CN105111101A - 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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Publication number
CN105111101A
CN105111101A CN201510565536.2A CN201510565536A CN105111101A CN 105111101 A CN105111101 A CN 105111101A CN 201510565536 A CN201510565536 A CN 201510565536A CN 105111101 A CN105111101 A CN 105111101A
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cyanoethyl
hso
anilino
ionic liquid
ethanol
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CN105111101B (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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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 utilizing ionic liquid to prepare N-cyanoethyl-N-β-anilino-ethanol
Technical field
The present invention relates to a kind of method preparing N-cyanoethyl-N-β-anilino-ethanol, particularly relate to the method utilizing ionic liquid to prepare N-cyanoethyl-N-β-anilino-ethanol, belong to organic chemical synthesis field.
Background technology
N-cyanoethyl-N-β-anilino-ethanol is as the broad-spectrum dyestuff intermediate of one.It is mainly for the production of the dispersed dye of the multiple coloured light such as Disperse Red S-FL, disperse scarlet 3GFL, Disperse Yellow Brown 2RFL.
Traditional synthetic method synthesizes N-cyanoethyl-N-β-anilino-ethanol by two-step approach: first aniline obtain cyanoethyl aniline with vinyl cyanide generation cyanoethylation reaction, then obtained cyanoethyl aniline obtains target compound again (see document: " study on the synthesis of cyanoethyl β-anilino-ethanol " with oxyethane generation ethoxyl etherification, " changing science and technology very much ", 1996,1,36).The method the first step uses metal chloride as catalyzer, Glacial acetic acid is as promotor, catalyzer be difficult to reclaim and unfriendly to environment, be difficult in reaction process invariably generate N, N-dicyanoethyl-aniline by product, can carry out next step reaction after therefore also needing to carry out purifying after the completion of reaction; Reaction second step, usually using metal chloride as catalyzer, carries out, operation more complicated under certain temperature and pressure; And the oxyethane used belongs to inflammable explosive article, there is certain danger.Current urgent need is the preparation method to N-cyanoethyl-N-β-anilino-ethanol improve, and meets industrial production demand.
Summary of the invention
In order to solve the severe reaction conditions existed in prior art, complicated operation, catalyzer is difficult to reclaim and to problems such as environment are unfriendly, the object of the invention is to provide a kind of novel method preparing N-cyanoethyl-N-β-anilino-ethanol.
For realizing the object of the invention, the present invention with to the very stable ionic liquid of water and air for catalysts and solvents, with aniline, chloroethanol and vinyl cyanide for raw material carries out one pot reaction synthesis N-cyanoethyl-N-β-anilino-ethanol, concrete technical scheme is as follows:
The ionic liquid formed with imidazoles or lactams or quaternary ammonium positively charged ion and tetrafluoride boron or phosphorus hexafluoride or bisulfate ion or dihydrogen phosphate or tosic acid root negatively charged ion for catalysts and solvents, with aniline, chloroethanol and vinyl cyanide for raw material carries out Reactive Synthesis N-cyanoethyl-N-β-anilino-ethanol; Through extraction after reaction terminates, merge organic layer, the thick product that rotary evaporation removes desolventizing obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation again.Ionic liquid is cycle applications after treatment.Reaction formula is as follows:
Ionic liquid of the present invention comprises: [NMPH] H 2pO 4, [NMPH] HSO 4, [NMPH] TSOH, [HMIM] H 2pO 4, [HMIM] HSO 4, [BMIM] HSO 4, [EMIM] HSO 4, [Me 3nH] HSO 4, [Et 3nH] HSO 4, [Pr 3nH] HSO 4, [Bu 3nH] HSO 4, [Me 2nH] HSO 4, [Et 3nH] H 2pO 4, [BMIM] BF 4, [BMIM] PF 6, [Pr 3nH] H 2pO 4, [Bu 3nH] H 2pO 4, [Me 2nH] H 2pO 4, [Et 2nH 2] H 2pO 4, [Pr 2nH 2] H 2pO 4, [Bu 2nH 2] H 2pO 4, [MeNH 3] H 2pO 4, [EtNH 3] H 2pO 4, [PrNH 3] H 2pO 4or [Bu 2nH 2] H 2pO 4.
Aniline of the present invention: chloroethanol: the mol ratio of vinyl cyanide 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.
