CN102260175A - Method for synthesizing 2-aminoethyl(ethyl)amine - Google Patents
Method for synthesizing 2-aminoethyl(ethyl)amine Download PDFInfo
- Publication number
- CN102260175A CN102260175A CN2011101516521A CN201110151652A CN102260175A CN 102260175 A CN102260175 A CN 102260175A CN 2011101516521 A CN2011101516521 A CN 2011101516521A CN 201110151652 A CN201110151652 A CN 201110151652A CN 102260175 A CN102260175 A CN 102260175A
- Authority
- CN
- China
- Prior art keywords
- ethylethylenediamine
- alcohol
- reaction
- sodium
- quadrol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2-aminoethyl(ethyl)amine. The method comprises the following steps of: performing substitution reaction on raw materials of ethanediamine and chloroethane at the temperature of between 40 and 80DEG C under the pressure of between 0.2 and 2MPa for 3 to 6 hours in a high pressure autoclave by taking alcohol as a solvent and sodium alcoholate as an acid binding agent, wherein a molar ratio of the ethanediamine to the chloroethane is (1.45-3.1):1, and a molar ratio of the chloroethane to the acid binding agent is 1:(1.09-1.4); and desalting and rectifying the obtained reaction product to obtain the 2-aminoethyl(ethyl)amine. The method for synthesizing the 2-aminoethyl(ethyl)amine has the characteristics of concise process, simple separation, high yield and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly a kind of synthetic method of N-ethylethylenediamine.
Background technology
N-ethylethylenediamine (being called for short NEED) molecular formula is H
2NCH
2CH
2NHCH
2CH
3, structural formula is shown in S-1; Colourless transparent liquid, proportion 0.837, refractive index 1.4385,128-130 ℃ of boiling range (101.325KPa), 50 ℃ of flash-points, soluble in water.N-ethylethylenediamine (NEED) is the important intermediate of synthetic many antibiotic medicines, the cefoperazone of cephalosporins, and one of basic raw material of the cefbuperazone of the piperacillin of penicillins and cephamycin derivative is exactly the N-ethylethylenediamine.
The comprehensive literature report, following method is mainly adopted in the preparation of N-ethylethylenediamine at present:
(1) be raw material with ethamine and aminoethyl sulfuric acid, water is solvent, and sodium hydroxide is acid binding agent.Reaction finishes the back distillation and reclaims excessive ethamine, adds 40% sodium hydroxide solution again and tell oily matter in residuum, and all the other liquid are used extracted with diethyl ether again, combining extraction liquid and oily matter, and fractionation is collected cut, productive rate about 40% at 126-132 ℃ then.Reaction formula is shown in S-2.This method productive rate only about 40%, and ethamine consumption about 10 times of theoretical consumption normally.It is also comparatively dangerous to carry out distillation procedure with ether, easier generation security incident when envrionment temperature is high especially, be unfavorable for scale operation (Shandong Normal University's journal, 1998,13 (1): 112-113, Gao Zhanting).
(2) with thanomin, thionyl chloride and ethamine are raw material, and toluene is solvent, and sodium hydroxide is acid binding agent.Elder generation's thanomin and thionyl chloride react the generation chloroethylamine hydrochloride, separate through ethamine ammonia and obtain NEED.Reaction formula is shown in S-3.Thionyl chloride is highly toxic substance and pungency is arranged in the thanomin route method, meet water and emit poisonous sulfurous gas and hydrogenchloride, and in reaction process, have aquatic paired aftertreatment bring certain trouble (the Shanghai chemical industry, 2004,8:19-20, Yi Ting).
(3) generate acrylamide by vinyl cyanide through hydrolysis, acrylamide and ethamine generation addition reaction generate β-aminoethyl propionic acid amide then, obtain the N-ethylethylenediamine by the Hofmann rearrangement reaction at last.Reaction formula is shown in S-4.This reaction is carried out in two steps, causes the prolongation of whole process time, is unfavorable for the carrying out that produce, and the synthetic control of intermediate product β-aminoethyl propionic acid amide difficult (the Tianjin chemical industry, 2003,17 (6): 27-28, Qian Ling).
(4) be raw material with acetate and quadrol, methyl alcohol is solvent, and 5%Pd/C is a catalyzer, under the atmosphere of hydrogen, carry out in autoclave, reaction pressure is 7bar, reacted 4 hours down at 100 ℃, the transformation efficiency of quadrol is 40.9%, and the selectivity of N-ethylethylenediamine is approximately 78.9%.Should use expensive catalysts in the acetate route method, taller pressure ring is operated in the border, and reaction conditions is comparatively harsh.
