CN102030656B - Synthesis method of N-ethyl ethidene diamine - Google Patents
Synthesis method of N-ethyl ethidene diamine Download PDFInfo
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- CN102030656B CN102030656B CN2010105820583A CN201010582058A CN102030656B CN 102030656 B CN102030656 B CN 102030656B CN 2010105820583 A CN2010105820583 A CN 2010105820583A CN 201010582058 A CN201010582058 A CN 201010582058A CN 102030656 B CN102030656 B CN 102030656B
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Abstract
The invention relates to a synthesis method of N-ethyl ethidene diamine. Ethidene diamine and bromoethane serve as raw materials and are subjected to an alkyl halide ammonolysis reaction under the alkali condition; after bromide hydride generated in the reaction process is neutralized by inorganic alkali, generated water is taken out of a reaction system by a water absorbent, thus the reaction continuously progresses towards the positive direction; and after the reaction ends, a product is steamed out by fractionation to obtain a target compound. The invention has the main characteristic that the water absorbent is introduced in to quickly take water generated by the reaction out of the reaction system, thus achieving the purpose of quickly reacting and improving yield. In the method, the final yield can be 84%; and meanwhile, the recovery rate is about 85% after the water absorbent is processed, thus the water absorbent can be reused, thereby lowering production cost and bringing greater application value and economical benefit.
Description
Technical field
The present invention relates to a kind of synthetic method of NEED.
Background technology
NEED, proterties: the water white transparency thick liquid has the smell of ammonia.128～130 ℃ of boiling points, soluble in water, pure, be slightly soluble in ether, benzene.Volatile, in air, be fuming, be alkalescence, absorb Carbon Dioxide in Air and generate non-volatile carbonate.
NEED is important organic synthesis raw material and medicine intermediate, is that antibacterials Pipril, piperacillin, cephalo draw one of basic synthesis material of hydrazone and cefoperazone etc.
In prior art, the main synthetic method of NEED has: thanomin route method, acetic acid route method, aminoethyl sulfuric ester method and haloalkane ammonolysis process.Wherein, girbotol process need to have higher temperature of reaction, and productive rate is lower.Acetic and aminoethyl sulfuric ester method reaction conditions require comparatively harsh, need in autoclave, carry out, and Acetic need catalyzer and higher temperature.Traditional haloalkane ammonolysis process synthesis technique has, and equipment is simple, reaction is easy to the advantages such as control, suitability for industrialized production, but has the shortcomings such as product separation is difficult, yield is low, purity is low.
Summary of the invention
The application's goal of the invention, be by the improvement of the haloalkane ammonolysis process synthesis technique to traditional, solved the product separation difficulty, and yield is low, the drawback of purity difference.
The application implements by following technical solution:
Develop a kind of synthetic method of NEED, take quadrol and monobromethane as raw material, synthetic by the haloalkane ammonolysis reaction, the hydrogen bromide that reaction produces is neutralized with mineral alkali, finally by fractionation, obtains target compound; It is characterized in that:
Use water-retaining agent to remove in mineral alkali and the water generated; Water-retaining agent, from polyacrylic acid, is selected in starch graft acrylic acid multipolymer or cellulose graft vinylformic acid;
Monobromethane and water-retaining agent consumption mass ratio are 1: 0.002～0.018;
The ammonolysis reaction mol ratio is monobromethane: quadrol=1: 4～7;
The time for adding of monobromethane is 30～100min, and soaking time is 1～3h; Temperature of reaction is 0～60 ℃;
Mineral alkali is selected from sodium hydroxide or potassium hydroxide;
The mol ratio of monobromethane and mineral alkali is 1: 1～2.
The synthetic method of above-mentioned NEED, is characterized in that water-retaining agent is through can destroy the hydrogen bond dehydration formed between water-retaining agent and water molecules by alkali lye, recycled after 100 ℃ of dry 2h then, and the rate of recovery is about 85%.
The synthetic method of above-mentioned NEED, is characterized in that collecting the cut of 120～135 ℃ by the normal pressure fractionation, obtains the NEED product.
The principal reaction principle of present techniques is as follows:
The present invention relates to a kind of synthetic method of NEED.Take quadrol, monobromethane is raw material, the haloalkane ammonolysis reaction occurs under alkaline condition, the hydrogen bromide produced in reaction process through in mineral alkali and after, utilize water-retaining agent will react the water produced and take reaction system out of, reaction is constantly carried out to positive dirction, react complete and by the normal pressure fractionation, product steamed, obtain target compound---the NEED product.
Principal feature of the present invention is that water-retaining agent is introduced in reaction, and the water that can rapidly reaction be produced takes away reaction system, plays and adds fast response, improves the purpose of yield.Simultaneously water-retaining agent can destroy the hydrogen bond dehydration formed between water-retaining agent and water molecules by alkali lye, recycled after 100 ℃ of dry 2h then, and the rate of recovery is about 85%, thereby reduces production costs, and has larger implementary value and economic benefit.
