CN101928222A - Synthesis method of N, N, N', N'-tetraisopropyl ethylene diamine - Google Patents
Synthesis method of N, N, N', N'-tetraisopropyl ethylene diamine Download PDFInfo
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- CN101928222A CN101928222A CN2010102233671A CN201010223367A CN101928222A CN 101928222 A CN101928222 A CN 101928222A CN 2010102233671 A CN2010102233671 A CN 2010102233671A CN 201010223367 A CN201010223367 A CN 201010223367A CN 101928222 A CN101928222 A CN 101928222A
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Abstract
The invention discloses a synthesis method of N, N, N', N'-teraisopropyl ethylene diamine. Diisopropylamine and dichloroethane are taken as raw materials, reaction is carried out in a high pressure autoclave under the conditions of no solvent and no catalyst, the mol ratio of diisopropylamine and [to] dichloroethane is 1: 1-4, reaction temperature is 100-200 DEG C, reaction pressure is 0.2-1.1MPa, reaction time is 4-10 hours, so as to obtain solid liquid mixture; alkaline aqueous solution is added into the solid liquid mixture until pH value is 11.5-13.5; and finally separation and reduced pressure rectification are carried out, thus obtaining N, N, N', N'-teraisopropyl ethylene diamine. The method for synthesizing N, N, N', N'-teraisopropyl ethylene diamine of the invention has the characteristics of simple process and high yield and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, particularly N, N, N ', the synthetic method of N '-tetra isopropyl quadrol.
Background technology
N, N, N ', N '-tetra isopropyl quadrol (N, N, N ', N '-Tetraisopropylethylenediamine), its molecular formula is C
14H
32N
2, its structural formula is shown in S-1, and 237.3～238.2 ℃ of boiling points have the wide industrial purposes, are a kind of important fine chemical materials, not only can be used as biochemical reagents, epoxy resin cross-linking agent, also are a kind of quaternary ammonium compound intermediates.
The comprehensive literature report, present N, N, N ', following method is adopted in the preparation of N '-tetra isopropyl quadrol: 1, adopt the reaction of diethyl acyl chlorides and Diisopropylamine to generate acid amides, after the lithium aluminium hydride reduction, make N again, N, N ', N '-tetra isopropyl quadrol, two step total recoverys are about 74%, and reaction formula is shown in S-2.This method flow is long, complex operation, and need to use solvent to reach the expensive original reagent of going back, the production cost height is unsuitable for suitability for industrialized production.2, quadrol and 2-iodopropane carry out amination reaction earlier, again with salt of wormwood in and after obtain N, N, N ', N '-tetra isopropyl quadrol, total recovery is about 87%, reaction formula is shown in S-3.This method raw materials cost height, by product is more, causes iodine to pollute easily, is difficult to accomplish scale production.3, in alcohol solvent, Diisopropylamine and ethylene dibromide carry out amination reaction (Shepherd, R.G., Wilkinson, R.G.Journal of Medicinal and Pharmaceutical Chemistry, 1962,823-835.), again through obtaining N after the neutralization, N, N ', N '-tetra isopropyl quadrol, total recovery is about 70%, and reaction formula is shown in S-4.It is solvent that this method adopts ethanol, has increased the product separation difficulty, and solvent recuperation is applied mechanically difficulty, while raw material ethylene dibromide price height, and yield is lower, and is seriously polluted.
Summary of the invention
The technical problem that invention will solve provides a kind of environmental friendliness, technology is simple, yield is high N, N, N ', the synthetic method of N '-tetra isopropyl quadrol.
In order to solve the problems of the technologies described above, the invention provides a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol, with Diisopropylamine and ethylene dichloride is raw material, under the condition of solvent-free, catalyst-free, in autoclave, react, the mol ratio of described Diisopropylamine and ethylene dichloride 1: 1～4, temperature of reaction is 100～200 ℃, reaction pressure is 0.2～1.1Mpa, and the reaction times is 4～10 hours, gets solidliquid mixture (this solidliquid mixture is made up of the reaction solution and the solid product of gained); In solidliquid mixture, add alkaline aqueous solution until pH=11.5～13.5; Pass through separatory and rectification under vacuum at last, get N, N, N ', N '-tetra isopropyl quadrol.
As N of the present invention, N, N ', the improvement of the synthetic method of N '-tetra isopropyl quadrol: alkaline aqueous solution is the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide, the aqueous solution of yellow soda ash or the aqueous solution of salt of wormwood.
As N of the present invention, N, N ', the further improvement of the synthetic method of N '-tetra isopropyl quadrol: the mass concentration of alkaline aqueous solution is 20～50%.
