CN1597663A - Method of synthesining isoprutuion using dionethyl amine water solution - Google Patents
Method of synthesining isoprutuion using dionethyl amine water solution Download PDFInfo
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Abstract
A process for preparing isoprotuion from the aqueous solution of dimethylamine, p-isopropylnitrobenzene and CD includes such steps as catalytic redox reaction by use of Se as catalyst and inorganic alkali as cocatalyst and pH regulator,and carbonylation.
Description
Technical field
The present invention relates to a kind of method, relate to a kind of method of the synthetic isoproturon of catalysis of alternative phosgene specifically with the synthetic Alon of dimethylamine agueous solution.
Background technology
Isoproturon is a kind of asymmetric phenyl ureagroup herbicides, and every year, demand was about 7000 tons in the world, and China is the big country that produces isoproturon, and product is mainly used in outlet and composite herbicide etc.At present, industrial synthetic these compounds mainly adopt phosgenation, because phosgenation or class phosgenation all will use the phosgene of severe toxicity, produce the big chlorine byproducts of macro-corrosion in reaction, cause equipment to be subjected to heavy corrosion, and cause environmental pollution.Along with the enhancing of people's environmental consciousness, do one's utmost to seek eco-friendly synthetic method in recent years.So seeking the environmental friendliness synthetic method is the main direction of studying of isoproturon production field.There is document (tight Xi, Luo Shiqiong, Yuan Rui, Yang Jiqiu, chemistry world, 8342-8345 (1989)) report to adopt the synthetic asymmetric urea of amine method of substitution, but, on industrial production, promotes owing to the technical process complexity.Document (Sonoda, N., Yasuhara are also arranged, T., Kondo, K., J.Am.Chem.Soc., 23,6344-6351 (1971)) and document (Kondo, K., Sonoda, N., Tsutsumi, S., Tetrahedron Lett., 51,4885-4887 (1971)) and document (Zhang Shanyan, Zheng Yan, gas chemical industry, 17,27 (1992)) etc. report uses inexpensive nonmetal selenium to substitute precious metal as catalyzer, with nitro-compound or amine is raw material, and it is synthetic to carry out carbonylation, but what only obtain is symmetrical carbamide compounds.
The preparation of asymmetric carbamide weedicide can adopt symmetric sym-diphenylurea and organic amine to make in the atmospheric pressure reflux reaction.(document: Yang Ying, Lu Shiwei, Chinese patent application 99112921.1.0,1999) are non-to becoming the preparation of also available aromatic nitro compound of carbamide weedicide and dimethylamine oxidation step reducing carbonyl.Document (Yang Ying, Lu Shiwei. the gas chemical industry, 2001, and Mei Jianting, Lu Shiwei, former dawn China, Yang Ying. Chinese patent application 01134394.X, 2001) report prepared asymmetrical urea by this method.Document (Mei Jianting, land generation dimension Chinese patent application number 02147378.1,2002) report has prepared isoproturon by this method, used is the gas of dimethylamine, their used promotor is triethylamine or other organic basess, but all do not relate to mineral alkali, reaction process does not relate to two temperature sections yet.Reaction yield is no more than 80%.
Summary of the invention
The object of the present invention is to provide a kind of method of the synthetic Alon of catalysis of alternative phosgenation, adopt selenium-mineral alkali catalyst system, and in reaction process reaction conditions such as control reaction temperature, reaction is to carry out in the mixing solutions of water and acetone, the productive rate of this method can reach about 90%, selenium catalyst system and mother liquor also can be recycled, and selenium easily reclaims in this invention, and its catalyst activity is constant substantially.Solved that catalyzer separates difficult difficulty in the homogeneous catalysis with product.
For achieving the above object, the technical solution used in the present invention is as follows:
In the presence of CO, the synthetic Alon of carbonylation takes place with dimethylamine agueous solution and p-isopropyl oil of mirbane, its reaction is as follows:
Specifically, step of the present invention is:
1) add catalyzer selenium and promotor mineral alkali in reactor, the consumption of catalyzer selenium is the 0.1-10%mol of reactant; Promotor mineral alkali consumption is the 10-200%mol of reactant;
2) add p-isopropyl oil of mirbane and organic solvent, sealing, with air in the carbon monoxide displacement still, the injection dimethylamine agueous solution, the pressure that fills carbon monoxide then is the 0.1-10Mpa of gauge pressure, the material ratio of dimethylamine and p-isopropyl oil of mirbane is 10: 1-1: 10mol, and the ratio of reactant and organic solvent is 1: 0-1: 50mol;
3) reactor is put into the oil bath pan stirring reaction of the initial reaction temperature that is raised to 100-200 ℃, the temperature of reaction of temperature adjustment to the step-down after being depressurized to 0-10MPa, this temperature is lower than its initial reaction temperature, is 20-80 ℃;
4) reaction is after 0.5-20 hour, with the reactor cool to room temperature, with filter the solid of gained and concentrate with mother liquor after refilter gained solid merge, recrystallization obtains final product;
5) heat filtering is removed the carbonate of selenium and mineral alkali in recrystallization process, to reclaim catalyzer selenium.