Summary of the invention
The technical problem to be solved in the present invention provides the synthetic method of the N-ethylethylenediamine that a kind of technology is succinct, easily separated, yield is high.
In order to solve the problems of the technologies described above, the invention provides a kind of synthetic method of N-ethylethylenediamine, with quadrol and monochloroethane is raw material, alcohol is solvent, sodium alkoxide is an acid binding agent, carries out substitution reaction in autoclave, and reaction pressure is 0.2～2Mpa, temperature of reaction is 40～80 ℃, and the reaction times is 3～6 hours; The mol ratio of quadrol and monochloroethane is 1.45～3.1: 1, and the mol ratio of monochloroethane and acid binding agent is 1: 1.09～1.4;
The gained reaction product gets the N-ethylethylenediamine successively through desalination, rectifying.
Improvement as the synthetic method of N-ethylethylenediamine of the present invention: quadrol is 1: 2～5 with the mass ratio of alcohol.
Further improvement as the synthetic method of N-ethylethylenediamine of the present invention: alcohol is the lower aliphatic monohydroxy-alcohol, and described sodium alkoxide is a lower aliphatic monobasic sodium alkoxide.
Further improvement as the synthetic method of N-ethylethylenediamine of the present invention: the lower aliphatic monohydroxy-alcohol is methyl alcohol, ethanol or Virahol; Lower aliphatic monobasic sodium alkoxide is sodium methylate, sodium ethylate or sodium isopropylate.
Reaction scheme of the present invention is as follows:
The mass spectrum of gained N-ethylethylenediamine of the present invention as shown in Figure 1.
The advantage of production method of the present invention is as follows:
1. introducing alcohol is solvent, and sodium alkoxide is an acid binding agent, synthetic under anhydrous condition, has alleviated the burden of aftertreatment, good product selectivity, and technological process is simple, the product yield height.
2. reaction solution mainly contains solvent methanol, and in addition raw material quadrol and product N-ethylethylenediamine also have polysubstituted by product, and above-mentioned each component all can not form azeotrope, can it be separated by conventional rectification.
3. reclaim solvent alcohol and excessive raw material quadrol by rectifying, and separation obtains product N-ethylethylenediamine.Recycle solvent alcohol and excessive quadrol, improve solvent and utilization ratio of raw materials, reduced production cost as far as possible.
4. the solubleness (19g/L) of sodium-chlor in alcohol by with alcohol being the concentration that solvent reduces chlorion, reduces the corrosion to stainless steel equipment much smaller than the solubleness in water (360g/L).
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the mass spectrum of N-ethylethylenediamine of the present invention.
Embodiment
The synthetic method of embodiment 1, N-ethylethylenediamine:
In the autoclave of band stirring temperature measuring equipment, add quadrol 110g (1.6mol), methyl alcohol 550g, sodium methylate 60g (1.12mol) is pressed into monochloroethane 52g (0.8mol) behind the kettle cover that closes; Be warming up to 40 ℃ in 1h, this moment, pressure was 0.5Mpa.Keep this thermotonus 6h to finish reaction, having reacted pressure is 0.3Mpa.
With the sodium-chlor elimination in the reaction solution, get filtrate rectifying after reaction finishes, collect 128-130 ℃ of cut, get product N-ethylethylenediamine 49.3g, yield 69.89%.
Collect 62-64 ℃ of cut, be methyl alcohol, the rate of recovery is 84.26%; Collect 114-118 ℃ of cut, be quadrol, the rate of recovery is 58.25%, 2 all recyclable utilization.
The synthetic method of embodiment 2, N-ethylethylenediamine:
In the autoclave of band stirring temperature measuring equipment, add quadrol 110g (1.6mol), methyl alcohol 220g, sodium methylate 47.5g (0.88mol) is pressed into monochloroethane 52g (0.8mol) behind the kettle cover that closes, be warming up to 60 ℃ in 1h, and this moment, pressure was 0.7Mpa.Keep this thermotonus 3h to finish reaction, having reacted pressure is 0.36Mpa.
With the sodium-chlor elimination in the reaction solution, get filtrate rectifying after reaction finishes, collect 128-130 ℃ of cut, get product N-ethylethylenediamine 43.2g, yield 61.25%.
Simultaneously, collect solvent methanol and excessive quadrol, 2 the rate of recovery is respectively 84.54% and 58.12%.