N of the present invention, N, N ', the synthetic method of N '-tetra isopropyl quadrol is earlier put into autoclave with Diisopropylamine and ethylene dichloride, is heated to certain temperature then and reacts, add after the end in the alkali lye with after obtain product.Synthetic method of the present invention, its synthetic route is as follows:
Cl-(CH
2)
2-Cl+(i-Pr)
2NH→(i-Pr)
2N-(CH
2)
2-N(i-Pr)
2
N of the present invention, N, N ', the synthetic method of N '-tetra isopropyl quadrol has following advantage:
1, this method is carried out under solvent-free, catalyst-free condition, and the reaction cleaning is polluted fewly, has reduced the pressure of wastewater treatment.
2, this method raw material availability height, flow process is short, and is simple to operate, compares cost with other technologies and reduces greatly.
3, this method cost of material is cheap, the yield height, and the reaction conditions gentleness, aftertreatment is simple, is applicable to suitability for industrialized production.
Embodiment
Embodiment 1, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 39.6g (0.4mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 100 ℃ for several times, and pressure is 0.2MPa.Keep finishing reaction behind this thermotonus 4h.
In the solidliquid mixture of gained, add the NaOH aqueous solution (mass concentration 50%) until PH=13.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 38.9g, yield is 85.2%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 2, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 79.2g (0.8mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 150 ℃ for several times, and pressure is 0.6MPa.Keep finishing reaction behind this thermotonus 6h.
In the solidliquid mixture of gained, add the KOH aqueous solution (mass concentration 50%) until PH=13.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 40.3g, yield is 88.2%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 3, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 79.2g (0.8mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 140 ℃ for several times, and pressure is 0.5MPa.Keep finishing reaction behind this thermotonus 8h.
In the solidliquid mixture of gained, add Na
2CO
3The aqueous solution (mass concentration 20%) is until PH=11.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 40.2g, yield is 88.0%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 4, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 118.8g (1.2mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 120 ℃ for several times, and pressure is 0.5MPa.Keep finishing reaction behind this thermotonus 5h.
In the solidliquid mixture of gained, add K
2CO
3The aqueous solution (mass concentration 50%) is until PH=12.0, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 40.1g, yield is 87.8%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 5, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 118.8g (1.2mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 150 ℃ for several times, and pressure is 0.6MPa.Keep finishing reaction behind this thermotonus 8h.
In the solidliquid mixture of gained, add the NaOH aqueous solution (mass concentration 50%) until PH=13.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 40.5g, yield is 88.7%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 6, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 118.8g (1.2mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 180 ℃ for several times, and pressure is 0.8MPa.Keep finishing reaction behind this thermotonus 6h.
In the solidliquid mixture of gained, add the KOH aqueous solution (mass concentration 50%) until PH=13, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 40.6g, yield is 88.9%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 7, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 158.4g (1.6mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 120 ℃ for several times, and pressure is 0.5MPa.Keep finishing reaction behind this thermotonus 5h.
In the solidliquid mixture of gained, add Na
2CO
3The aqueous solution (mass concentration 20%) is until PH=11.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 39.9g, yield is 87.4%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 8, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 158.4g (1.6mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 180 ℃ for several times, and pressure is 0.8MPa.Keep finishing reaction behind this thermotonus 8h.
In the solidliquid mixture of gained, add the NaOH aqueous solution (mass concentration 50%) until PH=13, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 41.2g, yield is 90.2%, purity is 99%, and products therefrom is correct through characterizing structure.
Embodiment 9, a kind of N, N, N ', the synthetic method of N '-tetra isopropyl quadrol:
In the autoclave of band stirring temperature measuring equipment, add Diisopropylamine 40.5g (0.4mol), ethylene dichloride 158.4g (1.6mol), kettle cover closes.Use N
2Leak detection and displaced air are warming up to 200 ℃ for several times, and pressure is 1.1MPa.Keep finishing reaction behind this thermotonus 10h.
In the solidliquid mixture of gained, add KOH solution (mass concentration 50%) until PH=13.5, standing demix, tell organic phase (being positioned at the upper strata) (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 41.0g, yield is 89.8%, purity is 99%, and products therefrom is correct through characterizing structure.
The comparative example:
In stirring the autoclave of temperature measuring equipment, band adds Diisopropylamine 40.5g (0.4mol), ethylene dichloride 118.8g (1.2mol), ethanol 46g (1.0mol) kettle cover that closes.Use N
2Leak detection and displaced air are warming up to 150 ℃ for several times, and pressure is 0.8MPa.Keep finishing reaction behind this thermotonus 6h.
