CN103159688A - Recovery method of carfentrazone-ethyl - Google Patents
Recovery method of carfentrazone-ethyl Download PDFInfo
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- CN103159688A CN103159688A CN2013101106047A CN201310110604A CN103159688A CN 103159688 A CN103159688 A CN 103159688A CN 2013101106047 A CN2013101106047 A CN 2013101106047A CN 201310110604 A CN201310110604 A CN 201310110604A CN 103159688 A CN103159688 A CN 103159688A
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Abstract
The invention discloses a recovery method of carfentrazone-ethyl. The recovery method is characterized in that the carfentrazone-ethyl in low-boiling wastes is hydrolyzed under an alkaline condition so that high-purity 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxy-1H-1,2,4-triazole-1-yl]-4-fluorophenyl] propionic acid is obtained; and then the high-purity 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxy-1H-1,2,4-triazole-1-yl]-4-fluorophenyl] propionic acid is esterified so that the carfentrazone-ethyl is obtained; the recovery rate reaches 92% and the content of the product is more than 96%. The new recover process provided by the invention is simple and efficient, safe for operation, high in recovery rate and suitable for industrial production.
Description
Technical field
The invention belongs to the recovery method of chemical, be specifically related to a kind of recovery novel process of high purity carfentrazone.
Background technology
[0002] carfentrazone, have another name called carfentrazoneethyl, triazolone grass ester, chemistry (RS)-2-chloro-3-[2-chloro-5-(4-difluoromethyl-4 by name, 5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl)-the 4-fluorophenyl] ethyl propionate, CAS No:128639-02-1 is by the triazolineone weedicide (WO9002120) of FMC Corp. at a kind of high-efficiency low-toxicity of 1988 exploitations.Molecular formula: C
15H
14Cl
2F
3N
3O
3, relative molecular mass: 412.19, its chemical structure is as follows:
The technique of present industrial production carfentrazone generally adopts the reaction of Meerwein arylation, take acetonitrile or acetone as solvent, cuprous chloride is catalyzer, Sodium Nitrite is that diazo reagent is to 1-(5-amino-4-chloro-, 2-fluorophenyl)-4-(difluoromethyl)-3-methyl isophthalic acid H-1,2,4-triazole-5(4H)-ketone carries out diazotization, and the diazonium salt of generation obtains carfentrazone (WO9002120 with the reaction of excessive ethyl propenoate at once, WO97007107), its reaction formula is as follows:
The reaction of Meerwein arylation relates to diazotization reaction, it is a kind of radical reaction mechanism of copper catalysis, so there are many side reactions, diazotizing chloro (Sandmeyer reaction) for example, thermolysis, coupling etc. is so the crude product that obtains after reaction finishes must distill the finished product that could obtain high-content.Carfentrazone is a kind of than the thickness yellow liquid, boiling point high (b.p.=350-355 ℃/760mmHg), it is at high temperature unstable, is the compound that belongs to thermo-sensitivity, so be all generally to adopt thin film distillation to come purified product, produces simultaneously 10 ~ 15% low-boiling-point substance.Because the content of carfentrazone in low-boiling-point substance is lower, usually only have 30 ~ 50%, can't directly apply mechanically, otherwise can't meet the quality requirement of product, thus be all generally direct burning disposal, so namely in vain waste product and energy consumption, be unfavorable for again environment.
Summary of the invention
The object of the present invention is to provide a kind of technique that reclaims out the high-content carfentrazone from low-boiling-point substance efficiently, turn waste into wealth, reduce costs and better protection of the environment.
Recovery novel process of the present invention, it is characterized in that existing at water by the form that carfentrazone in low-boiling-point substance is hydrolyzed to its sour sodium, and other impurity concentrates in organic phase, after phase-splitting, aqueous phase as acidified is filtered, and obtains corresponding propionic acid intermediate (carfentrazone), then should acid through ethyl esterification, just obtain the carfentrazone (carfentrazone-ethyl) of high-content.