Temperature of reaction of the present invention is 15 DEG C ~ 120 DEG C.
Reaction times of the present invention was at 1 ~ 24 hour.
The invention has the advantages that: with to the very stable ionic liquid of water and air for catalysts and solvents, with aniline, chloroethanol and vinyl cyanide for raw material carries out one pot reaction synthesis N-cyanoethyl-N-β-anilino-ethanol.Compared with conventional two-step, the method does not use poisonous and hazardous metal catalyst and promotor, does not use the reaction reagent that oxyethane etc. is inflammable and explosive, without the need to carrying out purifying and process to reaction intermediate, reaction process is simple, and easy and simple to handle, catalyzer can also recycle; In addition; the three components reaction of aniline, chloroethanol and vinyl cyanide can obtain comprising N-cyanoethyl-N-β-anilino-ethanol, N-cyanoethyl aniline, N usually; N-dicyanoethyl-aniline, N-β-anilino-ethanol, N; N-dihydroxy ethyl aniline etc. are at interior multi-products; and the generation of by product effectively can be suppressed in ionic liquid; improve the selectivity of target product N-cyanoethyl-N-β-anilino-ethanol, the N-cyanoethyl-N-β-anilino-ethanol productive rate utilizing present method to synthesize can reach more than 80%.
Embodiment
Following case study on implementation will describe more comprehensively to the present invention.
Embodiment 1
0.1 mole aniline is dropped into, 0.15 mole of chloroethanol, 0.15 mol propylene nitrile and 0.3 mole of [NMPH] HSO in reaction vessel 4ionic liquid, 30 DEG C of stirring reactions 20 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 80%; Ionic liquid after simple process, for testing next time.
IR(neat)ν:3398,3060,3023,2958,2923,2847,2245,1720,1601,1508,1433,1419,1364,1312,1261,1179,1151,1103,1070,1019,991,873,801,748,749,692,504cm -1; 1HNMR(400MHz,CDCl 3):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 dropped into, 0.5 mole of chloroethanol, 0.75 mol propylene nitrile and 0.8 mole of [Me in reaction vessel 3nH] HSO 4ionic liquid, 40 DEG C of stirring reactions 18 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 87%; Ionic liquid after simple process, for testing next time.
Embodiment 3
1.5 mole aniline are dropped into, 1.5 moles of chloroethanols, 1.75 mol propylene nitriles and 1 mole of [Et in reaction vessel 3nH] HSO 4ionic liquid, 100 DEG C of stirring reactions 6 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 85%; Ionic liquid after simple process, for testing next time.
Embodiment 4
0.4 mole aniline is dropped into, 0.4 mole of chloroethanol, 0.8 mol propylene nitrile and 0.6 mole of [BMIM] HSO in reaction vessel 4ionic liquid, 90 DEG C of stirring reactions 10 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 80%; Ionic liquid after simple process, for testing next time.
Embodiment 5
0.4 mole aniline is dropped into, 0.5 mole of chloroethanol, 0.5 mol propylene nitrile and 0.4 mole of [HMIM] HSO in reaction vessel 4ionic liquid, 70 DEG C of stirring reactions 10 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 85%; Ionic liquid after simple process, for testing next time.
Embodiment 6
0.6 mole aniline is dropped into, 0.3 mole of chloroethanol, 0.3 mol propylene nitrile and 0.6 mole of [HMIM] H in reaction vessel 2pO 4ionic liquid, 120 DEG C of stirring reactions 12 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 82%; Ionic liquid after simple process, for testing next time.
Embodiment 7
0.7 mole aniline is dropped into, 0.7 mole of chloroethanol, 0.7 mol propylene nitrile and 0.7 mole of [EMIM] HSO in reaction vessel 4ionic liquid, 50 DEG C of stirring reactions 24 hours.Add extraction into ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation, and the productive rate of reaction is 88%; Ionic liquid after simple process, for testing next time.
