CN102702030A - Method for synthesizing diuron original drug - Google Patents
Method for synthesizing diuron original drug Download PDFInfo
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- CN102702030A CN102702030A CN201210191499XA CN201210191499A CN102702030A CN 102702030 A CN102702030 A CN 102702030A CN 201210191499X A CN201210191499X A CN 201210191499XA CN 201210191499 A CN201210191499 A CN 201210191499A CN 102702030 A CN102702030 A CN 102702030A
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- phosgene
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- diuron tech
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Abstract
The invention discloses a method for synthesizing a diuron original drug. Phosgene, dimethylamine and 3,4-dichloroaniline as raw materials are reacted to obtain the diuron original drug in the presence of an organic solvent under the action of a catalyst JH-102 accelerant. The catalyst JH-102 comprises 5-10 parts by weight of 4-dimethylamino pyridine and 1 part by weight of dibutyl diphenyl tin. The process flow is short, the operation process conditions are easy to control, the purity of a product is high, and the yield is high.
Description
Technical field
The present invention relates to the method for the former medicine of a kind of synthetic Diuron Tech.
Background technology
Dimethyl urea.Be a kind of selectivity inner sucting conduction type weedicide, can be absorbed by the root of plant, leaf, suppress the Hill reaction in the photosynthesis, to most of annual effective with perennial weeds, drug effect is sustainable more than 60 days.Be mainly used in and prevent and kill off the noncrop area weeds.
The synthetic two-step reaction that comprises of Diuron Tech: (1) 3,4-dichlorphenamide bulk powder photoreactive gas generation photochmeical reaction generates 3, the 4-dichlorophenyl isocyanate.(2) 3,4-dichlorophenyl isocyanates and the reaction of n n dimetylaniline generation amination reaction generate Diuron Tech.
According to Literature Consult, (1) step reaction generates 3, and the method for 4-dichlorophenyl isocyanate mainly contains two kinds: a, earlier will between 3, behind 4-dichlorphenamide bulk powder and the hydrogenchloride salify, carry out the high temperature photochmeical reaction again.It is many that this method takies equipment, and seriously corroded, hydrogen chloride gas takes place in addition know from experience a large amount of spent acid of generation.B, will between 3, the 4-dichlorphenamide bulk powder is dissolved in the organic solvent, first then low temperature feeds phosgene and carries out the cold light reaction, heats up and carries out hot photochmeical reaction.Difficult control of temperature in this method production process is prone to the caking parcel, and yield is low, and content is low.The method that (2) step reaction generates Diuron Tech is: will between 3,4-dichlorophenyl isocyanate drips of solution adds in the dimethylamine agueous solution reacts.This method is owing to have moisture content to exist in the system, between causing 3, and 4-dichlorophenyl isocyanate and water hydrolytic reactions, generation by product N, N '-two (3,4-dichloro phenylbenzene) urea causes that product yield is low, content is low, difficult separation and purification.Therefore, how to improve Diuron Tech yield and content, to reduce the three wastes are problems that those skilled in the art study always.
Summary of the invention
The object of the present invention is to provide a kind of technical process weak point, operating procedure condition to be easy to control, the method for the former medicine of synthetic Diuron Tech that product purity is high, yield is high.
Technical solution of the present invention is:
The method of the former medicine of a kind of synthetic Diuron Tech is characterized in that: with phosgene, n n dimetylaniline, 3, the 4-dichlorphenamide bulk powder is a raw material, and under the effect of organic solvent existence and catalyzer JH-102 catalyst, reaction makes the former medicine of Diuron Tech; Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=5～10:1.
Phosgene and n n dimetylaniline directly feed 3 after in Y type reactor drum, reacting and mixing, and 4-dichlorphenamide bulk powder toluene solution reacts.
When mixing with n n dimetylaniline, phosgene feeds nitrogen: the consumption volume ratio 1～2:1 of nitrogen and phosgene.
The mol ratio of phosgene and n n dimetylaniline consumption is: 1.0～1.5:1; Phosgene and 3, the mol ratio of 4-dichlorphenamide bulk powder consumption is: 1.0～1.5:1.
Described organic solvent is any one in toluene, YLENE, chlorobenzene, orthodichlorobenzene, ethylene dichloride, the tetracol phenixin, the quality of organic solvent be between 3,4～10 times of 4-dichlorphenamide bulk powder quality.
Catalyst quality be between 3,0.5%～2.0% of 4-dichlorphenamide bulk powder quality.
After finishing, reaction feeds nitrogen, rush phosgene and hydrogenchloride.
After reaction finishes, in reactant, add entry, be warming up to material then and be dissolved in fully in the organic phase, treat layering after, organic layer is separated, decrease temperature crystalline, separation, dry the former medicine of solid Diuron Tech.
The quality that adds entry be between 3,2～7 times of 4-dichlorphenamide bulk powder quality.
