CN101786965A - Method for synthesizing N-alkyl-N-cyanoethyl arylamine - Google Patents
Method for synthesizing N-alkyl-N-cyanoethyl arylamine Download PDFInfo
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- CN101786965A CN101786965A CN 201010119643 CN201010119643A CN101786965A CN 101786965 A CN101786965 A CN 101786965A CN 201010119643 CN201010119643 CN 201010119643 CN 201010119643 A CN201010119643 A CN 201010119643A CN 101786965 A CN101786965 A CN 101786965A
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Abstract
The invention discloses a method for synthesizing a N-alkyl-N-cyanoethyl arylamine. The method is characterized by comprising the following steps: adding N-alkyl arylamine, acrylonitrile, catalyst and polymerization inhibitor into a reactor; stirring and heating the mixture to 60-120 DEG C at the temperature rate of 2-5 DEG C/min; carrying out reaction on the mixture for 3-10h, then cooling and standing the mixture; washing organic phase with water with the same volume of the materials; then separating and vacuum dehydrating to obtain the N-alkyl-N-cyanoethyl arylamine. The components have the following parts by weight: 100 parts of N-alkyl arylamine, 140-180 parts of acrylonitrile, 15-30 parts of catalyst and 1-5 parts of polymerization inhibitor. In the method, 17-36 parts of organic acid and 12-25 parts of water are also provided. The method features mild reaction conditions, simple operation processes, low requirements on equipment, small investment and high purity of targeted products.
Description
Technical field
The invention belongs to technical field of organic synthesis, being specifically related to a kind of is the method for the synthetic N-alkyl-N-cyanoethyl arylamine of raw material with N-alkylarylamine and vinyl cyanide.
Background technology
The N-alkyl-N-cyanoethyl arylamine is as the important derivatives of arylamine, be organic raw material and the organic reaction intermediate of using always, be widely used in aspects such as dyestuff, antioxidant, pigment dyestuff, agricultural chemicals, textile auxiliary, spices, photographic chemistry product, be used as dyestuff intermediates such as dispersion 65,88,153,159 as N-ethyl-N-cyanoethyl meta-aminotoluene.Though known N-alkyl-N-cyanoethyl arylamine has this purposes widely, the method for synthetic this material is not too desirable at present, is with Cu (Ac) as industrial normally used method
2-HAc is a catalyzer, and Resorcinol is the synthetic N-alkyl-N-cyanoethyl arylamine of stopper, though this technology can suitability for industrialized production, has severe reaction conditions, and temperature of reaction is higher, and pressure is big, to the high deficiency of equipment requirements.The three-element catalytic system that HAc-HCl and certain catalyzer constitute of adopting is also arranged, but the total amount of the required catalyzer of this technology up to more than 30% of total raw material, the wasting of resources is many, the cost height, technological process is more complicated also.In the face of the extensive use and the less-than-ideal processing condition of N-alkyl-N-cyanoethyl arylamine, it is imperative to improve its synthetic method, significant.
Summary of the invention
Purpose of the present invention is intended to overcome above-mentioned shortcoming, and providing a kind of is the method for the synthetic N-alkyl-N-cyanoethyl arylamine of raw material with N-alkylarylamine and vinyl cyanide, this method reaction conditions gentleness, and operating process is simple, and target product purity height.
For achieving the above object, the technical scheme that the present invention takes is: with N-alkylarylamine and vinyl cyanide is raw material, in reactor, add catalyzer and stopper again, temperature rise rate with 2～5 ℃/min, be heated with stirring to 60～120 ℃, reacted 3～10 hours, be cooled to 0～50 ℃, and standing demix, bleed off lower floor's water, with the water yield washing upper organic phase suitable with material, separate, vacuum hydro-extraction gets the N-alkyl-N-cyanoethyl arylamine, and wherein the shared mass fraction of each component is: 100 parts of N-alkylarylamines, 140～180 parts of vinyl cyanide, 15～30 parts of catalyzer, 1～5 part of stopper.
