CN103965084A - Production method of mesotrione - Google Patents
Production method of mesotrione Download PDFInfo
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- CN103965084A CN103965084A CN201410203549.0A CN201410203549A CN103965084A CN 103965084 A CN103965084 A CN 103965084A CN 201410203549 A CN201410203549 A CN 201410203549A CN 103965084 A CN103965084 A CN 103965084A
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- mesotrione
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Abstract
The invention discloses a production method of mesotrione. The production method comprises the steps of carrying out rearrangement reaction on 3-(2-nitro-4-methylsulfurylbenzoyloxy)-2-cyclohexene-1-ketone under the action of a translocation agent, and then, filtering and separating the reaction liquid to obtain mesotrione, wherein the translocation agent (potassium ferricyanide/potassium ferrocyanide) can be recycled. The production method has the beneficial effects that (1) as the translocation agent in the production method of mesotrione, potassium ferricyanide or potassium ferrocyanide is basically nontoxic and environment-friendly; (2) the translocation agent used in the production method of mesotrione can be filtered, recovered and reutilized, so that the production cost is lowered.
Description
Technical field
Invention relates to the production method of a kind of novel herbicide Mesotrione (Mesotrione), specifically, is the method for Mesotrione of being produced through rearrangement reaction by 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone.
Background technology
Mesotrione be applicable to before corn field bud and seedling after the weedicides of weeds, there is wide spectrum, efficient, good and to Mammals and the feature such as hydrobiont toxicity is low with Environmental compatibility.
Prior art is all (can use 2-nitro-4-methylsulfonyl-Benzoyl chloride and 1 with 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone, hydroresorcinol obtains easily) under alkaline condition, select rearrangement agent to reset to produce Mesotrione.
US476255, US4775411 and US20030232984 disclose take triethylamine as alkaline reagents, under the effect of acetone cyanohydrin, resets and generates Mesotrione.Shortcoming is that acetone cyanohydrin is highly toxic product.
US5886231 discloses take sodium carbonate as alkaline reagents, under the effect of prussiate, resets and generates Mesotrione.Shortcoming is that sodium cyanide and potassium cyanide are all also highly toxic product.
US6218579 discloses take salt of wormwood as alkaline reagents, under the effect of triazole, resets and generates Mesotrione.CN101735119A discloses under alkaline condition, the method with substituted purin as the synthetic Mesotrione of transposition agent.That triazole or substituted purin all cannot be mentioned in the same breath with United States Patent (USP) economically.
Summary of the invention
The production method that the object of this invention is to provide a kind of new production Mesotrione.
Through a large amount of research, our discovery is unexpectedly used the Tripotassium iron hexacyanide or yellow prussiate of potash can from 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone, produce Mesotrione easily as transposition agent, and can reclaim them and continue to use.
Technical scheme of the present invention is as follows:
A production method for Mesotrione, it comprises the following steps:
1. a production method for Mesotrione, is characterized in that it comprises the following steps:
Step 1. is dissolved in 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone in aprotic organic solvent;
In the solution that step 2. obtains in step 1, add amine, the add-on of amine is: 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone: the mol ratio of amine is: 1:0.05-1:5.
In the solution that step 3. obtains in step 2, add transposition agent, the amount mass ratio that transposition agent adds is: transposition agent: 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone=1-100:100, and described transposition agent is yellow prussiate of potash or the Tripotassium iron hexacyanide;
The reaction system that step 4. obtains step 3, at 0-50 ℃, reaction 2-30 hour;
Then step 6. filters out transposition agent, and filtrate to pH value 2-3, adds aprotic organic solvent with hcl acidifying after precipitation, stirs, and layering, separates organic layer, washes organic phase with water, organic phase precipitation, and crystallization obtains Mesotrione,
The production method of above-mentioned Mesotrione, described aprotic organic solvent is methylene dichloride, 1,2-ethylene dichloride, trichloromethane, acetonitrile or toluene, preferably acetonitrile.
The production method of above-mentioned Mesotrione, described amine is triethylamine, tri-n-butylamine or morpholine.
The production method of above-mentioned Mesotrione, described transposition agent can direct filtration out recycle.
The invention has the beneficial effects as follows: the method for (1) production Mesotrione of the present invention, use in the Tripotassium iron hexacyanide or yellow prussiate of potash at least one as transposition agent, substantially nontoxic, environmentally friendly.(2) method of production Mesotrione of the present invention, in reaction process, owing to having used, in the Tripotassium iron hexacyanide or yellow prussiate of potash, at least one,, as transposition agent, can reclaim, and has reduced production cost.
Embodiment
Below in conjunction with specific examples, to Mesotrione, invention further describes:
Equation:
Embodiment 1
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml acetonitrile, 4.5g (0.044mol) triethylamine, 30g yellow prussiate of potash (0.071mol), stirring heating, temperature of reaction is at 50 ℃, reaction 15h, cooling, filter, obtain 31.8 grams of wet product transposition agent, filtrate, use 2mol/L hcl acidifying, make pH value 2-3, after precipitation, add 2500ml methylene dichloride to dissolve layering, organic layer under minute, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 264g Mesotrione, yield 88%.
Embodiment 2
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml acetonitrile, 4.5g (0.044mol) triethylamine, embodiment 1 filter out 31.8 grams of the wet product yellow prussiate of potash of recovery, stirring heating, temperature of reaction is at 50 ℃, reaction 15h, cooling, filter, use 2mol/L hcl acidifying, make pH value 2-3, after precipitation, add 2500ml methylene dichloride to dissolve layering, minute lower organic layer, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 255g Mesotrione, yield 85%.
