CN104592014A - Preparation method of dicamba dimethylamine raw pesticide - Google Patents
Preparation method of dicamba dimethylamine raw pesticide Download PDFInfo
- Publication number
- CN104592014A CN104592014A CN201510000777.2A CN201510000777A CN104592014A CN 104592014 A CN104592014 A CN 104592014A CN 201510000777 A CN201510000777 A CN 201510000777A CN 104592014 A CN104592014 A CN 104592014A
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- dicamba
- dimethylamine
- preparation
- temperature
- dimethylamine salt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
Abstract
The invention relates to a preparation method of a dicamba dimethylamine raw pesticide. The preparation method mainly comprises the following steps: (1) adding an aqueous dimethylamine solution and a dicamba raw pesticide in a conventional reactor, fully stirring, controlling the reaction temperature at 20-100 DEG C, and controlling the stirring speed and the stirring reaction time; carrying out vacuum distillation on a solution after reaction, then cooling an obtained concentrated solution, after reaction is complete and the temperature is slowly reduced to a certain temperature, adding a dicamba dimethylamine crystal nucleus, and starting to precipitate a dicamba dimethylamine crystal; and after the crystal slowly grows up, carrying out air pump filtration to obtain a dicamba dimethylamine wet product, and drying to obtain a dicamba dimethylamine solid. The preparation method has the beneficial effects that the preparation process is simple, the operation is convenient, the yield of obtained product is high, and the purity is high; compared with the traditional method, the preparation method is suitable for preparing dicamba amine salt agent in different concentrations and is capable of lowering the package, storage and transportation costs.
Description
Technical field
The present invention relates to agricultural chemicals and manufacture field, a kind of preparation method of dicamba 98 dimethylamine salt bulk drug.
Background technology
Dicamba 98 (Dicamba) has another name called Dicamba, chemical name 2-methoxyl group-3,6-dichlorobenzoic acid, belongs to acid herbicides of resting in peace, there is Uptake and translocation effect, to annual and perennial broadleaf weed, there is remarkable preventive effect, and safer to gramineous crops such as wheat and corn millet water, because its consumption is few, use cost is low, belong to high-efficiency low-toxicity weedicide, and the forbidding of and metsulfuronmethyl preparation grand along with green sulphur and limiting the use of, the usage quantity of dicamba 98 is by increasing.Dicamba 98 sterling is white crystal, and in water, solubleness is low, is soluble in the organic solvent such as ethanol, benzene.But its sodium salt, amine salt are then very easily water-soluble.Dicamba 98 has two kinds of formulations respectively: the missible oil containing ester class and the aqua containing amine salt.Because missible oil is comparatively large to environmental hazard, thus missible oil formulation gradually replace by the aqua of amine salt.It is reported at present about the report of dicamba 98 dimethylamine salt bulk drug preparation method yet there are no all documents.
Summary of the invention
For above-mentioned situation, for solving problems of the prior art, the invention provides a kind of preparation method of dicamba 98 dimethylamine salt bulk drug, and the mother liquor after crystallization thing contains a small amount of dicamba 98 dimethylamine salt, can return and continue lower batch reaction, after recycle 6 ~ 10 batches, last batch of mother liquor is after distillation or rectifying recycling design, raffinate can be used for the dicamba 98 amine salt aqua preparing various content, and this greatly reduces packaging and carrying cost.
The present invention is achieved by the following technical solutions:
A preparation method for dicamba 98 dimethylamine salt bulk drug, comprises the following steps:
(1) in reaction vessel, add dimethylamine agueous solution and the former medicine of dicamba 98, the dicamba 98 wherein dropped into and the mol ratio of dimethylamine are 1:1 ~ 5, preferred 1:1.5, and controlling temperature of reaction is 20 ~ 100 DEG C, and preferable reaction temperature is 30 ~ 80 DEG C; Abundant stirring reaction 0.5h ~ 3h, forms the suspension system of white after reacting completely;
(2) after abundant stirring reaction, concentrating under reduced pressure is carried out to the suspension of step (1) white, the concentrated solution obtained is carried out cooling process, when temperature is down to 0-20 DEG C, add the dicamba 98 dimethylamine salt nucleus of the 0.001-0.01% accounting for concentrated solution weight, dicamba 98 dimethylamine salt crystal starts to separate out; Continue to be cooled to-5-30 DEG C under whipped state, treat that crystal is slowly grown up, suction filtration obtains dicamba 98 dimethylamine salt wet product, namely obtains the former medicine of dicamba 98 dimethylamine salt solid after oven dry.
