CN103012156A - Preparation method of N,N-diethylethylenediamine - Google Patents
Preparation method of N,N-diethylethylenediamine Download PDFInfo
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- CN103012156A CN103012156A CN2012105405471A CN201210540547A CN103012156A CN 103012156 A CN103012156 A CN 103012156A CN 2012105405471 A CN2012105405471 A CN 2012105405471A CN 201210540547 A CN201210540547 A CN 201210540547A CN 103012156 A CN103012156 A CN 103012156A
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Abstract
The invention discloses a preparation method of N,N-diethylethylenediamine, which comprises the following steps: carrying out reaction on raw materials diethylamine and 2-chlorethamin hydrochloride in a high-pressure autoclave by using a sodium methoxide methanol solution as an acid binding agent at 100-200 DEG C under the reaction pressure of 0.52-1.60 MPa for 3-8 hours, wherein the mol ratio of diethylamine to 2-chlorethamin hydrochloride is (1-8):1, and the mol ratio of sodium methoxide in the sodium methoxide methanol solution to 2-chlorethamin hydrochloride is (0.9-1.1):1; and regulating the pH value of the reaction solution to at least 13 with alkali liquor, stratifying to obtain an oil phase, and rectifying the oil phase to obtain the N,N-diethylethylenediamine. The method disclosed by the invention has the characteristics of low raw material cost, high yield, high economy and safety and the like, and is simple to operate and easy to implement.
Description
Technical field
The invention belongs to the organic compound preparation field, be specifically related to a kind of N, the preparation method of N-diethyl ethylenediamine.
Background technology
N, the N-diethyl ethylenediamine is important fine chemicals intermediate, be applied to medicine, tensio-active agent and paint field, synthetically AH2250, ambenonium chloride, procainamide, Reglan and Tai Bili aspect medical, but the textile industry combination colour must bright BCH, cats product, aspect coating, can be used as solidifying agent and the sequestrant of epoxide powder coating.The at present preparation of this compound mainly contains following several method:
The cyanomethylation of a, diethylamide, reduction method: the method is that Bloom M S etc. delivered in 1945, building-up process is in two steps: 1) the dialkyl amino acetonitrile is synthetic: formaldehyde and sodium bisulfite synthesize sodium hydroxymethane sulfonate, the dialkylamine substituted hydroxy obtains the dialkyl amino novalgin, and itrile group substituted sulfonic acid base obtains the dialkyl amino formonitrile HCN; 2) Dialkylaminoethylamine is synthetic: in ethanol or butanols solvent, with sodium Metal 99.5 itrile group is reduced into amido, obtains Dialkylaminoethylamine.The yield of document record reduction step only is 50%, and prussiate belongs to violent in toxicity, and the reduction reaction complex steps is not easy to operate, has very large danger in the process.
B, dialkylamine and ethylenimine reaction: Dong Yanfei etc. once prepared diisopropyl ethylenediamine with the method, synthetic minute three steps: 1) sulfuric acid-beta-amino hydrogen ethyl ester is synthetic: react under thanomin and the vitriol oil high temperature, Dehydration gets sulfuric acid-beta-amino hydrogen ethyl ester; 2) preparation of aziridine: sulfuric acid-beta-amino hydrogen ethyl ester and sodium hydroxide are heated to boiling, and three distillations obtain aziridine; 3) N, N-diisopropyl ethylenediamine synthetic.The record total recovery is about 60% in the document, but process is loaded down with trivial details, and not easy to operate, pyroreaction is difficult for industrialization.
C, monoacylated, the alkylation of quadrol, then hydrolysis: the method exists process loaded down with trivial details, the shortcoming that raw materials cost is high, and relate to Poisons sulfuric acid dialkyl, there is certain danger.
D, diethylamine and acrylamide addition, then reset degradation: Gao Jianhua etc. utilize diethylamine and acrylamide addition, then affixture are carried out hoffman degradation reaction, and distillation makes target product, and yield is about about 30%.
E, Li Wenjuan etc. react in flask with diethylamine and bromine ethamine bromate, with sodium hydroxide as acid binding agent, utilize target product and diethylamine to the complexing competition of cupric ion, in reaction solution, add copper sulfate, remove remaining copper sulfate with sodium sulphite, oil phase obtains target product through fractionation, and productive rate reaches 80%.The method yield is higher, but the bromine ethamine bromate that uses is expensive, and reaction generation cupric sulfide, is difficult for processing, and is unsuitable for suitability for industrialized production.
Summary of the invention
The technical problem to be solved in the present invention provides that a kind of raw materials cost is low, productive rate is high, operation is simple, the N of economic security, the preparation method of N-diethyl ethylenediamine.