Above-mentioned reaction can or be carried out under the normal pressure in the autoclave of sealing.
In catalyzed reaction of the present invention, solid selenium powder catalyzer and sodium hydroxide co-catalyst are insoluble in the system before the reaction beginning, the selenium of solid phase and the active specy that sodium hydroxide becomes the system of being dissolved in carry out the homogeneous catalyzed reaction in the process of reaction, after reaction finishes, the carbonate of selenium and sodium mixes with the solid form again separates out, very easy the separation with product and easily recovery.The catalyzer that reclaims can be recycled, and is active constant in recycling.And the mother liquor of isolating product also can be recycled, and makes entire reaction course become cleaning, efficiently technical process.
Raw material of the present invention is simple, the non-metallic catalyst selenium of use, and promotor sodium hydroxide, the dimethylamine agueous solution price is all low, and promotor sodium hydroxide not only plays and help catalytic effect, but also can absorb the CO of generation
2, reduce CO
2Aerial quantity discharged.Simultaneously, the carbonate of the sodium of generation can reclaim together with selenium and is easily separated, makes little amount of catalyst selenium easily reclaim.The present invention is the cheap also phosgene of severe toxicity of no use of raw material not only, and the present invention or single step reaction are compared with phosgenation or class phosgenation, and Atom economy has improved a lot, helps large-scale commercial production.
Embodiment
Below by embodiment in detail the present invention is described in detail.Certainly, the invention is not restricted to following embodiment.
Embodiment 1
In the stainless steel autoclave of 100ml, add Se (0.76mmol), NaOH (12.5mmol), p-isopropyl oil of mirbane (24.1mmol), acetone (10.0ml), behind twice of air in the carbon monoxide displacement still, inject 33% dimethylamine agueous solution 2.2g (16.1mmol), and then fill carbon monoxide to 3.5Mpa, still is put into the oil bath pan stirring reaction that is raised to 155 ℃ (initial reaction temperatures), up to step-down, and step-down relaxes the back slightly and (relaxes or need 10-20 minute to temperature adjustment from beginning to be depressured to, this moment, about 0.7MPa fell in pressure, and 80 ℃ of the temperature of reaction of temperature adjustment after the step-down are got still from beginning to be reacted to, need 125 minutes, get the still postcooling to room temperature, open still then, the solid that refilters gained after concentrating with the solid of filtration gained with mother liquor merges, recrystallization wants heat filtering to remove the carbonate of selenium and sodium in recrystallization process.Claim after the recrystallization drying the 3.01g isoproturon, yield is 90.3%, (calculating) according to dimethylamine, and the HPLC purity assay is more than 97%, assay adopts the Waters highly effective liquid phase chromatographic system, comprise two 515 pumps, 486 type UV monitors, SpherisorbODS-2 post (5 μ m, 4.6 * 250mm), with the methanol-water is moving phase, and flow velocity: 1ml/min, monitor wavelength are the λ of each compound
Max, column temperature: room temperature, external standard method.
Embodiment 2
The amount of p-isopropyl oil of mirbane: the amount of dimethylamine=10: 1, experimental technique and step are with embodiment 1, and yield is 63.1% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 3
The amount of p-isopropyl oil of mirbane is increased to 32.2mmol, and experimental technique and step are with embodiment 1, and yield is 90.9% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 4
The amount of p-isopropyl oil of mirbane is 16.1mmol, and the amount of dimethylamine is 16.1mmol, and experimental technique and step are with embodiment 1, and yield is 24.1%, and the HPLC purity assay is more than 97%.
Embodiment 5
The amount of p-isopropyl oil of mirbane is 16.1mmol, and the amount of dimethylamine is 20.1mmol, and experimental technique and step are with embodiment 1, and yield is 30.3% (calculating with p-isopropyl oil of mirbane), and the HPLC purity assay is more than 97%.
