CN103086896A - Method for preparing 2, 4-D choline - Google Patents
Method for preparing 2, 4-D choline Download PDFInfo
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- CN103086896A CN103086896A CN2013100288902A CN201310028890A CN103086896A CN 103086896 A CN103086896 A CN 103086896A CN 2013100288902 A CN2013100288902 A CN 2013100288902A CN 201310028890 A CN201310028890 A CN 201310028890A CN 103086896 A CN103086896 A CN 103086896A
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- choline
- trimethylamine
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Abstract
The invention discloses a method for preparing a 2, 4-D choline water solution and an active pharmaceutical ingredient. The method comprises the following steps: reacting 2, 4-D and trimethylamine in a water environment to get trimethylamine 2, 4-D acid salt, introducing epoxy ethane gas into a reaction solution after reaction, and reacting under air-tight and stirring conditions to get the 2, 4-D choline water solution; and further concentrating, cooling, crystallizing, filtering, washing and drying the water solution to get the 2, 4-D choline active pharmaceutical ingredient. The method disclosed by the invention has the advantages of simple process, easiness in getting raw materials, good product quality, high yield of 96%-99%, no emission of three wastes, high productivity, good environment-friendly property and high large-scale application value.
Description
Technical field
The present invention relates to a kind of method for preparing 2,4-D choline, be specifically related to a kind of simplely 2, the preparation method of 4-D aqueous choline base solution and former medicine belongs to technical field of pesticide.
Background technology
2,4-D choline is a kind of in 2,4-D amine salt, it has and 2, the effect that 4-D is identical and environment-friendly advantage also have some other advantages in addition, and for example volatility is low, the diffusion drift is less, peculiar smell is lighter, easy handling and being mixed, and application opportunity is more extensive etc., so 2, the 4-D choline has better environment-friendly advantage.It is a kind of 2 that patent CN 102180804 A disclose, and it is the technology that raw material prepares 2,4-D choline aqua and former medicine that the preparation method of 4-D choline amine, this method disclose with aqueous choline base solution and the former medicine of 2,4-D.The method make 2, the former medicine purity of 4-D choline is high, stability strong, good without dust, solvability, the gained aqua crystallization can not occur, and is easy to use, packing and carrying cost are also lower, are environmentally friendly formulations.
Due to 2,4-D choline environmental friendliness, easy to use, so its synthetic will inevitably more and more attention by people.It is reported, outside the report to 2,4-D choline in patent CN 102180804 A, do not have at present other 2, the report of 4-D choline synthetic method is seen in document.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing 2,4-D aqueous choline base solution and former medicine, the method is simple, raw material is easy to get, and is that 2,4-D choline synthetic provides a kind of new thinking, is conducive to applying of 2,4-D choline.
The present invention is achieved by the following measures:
A kind ofly prepare 2, the method of 4-D aqueous choline base solution, it is characterized in that comprising the following steps: with 2,4-D(2.4-dichlorphenoxyacetic acid) react in water surrounding with Trimethylamine 99, Trimethylamine 99 2, the 4-D hydrochlorate reacts in backward reaction solution and passes into ethylene oxide gas, sealing, react under agitation condition 2, the 4-D aqueous choline base solution.
In aforesaid method, the mol ratio of 2,4-D and Trimethylamine 99 is 1:1-1.5, and Trimethylamine 99 generally adds with the form of the aqueous solution.2,4-D and Trimethylamine 99 react at normal temperatures and pressures, and be general, and the reaction times is 10-60min.
In aforesaid method, reaction is carried out in water surrounding, and the add-on of water does not require, according to required 2, and the concentration of 4-D aqueous choline base solution and decide, preferred 2 when making former medicine, the concentration of 4-D aqueous choline base solution is 50-80wt%.
In aforesaid method, Trimethylamine 99 2, the mol ratio of 4-D hydrochlorate and oxyethane is 1:1-4, is preferably 1:2.5.
In aforesaid method, Trimethylamine 99 2, the temperature of reaction of 4-D hydrochlorate and oxyethane is 30-70 ℃, and is general, the reaction times is 0.5-2.0h.
2, the 4-D aqueous choline base solution can directly be sold as aqua, but in order to make product more convenient when transporting and use, can further prepare former medicine with the aqueous solution, the preparation method is: will prepare 2, the 4-D aqueous choline base solution is concentrated, decrease temperature crystalline, filtration, washing, oven dry, gets the former medicine of 2,4-D choline.