Concrete synthetic method of the present invention is as follows: add quadrol in reaction flask, dropwise splash into monobromethane under stirring, dropwise, be incubated 1～3h.React complete, in debris, add mineral alkali, continue to stir 0.5～2h.Separatory adds water-retaining agent in organic layer, stirs 0.5～1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap, and cut is collected in air distillation.Mole proportioning of its reactant is quadrol: monobromethane: mineral alkali=(4～7): 1: (1～3), and the mass ratio of monobromethane and water-retaining agent is 1: 0.001～0.01;
The present invention adopts the water-retaining agent of green non-pollution, change in traditional mode of production the method that organic solvents such as utilizing benzene, toluene, hexanaphthene and water component distillation dewater, simplified operation steps, reduced energy consumption, improved production environment, eliminated the injury of the organic solvents such as benzene, toluene to human body, the water removal effect due to water-retaining agent is better than component distillation greatly in addition, thereby has improved yield and the quality of product.
The preferred technical qualification of the present invention are: the quadrol mole dosage is 42～5.5 times of monobromethane mole dosage, the mineral alkali mole dosage is 1.3～1.8 times of monobromethane mole dosage, the monobromethane quality is 200～2000 times of water-retaining agent quality, temperature of reaction is 5～40 ℃, the preferential polyacrylic acid of water-retaining agent, preferential 126～132 ℃ of cut point.
Advantage of the present invention:
The present invention is on the traditional technology basis, introducing has the material of high-hydroscopicity, the high toxic materials such as benzene, toluene have been eliminated to the pollution of environment and the injury of human body, overcome traditional technology product separation difficulty, yield is low simultaneously, the drawback of purity difference, obtained yield high, the product that purity is high, water-retaining agent used is recyclable in addition, has larger implementary value and economic benefit.
The present invention compares with traditional haloalkane ammonolysis process technique, has equipment simple, and reaction is easy to control, and product separation is simple, and yield is high, the purity advantages of higher, relatively suitability for industrialized production.
Quality product reaches following technical indicator:
| Index name | Index |
| Outward appearance | The water white transparency thick liquid |
| Purity | ≥99.0％ |
| Boiling point | 128～130℃ |
Embodiment
The present invention is described by the following examples, but protection scope of the present invention is not limited in this:
Embodiment 1
Add quadrol 61.33g (content 98.0%, pure 60.1g, 1mol) in reaction flask, stir lower 5 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 40min, dropwises and is warming up to 25 ℃, insulation 2h.React complete, in debris, add 02mol KOH, continue to stir 0.5h.Separatory adds water-retaining agent polyacrylic acid 0.05g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 25.03g, content 98.87% (HPLC method mensuration), and pure 24.75g, yield (in monobromethane) 83.31%,, 128.9 ℃ of boiling points.
Embodiment 2
Add quadrol 49.06g (content 98.0%, pure 48.08g, 0.8mol) in reaction flask, stir lower 0 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 30min, dropwises and is warming up to 45 ℃ of insulation 3h.React complete, in debris, add 0.3mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent polyacrylic acid 0.2g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 23.87g content 99.01% (HPLC method mensuration), pure 23.64g, and yield (in monobromethane) 79.56%,, 129.8 ℃ of boiling points.
Embodiment 3
Add quadrol 85.86g (content 98.0%, pure 84.14g, 1.4mol) in reaction flask, stir lower 10 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 60min, dropwises and is warming up to 55 ℃ of insulation 1h.React complete, in debris, add 0.4mol KOH, continue to stir 0.5h.Separatory adds water-retaining agent polyacrylic acid 0.4g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 24.95g, content 99.32% (HPLC method mensuration), pure 24.78g, yield 83.42%, 129.0 ℃ of boiling points.
Embodiment 4
Add quadrol 85.86g (content 98.0%, pure 84.14g, 1.4mol) in reaction flask, stir lower 5 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 100min, dropwises and is warming up to 60 ℃ of insulation 2.5h.React complete, in debris, add 0.3mol KOH, continue to stir 0.5h.Separatory adds water-retaining agent tapioca (flour) grafted polyacrylic acid sodium 0.05g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 24.01g, content 99.02% (HPLC method mensuration), pure 23.77g, yield 80.02%, 129.5 ℃ of boiling points.
Embodiment 5
Add quadrol 61.33g (content 98.0%, pure 60.1g, 1mol) in reaction flask, stir lower 5 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 40min, dropwises and is warming up to 45 ℃ of insulation 2h.React complete, in debris, add 0.2mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent tapioca (flour) grafted polyacrylic acid sodium 0.2g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 25.33g, content 98.89% (HPLC method mensuration), and pure 25.05g, yield (in monobromethane) 84.31%,, 129.2 ℃ of boiling points.
Embodiment 6
Add quadrol 61.33g (content 98.0%, pure 60.1g, 1mol) in reaction flask, stir lower 0 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 60min, dropwises and is warming up to 45 ℃ of insulation 1h.React complete, in debris, add 0.4mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent tapioca (flour) grafted polyacrylic acid sodium 0.4g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 23.70g, content 99.42% (HPLC method mensuration), and pure 23.56g, yield (in monobromethane) 79.31%,, 129.6 ℃ of boiling points.