Embodiment 8-23
Be similar to embodiment 1, use [BMIM] BF respectively 4, [BMIM] PF 6, [Pr 3nH] HSO 4,
[Bu 3nH] HSO 4, [Me 2nH] HSO 4, [Et 3nH] H 2pO 4, [Pr 3nH] H 2pO 4, [Bu 3nH] H 2pO 4, [Me 2nH] H 2pO 4, [Et 2nH 2] H 2pO 4, [Pr 2nH 2] H 2pO 4, [Bu 2nH 2] H 2pO 4, [MeNH 3] H 2pO 4, [EtNH 3] H 2pO 4, [PrNH 3] H 2pO 4, [Bu 2nH 2] H 2pO 4make catalyzer, react under similarity condition, after reaction terminates, obtain following result (table one):
Table one
Embodiment Ionic liquid Productive rate (%)
8 [BMIM]BF 4 80
9 [BMIM]PF 6 85
10 [Pr 3NH]HSO 4 82
11 [Bu 3NH]HSO 4 85
12 [Me 2NH]HSO 4 80
13 [Et 3NH]H 2PO 4 85
14 [Pr 3NH]H 2PO 4 87
15 [Bu 3NH]H 2PO 4 83
16 [Me 2NH]H 2PO 4 88
17 [Et 2NH 2]H 2PO 4 84
18 [Pr 2NH 2]H 2PO 4 87
19 [Bu 2NH 2]H 2PO 4 85
20 [MeNH 3]H 2PO 4 82

Claims (5)

1. the method utilizing ionic liquid to prepare N-cyanoethyl-N-β-anilino-ethanol, it is characterized in that, realize in the following way: under the condition that the ionic liquid formed with imidazoles or lactams or quaternary ammonium positively charged ion and tetrafluoride boron or phosphorus hexafluoride or bisulfate ion or dihydrogen phosphate or tosic acid root negatively charged ion is catalysts and solvents, with aniline, chloroethanol, vinyl cyanide for raw material is by one pot reaction synthesis N-cyanoethyl-N-β-anilino-ethanol.
2. preparation N-cyanoethyl-N-β-anilino-ethanol method according to claim 1, is characterized in that, described ionic liquid choosing [NMPH] H 2pO 4, [NMPH] HSO 4, [NMPH] PTSA, [HMIM] H 2pO 4, [HMIM] HSO 4, [BMIM] HSO 4, [EMIM] HSO 4, [Me 3nH] HSO 4, [Et 3nH] HSO 4, [Pr 3nH] HSO 4, [Bu 3nH] HSO 4, [Me 2nH 2] HSO 4, [Et 3nH] H 2pO 4, [Pr 3nH] H 2pO 4, [Bu 3nH] H 2pO 4, [Me 2nH 2] H 2pO 4, [Et 2nH 2] H 2pO 4, [Pr 2nH 2] H 2pO 4, [BMIM] BF 4, [BMIM] PF 6, [Bu 2nH 2] H 2pO 4, [MeNH 3] H 2pO 4, [EtNH 3] H 2pO 4, [PrNH 3] H 2pO 4or [Bu 2nH 2] H 2pO 4.
3. prepare N-cyanoethyl-N-β-anilino-ethanol method according to claim 1, it is characterized in that, aniline: chloroethanol: the mol ratio of vinyl cyanide 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-β-anilino-ethanol method according to claim 1, it is characterized in that, temperature of reaction is 15 DEG C ~ 120 DEG C, and the reaction times was at 1 ~ 24 hour.
5. according to claim 1-4 any one, prepare N-cyanoethyl-N-β-anilino-ethanol method, it is characterized in that, after reaction terminates, be extracted with ethyl acetate, merge organic layer, rotary evaporation removes desolventizing and obtains thick product, then obtains N-cyanoethyl-N-β-anilino-ethanol through column chromatography for separation.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114890913A (en) * 2022-06-07 2022-08-12 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
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
CN102942494A (en) * 2012-12-13 2013-02-27 河南省科学院高新技术研究中心 Method for preparing N-hydroxyethylaniline by using ionic liquid

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* Cited by examiner, † Cited by third party
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US3496213A (en) * 1967-07-11 1970-02-17 Du Pont Mono-cyanoethylation of aromatic amines with an aqueous zinc chloride catalyst
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
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
CN102942494A (en) * 2012-12-13 2013-02-27 河南省科学院高新技术研究中心 Method for preparing N-hydroxyethylaniline by using ionic liquid

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN114890913A (en) * 2022-06-07 2022-08-12 万华化学集团股份有限公司 Method for preparing dicyanoethyl cyclohexylamine
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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