The synthetic method of above-mentioned N-alkyl-N-cyanoethyl arylamine is characterized in that: this method also comprises organic acid and water, and wherein organic acid is 17～36 parts, 12～25 parts in water.
The synthetic method of above-mentioned N-alkyl-N-cyanoethyl arylamine is characterized in that: described N-alkylarylamine is N-ethyl-m-toluidine, N-ethylaniline or methylphenylamine.
The synthetic method of above-mentioned N-alkyl-N-cyanoethyl arylamine is characterized in that: described stopper is Resorcinol, para benzoquinone, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.
The synthetic method of above-mentioned N-alkyl-N-cyanoethyl arylamine is characterized in that: described catalyzer is a metal chloride.
Compared with prior art, reaction conditions gentleness of the present invention, cost is low, and operating process is simple, and is low for equipment requirements, less investment and target product purity height.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.Below in the elaboration of embodiment, reaction mixture is formed and is used gas chromatographic analysis.
Embodiment 1:
In flask, add 25 parts in 100 parts of N-ethyl-m-toluidines, 140 parts of vinyl cyanide, 2 parts of Resorcinol, 15 parts of zinc chloride, 17 parts of acetic acid and water respectively, temperature rise rate with 2 ℃/min, be heated with stirring to 99 ℃, back flow reaction 5 hours, after reaction finishes, be cooled to 25 ℃, and standing demix, bleed off lower floor's water, with 300 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets N-ethyl-N-cyanoethyl meta-aminotoluene, is 94.25% through its weight content of gas chromatographic analysis.
Embodiment 2:
In flask, add 25 parts in 100 parts of N-ethyl-m-toluidines, 145 parts of vinyl cyanide, 2 parts of para benzoquinone, 19 parts in magnesium chloride, 20 parts of acetic acid and water respectively, temperature rise rate with 3 ℃/min, be heated with stirring to 99 ℃, back flow reaction 5 hours, after reaction finishes, be cooled to 25 ℃, and standing demix, bleed off lower floor's water, with 307 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets N-ethyl-N-cyanoethyl meta-aminotoluene, is 95.71% through its weight content of gas chromatographic analysis.
Embodiment 3:
In flask, add 16 parts in 100 parts of N-ethylanilines, 155 parts of vinyl cyanide, 4 parts of 2-Tert. Butyl Hydroquinones, 22 parts of zinc chloride, 25 parts of acetic acid and water respectively, temperature rise rate with 3 ℃/min, be heated with stirring to 90 ℃, back flow reaction 7 hours, after reaction finishes, be cooled to 20 ℃, and standing demix, bleed off lower floor's water, with 320 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets the N-ethyl-N-cyanoethyl aniline, is 97.39% through its weight content of gas chromatographic analysis.
Embodiment 4:
In flask, add 16 parts in 100 parts of N-ethylanilines, 160 parts of vinyl cyanide, 4 parts of 2-Tert. Butyl Hydroquinones, 27 parts of cupric chlorides, 27 parts of acetic acid and water respectively, temperature rise rate with 3 ℃/min, be heated with stirring to 95 ℃, back flow reaction 7 hours, after reaction finishes, be cooled to 20 ℃, and standing demix, bleed off lower floor's water, with 330 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets the N-ethyl-N-cyanoethyl aniline, is 96.37% through its weight content of gas chromatographic analysis.
Embodiment 5:
In flask, add 25 parts in 100 parts of methylphenylamines, 160 parts of vinyl cyanide, 4 parts of 2-Tert. Butyl Hydroquinones, 30 parts of cupric chlorides, 36 parts in formic acid and water respectively, temperature rise rate with 4 ℃/min, be heated with stirring to 95 ℃, back flow reaction 6 hours, after reaction finishes, be cooled to 20 ℃, and standing demix, bleed off lower floor's water, with 350 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets N-methyl-N-cyanoethyl aniline, is 88.65% through its weight content of gas chromatographic analysis.