In aforesaid method, thickening temperature is 50～140 ℃, concentrated relative pressure is 0～-0.1Mp.
In aforesaid method, Tc is less than or equal to 50 ℃.
In aforesaid method, bake out temperature is 90-110 ℃.
Further, the filtrate reusable edible of gained is used for preparation 2,4-D aqueous choline base solution, perhaps will concentrate after many batches of filtrates merging, decrease temperature crystalline prepares the former medicine of 2,4-D choline again.
The present invention has the following advantages:
1, simple, the raw material of technique of the present invention is easy to get.
2, Trimethylamine 99 2, and 4-D hydrochlorate and excessive reacting ethylene oxide have improved the productive rate of 2,4-D choline, and excessive oxyethane can be used for 2 of next batch, 4-D choline building-up process, powerlessness waste.
3, whole preparation is simple, realized automatization serialization production, three-waste free discharge, and production capacity is high, and the feature of environmental protection is good, and the mass-producing using value is high.
4, the products obtained therefrom quality is good, and yield 96%-99% is used 2, and during the former medicine of 4-D content 99.5%, product purity is up to 99.5%, and is used 2, and during the former medicine of 4-D content 98%, product purity also can reach 97.5%-98.0%, is fit to scale production and uses.
Embodiment
The invention will be further described below in conjunction with specific embodiment, should be understood that, following explanation is only in order to explain the present invention, its content not to be limited.
the present invention prepares 2, the method of 4-D aqueous choline base solution and former medicine is: with raw material 2, 4-D (2.4-dichlorphenoxyacetic acid) and Trimethylamine 99 are take water as medium, fully reaction under normal temperature and pressure, obtain Trimethylamine 99 2, 4-D acid salt solution (Trimethylamine 99 2.4-dichlorphenoxyacetic acid salt), again this solution is placed in annular airway, in the sealed reactor of stirring and refrigerating unit, pass into ethylene oxide gas, stirring reaction obtains 2, the 4-D aqueous choline base solution, gained 2, the 4-D aqueous choline base solution is concentrated through heating, decrease temperature crystalline, filter, washing, oven dry, namely obtain 2, the former medicine of 4-D choline.The below enumerates several preferred embodiment of the present invention.
Embodiment 1
With 100g 2, the former medicine of 4-D (content 98%) and 90.7g trimethylamine aqueous solution (wherein the weight of water is 64.5g), under normal temperature and pressure, reaction 60min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 48.8g ethylene oxide gas, at 50 ℃ of temperature, stirring reaction 1.5h, obtain 60% 2,4-D aqueous choline base solution 239.5g.
Embodiment 2
With 100g 2, the former medicine of 4-D (content 98%) and 60.1g trimethylamine aqueous solution (wherein the weight of water is 31.3g), under normal temperature and pressure, reaction 50min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 19.5g ethylene oxide gas, at 30 ℃ of temperature, stirring reaction 2.0h, obtain 80% 2,4-D aqueous choline base solution 179.6g.
Embodiment 3
With 100g 2, the former medicine of 4-D (content 98%) and 148.3g trimethylamine aqueous solution (wherein the weight of water is 116.9g), under normal temperature and pressure, reaction 40min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 39.1g ethylene oxide gas, at 70 ℃ of temperature, stirring reaction 0.5h, obtain 50% 2,4-D aqueous choline base solution 287.4g.
Embodiment 4
With 100g 2, the former medicine of 4-D (content 98%) and 102.7g trimethylamine aqueous solution (wherein the weight of water is 68.6g), under normal temperature and pressure, reaction 30min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 58.6g ethylene oxide gas, at 35 ℃ of temperature, stirring reaction 1.0h, obtain 55% 2,4-D aqueous choline base solution 261.3g.
Embodiment 5
With 100g 2, the former medicine of 4-D (content 98%) and 43.0g trimethylamine aqueous solution (wherein the weight of water is 6.3g), under normal temperature and pressure, reaction 20min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 78.1g ethylene oxide gas, at 45 ℃ of temperature, stirring reaction 0.8h, obtain 65% 2,4-D aqueous choline base solution 221.1g.
