CN103113234A - Method for synthesizing N-methyl paranitroaniline - Google Patents
Method for synthesizing N-methyl paranitroaniline Download PDFInfo
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- CN103113234A CN103113234A CN2013100218030A CN201310021803A CN103113234A CN 103113234 A CN103113234 A CN 103113234A CN 2013100218030 A CN2013100218030 A CN 2013100218030A CN 201310021803 A CN201310021803 A CN 201310021803A CN 103113234 A CN103113234 A CN 103113234A
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Abstract
The invention discloses a method for synthesizing N-methyl paranitroaniline (MNA). The method comprises the following steps of: performing aminolysis on p-nitrchlorobenzene and methylamine water solution in a pressure kettle under the effect of a catalyst, wherein the reaction temperature of aminolysis is 160-180 DEG C, and the pressure is 1.6-2.0MPa; after high-pressure aminolysis, releasing at 100-115 DEG C to remove dissociative methylamine and part of water in the pressure kettle, wherein the discharged methylamine and water are absorbed by a methylamine absorption tower; placing materials in the pressure kettle in a filter for suction filtration, wherein the filter cakes are MNA crude products; and decocting, refining, filtering and drying the MNA crude products to prepare MNA products. According to the method disclosed by the invention, the synthetic materials are few in type, the source is widely accessible, synthesis is completed by one step, the yield is high, and the product is stable in quality; the method is short in period, low in cost and safe, reliable and stable in process; and the total yield of the product is over 90%, and the purity is over 99.0%.
Description
Technical field:
The present invention relates to industrial chemicals and synthesize field, particularly a kind of method of synthetic N-methyl paranitroaniline.
Background technology:
N-methyl paranitroaniline (MNA), 150 ℃ of fusing points can be used as the tranquilizer of gunpowder, and the deterrent of explosive is widely used organic intermediate, and can be used as the benchmark that detects other materials, more and more receives people's concern now.
The synthetic method of relevant MNA, as far back as the Britain Kemal eighties in 20th century, Oznur and Reese, Colin B have just synthesized MNA take p-Nitroaniline with to sulphur toluene as main raw material.China in the nineties in 20th century just by Zhou Jihua and female this material that synthesizes take p-Nitrophenyl chloride, Potassium monofluoride and methylamine as main raw material of Chen Shen in 204, Xi'an.Integrate its synthetic method and mainly contain five classes:
The one, p-Nitroaniline method: p-Nitroaniline, methylbenzene phenyl-sulfhydrate and formaldehyde are heated 2.5h in ethanolic soln, get an intermediate, this intermediate and NaBH
4Be placed in together CH
3OCH
2CH
2OCH
3In solution, can get MNA.Raw materials used high to the methylbenzene phenyl-sulfhydrate cost, in reduction process, use NaBH
4, be unfavorable for suitability for industrialized production.
The 2nd, p-Nitrophenyl chloride fluoro reamination: p-Nitrophenyl chloride and Potassium monofluoride are made catalyzer with tetramethyl ammonium chloride under 170-175 ℃, can obtain fluoronitrobenzene, then get MNA with the methylamine amination.What produce in this reaction process is all severe toxicity or corrosive material to fluoronitrobenzene, HF, higher to conversion unit and operational requirement.
The 3rd, the p-Nitrophenyl chloride sulfonation is aminolysis again: will be neutralized into sodium salt after the p-Nitrophenyl chloride sulfonation, add methylamine and carry out aminolysis, slough sulfo group and namely get MNA, yield 78.5%.This reaction synthetic route is long, consumes a large amount of soda acids, produces a large amount of waste water.
The 4th, N-methyl first (second) acid amides method: p-Nitrophenyl chloride and N-methyl first (second) acid amides reflux and approximately made the MNA crude product in 11 hours under alkaline condition.