The synthetic method of embodiment 3, N-ethylethylenediamine:
In the autoclave of band stirring temperature measuring equipment, add quadrol 110g (1.6mol), methyl alcohol 550g, sodium methylate 52g (0.96mol) is pressed into monochloroethane 52g (0.8mol) behind the kettle cover that closes, be warming up to 80 ℃ in 1h, and this moment, pressure was 1.2Mpa.Keep this thermotonus 4h to finish reaction, having reacted pressure is 0.5Mpa.
With the sodium-chlor elimination in the reaction solution, get filtrate rectifying after reaction finishes, collect 128-130 ℃ of cut, get product N-ethylethylenediamine 42.9g, yield 60.82%.
Simultaneously, collect solvent methanol and excessive quadrol, 2 the rate of recovery is respectively 86.65% and 59.02%.
The synthetic method of embodiment 4, N-ethylethylenediamine:
In the autoclave of band stirring temperature measuring equipment, add quadrol 110g (1.6mol), methyl alcohol 550g, sodium methylate 65g (1.2mol) is pressed into monochloroethane 69g (1.1mol) behind the kettle cover that closes, be warming up to 40 ℃ in 1h, and this moment, pressure was 0.6Mpa.Keep this thermotonus 4h to finish reaction, having reacted pressure is 0.3Mpa.
With the sodium-chlor elimination in the reaction solution, get filtrate rectifying after reaction finishes, collect 128-130 ℃ of cut, get product N-ethylethylenediamine 66.3g, yield 68.35%.
Simultaneously, collect solvent methanol and excessive quadrol, 2 the rate of recovery is respectively 84.45% and 58.55%.
The synthetic method of embodiment 5, N-ethylethylenediamine:
In the autoclave of band stirring temperature measuring equipment, add quadrol 110g (1.6mol), methyl alcohol 330g, sodium methylate 33g (0.6mol) is pressed into monochloroethane 34.5g (0.53mol) behind the kettle cover that closes; Be warming up to 40 ℃ in 1h, this moment, pressure was 0.45Mpa.Keep this thermotonus 4h to finish reaction, having reacted pressure is 0.3Mpa.
With the sodium-chlor elimination in the reaction solution, get filtrate rectifying after reaction finishes, collect 128-130 ℃ of cut, get product N-ethylethylenediamine 33.6g, yield 71.90%.
Simultaneously, collect solvent methanol and excessive quadrol, 2 the rate of recovery is respectively 84.65% and 58.34%.
What more than enumerate only is several specific embodiment 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 (4)
1.N-the synthetic method of ethylethylenediamine is characterized in that: with quadrol and monochloroethane is raw material, and alcohol is solvent, sodium alkoxide is an acid binding agent, carries out substitution reaction in autoclave, and reaction pressure is 0.2～2Mpa, temperature of reaction is 40～80 ℃, and the reaction times is 3～6 hours; The mol ratio of described quadrol and monochloroethane is 1.45～3.1: 1, and the mol ratio of described monochloroethane and acid binding agent is 1: 1.09～1.4;
The gained reaction product gets the N-ethylethylenediamine successively through desalination, rectifying.
2. the synthetic method of N-ethylethylenediamine according to claim 1 is characterized in that: described quadrol is 1: 2～5 with the mass ratio of alcohol.
3. the synthetic method of N-ethylethylenediamine according to claim 1 and 2 is characterized in that: described alcohol is the lower aliphatic monohydroxy-alcohol, and described sodium alkoxide is a lower aliphatic monobasic sodium alkoxide.