Embodiment 6
With 100g 2, the former medicine of 4-D (content 98%) and 56.5g trimethylamine aqueous solution (wherein the weight of water is 17.2g), under normal temperature and pressure, reaction 10min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 48.8g ethylene oxide gas, at 60 ℃ of temperature, stirring reaction 1.2h, obtain 70% 2,4-D aqueous choline base solution 205.3g.
Embodiment 7
With 100g 2, the former medicine of 4-D (content 99.5%) and 93.6g trimethylamine aqueous solution (wherein the weight of water is 67.0g), under normal temperature and pressure, reaction 60min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 49.6g ethylene oxide gas, at 50 ℃ of temperature, stirring reaction 1.5h, obtain 60% 2,4-D aqueous choline base solution 243.2g.
Embodiment 8
With 100g 2, the former medicine of 4-D (content 97%) and 88.8g trimethylamine aqueous solution (wherein the weight of water is 62.9g), under normal temperature and pressure, reaction 60min, obtain Trimethylamine 99 2, the 4-D acid salt solution, then this solution is placed in sealed reactor with annular airway, stirring and refrigerating unit, pass into the 48.3g ethylene oxide gas, at 50 ℃ of temperature, stirring reaction 1.5h, obtain 60% 2,4-D aqueous choline base solution 237.1g.
Embodiment 9
With 2 of embodiment 1 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 110 ℃ under 0.06Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 100-110 ℃ of oven dry, get 2, the former medicine 145.2g of 4-D choline, content is 98.0%, yield is 99.0%.
Embodiment 10
With 2 of embodiment 2 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 100 ℃ under 0.08Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 90-100 ℃ of oven dry, get 2, the former medicine 143.0g of 4-D choline, content is 97.0%, yield is 96.5%.
Embodiment 11
With 2 of embodiment 3 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 70 ℃ under 0.095Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 105-110 ℃ of oven dry, get 2, the former medicine 141.8g of 4-D choline, content is 97.3%, yield is 96.0%.
Embodiment 12
With 2 of embodiment 4 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 120 ℃ under 0.04Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 95-105 ℃ of oven dry, get 2, the former medicine 144.4g of 4-D choline, content is 97.5%, yield is 98.0%.
Embodiment 13
With 2 of embodiment 5 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 135 ℃ under 0.01Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 100-110 ℃ of oven dry, get 2, the former medicine 143.4g of 4-D choline, content is 97.2%, yield is 97.0%.
Embodiment 14
With 2 of embodiment 6 gained, the 4-D aqueous choline base solution is placed in the reactor that stirring, cooling and water distilling apparatus are housed and is concentrated, and is distilled to 140 ℃ under normal pressure, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 90-100 ℃ of oven dry, get 2, the former medicine 145.0g of 4-D choline, content is 97.9%, yield is 98.8%.
Embodiment 15
With 2 of embodiment 7 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 110 ℃ under 0.06Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 100-110 ℃ of oven dry, get 2, the former medicine 145.2g of 4-D choline, content is 99.5%, yield is 99.0%.
Embodiment 16
With 2 of embodiment 8 gained, the 4-D aqueous choline base solution is placed in the reactor that stirrings, cooling and water distilling apparatus are housed and is concentrated, and at relative pressure is-be distilled to 110 ℃ under 0.06Mpa, then begin cooling, temperature is down to 50 ℃ of beginning crystallizatioies, after crystallization is complete, carrying out suction filtration separates, obtain 2,4-D choline wet product, this wet product is again through 100-110 ℃ of oven dry, get 2, the former medicine 145.2g of 4-D choline, content is 97.0%, yield is 99.0%.
Claims (10)
1. one kind prepares 2, the method of 4-D aqueous choline base solution, it is characterized in that comprising the following steps: with 2,4-D and Trimethylamine 99 react in water surrounding, Trimethylamine 99 2, the 4-D hydrochlorate reacts in backward reaction solution and passes into ethylene oxide gas, sealing, react under agitation condition 2, the 4-D aqueous choline base solution.
2. method according to claim 1, it is characterized in that: the mol ratio of 2,4-D and Trimethylamine 99 is 1:1-1.5; Trimethylamine 99 2, the mol ratio of 4-D hydrochlorate and oxyethane are 1:1-4.