Concrete steps are as follows:
(1) hydrolysis, reaction formula is as follows:
1 kilogram of low-boiling-point substance (wherein containing 0.6 mole of carfentrazone) after stirring and dissolving, is dripped alkali lye in organic solvent, hydrolysising reacting temperature is 0～60 ℃, preferred 20～30 ℃.Organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, Virahol, the trimethyl carbinol or acetone, is preferably ethanol, and solvent load is 0.5～5 times of weight ratio of low-boiling-point substance, preferred 1.5～2.5 times; Alkali is selected from the mineral alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, preferred sodium hydroxide or potassium hydroxide.The consumption of alkali is 1.0～5.0 times of carfentrazone mol ratio, preferred 1.5～2.0 times.After hydrolysis reaction finishes, add benzene class or halogenated hydrocarbon solvent extraction organic impurity, after layering, water adds hydrochloric acid or sulfuric acid transfers to acidity, and suction filtration obtains 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] propionic acid.Benzene kind solvent is benzene, toluene, dimethylbenzene, chlorobenzene etc., preferred toluene; Halogenated hydrocarbon solvent is methylene dichloride, ethylene dichloride etc., preferred ethylene dichloride.The amount of extraction solvent is 1～10 times of weight ratio of low-boiling-point substance, preferred 3～6 times.
(2) esterification, reaction formula is as follows:
With the 2-chloro-3-[2-chloro-5-[4 of 0.5 mole-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, ethanol, and an acidic catalyst is added in benzene kind solvent, reflux is removed the moisture that reaction generates simultaneously.After reaction finished, through alkali cleaning, then the saturated salt washing obtained the carfentrazone finished product after desolvation.The ethanol consumption is 5 ~ 30 mol ratios, preferred 10～20 mol ratios.An acidic catalyst consumption 0.05 ~ 1 mol ratio, preferred 0.1～0.5 mol ratio; An acidic catalyst is the vitriol oil, trichoroacetic acid(TCA) or methylsulphonic acid etc., the preferred vitriol oil.The benzene kind solvent consumption is 5～20 times of weight ratios of propionic acid intermediate, preferred 7～10 times; Benzene kind solvent is benzene, toluene, dimethylbenzene, chlorobenzene etc., preferred toluene.
The invention has the advantages that: present method provide a kind of from the low-boiling-point substance waste material high efficiente callback carfentrazone novel method, through the hydrolysis and esterification, the rate of recovery of carfentrazone is up to 92%, the content of product reaches more than 96%.This reclaims succinct efficient, the operational safety of novel process, and the rate of recovery is high, is fit to suitability for industrialized production.
Embodiment
Following type reaction is used for illustrating the present invention, within simple replacement that those skilled in the art do the present invention or improvement etc. all belong to the technical scheme that the present invention protects.
Embodiment 1
Hydrolysis: 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] preparation of propionic acid
Add 500 gram low-boiling-point substances (containing 0.3 mole of carfentrazone) in reaction flask, 800 gram methyl alcohol are stirred to dissolving, then under 20 ~ 25 ° of C, drip 5% aqueous sodium hydroxide solution (0.45 mole), finish, and continue reaction one hour.After hydrolysis reaction finishes, with toluene extraction organic impurity three times (each toluene amount is 500 grams), after minute removing organic layer, water adds 30% hydrochloric acid, and to be transferred to pH be 3, suction filtration, oven dry, obtain the 2-chloro-3-[2-chloro-5-[4 of 109 gram whites-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, content is 96.2%.
Esterification: the preparation of carfentrazone
In 109 gram 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4 that add the step to obtain in reaction flask, 5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, 200 gram ethanol, 2.6 gram 98% sulfuric acid, 700 gram toluene, reflux dewater 2 hours to reacting completely.Then steam ethanol, reaction solution is chilled to room temperature, adds 100 gram 10% aqueous sodium carbonate washings, then washs with 100 gram saturated brines, and toluene obtains lurid carfentrazone product after the decompression precipitation, and content is that 96.5%, two step total recovery is 89%.
