CN113121597A - Method for preparing chlorpyrifos in condensed state - Google Patents
Method for preparing chlorpyrifos in condensed state Download PDFInfo
- Publication number
- CN113121597A CN113121597A CN202110434403.7A CN202110434403A CN113121597A CN 113121597 A CN113121597 A CN 113121597A CN 202110434403 A CN202110434403 A CN 202110434403A CN 113121597 A CN113121597 A CN 113121597A
- Authority
- CN
- China
- Prior art keywords
- chlorpyrifos
- condensed state
- sodium
- preparation
- condensation reaction
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- 239000005944 Chlorpyrifos Substances 0.000 title claims abstract description 34
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 11
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960003750 ethyl chloride Drugs 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006482 condensation reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- WLARTYCFUUGKSW-UHFFFAOYSA-N ClC1=C(C(=NC=C1)Cl)Cl.[Na] Chemical compound ClC1=C(C(=NC=C1)Cl)Cl.[Na] WLARTYCFUUGKSW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- UWICOIBBNNVXFV-UHFFFAOYSA-N sodium;3,4,5-trichloro-1h-pyridin-2-one Chemical compound [Na].ClC1=CNC(=O)C(Cl)=C1Cl UWICOIBBNNVXFV-UHFFFAOYSA-N 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- -1 cyclic crown ether Chemical class 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- YAXDBEZBVYFNDT-UHFFFAOYSA-M triethyl(hexyl)azanium;chloride Chemical compound [Cl-].CCCCCC[N+](CC)(CC)CC YAXDBEZBVYFNDT-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
Abstract
The invention discloses a method for preparing chlorpyrifos in a condensed state, which takes trichloropyridine sodium alcoholate and ethyl chloride as raw materials to carry out condensation reaction under the action of a catalyst and alkali. According to the invention, water is not added during the condensation reaction, so that the equipment utilization rate is greatly improved, the hydrolysis of ethyl chloride is greatly reduced, the generation of impurities is reduced, and the product purity is improved; and after the condensation reaction is finished, a small amount of water is added to wash off the salt generated in the reaction, so that the production amount of wastewater per ton of products is reduced to below 1.5 tons, and the yield and the purity of the obtained chlorpyrifos are above 99 percent.
Description
The invention relates to a synthesis method of chlorpyrifos.
Background
The chlorpyrifos is a high-efficiency, low-toxicity and low-residue broad-spectrum pesticide, has triple effects of stomach toxicity, contact killing and fumigation, has multiple action modes, is used for preventing and controlling various crop pests, is a large-tonnage pesticide variety which is not weakened in the world for a long time, is one of the substitute products of the high-toxicity organophosphorus pesticide recommended by the nation, and has wide market prospect.
US4814448 uses a hydrocarbon-water or chlorohydrocarbon-water dual solvent system to prepare chlorpyrifos, wherein an example of the preparation method uses water with more than three times of the mass of the sodium trichloropyridinol and dichloromethane with about one third of the volume of water as solvents, and the sodium trichloropyridinol reacts with ethyl chloride under the action of 4-dimethylaminopyridine, polyethylene glycol 26-2, sodium hydroxide and sodium chloride to prepare chlorpyrifos, wherein the purity is 97%, the yield is 95.5%, the yield is about 3 tons of wastewater generated by one ton of products, the content of sodium chloride is up to 12%, the wastewater treatment difficulty is increased, and dichloromethane is volatile, so that the loss is large and the environment is polluted. US5120846 uses an aqueous phase method to prepare chlorpyrifos, and uses hexyltriethylammonium chloride to replace polyethylene glycol 26-2 in US4814448, the yield is 97%, the method does not introduce an organic solvent, but about 3 tons of high-salinity wastewater can still be generated by one ton of products. Whether the double-solvent or aqueous phase method is adopted to produce the chlorpyrifos, the equipment utilization rate is not high, and the production efficiency is low.
Disclosure of Invention
The invention aims to provide a method for preparing chlorpyrifos in a condensed state with low wastewater, high yield and high production efficiency.