In the solidliquid mixture of gained, add the KOH aqueous solution (mass concentration 50%) until PH=13, standing demix, tell upper organic phase (1266.6Pa) batch fractionating that reduces pressure, collect 86.5～97.0 ℃ of cuts, product N, N, N ', N '-tetra isopropyl quadrol 28.4g, yield is 62.5%, purity is 99%, and products therefrom is correct through characterizing structure.
We learn according to above comparative example: even the method 3 of informing according to background technology, adopt ethylene dichloride to replace ethylene dibromide to produce, because the ethylene dichloride activity is low than ethylene dibromide, product yield descends under the same terms, raw material availability reduces, thereby increased the difficulty of the problem of raw material, solvent, product separation, improved production cost.
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 (3)
1. N, N, N ', the synthetic method of N '-tetra isopropyl quadrol is characterized in that: with Diisopropylamine and ethylene dichloride is raw material, under the condition of solvent-free, catalyst-free, in autoclave, react, the mol ratio of described Diisopropylamine and ethylene dichloride 1: 1～4, temperature of reaction are 100～200 ℃, and reaction pressure is 0.2～1.1Mpa, reaction times is 4～10 hours, gets solidliquid mixture; In solidliquid mixture, add alkaline aqueous solution until pH=11.5～13.5; Pass through separatory and rectification under vacuum at last, get N, N, N ', N '-tetra isopropyl quadrol.
2. N according to claim 1, N, N ', the synthetic method of N '-tetra isopropyl quadrol is characterized in that: described alkaline aqueous solution is the aqueous solution of sodium hydroxide, the aqueous solution of potassium hydroxide, the aqueous solution of yellow soda ash or the aqueous solution of salt of wormwood.
3. N according to claim 1 and 2, N, N ', the synthetic method of N '-tetra isopropyl quadrol is characterized in that: the mass concentration of described alkaline aqueous solution is 20～50%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180797A (en) * | 2011-03-17 | 2011-09-14 | 浙江大学 | Synthesis method of N,N-diethyl isopropylamine |
| CN102796005A (en) * | 2012-08-28 | 2012-11-28 | 杭州新德环保科技有限公司 | Synthetic method of N,N'-diisopropylamino ethylamine |
| CN102976952A (en) * | 2012-12-01 | 2013-03-20 | 张家港市大伟助剂有限公司 | Preparation method of octyl diethylenetriamine |
| CN103664652A (en) * | 2013-09-25 | 2014-03-26 | 南京工业大学 | Synthesis method of N, N, N', N'-tetrakis (2-hydroxyethyl)-ethylenediamine (THEEDA) |
| CN108997143A (en) * | 2018-08-31 | 2018-12-14 | 之江（四川）高新材料应用技术研究院有限公司 | N, N- dimethyl chloride ethamine and tetramethylethylenediamine tie up sour integrated production method certainly |
Citations (1)
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| CN101759571A (en) * | 2010-01-28 | 2010-06-30 | 浙江大学 | Preparation method of N,N-diisopropylethylamine |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101759571A (en) * | 2010-01-28 | 2010-06-30 | 浙江大学 | Preparation method of N,N-diisopropylethylamine |
Non-Patent Citations (2)
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| R．G．SHEPHERD 等: "s", 《JOURNAL OF MEDICINAL AND PHARMACEUTICAL CHEMISTRY》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180797A (en) * | 2011-03-17 | 2011-09-14 | 浙江大学 | Synthesis method of N,N-diethyl isopropylamine |
| CN102796005A (en) * | 2012-08-28 | 2012-11-28 | 杭州新德环保科技有限公司 | Synthetic method of N,N'-diisopropylamino ethylamine |
| CN102976952A (en) * | 2012-12-01 | 2013-03-20 | 张家港市大伟助剂有限公司 | Preparation method of octyl diethylenetriamine |
| CN103664652A (en) * | 2013-09-25 | 2014-03-26 | 南京工业大学 | Synthesis method of N, N, N', N'-tetrakis (2-hydroxyethyl)-ethylenediamine (THEEDA) |
| CN108997143A (en) * | 2018-08-31 | 2018-12-14 | 之江（四川）高新材料应用技术研究院有限公司 | N, N- dimethyl chloride ethamine and tetramethylethylenediamine tie up sour integrated production method certainly |
| CN108997143B (en) * | 2018-08-31 | 2021-04-16 | 之江（四川）高新材料应用技术研究院有限公司 | Self-acid-binding integrated production method of N, N-dimethyl chloroethylamine and tetramethyl ethylenediamine |
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