Embodiment 6:
In flask, add 20 parts in 100 parts of N-butylanilines, 160 parts of vinyl cyanide, 2 parts of 2-Tert. Butyl Hydroquinones, 30 parts of cupric chlorides, 35 parts in formic acid and water respectively, temperature rise rate with 4 ℃/min, be heated with stirring to 110 ℃, back flow reaction 6 hours, after reaction finishes, be cooled to 20 ℃, and standing demix, bleed off lower floor's water, with 400 parts of water washing organic phases, organic phase after the washing is distillation dehydration under pressure 10.6～12kPa, promptly gets N-butyl-N-cyanoethyl aniline, is 84.18% through its weight content of gas chromatographic analysis.
Claims (5)
1. the synthetic method of a N-alkyl-N-cyanoethyl arylamine, it is characterized in that: this method comprises the steps: in reactor, add the N-alkylarylamine, vinyl cyanide, catalyzer and stopper, temperature rise rate with 2～5 ℃/min, be heated with stirring to 60～120 ℃, react after 3～10 hours, be cooled to 0～50 ℃, and standing demix, bleed off lower floor's water, use the water yield washing upper organic phase suitable, separate with material, vacuum hydro-extraction gets the N-alkyl-N-cyanoethyl arylamine, and wherein the shared mass fraction of each component is: 100 parts of N-alkylarylamines, 140～180 parts of vinyl cyanide, 15～30 parts of catalyzer, 1～5 part of stopper.
2. the synthetic method of N-alkyl-N-cyanoethyl arylamine according to claim 1 is characterized in that: it also comprises 12～25 parts in 17～36 parts of organic acids and water.
3. N-alkyl-N-cyanoethyl arylamine synthetic method according to claim 1 and 2 is characterized in that: described N-alkylarylamine is N-ethyl-m-toluidine, N-ethylaniline or methylphenylamine.
4. N-alkyl-N-cyanoethyl arylamine synthetic method according to claim 1 and 2 is characterized in that: described stopper is Resorcinol, para benzoquinone, 2-Tert. Butyl Hydroquinone or 2,5 di tert butyl hydroquinone.
5. N-alkyl-N-cyanoethyl arylamine synthetic method according to claim 1 and 2 is characterized in that: described catalyzer is a metal chloride.
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| CN 201010119643 CN101786965A (en) | 2010-03-03 | 2010-03-03 | Method for synthesizing N-alkyl-N-cyanoethyl arylamine |
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| CN 201010119643 CN101786965A (en) | 2010-03-03 | 2010-03-03 | Method for synthesizing N-alkyl-N-cyanoethyl arylamine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956178A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diaminodiphenylmethane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076189A (en) * | 1992-09-19 | 1993-09-15 | 董源 | The preparation method of cyanoethyl alkyl aryl tertiary amine |
| CN101307011A (en) * | 2008-07-09 | 2008-11-19 | 吴江梅堰三友染料化工有限公司 | Preparation method of N-ethyl-N-cyanoethylaniline |
-
2010
- 2010-03-03 CN CN 201010119643 patent/CN101786965A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076189A (en) * | 1992-09-19 | 1993-09-15 | 董源 | The preparation method of cyanoethyl alkyl aryl tertiary amine |
| CN101307011A (en) * | 2008-07-09 | 2008-11-19 | 吴江梅堰三友染料化工有限公司 | Preparation method of N-ethyl-N-cyanoethylaniline |
Non-Patent Citations (1)
| Title |
|---|
| 《染料与染色》 20041231 龚建良等 N-氰乙基苯胺的合成研究 第371-372页 2-5 第41卷, 第6期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956178A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diaminodiphenylmethane and preparation method thereof |
| CN113956178B (en) * | 2021-09-23 | 2023-08-11 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diamino diphenyl methane and preparation method thereof |
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Application publication date: 20100728 |