid Body is selected from [nmph] h2po4、[nmph]hso4、[nmph]ptsa、[hmim]h2po4、[hmim]hso4、[bmim]hso4、 [emim]hso4、[me3nh]hso4、[et3nh]hso4、[pr3nh]hso4、[bu3nh]hso4、[me2nh2]hso4、[et3nh] h2po4、[pr3nh]h2po4、[bu3nh]h2po4、[me2nh2]h2po4、[et2nh2]h2po4、[pr2nh2]h2po4、[bmim]bf4 、[bmim]pf6、[bu2nh2]h2po4、[menh3]h2po4、[etnh3]h2po4、[prnh3]h2po4Or [bu2nh2]h2po4.
3. prepare n- cyanoethyl-n- hydroxyethylaniline method according to claim 1 it is characterised in that aniline: 2-chloroethyl alcohol: The mol ratio of acrylonitrile is 1:0.1～2:0.1～3；The mol ratio of aniline and ionic liquid is 1:0.1～8.
4. prepare n- cyanoethyl-n- hydroxyethylaniline method according to claim 1 it is characterised in that reaction temperature is 15 DEG C～120 DEG C, the response time was at 1～24 hour.
5. according to any described preparation n- cyanoethyl-n- hydroxyethylaniline method of claim 1-4 it is characterised in that instead After should terminating, it is extracted with ethyl acetate, merges organic layer, rotary evaporation removes solvent and obtains crude product, then obtains through column chromatography for separation To n- cyanoethyl-n- hydroxyethylaniline.
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CN113896644A (en) * 2021-10-15 2022-01-07 河南省科学院高新技术研究中心 Method for preparing N-ethyl-N- (beta-methoxycarbonylethyl) aniline by using ionic liquid
CN114890913B (en) * 2022-06-07 2023-05-26 万华化学集团股份有限公司 Method for preparing dicyanoethyl cyclohexylamine

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SU722077A1 (en) * 1971-06-09 1982-12-15 Предприятие П/Я А-7850 Process for producing n-(beta-hydroxyethyl)-n-(beta-cyanoethyl)-aniline
PL95915B1 (en) * 1975-10-22 1977-11-30 METHOD OF OBTAINING N-CYANOETHYL-N-ETHANOLOANILINE
CN102942494B (en) * 2012-12-13 2014-07-09 河南省科学院高新技术研究中心 Method for preparing N-hydroxyethylaniline by using ionic liquid
CN102942478A (en) * 2012-12-13 2013-02-27 河南省科学院高新技术研究中心 Method for preparing phenylacetate by using ionic liquid

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