CN102295597B - Preparation method of triclopyr butoxyethyl ester - Google Patents
Preparation method of triclopyr butoxyethyl ester Download PDFInfo
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- CN102295597B CN102295597B CN201110195725.7A CN201110195725A CN102295597B CN 102295597 B CN102295597 B CN 102295597B CN 201110195725 A CN201110195725 A CN 201110195725A CN 102295597 B CN102295597 B CN 102295597B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a preparation method of triclopyr butoxyethyl ester, the method comprises the following steps: adding chloroacetic acid, glycol monobutyl ether, a solvent I and solid acid for reacting, separating by a water separator to generate water, finishing the water separation after 4-7 hours, filtering and recovering solid acid, performing a pressure reduction to a filtrate to remove a solvent I, distilling to obtain chloroacetic acid butoxyethyl ester; adding chloroacetic acid butoxyethyl ester, trichloropyridine sodium alcoholate, a solvent II and a composite catalyst in a reactor for an etherifying reaction, wherein the reaction temperature is 40-100 DEG C and the reaction time is for 5-10 hours, filtering, desalting and removing the solvent II, washing a toluene layer by water, performing a process of pressure reduction and removing toluene to obtain chloroacetic acid butoxyethyl ester. The invention has the advantages of simple process, high overall yield, low cost and low pollution, and abolishes the discharge of methanol as well as reduces the discharge of waste water.
Description
Technical field
The present invention relates to a kind of preparation method of triclopyr butoxyethyl ester.
Background technology
Triclopyr butoxyethyl ester (having another name called TRICLOPYR ACID butoxyethyl) is pyridine oxycarboxylic acid class weedicide.This compound can be by the leaf of plant and root absorption, and transfers to plant, can prevent and treat rice field and weeds of wheat.Also can be used for plantation and prevent and kill off unhelpful forest, shrub and the broadleaf weeds of cover plant and control forest.According to the literature, this product mainly be take trichloro pyridyl sodium alcoholate and is become trichlopyr methyl esters with methyl chloroacetate etherificate as raw material, then be hydrolyzed, acidifying becomes trichlopyr, then obtain with ethylene glycol monobutyl ether esterification.
The main preparation methods of bibliographical information is that trichloro pyridyl sodium alcoholate is raw material, generate trichlopyr methyl esters with methyl chloroacetate etherification reaction, through hydrolysis, generate trichlopyr sodium, discharge methyl alcohol, acidifying becomes trichlopyr, then under sulfuric acid catalysis, carries out esterification with ethylene glycol monobutyl ether and obtain triclopyr butoxyethyl ester.Total like this four-step reaction, total recovery is low and have a large amount of methyl alcohol and discharge of wastewater when hydrolysis, is unfavorable for safety and the environment protection of production plant.
Summary of the invention
The object of the present invention is to provide that a kind of technique is simple, total recovery is high, cost is low, pollute the preparation method of little triclopyr butoxyethyl ester.
Technical solution of the present invention is:
A preparation method for triclopyr butoxyethyl ester, is characterized in that: comprise the following steps:
1) in reactor, add Mono Chloro Acetic Acid, ethylene glycol monobutyl ether, solvent I and solid acid, temperature rising reflux under agitation, esterification, separates generation water with water trap, and within 4～7 hours minutes, water is finished, filtered and recycled solid acid, filtrate decompression is sloughed after solvent I, and through distilling to obtain Mono Chloro Acetic Acid butoxyethyl, solvent I is toluene, cyclohexane or sherwood oil;
2) in reactor, add Mono Chloro Acetic Acid butoxyethyl, trichloro pyridyl sodium alcoholate, solvent II and composite catalyst to carry out etherification reaction, 40～100 ℃ of temperature of reaction, 5～10 hours reaction times, after filtering desalination, slough solvent II, add toluene dissolved product, toluene layer washes with water, and toluene is sloughed in decompression, obtains product triclopyr butoxyethyl ester.