Embodiment 2.
Hydrolysis: 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] preparation of propionic acid
Add 500 gram low-boiling-point substances (containing 0.3 mole of carfentrazone) in reaction flask, 1000 gram ethanol are stirred to dissolving, then under 20 ~ 25 ° of C, drip 2% aqueous sodium hydroxide solution (0.45 mole), finish, and continue reaction one hour.After hydrolysis reaction finishes, with toluene extraction organic impurity three times (each toluene amount is 800 grams), after minute removing organic layer, water adds 30% hydrochloric acid, and to be transferred to pH be 3, suction filtration, oven dry, obtain the 2-chloro-3-[2-chloro-5-[4 of 110 gram whites-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, content is 97.5%.
Esterification: the preparation of carfentrazone
In 110 gram 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4 that add the step to obtain in reaction flask, 5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, 200 gram ethanol, 2.6 gram 98% sulfuric acid, 1000 gram toluene, reflux dewater 2 hours to reacting completely.Then steam ethanol, reaction solution is chilled to room temperature, adds 100 gram 10% aqueous sodium carbonate washings, then washs with 100 gram saturated brines, and toluene obtains lurid carfentrazone product after the decompression precipitation, and content is that 98.2%, two step total recovery is 91.8%.
Embodiment 3.
Hydrolysis: 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] preparation of propionic acid
Add 500 gram low-boiling-point substances (containing 0.3 mole of carfentrazone) in reaction flask, 1000 gram ethanol are stirred to dissolving, then under 20 ~ 25 ° of C, drip 2% potassium hydroxide aqueous solution (0.45 mole), finish, and continue reaction one hour.After hydrolysis reaction finishes, with toluene extraction organic impurity three times (each toluene amount is 800 grams), after minute removing organic layer, water adds 30% hydrochloric acid, and to be transferred to pH be 3, suction filtration, oven dry, obtain the 2-chloro-3-[2-chloro-5-[4 of 108 gram whites-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, content is 97.3%.
Esterification: the preparation of carfentrazone
In 108 gram 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4 that add the step to obtain in reaction flask, 5-dihydro-3-methyl-5-oxygen-1H-1,2, the 4-triazol-1-yl]-the 4-fluorophenyl] propionic acid, 200 gram ethanol, 5 gram 98% sulfuric acid, 1000 gram toluene, reflux dewater 2 hours to reacting completely.Then steam ethanol, reaction solution is chilled to room temperature, adds 200 gram 10% aqueous sodium carbonate washings, then washs with 200 gram saturated brines, and toluene obtains lurid carfentrazone product after the decompression precipitation, and content is that 98.5%, two step total recovery is 91.2%.
Claims (8)
1. the recovery method of a carfentrazone, it is characterized in that: step is as follows:
(1) hydrolysis reaction: the low-boiling-point substance (containing 30 ~ 50% carfentrazones) of discarding during carfentrazone is produced adds alkali carfentrazone is hydrolyzed to 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4 in organic solvent, 5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] propionic acid;
(2) esterification: with 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] propionic acid under acid catalysis with ethanol generation esterification, obtain the carfentrazone of high-content.
2. the recovery method of the carfentrazone described according to claim 1, it is characterized in that, in described reactions steps (1), alkali is selected from sodium hydroxide or potassium hydroxide or lithium hydroxide or calcium hydroxide kind mineral alkali, and the consumption of alkali is 1.0～5.0 times of carfentrazone mol ratio.
3. the recovery method of the carfentrazone described according to claim 1, it is characterized in that: described hydrolysising reacting temperature is 0～60 ℃.
4. the recovery method of the carfentrazone described according to claim 3, it is characterized in that: described hydrolysising reacting temperature is 20～30 ℃.