The 5th, paranitroacetanilide, methyl iodide and ethanol are that raw material makes: paranitroacetanilide, potassium hydroxide mixing post-heating reflux, drip the acetone soln of methyl iodide, finish, continue to reflux 4 hours, placement is spent the night and is separated out N-methyl paranitroacetanilide, then it is mixed with ethanol and refluxed 8 hours, dilute with water gets crude product.
At present, the method for above five kinds of synthetic MNA all exists the problem that synthetic route is long, the time is long, seriously polluted, cost is high, and quality product also remains further to be improved, and the novel method of synthetic MNA also needs further research better.
Summary of the invention:
The object of the invention is to overcome that the synthetic route that existing MNA synthetic method exists is long, the time is long, seriously polluted, the high in cost of production problem, provide that a kind of production cost is low, synthetic route is short, the industrial preparative method of the MNA of low pollution, high yield.
The method concrete steps of a kind of synthetic N-methyl paranitroaniline of the present invention are:
(1) aminolysis generation MNA occurs in p-Nitrophenyl chloride and aqueous methylamine solution in autoclave pressure under catalyst action, adds catalyzer in autoclave pressure, autoclave pressure nitrogen replacement 3 times, the seal-off pressure still, be warming up to 160-180 ℃, pressure 1.6-2.0MPa, insulation 40-100min;
(2) after the high pressure aminolysis reaction finished, with the free methylamine in the emptying autoclave pressure and part water, the free methylamine of discharge and water were absorbed by the methylamine absorption tower in 100-115 ℃ of lower pressure release; Continue to be cooled to 50-60 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
(3) MNA is refining: the solvent that MNA crude product and 3-8 are doubly measured adds in reactor, is warming up to 60-70 ℃ and boils and wash 20-40min, is cooled to 15-30 ℃, filters, washs, dries and to get the MNA finished product.
Aqueous methylamine solution concentration 20-45%(mass concentration in described step (1)).
In described step (1), p-Nitrophenyl chloride and aqueous methylamine solution mass ratio are 1:3-1:8.
In described step (1), catalyzer can be copper, mantoquita, copper oxide, copper oxyhydroxide or their mixture; Described catalyzer is preferably copper sulfate or neutralized verdigris;
In described step (1), catalyst levels is the 0.5-1.5% of p-Nitrophenyl chloride quality.
After described step (2) mesohigh aminolysis reaction finished, the pressure release temperature can be carried out under 30-115 ℃; Described pressure release temperature is preferably 100-115 ℃.
In described step (3), solvent for use is methyl alcohol, ethanol, acetone, ethyl acetate, ether or their mixture; Described solvent is preferably methyl alcohol or ethanol or their mixture.
Beneficial effect:
The method of a kind of synthetic N-methyl paranitroaniline of the present invention, the synthesis material kind is few, wide material sources are easy to get, and each starting material harm less; A synthetic step completes, and yield is high, constant product quality; Cycle is short, pollutes littlely, and cost is low, and process safety is reliable, steadily.Total yield of products is more than 90%, and purity is more than 99.0%.
Embodiment:
Method below by a kind of synthetic N-methyl paranitroaniline in specific embodiment narration the present invention.Unless stated otherwise, in the present invention, technique means used is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention are only limited by claims.To those skilled in the art, under the prerequisite that does not deviate from essence of the present invention and scope, various changes that the material component in these embodiments and consumption are carried out or change and also belong to protection scope of the present invention.
Embodiment 1:
The p-Nitrophenyl chloride of 150g and the aqueous methylamine solution of 600g30% are joined in the 1L autoclave pressure, add 1.5g copper sulfate, nitrogen replacement 3 times, the seal-off pressure still, heat up, 165 ℃ of temperature, pressure approximately is incubated 60min under 1.8MPa, be cooled to 105 ℃ of beginning pressure releases, the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 55 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
The methyl alcohol of MNA crude product and 5 times of amounts is added in there-necked flask, be warming up to 65 ℃ and boil and wash 30min, be cooled to 30 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 92%, purity 99.4%.