The mol ratio of Mono Chloro Acetic Acid and ethylene glycol monobutyl ether is 1: 1～1: 1.2, the weight ratio of Mono Chloro Acetic Acid and solvent I 1: 1～1: 4, and Mono Chloro Acetic Acid and solid acid weight ratio are 1: 0.1～1: 0.3; The mol ratio of Mono Chloro Acetic Acid butoxyethyl and trichloro pyridyl sodium alcoholate is 1: 1～1: 0.8; Mono Chloro Acetic Acid butoxyethyl and solvent II weight ratio are 1: 1～1: 4.
Described solvent II is DMF, methyl-sulphoxide or acetonitrile.
Etherification reaction temperature is 50-70 ℃.
Described composite catalyst is DMAP and triethyl benzyl ammonia chloride.
The beneficial effect that the present invention compared with prior art has:
1. adopted the catalyzer of solid acid Nafion H as esterification, as long as simple, filtered and just can from reactant, separate, directly recycling, has avoided loaded down with trivial details post-reaction treatment step.
2. in etherification reaction, adopted composite catalyst, improved reaction efficiency and selectivity, the reaction times is short, and side reaction is few, and the triclopyr butoxyethyl ester purity obtaining is high, and reaction solvent is recyclable to be applied mechanically.
3. present method technological operation is simple, and reaction conditions is gentle, and yield is high, and the three wastes are few, is applicable to suitability for industrialized production.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Reaction equation of the present invention is:
1. Mono Chloro Acetic Acid butoxyethyl is synthetic
2. triclopyr butoxyethyl ester is synthetic
Example below further for example understands features more of the present invention, but the present invention applies for the content of protection and the restriction that scope is not subject to following embodiment.
Comparative example 1:
1), in three mouthfuls of reaction flasks of stirring motor, prolong, dropping funnel, water-and-oil separator are housed, drop into 66.1 grams of Mono Chloro Acetic Acids (0.7mol), 76.4 grams of ethylene glycol monobutyl ethers (0.735mol), toluene 240ml, 19 grams of solid acids.Finish, be warming up to backflow, start esterification and divide water, esterification divides the 4 hours reaction times of water.Divide water to finish, toluene is sloughed in decompression, and distillage, obtains 100.5 grams of Mono Chloro Acetic Acid butoxyethyls, content 99.6%, yield 78%;
2) in three mouthfuls of reaction flasks of stirring motor, prolong, dropping funnel are housed, add 22 grams of trichloro pyridyl sodium alcoholates (0.1mol), 18 grams of Mono Chloro Acetic Acid butoxyethyls, N, dinethylformamide 100ml, 0.2 gram of triethyl benzyl ammonia chloride, finish and be warming up to 80 ℃, insulation reaction 10 hours, after filtration desalination, decompression removes N, dinethylformamide, de-finishing adds 100ml toluene dissolved product, and toluene layer washes with water, and decompression is sloughed toluene and obtained 32.2 grams of product triclopyr butoxyethyl esters, content 90.4%, yield 89.7%.
Embodiment 1:
1) in tri-mouthfuls of reaction flasks of 250ml, add 68.6 grams of ethylene glycol monobutyl ethers, 6 grams of 56.7 grams of Mono Chloro Acetic Acids, 60ml cyclohexane, solid acid, install reflux water-dividing device, stirs temperature rising reflux reaction, and after 6 hours, washing is finished.Filtered and recycled solid acid, obtains 104.3 grams of Mono Chloro Acetic Acid butoxyethyls, content 97.6%, yield 94.0% after organic layer reclaim under reduced pressure cyclohexane;
2) stirring motor is being housed, prolong, in three mouthfuls of reaction flasks of dropping funnel, add 22 grams of trichloro pyridyl sodium alcoholates (0.1mol), 18 grams of Mono Chloro Acetic Acid butoxyethyls, N, dinethylformamide 100ml, 0.2 gram of DMAP, 0.2 gram of triethyl benzyl ammonia chloride, finish and be warming up to 70 ℃, insulation reaction 10 hours, after filtering desalination, decompression removes N, dinethylformamide, de-finishing adds 100ml toluene dissolved product, toluene layer washes with water, decompression is sloughed toluene and is obtained 33.2 grams of product triclopyr butoxyethyl esters, content 95.4%, yield 92.5%.