Embodiment 6
The amount of p-isopropyl oil of mirbane: the amount of dimethylamine=1: 10, experimental technique and step are with embodiment 1, and yield is 5%.
Embodiment 7
Se is 1.77mmol, acetone 14ml, and experimental technique and step are with embodiment 1, and yield is 76.2% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 8
NaOH 22.5mmol, acetone 14ml, experimental technique and step are with embodiment 1, and yield is 46.1% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 9
NaOH 10.0mmol, acetone 14ml, experimental technique and step are with embodiment 1, and yield is 43.3% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 10
NaOH 13.75mmol, experimental technique and step are with embodiment 1, and yield is 93.3% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 11
Mineral alkali is KOH 13.75mmol, and test method is closed step with embodiment 1, and yield is 30.1% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 12
Initial reaction temperature is 200 ℃, and step-down afterreaction temperature is 60 ℃, and experimental technique and step are with embodiment 1, and yield is 44.5% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 13
Initial reaction temperature is 170 ℃, and experimental technique and step are with embodiment 1, and yield is 76.8% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 14
Initial reaction temperature is 130 ℃, and experimental technique and step are with embodiment 1, and yield is 15.0% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 15
Temperature of reaction after the step-down is 20 ℃, and experimental technique and step are with embodiment 1, and yield is 72.9% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 16
Temperature of reaction after the step-down is 70 ℃, and experimental technique and step are with embodiment 1, and yield is 81.6% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 17
In the reaction of 155 ℃ of starting temperatures after 65 minutes, i.e. stopped reaction, experimental technique and step are with embodiment 1, and yield is 57.8% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 18
Total reaction time is 150 minutes, and experimental technique and step are with embodiment 1, and yield is 84.6% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 19
Total reaction time is 90 minutes, and experimental technique and step are with embodiment 1, and yield is 75.9% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 20
The pressure of carbon monoxide is 1.5Mpa, and experimental technique and step are with embodiment 1, and yield is 51.0% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 21
The pressure of carbon monoxide is 2.5Mpa, and experimental technique and step are with embodiment 1, and yield is 74.4% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 22
Acetone 6ml, experimental technique and step are with embodiment 1, and yield is 10.2% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 23
Acetone 14m1, experimental technique and step are with embodiment 1, and yield is 75.9% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 24
Solvent is tetrahydrofuran (THF) 10ml, and test methods and procedures is with embodiment 1, and yield is 79.8% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 25
When pressure is reduced to 0.2MPa, temperature adjustment, experimental technique and step are with embodiment 1, and yield is 84.3% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 26
When pressure is reduced to 1.1MPa, temperature adjustment, yield is 67.5% (calculating with dimethylamine), the HPLC purity assay is more than 97%.
Embodiment 27
Between sec.-propyl oil of mirbane 24.1mmol, experimental technique and step are with embodiment 1, yield is 10%.
Embodiment 28
O-isopropyl oil of mirbane 24.1mmol, experimental technique and step are with embodiment 1, and yield is 0%.
Embodiment 29
Promotor is triethylamine 12.5mmol, and experimental technique and step are with embodiment 1, and yield is 60.2% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Embodiment 30
Repeat embodiment 1.Yield is 91.5%, its mother liquor of collecting is poured in the stainless steel autoclave of 100ml, add Se (0.76mmol) again, NaOH (12.5mmol), p-isopropyl oil of mirbane (24.1mmol), acetone (10.0ml), behind twice of air in the carbon monoxide displacement still, inject 33% dimethylamine agueous solution 2.2g (16.1mmol), and then fill carbon monoxide to 3.5Mpa, still is put into the oil bath pan stirring reaction that is raised to 155 ℃ (initial reaction temperatures), and up to step-down, and step-down relaxes back (relax or need 10-20 minute to temperature adjustment from beginning to be depressured to) slightly, temperature adjustment to 50 ℃ (temperature of reaction after the step-down), get still from beginning to be reacted to, need 125 minutes, get the still postcooling to room temperature, open still then, with filter the solid of gained and concentrate with mother liquor after refilter gained solid merge, recrystallization wants heat filtering to remove the carbonate of selenium and sodium in recrystallization process.Claim after the drying the 3.10g isoproturon, yield is 93.0% (calculating with dimethylamine), the HPLC purity assay is more than 97%.