5. the recovery method of the carfentrazone described according to claim 1, it is characterized in that: described organic solvent is selected from methyl alcohol or ethanol or propyl alcohol or Virahol or the alcohol agent of trimethyl carbinol class or acetone, and consumption of organic solvent is 0.5～5 times of weight ratio of low-boiling-point substance.
6. the recovery method of the carfentrazone described according to claim 1, it is characterized in that: after described hydrolysis reaction finishes, add benzene class or halogenated hydrocarbon solvent extraction organic impurity, the amount of extraction solvent is 1～10 times of weight ratio of low-boiling-point substance; After layering, water adds hydrochloric acid or sulfuric acid transfers to acidity, and suction filtration obtains 2-chloro-3-[2-chloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxygen-1H-1,2,4-triazol-1-yl]-the 4-fluorophenyl] propionic acid.
7. the recovery method of the carfentrazone described according to claim 1, is characterized in that, in described reactions steps (2), the ethanol consumption is 5 ~ 30 mol ratios, an acidic catalyst is the vitriol oil, trichoroacetic acid(TCA) or methylsulphonic acid class, and benzene kind solvent is benzene or toluene or dimethylbenzene or chlorobenzene class, the benzene kind solvent consumption is 5～20 times of weight ratios of propionic acid intermediate, the reflux dehydration is after reaction finishes, through alkali cleaning, then the saturated salt washing obtains the carfentrazone finished product after desolvation.
8. the recovery method of the carfentrazone described according to claim 6, is characterized in that, the ethanol consumption is 10～20 mol ratios.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819417A (en) * | 2014-01-14 | 2014-05-28 | 泸州东方农化有限公司 | Purification method of carboxylic acid compound and application thereof |
| CN110208403A (en) * | 2019-05-30 | 2019-09-06 | 江苏恒生检测有限公司 | The detection method of impurity in a kind of azoles humulone |
| CN110372511A (en) * | 2019-07-15 | 2019-10-25 | 河南华商药业有限公司 | Utilize the method for 4 '-methyl biphenyl -2- carboxylate methyl ester waste residues preparation high-purity 4 '-methyl biphenyl -2- carboxylate methyl ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031307C (en) * | 1988-08-31 | 1996-03-20 | Fmc有限公司 | Herbicidal triazolinones |
| CN102174026A (en) * | 2011-03-11 | 2011-09-07 | 浙江省诸暨合力化学对外贸易有限公司 | Preparation method of carfentrazone-ethyl |
-
2013
- 2013-04-01 CN CN2013101106047A patent/CN103159688A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1031307C (en) * | 1988-08-31 | 1996-03-20 | Fmc有限公司 | Herbicidal triazolinones |
| CN102174026A (en) * | 2011-03-11 | 2011-09-07 | 浙江省诸暨合力化学对外贸易有限公司 | Preparation method of carfentrazone-ethyl |
Non-Patent Citations (1)
| Title |
|---|
| 韩红新等: "唑草酯及其三种主要酸性代谢物在谷物、饲料中残留分析方法研究", 《现代农药》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819417A (en) * | 2014-01-14 | 2014-05-28 | 泸州东方农化有限公司 | Purification method of carboxylic acid compound and application thereof |
| CN103819417B (en) * | 2014-01-14 | 2015-09-30 | 泸州东方农化有限公司 | A kind of purification process of carboxylic acid cpd and application thereof |
| CN110208403A (en) * | 2019-05-30 | 2019-09-06 | 江苏恒生检测有限公司 | The detection method of impurity in a kind of azoles humulone |
| CN110208403B (en) * | 2019-05-30 | 2021-12-03 | 江苏恒生检测有限公司 | Method for detecting impurities in carfentrazone-ethyl |
| CN110372511A (en) * | 2019-07-15 | 2019-10-25 | 河南华商药业有限公司 | Utilize the method for 4 '-methyl biphenyl -2- carboxylate methyl ester waste residues preparation high-purity 4 '-methyl biphenyl -2- carboxylate methyl ester |
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Application publication date: 20130619 |