Embodiment 2:
1) in tri-mouthfuls of reaction flasks of 250ml, add 6 grams of 56.7 grams of Mono Chloro Acetic Acids, 68.6 grams of ethylene glycol monobutyl ethers, 60ml sherwood oil, solid acid, install reflux water-dividing device, the reaction of stirring temperature rising reflux, after 5 hours, cools to room temperature, divide water to finish, organic layer filtered and recycled solid acid, organic layer reclaim under reduced pressure sherwood oil, obtains 105.6 grams of Mono Chloro Acetic Acid fourth 2-ethoxyethyl acetates, content 98.7%, yield 96.2%;
2) in three mouthfuls of reaction flasks that stirring motor, prolong, dropping funnel are housed, add 22.0 grams of trichloro pyridyl sodium alcoholates (0.1mol), 19 grams of Mono Chloro Acetic Acid butoxyethyls (0.105mol).Dimethyl sulfoxide (DMSO) 100ml, 0.2 gram of triethyl benzyl ammonia chloride and 0.2 gram of DMAP, finish and be warming up to 60 ℃, insulation reaction 10 hours, after filtration desalination, decompression removes dimethyl sulfoxide (DMSO), and de-finishing adds 100ml toluene dissolved product.Rare sodium bicarbonate water liquid and water washing for toluene layer, decompression is sloughed toluene and is obtained 34.2 grams of product triclopyr butoxyethyl esters, content 97.6%, yield 97.5%.
Embodiment 3:
1) in tri-mouthfuls of reaction flasks of 250ml, add 15 grams of 56.7 grams of Mono Chloro Acetic Acids, 68.6 grams of ethylene glycol monobutyl ethers, 160ml sherwood oil, solid acid, install reflux water-dividing device, the reaction of stirring temperature rising reflux, after 7 hours, divide water to finish, organic layer filtered and recycled solid acid, after organic layer reclaim under reduced pressure sherwood oil, obtains 103.6 grams of Mono Chloro Acetic Acid fourth 2-ethoxyethyl acetates, content 97.7%, yield 93.5%;
2) in three mouthfuls of reaction flasks that stirring motor, prolong, dropping funnel are housed, add 22 grams of trichloro pyridyl sodium alcoholates (0.1mol), 18 grams of Mono Chloro Acetic Acid butoxyethyls.Acetonitrile 100ml, 0.2 gram of DMAP, 0.2 gram of triethyl benzyl ammonia chloride, finishes and is warming up to 80 ℃, insulation reaction 10 hours, after filtering desalination, decompression removes acetonitrile, de-finishing adds 100ml toluene dissolved product, and toluene layer washes with water, and decompression is sloughed toluene and obtained 33.2 grams of products, content 96.4%, yield 93.4%.
Embodiment 4:
1) in tri-mouthfuls of reaction flasks of 250ml, add 15 grams of 56.7 grams of Mono Chloro Acetic Acids, 68.6 grams of ethylene glycol monobutyl ethers, 160ml hexanaphthene, solid acid, install reflux water-dividing device, the reaction of stirring temperature rising reflux, after 7 hours, minute water is finished, and organic layer filtered and recycled is removed solid acid, organic layer reclaim under reduced pressure hexanaphthene, obtain 103.4 grams of Mono Chloro Acetic Acid butoxyethyls, content 97.7%, yield 92.3%;
2) in three mouthfuls of reaction flasks that stirring motor, prolong, dropping funnel are housed, add 22 grams of trichloro pyridyl sodium alcoholates (0.1mol), 18 grams of Mono Chloro Acetic Acid butoxyethyls.Methyl-sulphoxide 100ml, 0.2 gram of DMAP, 0.2 gram of triethyl benzyl ammonia chloride, finishes and is warming up to 100 ℃, insulation reaction 10 hours, after filtering desalination, decompression removes methyl-sulphoxide, de-finishing adds 100ml toluene dissolved product, and toluene layer washes with water, and decompression is sloughed toluene and obtained 33.5 grams of products, content 96.4%, yield 94.2%.