4. the synthetic method of N-ethylethylenediamine according to claim 3 is characterized in that: described lower aliphatic monohydroxy-alcohol is methyl alcohol, ethanol or Virahol; Described lower aliphatic monobasic sodium alkoxide is sodium methylate, sodium ethylate or sodium isopropylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101516521A CN102260175B (en) | 2011-06-08 | 2011-06-08 | Method for synthesizing 2-aminoethyl(ethyl)amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101516521A CN102260175B (en) | 2011-06-08 | 2011-06-08 | Method for synthesizing 2-aminoethyl(ethyl)amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102260175A true CN102260175A (en) | 2011-11-30 |
| CN102260175B CN102260175B (en) | 2013-11-20 |
Family
ID=45007045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101516521A Expired - Fee Related CN102260175B (en) | 2011-06-08 | 2011-06-08 | Method for synthesizing 2-aminoethyl(ethyl)amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102260175B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816071A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
| CN103012156A (en) * | 2012-12-13 | 2013-04-03 | 浙江大学 | Preparation method of N,N-diethylethylenediamine |
| CN108069836A (en) * | 2017-12-19 | 2018-05-25 | 山东博苑医药化学有限公司 | It is a kind of to prepare three (3,6- dioxaheptyls）The new method of amine |
| CN109134274A (en) * | 2018-10-15 | 2019-01-04 | 太原科技大学 | A method of separation ethylenediamine and n-ethylethylenediamine mixed solution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120059A (en) * | 1978-01-30 | 1982-03-16 | Karel F. Bernady | Process for preparing n-ethylethylenediamine |
-
2011
- 2011-06-08 CN CN2011101516521A patent/CN102260175B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120059A (en) * | 1978-01-30 | 1982-03-16 | Karel F. Bernady | Process for preparing n-ethylethylenediamine |
Non-Patent Citations (1)
| Title |
|---|
| 魏文珑 等: "N-乙基乙二胺的合成", 《山西化工》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816071A (en) * | 2012-08-25 | 2012-12-12 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
| CN102816071B (en) * | 2012-08-25 | 2014-05-07 | 太原理工大学 | Synthesis method of N-ethyl ethylene diamine |
| CN103012156A (en) * | 2012-12-13 | 2013-04-03 | 浙江大学 | Preparation method of N,N-diethylethylenediamine |
| CN103012156B (en) * | 2012-12-13 | 2014-11-26 | 浙江大学 | Preparation method of N,N-diethylethylenediamine |
| CN108069836A (en) * | 2017-12-19 | 2018-05-25 | 山东博苑医药化学有限公司 | It is a kind of to prepare three (3,6- dioxaheptyls）The new method of amine |
| CN108069836B (en) * | 2017-12-19 | 2021-04-13 | 山东博苑医药化学股份有限公司 | Novel method for preparing tri (3, 6-dioxaheptyl) amine |
| CN109134274A (en) * | 2018-10-15 | 2019-01-04 | 太原科技大学 | A method of separation ethylenediamine and n-ethylethylenediamine mixed solution |
| CN109134274B (en) * | 2018-10-15 | 2021-01-15 | 太原科技大学 | Method for separating ethylenediamine and N-ethyl ethylenediamine mixed solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102260175B (en) | 2013-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10414716B2 (en) | Process for preparing a polyetheramine | |
| CN101759571B (en) | Preparation method of N,N-diisopropylethylamine | |
| CN102260175B (en) | Method for synthesizing 2-aminoethyl(ethyl)amine | |
| CN105585501B (en) | Ethylenediamine production method | |
| KR20110035705A (en) | A preparative method for 1,4-disubstituted cyclohexane derivatives | |
| CN102076652B (en) | High-purity n-ethylmethylamine and process for preparing same | |
| CN101928222B (en) | Synthesis method of N, N, N', N'-tetraisopropyl ethylene diamine | |
| CN109020849B (en) | Preparation method of deuterated dimethyl sulfoxide | |
| CN111620844B (en) | Preparation method of alpha-acetyl-gamma-butyrolactone | |
| CN112321557B (en) | Preparation method of Jiale musk | |
| CN101638370A (en) | Synthesizing method of N,N-diisopropyl butylamine | |
| CN108752217B (en) | Synthesis method of dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| CN102161623B (en) | Synthesis method of alkylhydroxyethylimide | |
| CN111620884B (en) | Synthetic method of triethylene diamine | |
| CN101723803A (en) | Preparation method of high purity tert-butyl alcohol magnesium | |
| CN103922945B (en) | Method for synthesizing bis(2-dialkyl aminoethyl)ether | |
| CN110003023B (en) | Preparation method of environment-friendly N, N-dimethylformamide dimethyl acetal | |
| TWI712596B (en) | Method for preparing cyclic carbonate compound | |
| CN102786427A (en) | Synthetic method of bis-(2-dimethylaminoethyl)ether | |
| CN108558673B (en) | Method for producing 2- (1-cyclohexenyl) ethylamine | |
| CN112375045B (en) | Synthetic method of piperazine | |
| CN102020586A (en) | Method for preparing isophorone nitrile | |
| CN108069836B (en) | Novel method for preparing tri (3, 6-dioxaheptyl) amine | |
| CN101676263A (en) | Method for synthesizing N-tert-butoxycarbonyl group-3-hydroxy azetidine | |
| CN114907219B (en) | Method for preparing monoisopropanolamine and diisopropanolamine by cracking triisopropanolamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131120 Termination date: 20140608 |
|
| EXPY | Termination of patent right or utility model |