Embodiment 3
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml methylene dichloride, 150g (1.4mol) triethylamine, 30g yellow prussiate of potash (0.071mol), stirring heating, temperature of reaction is at 10 ℃, reaction 20h, cooling, filter, with hcl acidifying, make pH value 2-3, stratification, organic layer under minute, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 240g Mesotrione, yield 80%.
Embodiment 4
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml1,2-ethylene dichloride, 50g (0.5mol) triethylamine, the 3g Tripotassium iron hexacyanide (0.0091mol), stirring heating, temperature of reaction, at 0 ℃, is reacted 30h, cooling, filter, with hcl acidifying, make pH value 2-3, stratification, organic layer under minute, washes organic phase precipitation for twice with 5000ml moisture, crystallization obtains 225g Mesotrione, yield 75%.
Embodiment 5
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml trichloromethane, 150g (01.4mol) tri-n-butylamine, the 30g Tripotassium iron hexacyanide (0.091mol), stirring heating, temperature of reaction is at 30 ℃, reaction 15h, cooling, filter, with hcl acidifying, make pH value 2-3, stratification, organic layer under minute, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 246g Mesotrione, yield 82%.
Embodiment 6
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml toluene, 450g (4.4mol) triethylamine, the 30g Tripotassium iron hexacyanide (0.091mol), stirring heating, temperature of reaction is at 25 ℃, reaction 10h, cooling, filter, with hcl acidifying, make pH value 2-3, stratification, organic layer under minute, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 228g Mesotrione, yield 76%.
Embodiment 7
The preparation of Mesotrione: in reaction flask, add 300g (0.88mol) 3-(2-nitro-4-methylsulfonyl benzoyl chloro)-2-tetrahydrobenzene-1-ketone, 2500ml methylene dichloride, 450g (4.4mol) morpholine, 300g yellow prussiate of potash (0.071mol), stirring heating, temperature of reaction is at 25 ℃, reaction 2h, cooling, filter, with hcl acidifying, make pH value 2-3, stratification, organic layer under minute, with 5000ml moisture, wash for twice, organic phase precipitation, crystallization obtains 216g Mesotrione, yield 72%.
Claims (5)
1. a production method for Mesotrione, is characterized in that it comprises the following steps:
Step 1. is dissolved in 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone in aprotic organic solvent;
In the solution that step 2. obtains in step 1, add amine, the add-on of amine is: 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone: the mol ratio of amine is: 1:0.05-1:5.
In the solution that step 3. obtains in step 2, add transposition agent, the amount mass ratio that transposition agent adds is: transposition agent: 3-(2-nitro-4-methylsulfonyl benzoyloxy)-2-tetrahydrobenzene-1-ketone=1-100:100, and described transposition agent is yellow prussiate of potash or the Tripotassium iron hexacyanide;
The reaction system that step 4. obtains step 3, at 0-50 ℃, reaction 2-30 hour;
Then step 6. filters out transposition agent, and filtrate to pH value 2-3, adds aprotic organic solvent with hcl acidifying after precipitation, stirs, and layering, separates organic layer, washes organic phase with water, organic phase precipitation, and crystallization obtains Mesotrione.
2. the production method of Mesotrione according to claim 1, is characterized in that: described aprotic organic solvent is methylene dichloride, 1,2-ethylene dichloride, trichloromethane, acetonitrile or toluene.
3. the production method of Mesotrione according to claim 1, is characterized in that: described aprotic organic solvent is acetonitrile.
4. the production method of Mesotrione according to claim 1, is characterized in that: described amine is triethylamine, tri-n-butylamine or morpholine.
5. the production method of Mesotrione according to claim 1, is characterized in that: described transposition agent direct filtration out recycles.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886231A (en) * | 1995-01-25 | 1999-03-23 | Zeneca Limited | Process for the production of 2-(substituted benzoyl) 1,3 cyclohexanediones |
| WO1999028282A1 (en) * | 1997-11-27 | 1999-06-10 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
| CN103172549A (en) * | 2011-12-26 | 2013-06-26 | 北京英力精化技术发展有限公司 | Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone |
| CN103588685A (en) * | 2013-10-18 | 2014-02-19 | 浙江省诸暨合力化学对外贸易有限公司 | Triketone ammonium salt compounds and preparation method and application thereof |
| CN103772243A (en) * | 2013-12-30 | 2014-05-07 | 北京英力精化技术发展有限公司 | Preparation method of mesotrione |
-
2014
- 2014-05-14 CN CN201410203549.0A patent/CN103965084A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5886231A (en) * | 1995-01-25 | 1999-03-23 | Zeneca Limited | Process for the production of 2-(substituted benzoyl) 1,3 cyclohexanediones |
| WO1999028282A1 (en) * | 1997-11-27 | 1999-06-10 | Zeneca Limited | Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds |
| CN103172549A (en) * | 2011-12-26 | 2013-06-26 | 北京英力精化技术发展有限公司 | Preparation method of 2-(2-nitryl-4-methyl sulfuryl-benzoyl) cyclohexane-1,3-diketone |
| CN103588685A (en) * | 2013-10-18 | 2014-02-19 | 浙江省诸暨合力化学对外贸易有限公司 | Triketone ammonium salt compounds and preparation method and application thereof |
| CN103772243A (en) * | 2013-12-30 | 2014-05-07 | 北京英力精化技术发展有限公司 | Preparation method of mesotrione |
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Application publication date: 20140806 |