CN105017118A - Method for preparing 2-methylaziridine by using microchannel reactor - Google Patents
Method for preparing 2-methylaziridine by using microchannel reactor Download PDFInfo
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- CN105017118A CN105017118A CN201510420019.6A CN201510420019A CN105017118A CN 105017118 A CN105017118 A CN 105017118A CN 201510420019 A CN201510420019 A CN 201510420019A CN 105017118 A CN105017118 A CN 105017118A
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- C07—ORGANIC CHEMISTRY
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- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
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- C—CHEMISTRY; METALLURGY
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/02—Preparation by ring-closure
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Abstract
A method for preparing 2-methylaziridine by using a microchannel reactor comprises that concentrated sulfuric acid and isopropanolamine are respectively inputted to the microchannel reactor and are mixed, an esterification reaction of concentrated sulfuric acid and isopropanolamine is carried out, a mixed liquid obtained from the reaction continues to undergo a cyclization reaction with a sodium hydroxide aqueous solution, a 2-methylaziridine aqueous solution is obtained, and the mass percentage is 40-60%. The microchannel reactor one-pot method is used for preparation of aziridine, the operation steps are simplified, the reaction time is greatly shortened, the reaction efficiency is significantly increased, a temperature runaway phenomenon possibly appearing in a kettle type reaction is avoided, formation of by-products is reduced, security is increased, the production cost is reduced, and the disadvantages of high labor intensity, long production cycle, low quality of products and more 'three wastes' generation in traditional production are overcome.
Description
Technical field
The invention belongs to the preparation method field of aziridine, be specifically related to a kind of method utilizing micro passage reaction to prepare 2-methylaziridine.
Background technology
Aziridine is a kind of conventional intermediate of organic synthesis, be usually used in the synthesis of reactive dyestuffs and cancer therapy drug etc., also be synthesizing new linking agent trimethylolpropane tris [3-(2-methylaziridine base) propionic ester], be called for short the key intermediate of TTMAP, aziridine can make TTMAP have good water-soluble and oil soluble.And TTMAP holds out broad prospects in fields such as water-borne coatingss, market potential is huge, the Dou Shi offshore company of production company that the linking agent in this field is main in the world, core technology is being held in the developed country such as moral, Japan and the United States, this field domestic starting is late, quality product is general, supporting Infrastructure imperfection, the preparation method of aziridines linking agent with still have gap abroad.Therefore the aziridine of high-quality seems particularly important for this product.
At present, the production of 2-methylaziridine mainly contains following several mode:
1) α-amino isopropyl alcohol and sulfuric acid are warm altogether dewaters, and reaction formula is as follows:
2) HCl of drying is passed into α-amino isopropyl alcohol salify hot altogether with sulfur oxychloride again, reaction formula is as follows:
Above-mentioned two kinds of production method preparation cycles are long, and productive rate is low, and aftertreatment is complicated.
3) α-amino isopropyl alcohol first becomes ester with sulfuric acid reaction, and then carry out isomerization reaction with alkali, reaction formula is as follows:
This is the technique of comparative maturity, but this route adopts traditional still reaction one kettle way, because convention stir can not reach good mass-and heat-transfer efficiency, may occur local superheating, concentration gradient etc. are unfavorable for reacting the phenomenon of carrying out, and therefore product concentration is low, purity is low, and quality product is not high.At present, in order to obtain the aziridine of high-quality, this route is still based on separate operations.
4) α-amino isopropyl alcohol direct intramolecular dehydration under solid-phase catalyst existent condition, reaction formula is as follows:
This method is solid-carried catalyst gas phase high temperature successive reaction, requires high to production unit.
Micro passage reaction (Microreactor/Microchannel reactor) is a kind of pipeline reactor of continuous flow, a kind of characteristic dimension manufactured by micro-processing technology between 10-1000 micron, the device of Control of chemical reaction in microresponse space.Microchannel narrow in microreactor shortens the Distance geometry time of mass transfer, and the specific surface area simultaneously increased also provides larger place for mass transfer process, thus the short mix of realization response material, realize radial direction within the scope of Millisecond and mix completely.The microchannel that microreactor is narrow too increases thermograde simultaneously, and the specific surface area of increase enhances the heat-transfer capability (25000W/ (m of reactor greatly
2* K)), an at least large order of magnitude compared with traditional heat exchangers.
At present, micro passage reaction has the nitration reaction of certain risk, and hydrogenation reaction etc. are obtained by reacting good utilization, the large security improving such reaction.And in esterification, in the reaction such as cyclization, due to the complicacy of response situation, the use of uncertain micro passage reaction also needs further to grope and trial.