The synthetic Diuron Tech technology of the present invention and phosgene isocyanic ester method relatively has following advantage:
1, under catalyst action, n n dimetylaniline gas photoreactive gas is mixed the back by a certain percentage feed 3, the toluene solution of 4-dichlorphenamide bulk powder reacts.The directly synthetic Diuron Tech of single stage method can solve shortcomings such as phosgene, the facility investment of isocyanic ester method is big, the production cycle is long, efficiency is low preferably.
2, add the JH-102 catalyst in the reaction system, improved speed of response, reduce the dehydrochlorination temperature, reduce by product N, the generation of N '-two (3, the 4-dichlorophenyl) urea.
3, the selection of W-response process can react reaction with the reaction system that efficient shear agitation still is a characteristic under higher reactant concn, has shortened the reaction times, has improved the production capacity of single device.
4, less energy consumption, the heat that phosgene and n n dimetylaniline salify are produced supply dehydrochlorination to use.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Embodiment 1
(1) in the 1000ml four-hole boiling flask, drops into toluene 150ml; Catalyzer JH-102 0.5g violent stirring is cooled to 0～20 ℃, in the Y type reactor drum that communicates with four-hole boiling flask respectively with the phosgene flow of 500ml/min; The n n dimetylaniline flow of the nitrogen flow of 1000ml/min and 450ml/min feeds; Logical 130 minutes, in four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 680g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 60～65 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=8:1.
(2) add water 200ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 99.7228.2g.Content 98.0%, yield 96.0% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 0.4%.
Embodiment 2
(1) in the 2000ml four-hole boiling flask, drops into toluene 300ml; Catalyzer JH-102 0.8g violent stirring is cooled to 0～10 ℃, in the Y type reactor drum that communicates with four-hole boiling flask respectively with the phosgene flow of 500ml/min; The n n dimetylaniline flow of the nitrogen flow of 1000ml/min and 450ml/min feeds; Logical 130 minutes, in four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 1360g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 60～65 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=5:1.
(2) add water 450ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 458g.Content 98.2%, yield 96.5% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 0.3%.
Embodiment 3
In the 1000ml four-hole boiling flask, drop into toluene 150ml; Catalyzer JH-102 0.8g violent stirring is cooled to 0～10 ℃, in the Y type reactor drum that communicates with four-hole boiling flask respectively with the phosgene flow of 500ml/min; The n n dimetylaniline flow of the nitrogen flow of 1000ml/min and 450ml/min feeds; Logical 135 minutes, in four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 680g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 45～50 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=10:1.
(2) add water 200ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 228.5g.Content 98.2%, yield 96.3% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 0.4%.
Embodiment 4
In the 2000ml four-hole boiling flask, drop into toluene 400ml; Catalyzer JH-102 1.0g violent stirring is cooled to 0～10 ℃, in the Y type reactor drum that communicates with four-hole boiling flask respectively with the phosgene flow of 1000ml/min; The n n dimetylaniline flow of the nitrogen flow of 1500ml/min and 800ml/min feeds; Logical 130 minutes, in four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 1360g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 60～65 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=6:1.
(2) add water 450ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 456.4.Content 97.0%, yield 95.0% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 0.5%.
Embodiment 5
(1) in the 2000ml four-hole boiling flask, drops into toluene 300ml; Catalyzer JH-102 0.8g violent stirring; Be cooled to 0～10 ℃, in the Y type reactor drum that communicates with four-hole boiling flask, feed logical 250 minutes with the phosgene flow of 500ml/min and the n n dimetylaniline flow of 450ml/min respectively; In four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 1360g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 60～65 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=7:1.
(2) add water 450ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 451g.Content 93%, yield 90% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 2.3%.
Embodiment 6
In the 1000ml four-hole boiling flask, drop into toluene 150ml; Violent stirring is cooled to 0～10 ℃, in the Y type reactor drum that communicates with four-hole boiling flask respectively with the phosgene flow of 500ml/min; The n n dimetylaniline flow of the nitrogen flow of 1000ml/min and 450ml/min feeds; Logical 135 minutes, in four-hole boiling flask, drip simultaneously 25% 3,4-dichlorphenamide bulk powder toluene solution 680g.Under this temperature, continued stirring reaction 1 hour.Slowly be warming up to 45～50 ℃ of reactions then.Insulation catches up with phosgene, hydrogenchloride to finish in 2 hours.Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=9:1.
(2) add water 200ml and stir and to be warming up to backflow, to leave standstill branch sub-cloud water layer and middle layer, organic layer cool to crystallization below 5 ℃, centrifugal, dry white products Diuron Tech 225.1g.Content 85%, yield 88% (with 3,4-dichlorphenamide bulk powder meter).By product N, N '-two (3,4-dichloro phenylbenzene) urea content 10.2%.
Claims (9)
1. the method for the former medicine of synthetic Diuron Tech, it is characterized in that: with phosgene, n n dimetylaniline, 3, the 4-dichlorphenamide bulk powder is a raw material, exists under the effect with catalyzer JH-102 catalyst at organic solvent, reacts to make the former medicine of Diuron Tech; Said catalyzer JH-102 is made up of 4-dimethylamino pyridine and dibutyl tin diphenyl, and the two part by weight is the 4-dimethylamino pyridine: dibutyl tin diphenyl=5～10:1.