In the present invention, in described dimethylamine agueous solution, the content of dimethylamine is 20 ~ 40%.Because dimethylamine content is too low can increase concentrated amount, too high levels then accelerates dimethylamine volatilization, more likely causes blast.
In the present invention, for ensureing that the former medicine of dicamba 98 and dimethylamine can react completely, the pH value in palpus control reaction system is in the scope of 7.0 ~ 12.0, and it is 8.0 ~ 10.0 that optimal ph is selected.
Concentrating under reduced pressure condition described in step (2) is vacuum tightness 0 ~ 0.1MPa, temperature 50 ~ 120 DEG C; Gained concentrated solution volume is 50% ~ 90% of concentrated front liquor capacity.
Preferred scheme: in the cooling crystallization stage, temperature should be down to-5 ~ 20 DEG C.Add nucleus separate out after still otherwise stop stirring more than 60 minutes, preferred 2h, dicamba 98 dimethylamine salt crystal is fully separated out.
Obtain after dicamba 98 dimethylamine salt bulk drug by the mother liquor containing crystal through suction filtration, residue mother liquor is dicamba 98 dimethylamine salt saturated solution, carries out concentrating under reduced pressure again, cooling adds nucleus, crystallization, suction filtration after many batches of mother liquors can being collected; Also obtained mother liquor can be directly used in preparation dicamba 98 dimethylamine salt aqua.
Beneficial effect of the present invention:
Adopt the inventive method, the dicamba 98 dimethylamine salt major part generated due to reaction is dissolved in reaction system, so the reaction times is short, easy to operate, react completely, the product yield obtained is high, purity is high.In addition, the dicamba 98 dimethylamine salt raw pesticide utilizing the method to generate is white powder, epigranular.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
Be equipped with stirring, cooling and vacuum distillation apparatus 500mL reactor in add 113g dimethylamine agueous solution (dimethylamine content is 40%) and the former medicine of 221g dicamba 98 (content is 96%), stirring makes it react, control the pH value of reaction system 8.0 ~ 10.0, heat release in reaction process, reacting liquid temperature is by 20 DEG C of rapid temperature increases to 80 DEG C, continue to stir and then find that reaction solution becomes clarification gradually, forms amber transparent solution.After reaction 1h, start to vacuumize and carry out warming temperature, when vacuum tightness in reactor is 0.1MPa, when reacting liquid temperature reaches 80 DEG C, solution comes to life, until when distillate quality is 36g, stops vacuumizing, and starts cooling simultaneously.When temperature is down to 20 DEG C, add account for concentrated solution weight 0.001 ~ 0.01% dicamba 98 dimethylamine salt crystal, at this moment have crystal soon to separate out, continue at whipped state borehole cooling, stir 10 ~ 60min, cooling is stopped when temperature is down to 0 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 175.4g, mother liquor 122g, obtain dicamba 98 dimethylamine salt 172.2g after oven dry, content is that 99.36%(is in dicamba 98 dimethylamine salt by analysis)
Embodiment 2
Be equipped with stirring, cooling and vacuum distillation apparatus 500mL reactor in add 104.2g dimethylamine agueous solution (dimethylamine content is 40%) and the former medicine of 221g dicamba 98 (content is 96%), stirring makes it react, control the pH value of reaction system 8.0 ~ 12.0, heat is released in reaction process, reacting liquid temperature rises to 85 DEG C very soon by 20 DEG C, continue stirring and can find that reaction solution is clarified gradually, form amber transparent solution.After reaction 1h, start to vacuumize and heat up, when vacuum tightness in reactor is 0.1MPa, coming to life during reacting liquid temperature 80 DEG C, until when distillate quality is 36g, stop vacuumizing, starting cooling simultaneously.Add when temperature is down to 20 DEG C account for concentrated solution weight 0.001 ~ 0.01% dicamba 98 dimethylamine salt crystal, crystal is had to separate out very soon, continue at whipped state borehole cooling, cooling is stopped when temperature is down to-5 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 174.2g, mother liquor 115g, obtain dicamba 98 dimethylamine salt 171.2g after oven dry, content is that 99.63%(is in dicamba 98 dimethylamine salt by analysis).