Claims (2)
1. a preparation method for triclopyr butoxyethyl ester, is characterized in that: comprise the following steps:
1) in reactor, add Mono Chloro Acetic Acid, ethylene glycol monobutyl ether, solvent I and solid acid, temperature rising reflux under agitation, esterification, separates generation water with water trap, and within 4～7 hours minutes, water is finished, filtered and recycled solid acid, filtrate decompression is sloughed after solvent I, and through distilling to obtain Mono Chloro Acetic Acid butoxyethyl, solvent I is toluene or sherwood oil;
2) in reactor, add Mono Chloro Acetic Acid butoxyethyl, trichloro pyridyl sodium alcoholate, solvent II and composite catalyst to carry out etherification reaction, 40～100 ℃ of temperature of reaction, 5～10 hours reaction times, after filtering desalination, slough solvent II, add toluene dissolved product, toluene layer washes with water, and toluene is sloughed in decompression, obtains product triclopyr butoxyethyl ester; The mol ratio of Mono Chloro Acetic Acid and ethylene glycol monobutyl ether is 1:1～1:1.2, the weight ratio 1:1～1:4 of Mono Chloro Acetic Acid and solvent I, and Mono Chloro Acetic Acid and solid acid weight ratio are 1:0.1～1:0.3; The mol ratio of Mono Chloro Acetic Acid butoxyethyl and trichloro pyridyl sodium alcoholate is 1:1～1:0.8; Mono Chloro Acetic Acid butoxyethyl and solvent II weight ratio are 1:1～1:4; Described solvent II is DMF, methyl-sulphoxide or acetonitrile; Described composite catalyst is DMAP and triethyl benzyl ammonia chloride.
2. the preparation method of triclopyr butoxyethyl ester according to claim 1, is characterized in that: etherification reaction temperature is 50-70 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102718700B (en) * | 2012-07-10 | 2016-03-23 | 南开大学 | 3,5,6-tri-Chloro-2-Pyridyle fluoroacetic acid derivative preparations and applicatio is studied |
| CN105566211A (en) * | 2016-02-18 | 2016-05-11 | 江苏丰山集团股份有限公司 | Triclopyr production method |
| CN109180570A (en) * | 2018-06-29 | 2019-01-11 | 湖北犇星农化有限责任公司 | A kind of preparation method of trichlopyr fourth 2-ethoxyethyl acetate |
| CN110839632A (en) * | 2018-08-20 | 2020-02-28 | 四川利尔作物科学有限公司 | Weeding composition |
| CN109232401B (en) * | 2018-11-13 | 2020-04-03 | 湖南比德生化科技股份有限公司 | Resource treatment method for triclopyr rectification residual liquid |
| CN110317163A (en) * | 2019-07-18 | 2019-10-11 | 利尔化学股份有限公司 | The preparation method of Triclopyr butoxyethyl |
| CN113461604B (en) * | 2021-09-02 | 2022-01-25 | 潍坊新绿化工有限公司 | Method for preparing triclopyr butoxyethyl ester by aqueous phase synthesis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4326882A (en) * | 1978-08-28 | 1982-04-27 | Ppg Industries, Inc. | Trichlorophenoxy alkanoic acid free of chlorinated dibenzo-p-dioxins |
| US4701531A (en) * | 1986-12-01 | 1987-10-20 | The Dow Chemical Company | Catalyzed alkylation of halopyridinates in the absence of added organic solvents |
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| US5808130A (en) * | 1996-06-27 | 1998-09-15 | Henkel Corporation | Esterification of phenols |
| WO2010023679A2 (en) * | 2008-09-01 | 2010-03-04 | Excel Crop Care Limited | Preparation of triclopyr, its intermediate and butoxyethyl ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4326882A (en) * | 1978-08-28 | 1982-04-27 | Ppg Industries, Inc. | Trichlorophenoxy alkanoic acid free of chlorinated dibenzo-p-dioxins |
| US4701531A (en) * | 1986-12-01 | 1987-10-20 | The Dow Chemical Company | Catalyzed alkylation of halopyridinates in the absence of added organic solvents |
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