2. the method for the former medicine of synthetic Diuron Tech according to claim 1 is characterized in that: phosgene and n n dimetylaniline directly feed 3 after in Y type reactor drum, reacting and mixing, and 4-dichlorphenamide bulk powder toluene solution reacts.
3. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2 is characterized in that: feed nitrogen when phosgene mixes with n n dimetylaniline: the consumption volume ratio 1～2:1 of nitrogen and phosgene.
4. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2 is characterized in that: the mol ratio of phosgene and n n dimetylaniline consumption is: 1.0～1.5:1; Phosgene and 3, the mol ratio of 4-dichlorphenamide bulk powder consumption is: 1.0～1.5:1.
5. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2; It is characterized in that: described organic solvent is any one in toluene, YLENE, chlorobenzene, orthodichlorobenzene, ethylene dichloride, the tetracol phenixin; The quality of organic solvent be between 3,4～10 times of 4-dichlorphenamide bulk powder quality.
6. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2 is characterized in that: catalyst quality be between 3,0.5%～2.0% of 4-dichlorphenamide bulk powder quality.
7. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2 is characterized in that: feed nitrogen, rush phosgene and hydrogenchloride after reaction finishes.
8. the method for the former medicine of synthetic Diuron Tech according to claim 1 and 2; It is characterized in that: after reaction finishes; In reactant, add entry, be warming up to material then and be dissolved in fully in the organic phase, treat layering after; Organic layer is separated, decrease temperature crystalline, separation, dry the former medicine of solid Diuron Tech.
9. the method for the former medicine of synthetic Diuron Tech according to claim 8 is characterized in that: the quality that adds entry be between 3,2～7 times of 4-dichlorphenamide bulk powder quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001123A (en) * | 2015-06-29 | 2015-10-28 | 安徽广信农化股份有限公司 | Cold synthesis technology of diuron |
| CN115555051A (en) * | 2022-10-08 | 2023-01-03 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1546228A (en) * | 1975-08-26 | 1979-05-23 | Du Pont | Selective herbicides |
| GB2106508A (en) * | 1981-07-31 | 1983-04-13 | Quimco Gmbh | Preparation of substituted ureas |
| US4906275A (en) * | 1986-12-18 | 1990-03-06 | Schering Aktiengesellschaft | Composition for defoliation of plants II |
| WO1997006134A1 (en) * | 1995-08-04 | 1997-02-20 | Ucb, S.A. | Method for preparing n,n-dimethyl-n'-phenylureas |
| CN101709041A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信集团铜陵化工有限公司 | Process for producing diuron |
| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
| CN102160956A (en) * | 2011-03-08 | 2011-08-24 | 江苏快达农化股份有限公司 | Method for absorbing and utilizing phosgene tail gas |
-
2012
- 2012-06-12 CN CN201210191499XA patent/CN102702030A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1546228A (en) * | 1975-08-26 | 1979-05-23 | Du Pont | Selective herbicides |
| GB2106508A (en) * | 1981-07-31 | 1983-04-13 | Quimco Gmbh | Preparation of substituted ureas |
| US4906275A (en) * | 1986-12-18 | 1990-03-06 | Schering Aktiengesellschaft | Composition for defoliation of plants II |
| WO1997006134A1 (en) * | 1995-08-04 | 1997-02-20 | Ucb, S.A. | Method for preparing n,n-dimethyl-n'-phenylureas |
| CN101709041A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信集团铜陵化工有限公司 | Process for producing diuron |
| CN101781236A (en) * | 2010-02-11 | 2010-07-21 | 江苏快达农化股份有限公司 | Method for preparing 3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea |
| CN102160956A (en) * | 2011-03-08 | 2011-08-24 | 江苏快达农化股份有限公司 | Method for absorbing and utilizing phosgene tail gas |
Non-Patent Citations (2)
| Title |
|---|
| 《农药》 20050531 许响生等 二(三氯甲基)碳酸酯'一锅法'合成1-芳基-3,3-二甲基脲除草剂 第210-211页 1-9 第44卷, 第5期 * |
| 许响生等: "二(三氯甲基)碳酸酯‘一锅法’合成1-芳基-3,3-二甲基脲除草剂", 《农药》, vol. 44, no. 5, 31 May 2005 (2005-05-31), pages 210 - 211 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001123A (en) * | 2015-06-29 | 2015-10-28 | 安徽广信农化股份有限公司 | Cold synthesis technology of diuron |
| CN115555051A (en) * | 2022-10-08 | 2023-01-03 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
| CN115555051B (en) * | 2022-10-08 | 2023-09-15 | 江苏快达农化股份有限公司 | Pd/CuMOF-x composite material catalyst, preparation method and application thereof |
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Application publication date: 20121003 |