3. method according to claim 2, it is characterized in that: Trimethylamine 99 2, the mol ratio of 4-D hydrochlorate and oxyethane are 1:2.5.
4. method according to claim 1, it is characterized in that: 2,4-D and Trimethylamine 99 react at normal temperatures and pressures, and the reaction times is 10-60min.
5. method according to claim 1, it is characterized in that: Trimethylamine 99 2, the temperature of reaction of 4-D hydrochlorate and oxyethane are 30-70 ℃.
6. method according to claim 1, it is characterized in that: Trimethylamine 99 2, the reaction times of 4-D hydrochlorate and oxyethane is 0.5-2.0h.
7. method according to claim 1 is characterized in that: in 2,4-D aqueous choline base solution 2, the quality percentage composition of 4-D choline is 50-80%.
8. a method for preparing the former medicine of 2,4-D choline, is characterized in that, prepare 2,4-D aqueous choline base solution by any method described in claim 1-7, then will make 2, the 4-D aqueous choline base solution is concentrated, decrease temperature crystalline, filtration, washing, oven dry, gets the former medicine of 2,4-D choline.
9. method according to claim 8, it is characterized in that: thickening temperature is 50～140 ℃, concentrated relative pressure is 0～-0.1Mpa; Tc is less than or equal to 50 ℃; Bake out temperature is 90-110 ℃.
10. method according to claim 8 is characterized in that: the filtrate cycle utilization of gained, be used for preparation 2,4-D aqueous choline base solution, and perhaps will concentrate again after many batches of filtrates merging, decrease temperature crystalline prepares the former medicine of 2,4-D choline.
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| CN2013100288902A CN103086896A (en) | 2013-01-25 | 2013-01-25 | Method for preparing 2, 4-D choline |
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| CN2013100288902A CN103086896A (en) | 2013-01-25 | 2013-01-25 | Method for preparing 2, 4-D choline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748808A (en) * | 2018-12-26 | 2019-05-14 | 济南蓬勃生物技术有限公司 | A kind of preparation method of Choline Bicarbonate and carbonate |
Citations (4)
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| US3141035A (en) * | 1961-07-17 | 1964-07-14 | Hoffman Taff Inc | Process for the preparation of choline salicylate |
| CN1373127A (en) * | 2001-02-23 | 2002-10-09 | 巴斯福股份公司 | Crystal choline ascorbate |
| CN102180804A (en) * | 2011-03-25 | 2011-09-14 | 山东潍坊润丰化工有限公司 | Method for preparing 2,4-D choline amine salt |
| US20110257012A1 (en) * | 2010-04-20 | 2011-10-20 | Dow Agrosciences Llc | Aqueous herbicidal concentrates of auxinic carboxylic acids with reduced eye irritancy |
-
2013
- 2013-01-25 CN CN2013100288902A patent/CN103086896A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3141035A (en) * | 1961-07-17 | 1964-07-14 | Hoffman Taff Inc | Process for the preparation of choline salicylate |
| CN1373127A (en) * | 2001-02-23 | 2002-10-09 | 巴斯福股份公司 | Crystal choline ascorbate |
| US20110257012A1 (en) * | 2010-04-20 | 2011-10-20 | Dow Agrosciences Llc | Aqueous herbicidal concentrates of auxinic carboxylic acids with reduced eye irritancy |
| CN102180804A (en) * | 2011-03-25 | 2011-09-14 | 山东潍坊润丰化工有限公司 | Method for preparing 2,4-D choline amine salt |
Non-Patent Citations (1)
| Title |
|---|
| 李杰: "三水杨酸胆碱镁的合成", 《医药工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109748808A (en) * | 2018-12-26 | 2019-05-14 | 济南蓬勃生物技术有限公司 | A kind of preparation method of Choline Bicarbonate and carbonate |
| CN109748808B (en) * | 2018-12-26 | 2021-12-24 | 济南蓬勃生物技术有限公司 | Preparation method of choline bicarbonate and carbonate |
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Address after: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Applicant after: Shandong Weifang Rainbow Chemical Co., Ltd. Address before: Haiyuan Binhai Economic and Technological Development Zone in Shandong province Weifang City 600 street 262737 No. 1 ranked No. 1 Applicant before: Shandong Weifang Rainbow Chemical Co., Ltd. |
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Application publication date: 20130508 |