In order to solve the problems of the technologies described above, the invention provides a kind of 1, N, the preparation method of N-diethyl ethylenediamine, take diethylamine and 2-chloroethyl amine hydrochloride as raw material, methanol solution of sodium methylate is as acid binding agent, in autoclave, react, temperature of reaction is 100 ~ 200 ℃, reaction pressure is 0.52 ~ 1.60MPa, reaction times is 3 ~ 8 hours, the mol ratio of diethylamine and 2-chloroethyl amine hydrochloride is 1 ~ 8:1, and the mol ratio of the sodium methylate in the methanol solution of sodium methylate and 2-chloroethyl amine hydrochloride is the best 1:1 of being of 0.9 ~ 1.1:1();
The reaction solution of gained is adjusted to pH 〉=13 with alkali lye, obtains oil phase (being positioned at the upper strata) after the layering, and oil phase obtains N, the N-diethyl ethylenediamine through rectifying.
As N of the present invention, the preparation method's of N-diethyl ethylenediamine improvement: add the Lewis acid catalyst in autoclave, the Lewis acid catalyst is 1% ~ 3% of 2-chloroethyl amine hydrochloride molar weight.
As N of the present invention, the preparation method's of N-diethyl ethylenediamine further improvement: the Lewis acid catalyst is cuprous chloride (preferably) or aluminum chloride.
As N of the present invention, the preparation method's of N-diethyl ethylenediamine further improvement: the mass concentration of the sodium methylate in the methanol solution of sodium methylate is 10% ~ 35%.
As N of the present invention, the preparation method's of N-diethyl ethylenediamine further improvement: alkali lye is the saturated aqueous solution of sodium hydroxide, the saturated aqueous solution of potassium hydroxide, the saturated methanol solution of sodium methylate or the saturated ethanolic soln of sodium ethylate.
As N of the present invention, the preparation method's of N-diethyl ethylenediamine further improvement: the mol ratio of diethylamine and 2-chloroethyl amine hydrochloride is 4:1, and the mol ratio of the sodium methylate in the methanol solution of sodium methylate and 2-chloroethyl amine hydrochloride is 1:1; As the Lewis acid catalyst, cuprous chloride is 2% of 2-chloroethyl amine hydrochloride molar weight with cuprous chloride;
Temperature of reaction is 150 ℃, and reaction pressure is 1MPa, and the reaction times is 5 hours.
Synthetic route of the present invention is as follows:
The present invention preparation and N, the mass spectrum of N-diethyl ethylenediamine is as shown in Figure 1.
The present invention generates target product---N by diethylamine and one step of chlorethamin (2-chloroethyl amine hydrochloride) substitution reaction, the N-diethyl ethylenediamine, and productive rate is all higher under the condition of adding or not adding catalyzer.Adopt method of the present invention to prepare N, the N-diethyl ethylenediamine has that raw materials cost is low, productive rate is higher, characteristics such as simple to operate, economic security.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is N of the present invention, the mass spectrum of N-diethyl ethylenediamine.
Embodiment
The invention will be further described below by specific embodiment, and following examples are descriptive, is not determinate, can not limit protection scope of the present invention with this.
Embodiment 1, N, the preparation method of N-diethyl ethylenediamine
In autoclave, add 0.60mol diethylamine, the 2-chloroethyl amine hydrochloride of 0.15mol, methanol solution of sodium methylate (wherein containing sodium methylate 0.15mol, methyl alcohol 40mL), 0.3g(0.003mol) cuprous chloride.Then shut kettle cover, open after the leak detection and stir, be heated to 150 ℃, boost to about 1.0MPa.Sustained reaction 5 hours, reaction pressure does not have to change substantially in the process.After reaction finishes, stopped heating, be cooled to room temperature after, stop to stir, drive still, pour out reaction solution, add saturated sodium hydroxide solution until be adjusted to pH 〉=13(and namely be strong basicity), purpose is for the hydrochloric acid in the neutralized reaction product, and natural layering must be positioned at the oil reservoir on upper strata and be positioned at the water layer of lower floor; Target product is arranged in oil reservoir, with oil reservoir rectifying, collects 145 ~ 147 ℃ cut, gets N, and N-diethyl ethylenediamine 13.68g(purity is 99.2%), productive rate is 78.6%.
Embodiment 2 ~ embodiment 12,
Change the consumption of diethylamine, 2-chloroethyl amine hydrochloride and methanol solution of sodium methylate among the embodiment 1, change kind and consumption or the cancellation use catalyzer of catalyzer, also change temperature of reaction, reaction pressure and reaction times, thereby obtained corresponding embodiment.The yield of concrete data and final gained sees table 1 for details.
Table 1
Comparative Examples 1, the methanol solution of sodium methylate in alcohol sodium alcohol solution (sodium ethylate is as 0.15mol, and ethanol the is 40mL) alternate embodiment 1; All the other are with embodiment 1.