Embodiment 3
Be equipped with stirring, cooling and vacuum distillation apparatus 500mL reactor in add 117.4g dimethylamine agueous solution (dimethylamine content is 40%) and the former medicine of 221g dicamba 98 (content is 96%), stirring makes it react, heat is released in reaction process, reacting liquid temperature rises to rapidly 80 DEG C by 20 DEG C, continue stirring and can find that reaction solution is clarified gradually, form amber transparent solution.React after 90 minutes, start to vacuumize and heat up, when vacuum tightness in reactor is 0.1MPa, come to life during reacting liquid temperature 80 DEG C, until when distillate quality is 36g, stop vacuumizing, start cooling simultaneously.The dicamba 98 dimethylamine salt crystal of micro-crystallization is added when temperature is down to 20 DEG C, at this moment have crystal very soon to separate out, continue at whipped state borehole cooling, cooling is stopped when temperature is down to-5 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 176.4g, mother liquor 126g, obtain dicamba 98 dimethylamine salt 172.2g after oven dry, content is that 98.95%(is in dicamba 98 dimethylamine salt by analysis).
Embodiment 4
Be equipped with stirring, cooling and vacuum distillation apparatus 1000mL reactor in add 221g dimethylamine agueous solution (dimethylamine content is 40%) and the former medicine of 442g dicamba 98 (content is 96%), stirring makes it react, heat is released in reaction process, reacting liquid temperature rises to rapidly 85 DEG C by 20 DEG C, continue stirring and can find that reaction solution is clarified gradually, form amber transparent solution.After reaction 1.5h, heat up, come to life when reacting liquid temperature is 100 DEG C, until when distillate quality is 72g, start cooling.Add the dicamba 98 dimethylamine salt crystal of micro-crystallization when temperature is down to 30 DEG C, at this moment have crystal very soon and separate out, continue at whipped state borehole cooling, stop cooling when temperature is down to 10 DEG C, and carry out suction filtration separation.Obtain dicamba 98 dimethylamine salt wet product 342g, mother liquor 249.3g, obtain dicamba 98 dimethylamine salt 338.2g after oven dry, content is that 99.58%(is in dicamba 98 dimethylamine salt by analysis).
Embodiment 5
Be equipped with stirring, cooling and vacuum distillation apparatus 2000L reactor in add 454kg dimethylamine agueous solution (dimethylamine content is 40%) and 884kg dicamba 98 (content is 96%), stirring makes it react, heat is released in reaction process, reacting liquid temperature rises to rapidly 80 DEG C by 20 DEG C, continue stirring and can find that reaction solution becomes clarification gradually, form amber transparent solution.After reaction 1.5h, carry out vacuumizing and warming temperature, come to life when reacting liquid temperature 80 DEG C, until when distillate quality is 150kg, start cooling.Add the dicamba 98 dimethylamine salt crystal of micro-crystallization when temperature is down to 10 DEG C, at this moment have crystal very soon and separate out, continue at whipped state borehole cooling, cooling is stopped when temperature is down to-5 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 744kg, mother liquor 444kg.Obtain dicamba 98 dimethylamine salt 700 kg after oven dry, content is that 99.91%(is in dicamba 98 dimethylamine salt by analysis).
Embodiment 6
Mother liquor totally 122 g that embodiment 1 obtains are added in the 500mL reactor that stirring, cooling and vacuum distillation apparatus be housed, carry out vacuumizing and heating up, when vacuum tightness in reactor is 0.1MPa, come to life during reacting liquid temperature 80 DEG C, until when distillate quality is 19.2g, stopping vacuumizes, and starts cooling simultaneously.The dicamba 98 dimethylamine salt crystal of micro-crystallization is added when temperature is down to 20 DEG C, crystal is had to separate out very soon, continue at whipped state borehole cooling, cooling is stopped when temperature is down to 0 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 61g, mother liquor 42.8g, obtain dicamba 98 dimethylamine salt 59.8g after oven dry, content is that 99.29%(is in dicamba 98 dimethylamine salt by analysis).