Embodiment 2:
40kg p-Nitrophenyl chloride and 170kg30% aqueous methylamine solution are added the 300L autoclave pressure, add 400g copper sulfate, nitrogen replacement 3 times, closed reactor heats up, 165 ℃ of temperature, pressure approximately is incubated 60min under 1.8MPa, is cooled to 105 ℃ of beginning pressure releases, and the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 55 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
The methyl alcohol of MNA crude product and 8 times of amounts is added in refining kettle, be warming up to 65 ℃ and boil and wash 30min, be cooled to below 30 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 90%, purity 99.2%.
Embodiment 3:
The p-Nitrophenyl chloride of 150g and the aqueous methylamine solution of 600g30% are joined in the 1L autoclave pressure, add neutralized verdigris 1.6g, nitrogen replacement 3 times, the seal-off pressure still, heat up, 165 ℃ of temperature, pressure approximately is incubated 60min under 1.8MPa, be cooled to 105 ℃ of beginning pressure releases, the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 55 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
The methyl alcohol of MNA crude product and 4 times of amounts is added in there-necked flask, be warming up to 65 ℃ and boil and wash 30min, be cooled to below 30 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 91%, purity 99.3%.
Embodiment 4
The p-Nitrophenyl chloride of 100g and the aqueous methylamine solution of 300g30% are joined in the 1L autoclave pressure, add neutralized verdigris 1.5g, nitrogen replacement 3 times, the seal-off pressure still, heat up, 160 ℃ of temperature are incubated 50min under pressure 1.8MPa, be cooled to 100 ℃ of beginning pressure releases, the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 60 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
The methyl alcohol of MNA crude product and 5 times of amounts is added in there-necked flask, be warming up to 65 ℃ and boil and wash 30min, be cooled to 20 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 90%, purity 99.2%.
Embodiment 5
The p-Nitrophenyl chloride of 100g and the aqueous methylamine solution of 400g30% are joined in the 1L autoclave pressure, add neutralized verdigris 0.5g, nitrogen replacement 3 times, the seal-off pressure still, heat up, 160 ℃ of temperature are incubated 50min under pressure 1.8MPa, be cooled to 100 ℃ of beginning pressure releases, the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 60 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
The ethanol of MNA crude product and 5 times of amounts is added in there-necked flask, be warming up to 70 ℃ and boil and wash 30min, be cooled to 30 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 93%, purity 99.5%.Aqueous methylamine solution concentration 35%(mass concentration in described step (1)).
Embodiment 6
The p-Nitrophenyl chloride of 100g and the aqueous methylamine solution of 400g30% are joined in the 1L autoclave pressure, add each 0.5g of acetic acid copper and copper sulfate, nitrogen replacement 3 times, the seal-off pressure still, heat up, 170 ℃ of temperature are incubated 50min under pressure 1.8MPa, be cooled to 100 ℃ of beginning pressure releases, the free methylamine of discharge absorbs by the absorption tower.
Continue to be cooled to 60 ℃, material in autoclave pressure is put into the strainer suction filtration, get the MNA crude product.
Ethanol and the carbinol mixture of MNA crude product and 5 times of amounts are added in there-necked flask, be warming up to 70 ℃ and boil and wash 20min, be cooled to 20 ℃, filter, wash, dry and to get the MNA finished product.Total recovery 91%, purity 99.1%.
Aqueous methylamine solution concentration 25%(mass concentration in described step (1)).