Embodiment 31
In the stainless steel autoclave of 100ml, add the not purified Se (about 0.76mmol) that reclaims, NaOH (6.0mmol), p-isopropyl oil of mirbane (12.0mmol), acetone (5.0ml), behind twice of air in the carbon monoxide displacement still, inject 33% dimethylamine agueous solution 1.1g (8.0mmol), and then fill carbon monoxide to 3.5Mpa, still is put into the oil bath pan stirring reaction that is raised to 100 ℃ (initial reaction temperatures), up to step-down, and step-down relaxes back (needing 137 minutes from beginning to be reacted to the step-down temperature adjustment) slightly, and temperature adjustment to 75 ℃ (temperature of reaction after the step-down) is got still from beginning to be reacted to, need 197 minutes, get the still postcooling to room temperature, open still then, the solid that refilters gained after concentrating with the solid of filtration gained with mother liquor merges, recrystallization wants heat filtering to remove the carbonate of selenium and sodium in recrystallization process.The 1.09g isoproturon that claims after the recrystallization drying, yield are 65.4% (calculating with dimethylamine), and the HPLC purity assay is more than 97%.
Claims (7)
1, a kind of method with the synthetic isoproturon of dimethylamine agueous solution uses dimethylamine agueous solution and p-isopropyl oil of mirbane in the presence of CO, and the synthetic Alon of carbonylation takes place, and its reaction is as follows:
Concrete steps are:
A) add catalyzer selenium and promotor mineral alkali in reactor, the consumption of catalyzer selenium is the 0.1-10%mol of reactant; Promotor mineral alkali consumption is the 10-200%mol of reactant;
B) add p-isopropyl oil of mirbane and organic solvent, sealing, with air in the carbon monoxide displacement still, the injection dimethylamine agueous solution, the pressure that fills carbon monoxide then is the 0.1-10Mpa of gauge pressure, the material ratio of dimethylamine and p-isopropyl oil of mirbane is 10: 1-1: 10mol, and the ratio of reactant and organic solvent is 1: 0-1: 50mol;
C) reactor is put into the oil bath pan stirring reaction of the initial reaction temperature that is raised to 100-200 ℃, the temperature of reaction of temperature adjustment to the step-down after being depressurized to 0-10MPa, this temperature is lower than its initial reaction temperature, is 20-80 ℃;
D) reaction is after 0.5-20 hour, with the reactor cool to room temperature, with filter the solid of gained and concentrate with mother liquor after refilter gained solid merge, recrystallization obtains the product isoproturon;
E) heat filtering is removed the carbonate of selenium and mineral alkali in recrystallization process, to reclaim selenium.
2, in accordance with the method for claim 1, it is characterized in that used promotor is sodium hydroxide, potassium hydroxide or yellow soda ash.
3, in accordance with the method for claim 1, it is characterized in that used organic solvent is easy and the miscible organic solvent of water.
According to claim 1 or 3 described methods, it is characterized in that 4, used organic solvent is acetone, tetrahydrofuran (THF) or dimethyl formamide.
5, in accordance with the method for claim 1, it is characterized in that be reflected in the mixing solutions of organic solvent and water and carry out, wherein the ratio of reactant and organic solvent is 1: 0-1: 50mol.
6, in accordance with the method for claim 1, it is characterized in that carbon monoxide can be industrial carbon monoxide tail gas.
7, in accordance with the method for claim 1, it is characterized in that reaction can or be carried out under the normal pressure in the autoclave of sealing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110938019A (en) * | 2019-12-10 | 2020-03-31 | 江苏快达农化股份有限公司 | Continuous synthesis method of isoproturon |
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| CN1063279A (en) * | 1992-03-05 | 1992-08-05 | 山东师范大学 | The method of synthetic herbicide isoproturon |
| CN1294123A (en) * | 1999-10-20 | 2001-05-09 | 中国科学院大连化学物理研究所 | Catalytic synthesis process of asymmetric aryl substituted carbamide compounds |
| CN1169786C (en) * | 2001-11-02 | 2004-10-06 | 中国科学院大连化学物理研究所 | Method for synthesizing compound of asymmetric substituted carbamide class from carbonyl |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110938019A (en) * | 2019-12-10 | 2020-03-31 | 江苏快达农化股份有限公司 | Continuous synthesis method of isoproturon |
| CN110938019B (en) * | 2019-12-10 | 2022-06-24 | 江苏快达农化股份有限公司 | Continuous synthesis method of isoproturon |
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