Summary of the invention
The object of the present invention is to provide a kind of method utilizing micro passage reaction to prepare 2-methylaziridine, reaction efficiency significantly promotes, Reaction time shorten greatly, avoids the temperature runaway phenomenon that still reaction may occur, decreases the generation of by product, add security, decrease production cost, overcome labour intensity in traditional mode of production large, the production cycle is long, quality product is low, and the three wastes produce more shortcoming.
In order to achieve the above object, the technical solution used in the present invention is as follows:
Utilize micro passage reaction to prepare a method for 2-methylaziridine, comprise the steps:
1) vitriol oil and α-amino isopropyl alcohol are inputted micro passage reaction respectively according to volume flow ratio 1:2-8, carry out esterification after mixing, temperature is 5-50 DEG C, reaction times 20-80s;
2) reaction solution after esterification and concentration are the aqueous sodium hydroxide solution generation cyclization of 5-45%, and temperature of reaction is 50-90 DEG C, reaction times 15-80s, and pressure is 0.1-1.2MPa;
3) reaction terminates rear discharging, and reaction effluent material pH is adjusted to 1-6.
Preferably, described esterification reaction temperature is 20-30 DEG C, and the time of esterification is 30-60s, and the time that material carries out cyclization is 40-80s, and cyclization temperature is 60-80 DEG C.
Preferably, the vitriol oil and α-amino isopropyl alcohol volume flow ratio are 1:3-7.
Further again, step 3) in the concentration of aqueous sodium hydroxide solution be 20-40%, the flow velocity of the vitriol oil is 5ml-20ml/min, and the flow velocity of α-amino isopropyl alcohol is 20-80ml/min, and the flow velocity of aqueous sodium hydroxide solution is 20-80ml/min.
Preferably, material carries out the pressure of esterification and cyclization is 0.3-1MPa.
Further, arrange some reaction modules in described micro passage reaction, reaction module material is withstand voltage glass, pottery, carbon composite or acid resisting material, is provided with reaction mass passage in reaction module, and reaction mass channel internal diameter is 0.5-5mm.
2-methylaziridine of the present invention obtains in form of an aqueous solutions, and the massfraction of 2-methylaziridine is 40-60%.
The present invention utilizes micro passage reaction, and with the vitriol oil and α-amino isopropyl alcohol for 2-methylaziridine prepared by raw material, the miniaturization yardstick that micro passage reaction has determines transmission characteristic and the macro-flow characteristic of the microfluid continuing flowing wherein.In micro passage reaction, its trickle pore passage structure has larger specific surface area, microchannel narrow in micro passage reaction shortens the Distance geometry time of mass transfer, the specific surface area simultaneously increased is also for mass transfer process provides larger place, thus realize the short mix of the vitriol oil and α-amino isopropyl alcohol, within the scope of Millisecond, realize radial direction mix completely, greatly promote mass-transfer efficiency.
The present invention adopts the micro passage reaction with two warm area, the vitriol oil and α-amino isopropyl alcohol input high-throughput micro passage reaction, carry out esterification, control temperature of reaction at 5-50 DEG C, cyclization is carried out further again with aqueous sodium hydroxide solution, control temperature of reaction at 50-90 DEG C, obtain the 2-methylaziridine aqueous solution, accurate control temperature of reaction, reaction is enable to reach the heat-transfer effect of high-quality at short notice, improve reaction efficiency, shorten the time of esterification and cyclization, the temperature runaway that the strong exothermic effect of the vitriol oil causes is effectively controlled, the one kettle way design of the two warm area of the present invention makes up the cost that traditional reactor separate operations brings to be increased and loss of product, add operability and the security of reaction simultaneously.
In micro passage reaction of the present invention, the internal diameter of reaction mass passage is 0.5-5mm, and the liquid form of its inner fluid passage is laminar flow, within the extremely narrow residence time, almost without air-teturning mixed phenomenon.
Compared with prior art, the present invention has following beneficial effect:
1) the present invention utilizes micro passage reaction, prepares 2-methylaziridine with the vitriol oil and α-amino isopropyl alcohol, and because reaction mass is able to fast fully mixing, improve mass-transfer efficiency, substantially reduce the reaction times, reaction efficiency is significantly improved.
2) due to the strong convection of micro passage reaction, strong characteristics of heat transfer, avoid the temperature runaway phenomenon that still reaction may occur, decrease the generation of by product, add security, decrease production cost, overcome labour intensity in traditional mode of production large, production cycle is long, and quality product is low, and the three wastes produce more inferior position.