The N of final gained, the productive rate of N-diethyl ethylenediamine is 68.0%.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (6)
1.N, the preparation method of N-diethyl ethylenediamine, it is characterized in that: take diethylamine and 2-chloroethyl amine hydrochloride as raw material, methanol solution of sodium methylate reacts in autoclave as acid binding agent, and temperature of reaction is 100 ~ 200 ℃, reaction pressure is 0.52 ~ 1.60MPa, reaction times is 3 ~ 8 hours, and the mol ratio of diethylamine and 2-chloroethyl amine hydrochloride is 1 ~ 8:1, and the mol ratio of the sodium methylate in the methanol solution of sodium methylate and 2-chloroethyl amine hydrochloride is 0.9 ~ 1.1:1;
The reaction solution of gained is adjusted to pH 〉=13 with alkali lye, obtains oil phase after the layering, and described oil phase obtains N, the N-diethyl ethylenediamine through rectifying.
2. N according to claim 1, the preparation method of N-diethyl ethylenediamine is characterized in that: add the Lewis acid catalyst in autoclave, the Lewis acid catalyst is 1% ~ 3% of 2-chloroethyl amine hydrochloride molar weight.
3. N according to claim 2, the preparation method of N-diethyl ethylenediamine is characterized in that: described Lewis acid catalyst is cuprous chloride or aluminum chloride.
4. according to claim 1,2 or 3 described N, the preparation method of N-diethyl ethylenediamine is characterized in that: the mass concentration of the sodium methylate in the methanol solution of sodium methylate is 10% ~ 35%.
5. N according to claim 4, the preparation method of N-diethyl ethylenediamine is characterized in that: described alkali lye is the saturated aqueous solution of sodium hydroxide, the saturated aqueous solution of potassium hydroxide, the saturated methanol solution of sodium methylate or the saturated ethanolic soln of sodium ethylate.
6. N according to claim 5, the preparation method of N-diethyl ethylenediamine is characterized in that:
The mol ratio of diethylamine and 2-chloroethyl amine hydrochloride is 4:1, and the mol ratio of the sodium methylate in the methanol solution of sodium methylate and 2-chloroethyl amine hydrochloride is 1:1; As the Lewis acid catalyst, cuprous chloride is 2% of 2-chloroethyl amine hydrochloride molar weight with cuprous chloride;
Temperature of reaction is 150 ℃, and reaction pressure is 1MPa, and the reaction times is 5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084033A (en) * | 2017-12-29 | 2018-05-29 | 山东诚汇双达药业有限公司 | A kind of preparation method of N, N- diethyl ethylenediamine |
| CN114835586A (en) * | 2022-07-04 | 2022-08-02 | 泽升科技(广州)有限公司 | Efficient preparation method for N, N-diethyl ethylenediamine |
Citations (3)
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| US2318729A (en) * | 1941-05-24 | 1943-05-11 | Carbide & Carbon Chem Corp | Process for making amino-alkyl compounds |
| CN101407519A (en) * | 2007-10-12 | 2009-04-15 | 天津药明康德新药开发有限公司 | Method for synthesizing 5,6,7,8-tetrahydrochysene- imidazo [1,5-alpha] pyrazine |
| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2318729A (en) * | 1941-05-24 | 1943-05-11 | Carbide & Carbon Chem Corp | Process for making amino-alkyl compounds |
| CN101407519A (en) * | 2007-10-12 | 2009-04-15 | 天津药明康德新药开发有限公司 | Method for synthesizing 5,6,7,8-tetrahydrochysene- imidazo [1,5-alpha] pyrazine |
| CN102260175A (en) * | 2011-06-08 | 2011-11-30 | 浙江大学 | Method for synthesizing 2-aminoethyl(ethyl)amine |
Non-Patent Citations (2)
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| 沈新安: "《药物合成技术》", 31 August 2006, article "药物合成技术", pages: 3 * |
| 袁招莲: "乙酸与乙二胺两步法制备N_乙基乙二胺", 《万方数据服务平台硕士学位论文》, 30 November 2012 (2012-11-30), pages 11 - 12 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108084033A (en) * | 2017-12-29 | 2018-05-29 | 山东诚汇双达药业有限公司 | A kind of preparation method of N, N- diethyl ethylenediamine |
| CN108084033B (en) * | 2017-12-29 | 2020-11-10 | 山东诚汇双达药业有限公司 | Preparation method of N, N-diethyl ethylenediamine |
| CN114835586A (en) * | 2022-07-04 | 2022-08-02 | 泽升科技(广州)有限公司 | Efficient preparation method for N, N-diethyl ethylenediamine |
| CN114835586B (en) * | 2022-07-04 | 2022-09-13 | 泽升科技(广州)有限公司 | Efficient preparation method for N, N-diethyl ethylenediamine |
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