Embodiment 7
In the 500mL reactor that stirring, cooling and vacuum distillation apparatus be housed, add the mother liquor 115g altogether that embodiment 2 obtains, carry out vacuumizing and heating up, come to life when reacting liquid temperature 108 DEG C, until when distillate quality is 14g, start cooling.The dicamba 98 dimethylamine salt crystal of micro-crystallization is added when temperature is down to 20 DEG C, crystal is had to separate out very soon, continue at whipped state borehole cooling, cooling is stopped when temperature is down to 0 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product 60g, mother liquor 41g, obtain dicamba 98 dimethylamine salt 57g after oven dry, content is that 99.16%(is in dicamba 98 dimethylamine salt by analysis).
Claims (4)
1. a preparation method for dicamba 98 dimethylamine salt bulk drug, is characterized in that, comprises the following steps:
(1) in reaction vessel, add dimethylamine agueous solution and the former medicine of dicamba 98, wherein the mol ratio of dicamba 98 and dimethylamine is 1:1 ~ 5, and control temperature is 30 ~ 80 DEG C, the pH value 8.0 ~ 10.0 of reaction system, abundant stirring reaction 0.5 ~ 3h;
(2) 50% ~ 90% of original volume is evaporated to step (1) reacted solution, then the concentrated solution obtained is lowered the temperature, when temperature is down to 20 DEG C, add the dicamba 98 dimethylamine salt nucleus of the 0.001-0.01% accounting for concentrated solution weight, continue at whipped state borehole cooling, stir 10 ~ 60min, cooling is stopped when temperature is down to-5 ~ 10 DEG C, and carry out suction filtration separation, obtain dicamba 98 dimethylamine salt wet product, after oven dry, namely obtain the former medicine of dicamba 98 dimethylamine salt solid.
2. the preparation method of dicamba 98 dimethylamine salt bulk drug according to claim 1, is characterized in that: the percentage composition of described dimethylamine agueous solution is 20 ~ 40%.
3. the preparation method of dicamba 98 dimethylamine salt bulk drug according to claim 1, is characterized in that: described dicamba 98 and the mol ratio of dimethylamine are 1:1.5.
4. the preparation method of dicamba 98 dimethylamine salt bulk drug according to claim 1 and 2, is characterized in that: the concentrating under reduced pressure condition described in step (2) is: vacuum tightness 0 ~ 0.1MPa, temperature 50 ~ 120 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510000777.2A CN104592014A (en) | 2015-01-04 | 2015-01-04 | Preparation method of dicamba dimethylamine raw pesticide |
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| CN201510000777.2A CN104592014A (en) | 2015-01-04 | 2015-01-04 | Preparation method of dicamba dimethylamine raw pesticide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548264A (en) * | 2020-04-10 | 2020-08-18 | 岳晟 | Herbicide dimethylamine salt and preparation method thereof |
| US11129388B2 (en) | 2016-08-09 | 2021-09-28 | Monsanto Technology Llc | Solid herbicidal concentrate compositions |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3013054A (en) * | 1958-08-04 | 1961-12-12 | Velsicol Chemical Corp | 2-methoxy-3, 6-dichlorobenzoates |
| CN101525288A (en) * | 2009-04-21 | 2009-09-09 | 山东潍坊润丰化工有限公司 | Preparation method of 2, 4-D dimethylamine salt material drug |
| CN101723973A (en) * | 2009-12-09 | 2010-06-09 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate dimethylamine salt solid |
-
2015
- 2015-01-04 CN CN201510000777.2A patent/CN104592014A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3013054A (en) * | 1958-08-04 | 1961-12-12 | Velsicol Chemical Corp | 2-methoxy-3, 6-dichlorobenzoates |
| CN101525288A (en) * | 2009-04-21 | 2009-09-09 | 山东潍坊润丰化工有限公司 | Preparation method of 2, 4-D dimethylamine salt material drug |
| CN101723973A (en) * | 2009-12-09 | 2010-06-09 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate dimethylamine salt solid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11129388B2 (en) | 2016-08-09 | 2021-09-28 | Monsanto Technology Llc | Solid herbicidal concentrate compositions |
| CN111548264A (en) * | 2020-04-10 | 2020-08-18 | 岳晟 | Herbicide dimethylamine salt and preparation method thereof |
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Application publication date: 20150506 |