Embodiment 7
Add quadrol 49.06g (content 98.0%, pure 48.08g, 0.8mol) in reaction flask, stir lower 0 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 50min, dropwises and is warming up to 60 ℃ of insulation 3h.React complete, in debris, add 0.2mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent CMC grafted polyacrylic acid amine 0.05g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 25.10g content 99.56% (HPLC method mensuration), pure 24.99g, and yield (in monobromethane) 84.11%,, 129.0 ℃ of boiling points.
Embodiment 8
Add quadrol 61.33g (content 98.0%, pure 60.1g, 1mol) in reaction flask, stir lower 0 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 60min, dropwises and is warming up to 45 ℃ of insulation 3h.React complete, in debris, add 0.3mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent CMC grafted polyacrylic acid amine 0.2g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 25.01g, content 99.54% (HPLC method mensuration), and pure 24.89g, yield (in monobromethane) 83.78%,, 128.7 ℃ of boiling points.
Embodiment 9
Add quadrol 61.33g (content 98.0%, pure 60.1g, 1mol) in reaction flask, stir lower 0 ℃ and dropwise splash into monobromethane 22.02g (content 99.0%, pure 21.8g, 0.2mol), the control time for adding is 60min, dropwises and is warming up to 45 ℃ of insulation 3h.React complete, in debris, add 0.3mol NaOH, continue to stir 0.5h.Separatory adds water-retaining agent CMC grafted polyacrylic acid amine 0.4g in organic layer, stirs 1h, filters, and filtrate pouring into is equipped with to reflux in the reaction flask of water trap.120～135 ℃ of cuts are collected in air distillation, are product NEED 25.29g, content 99.09% (HPLC method mensuration), and pure 25.06g, yield (in monobromethane) 84.35%,, 129.1 ℃ of boiling points.
Claims (1)
1. the synthetic method of a N-ethylethylenediamine, synthetic by the haloalkane ammonolysis reaction by quadrol and monobromethane, and the hydrogen bromide of reaction generation is neutralized with mineral alkali, finally by fractionation, obtains target compound, it is characterized in that:
Use water-retaining agent to remove in mineral alkali and the water generated; Water-retaining agent, from polyacrylic acid, is selected in tapioca (flour) grafted polyacrylic acid sodium or CMC grafted polyacrylic acid amine;
Monobromethane and water-retaining agent consumption mass ratio are 1:0.002～0.018;
The ammonolysis reaction mol ratio is monobromethane: quadrol=1:4～7;
The time for adding of monobromethane is 30～l00min, and soaking time is 1～3h; Temperature of reaction is 0～60 ℃;
Mineral alkali is selected from sodium hydroxide or potassium hydroxide;
The mol ratio of monobromethane and mineral alkali is 1:1～2;
Described water-retaining agent destroys the hydrogen bond dehydration formed between water-retaining agent and water molecules by alkali lye, then recycled after 100 ℃ of dry 2h;
Collect the cut of 120～135 ℃ by the normal pressure fractionation, obtain N-ethylethylenediamine product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010105820583A CN102030656B (en) | 2010-12-10 | 2010-12-10 | Synthesis method of N-ethyl ethidene diamine |
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| CN2010105820583A CN102030656B (en) | 2010-12-10 | 2010-12-10 | Synthesis method of N-ethyl ethidene diamine |
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| CN102030656B true CN102030656B (en) | 2013-12-04 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100763A (en) * | 1985-04-01 | 1986-08-13 | 山西大学 | The process for catalytic synthesis of alkyl diamine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA786951B (en) * | 1978-01-30 | 1979-11-28 | American Cyanamid Co | Process for preparing n-ethylethylenediamine |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100763A (en) * | 1985-04-01 | 1986-08-13 | 山西大学 | The process for catalytic synthesis of alkyl diamine |
Non-Patent Citations (8)
| Title |
|---|
| JP昭55-167258A 1980.12.26 |
| N-乙基乙二胺的合成;魏文珑等;《山西化工》;20061031;第26卷(第5期);第3-4，32页 * |
| 一种新的氧哌嗪合成路线;王永亮等;《太原理工大学学报》;20070131;第38卷(第1期);第26-27页 * |
| 周先波等.抗癫痫治疗药物左乙拉西坦的合成研究.《精细化工中间体》.2005,第35卷(第3期),第27页合成路线图，第28页实验部分2.2.4. |
| 抗癫痫治疗药物左乙拉西坦的合成研究;周先波等;《精细化工中间体》;20050630;第35卷(第3期);第27页合成路线图，第28页实验部分2.2.4 * |
| 王永亮等.一种新的氧哌嗪合成路线.《太原理工大学学报》.2007,第38卷(第1期),第26-27页. |
| 陈芬儿.哌拉西林钠.《有机药物合成法》.中国医药科技出版社,1999,第1卷第467-468页. * |
| 魏文珑等.N-乙基乙二胺的合成.《山西化工》.2006,第26卷(第5期),第3-4，32页. |
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