3) the present invention adopts micro passage reaction one pot reaction, the vitriol oil and α-amino isopropyl alcohol input high-throughput micro passage reaction first carry out esterification, cyclization is carried out again with aqueous sodium hydroxide solution, obtain the 2-methylaziridine aqueous solution, pass through one pot reaction, avoid the purification procedures that separate operations is too tediously long, reduce the product loss in purge process, be conducive to improving yield, quality product gets a promotion simultaneously, overall yield of reaction is promoted to more than 90% from 80% of autoclave, the α-amino isopropyl alcohol selectivity of reaction is promoted to 98% from 90%, α-amino isopropyl alcohol transformation efficiency is promoted to more than 95% from 90%.
Accompanying drawing explanation
Fig. 1 is the reacting flow chart of the embodiment of the present invention.
Embodiment
Below in conjunction with specific embodiments and the drawings, the invention will be further described, but content not thereby limiting the invention.
The micro passage reaction of the embodiment of the present invention adopts heart-shaped structure module micro passage reaction Corning G1 reactor, its material is corrosion-resistant withstand voltage glass, its pressure tolerance is 1.8MPa to the maximum, raw material is by volume pump input microchannel reactive system, and the charging capacity of material all controls by changing flow, and the conveying range of flow is from 0-120ml/min, its Location Detection of Medium Transportation Pipeline is provided with tensimeter, safety valve, check valve, back pressure valve etc.
In the micro passage reaction of the embodiment of the present invention, some reaction modules are set, connected by connecting passage between reaction module, form the first warm area and the second warm area, three modules are established respectively in first warm area and the second warm area, two-step reaction carries out at the first warm area and the second warm area respectively, the temperature of two warm areas is controlled by two cooling heating systems of isolated operation, temperature equilibrium can be reached at short notice, after the vitriol oil and α-amino isopropyl alcohol mix in mixing module, esterification is carried out in first warm area of input high-throughput micro passage reaction, to the second warm area input aqueous sodium hydroxide solution, carry out cyclization with the reaction solution from the first warm area and prepare the 2-methylaziridine aqueous solution (see Fig. 1).
Embodiment 1
By the vitriol oil with 15ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 45ml/min, and the temperature of the first warm area is set to 30 DEG C, residence time 30s, system pressure is 0.7MP, is pumped into the sodium hydroxide solution of 40% at the 5th reaction module place by volume pump, flow velocity 50ml/min, the second warm area temperature 60 C, the residence time is 40s, system pressure is 0.8MP, product flows out from outlet, acidified, obtains product, yield 91.2%, α-amino isopropyl alcohol selectivity is 97.7%.
Embodiment 2
By the vitriol oil with 10ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 60ml/min, and the temperature of the first warm area is set to 20 DEG C, residence time 35s, system pressure is 0.5MP, is pumped into the sodium hydroxide solution of 40% at the 5th reaction module place by volume pump, flow velocity 60ml/min, the second warm area temperature 65 DEG C, the residence time is 50s, system pressure is 0.5MP, product flows out from outlet, acidified, obtains product, yield 90.2%, α-amino isopropyl alcohol selectivity is 98.2%.
Embodiment 3
By the vitriol oil with 10ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 30ml/min, and the temperature of the first warm area is set to 20 DEG C, residence time 20s, system pressure is 0.3MP, is pumped into the sodium hydroxide solution of 25% at the 5th reaction module place by volume pump, flow velocity 30ml/min, the second warm area temperature 70 C, the residence time is 70s, system pressure is 0.35MP, product flows out from outlet, acidified, obtains product, yield 93.2%, α-amino isopropyl alcohol selectivity is 95.7%.
Embodiment 4
By the vitriol oil with 9ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 45ml/min, and the temperature of the first warm area is set to 37 DEG C, residence time 25s, system pressure is 0.7MP, is pumped into the sodium hydroxide solution of 40% at the 5th reaction module place by volume pump, flow velocity 50ml/min, the second warm area temperature 64 DEG C, the residence time is 40s, system pressure is 0.8MP, product flows out from outlet, acidified, obtains product, yield 91.2%, α-amino isopropyl alcohol selectivity is 97.7%.
Embodiment 5
By the vitriol oil with 20ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 70ml/min, and the temperature of the first warm area is set to 20 DEG C, residence time 50s, system pressure is 0.7MP, is pumped into the sodium hydroxide solution of 40% at the 5th reaction module place by volume pump, flow velocity 30ml/min, the second warm area temperature 75 DEG C, the residence time is 30s, system pressure is 0.7MP, product flows out from outlet, acidified, obtains product, yield 92.0%, α-amino isopropyl alcohol selectivity is 95.9%.
Embodiment 6
By the vitriol oil with 5ml/min, α-amino isopropyl alcohol enters micro passage reaction with the flow pump of 35ml/min, and the temperature of the first warm area is set to 25 DEG C, residence time 20s, system pressure is 0.4MP, is pumped into the sodium hydroxide solution of 30% at the 5th reaction module place by volume pump, flow velocity 30ml/min, the second warm area temperature 65 DEG C, the residence time is 68s, system pressure is 0.4MP, product flows out from outlet, acidified, obtains product, yield 94.2%, α-amino isopropyl alcohol selectivity is 98.2%.