Claims (8)
1. the method for a synthetic N-methyl paranitroaniline, comprise the steps:
(1) aminolysis generation N-methyl paranitroaniline occurs in p-Nitrophenyl chloride and aqueous methylamine solution in autoclave pressure under catalyst action, adds catalyzer in autoclave pressure, autoclave pressure nitrogen replacement 3 times, the seal-off pressure still, be warming up to 160-180 ℃, pressure 1.6-2.0MPa, insulation 40-100min;
(2) after the high pressure aminolysis reaction finishes, in 100-115 ℃ of lower pressure release with the free methylamine in the emptying autoclave pressure and part water, the free methylamine of discharging and water are absorbed by the methylamine absorption tower: continue to be cooled to 50-60 ℃, material in autoclave pressure is put into the strainer suction filtration, get N-methyl paranitroaniline crude product;
(3) the N-methyl paranitroaniline is refining: the solvent that N-methyl paranitroaniline crude product and 3-8 are doubly measured adds in reactor, is warming up to 60-70 ℃ and boils and wash 20-40min, is cooled to 15-30 ℃, filters, washs, dries and to get N-methyl paranitroaniline finished product.
2. the method for synthetic N-methyl paranitroaniline according to claim 1, is characterized in that in described step (1), p-Nitrophenyl chloride and aqueous methylamine solution mass ratio are 1:3-1:8, described aqueous methylamine solution concentration 20-45%.
3. the method for synthetic N-methyl paranitroaniline according to claim 1, it is characterized in that in described step (1), catalyzer is copper, mantoquita, copper oxide, copper oxyhydroxide or their mixture, and described catalyst levels is the 0.5-1.5% of p-Nitrophenyl chloride.
4. the method for according to claim 1 or 3 described synthetic N-methyl paranitroanilines, is characterized in that in described step (1), catalyzer is copper sulfate or neutralized verdigris.
5. the method for synthetic N-methyl paranitroaniline according to claim 1, is characterized in that in described step (2), and after the high pressure aminolysis reaction finished, the pressure release temperature was carried out under 30-115 ℃.
6. synthesize according to claim 1 or 5 the method for N-methyl paranitroaniline, it is characterized in that in described step (2), after the high pressure aminolysis reaction finished, the pressure release temperature was 100-115 ℃.
7. the method for synthetic N-methyl paranitroaniline according to claim 1, is characterized in that in described step (3), and solvent for use is methyl alcohol, ethanol, acetone, ethyl acetate, ether or their mixture.
8. the method for synthetic N-methyl paranitroaniline according to claim 7, is characterized in that in described step (3), and solvent for use is methyl alcohol or ethanol or their mixture.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774139A (en) * | 2018-05-14 | 2018-11-09 | 海门市新港医药科技有限公司 | The preparation method of N- methyl paranitroanilines |
| CN114394902A (en) * | 2021-12-07 | 2022-04-26 | 西安近代化学研究所 | Production process and production system of N-methyl-p-nitroaniline |
Citations (2)
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|---|---|---|---|---|
| EP0635483A1 (en) * | 1993-07-22 | 1995-01-25 | Sumitomo Chemical Company, Limited | Process for preparing nitroaniline derivatives |
| CN101580473A (en) * | 2009-06-25 | 2009-11-18 | 上海应用技术学院 | Method for preparing N-methyl paranitroaniline |
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2013
- 2013-01-21 CN CN201310021803.0A patent/CN103113234B/en active Active
Patent Citations (2)
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|---|---|---|---|---|
| EP0635483A1 (en) * | 1993-07-22 | 1995-01-25 | Sumitomo Chemical Company, Limited | Process for preparing nitroaniline derivatives |
| CN101580473A (en) * | 2009-06-25 | 2009-11-18 | 上海应用技术学院 | Method for preparing N-methyl paranitroaniline |
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| JIAO JIAO等: "A Facile and Practical Copper Powder-Catalyzed, Organic Solvent- and Ligand-Free Ullmann Amination of Aryl Halides", 《J. ORG. CHEM.》, vol. 76, no. 4, 24 January 2011 (2011-01-24), pages 1180 - 1183 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108774139A (en) * | 2018-05-14 | 2018-11-09 | 海门市新港医药科技有限公司 | The preparation method of N- methyl paranitroanilines |
| CN114394902A (en) * | 2021-12-07 | 2022-04-26 | 西安近代化学研究所 | Production process and production system of N-methyl-p-nitroaniline |
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