Claims (10)
1. utilize micro passage reaction to prepare a method for 2-methylaziridine, it is characterized in that, comprise the steps:
1) vitriol oil and α-amino isopropyl alcohol are inputted micro passage reaction respectively according to volume flow ratio 1:2-8, carry out esterification after mixing, esterification reaction temperature is 5-50 DEG C, reaction times 20-80s, and pressure is 0.1-1.2MPa;
2) reaction solution after esterification and concentration are the aqueous sodium hydroxide solution generation cyclization of 5-45%, and cyclization temperature is 50-90 DEG C, cyclization time 15-80s, and pressure is 0.1-1.2MPa;
3) reaction terminates rear discharging, reaction effluent material pH is adjusted to 1-6, obtains 2-methylaziridine.
2. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, described esterification reaction temperature is 20-30 DEG C, and the time of esterification is 30-60s.
3. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, cyclization temperature is 60-80 DEG C, and the time of cyclization is 40-80s.
4. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, the volume flow ratio of the described vitriol oil and α-amino isopropyl alcohol is 1:3-7.
5. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, step 3) in the concentration of aqueous sodium hydroxide solution be 20-40%.
6. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, the flow velocity of the vitriol oil is 5ml-20ml/min, and the flow velocity of α-amino isopropyl alcohol is 20-80ml/min.
7. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, is characterized in that, the flow velocity of described aqueous sodium hydroxide solution is 20-80ml/min.
8. micro passage reaction according to claim 1 prepares the method for 2-methylaziridine, it is characterized in that, step 1) and step 2) described pressure is 0.3-1MPa.
9. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 1, it is characterized in that, arrange some reaction modules in described micro passage reaction, described reaction module material is withstand voltage glass, pottery, carbon composite or acid resisting material.
10. the method utilizing micro passage reaction to prepare 2-methylaziridine according to claim 9, is characterized in that, be provided with reaction mass passage in described reaction module, and reaction mass channel internal diameter is 0.5-5mm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565499A (en) * | 2016-09-30 | 2017-04-19 | 多氟多化工股份有限公司 | Method for synthesizing tetraethylammonium tetrafluoroborate through using micro-channel reactor |
| CN106905172A (en) * | 2017-01-10 | 2017-06-30 | 田振民 | A kind of preparation method of utilization micro passage reaction methyl anthranilate |
| CN109824755A (en) * | 2019-04-09 | 2019-05-31 | 湖南华腾制药有限公司 | N- tertbutyloxycarbonyl-L- leucyl-L-phenylalanine methyl esters production method |
| CN110003072A (en) * | 2019-03-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation method of 2- methylaziridine |
| CN110229077A (en) * | 2019-06-19 | 2019-09-13 | 深圳市一正科技有限公司 | A method of continuously preparing methyl anthranilate |
| CN112159332A (en) * | 2020-09-23 | 2021-01-01 | 青岛科技大学 | Process and device for continuously producing bentazone intermediate anthranilic acid |
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| CN102627594A (en) * | 2012-03-20 | 2012-08-08 | 上海华谊（集团）公司 | Preparation method of waterless aziridine compound |
Non-Patent Citations (1)
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| 穆金霞，等: "微通道反应器在合成反应中的应用", 《化学进展》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565499A (en) * | 2016-09-30 | 2017-04-19 | 多氟多化工股份有限公司 | Method for synthesizing tetraethylammonium tetrafluoroborate through using micro-channel reactor |
| CN106905172A (en) * | 2017-01-10 | 2017-06-30 | 田振民 | A kind of preparation method of utilization micro passage reaction methyl anthranilate |
| CN110003072A (en) * | 2019-03-15 | 2019-07-12 | 宁夏倬昱新材料科技有限公司 | A kind of preparation method of 2- methylaziridine |
| CN109824755A (en) * | 2019-04-09 | 2019-05-31 | 湖南华腾制药有限公司 | N- tertbutyloxycarbonyl-L- leucyl-L-phenylalanine methyl esters production method |
| CN110229077A (en) * | 2019-06-19 | 2019-09-13 | 深圳市一正科技有限公司 | A method of continuously preparing methyl anthranilate |
| CN112159332A (en) * | 2020-09-23 | 2021-01-01 | 青岛科技大学 | Process and device for continuously producing bentazone intermediate anthranilic acid |
| CN112159332B (en) * | 2020-09-23 | 2023-05-30 | 青岛科技大学 | Process and device for continuously producing bentazone intermediate isopropyl anthranilate |
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Application publication date: 20151104 |