The technical solution of the invention is as follows:
a method for preparing chlorpyrifos in a condensed state is characterized in that trichloropyridinol sodium and ethyl chloride are used as raw materials and are subjected to condensation reaction under the action of a catalyst and alkali to prepare the chlorpyrifos.
Specifically, the trichloropyridine sodium alcoholate, the catalyst and the alkali can be uniformly mixed, and the ethyl chloride is added under stirring; or adding the evenly mixed trichloropyridine sodium alcoholate, catalyst and alkali into the ethyl chloride; or adding the catalyst into the ethyl chloride, and adding the uniformly mixed sodium trichloropyridinol and alkali while stirring. In general, the reaction materials may be brought together in any convenient manner and the resulting mixture maintained, as long as the reaction materials are uniformly mixed, without limitation to the manner of addition.
The condensation reaction temperature is 44-55 ℃, and the reaction time is 1-3 hours.
The molar ratio of the trichloropyridinol sodium to the ethyl chloride is 1: 1-1: 1.1.
The catalyst is one or more of polyether, cyclic crown ether, quaternary ammonium salt, tertiary amine, quaternary ammonium base and quaternary phosphonium salt, and the dosage of the catalyst is 1-10 per mill of the total molar amount of the trichloropyridine sodium alcoholate and the ethyl chloride.
The dosage of the alkali is 0.5-2% of the mass of the trichloropyridinol sodium.
And after the condensation reaction, washing with water, filtering, collecting filter residues as raw materials for synthesizing chlorpyrifos, carrying out phase separation on the filtrate, and carrying out vacuum dehydration on an oil phase to obtain a finished product of the chlorpyrifos.
The amount of the washing water is 0.72-2 times of the mass of the trichloropyridinol sodium.
According to the invention, water is not added during the condensation reaction, so that the equipment utilization rate is greatly improved, the hydrolysis of ethyl chloride is greatly reduced, the generation of impurities is reduced, and the product purity is improved; and after the condensation reaction is finished, a small amount of water is added to wash off the salt generated in the reaction, so that the production amount of wastewater per ton of products is reduced to below 1.5 tons, and the yield and the purity of the obtained chlorpyrifos are above 99 percent.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
putting 90.0kg of ethyl chloride, 0.53kg of benzyltriethylammonium chloride and 0.28kg of 4-dimethylaminopyridine into a reaction kettle, stirring, adding 111.1kg of trichloropyridinol sodium (90%) and 1.5kg of sodium hydroxide which are uniformly mixed, reacting for 2 hours at 44 ℃, adding 188.9kg of water, stirring for 5 minutes, filtering, and collecting 2.0kg of filter residue (the content of the trichloropyridinol sodium is 46.3 percent and the content of the chlorpyrifos is 41.5 percent). The phase of the filtrate is separated, and the separated oil phase is dehydrated in vacuum to obtain 156.2kg of chlorpyrifos finished product (with the purity of 99.4%).
Example 2:
the same procedure as in example 1 was repeated except that the amount of water was 60.9kg, to give 3.9kg of residue (48.2% sodium trichloropyridinol and 40.0% chlorpyrifos) and 154.2kg of finished product (99.2% purity).
Example 3:
the same procedure as in example 1 was repeated except that 0.57kg of 4-dimethylaminopyridine alone was added to produce 1.8kg of residue (42.6% sodium trichloropyridinol and 43.5% chlorpyrifos) to obtain 156.9kg of finished product (purity 99.1%).
Example 4:
the same conditions as in example 1 were applied except that the reaction temperature was 55 deg.C, to give 1.6kg of residue (37.7% sodium trichloropyridinol and 40.22% chlorpyrifos) to give 158.0kg of finished chlorpyrifos (purity 99.0%).
Example 5:
111.1kg of trichloropyridinol sodium (90%), 1.5kg of sodium hydroxide, 0.53kg of benzyltriethylammonium chloride and 0.28kg of 4-dimethylaminopyridine are uniformly mixed, put into a reaction kettle, stirred, added with 90kg of ethyl chloride, reacted for 2 hours at 44 ℃, added with 188.9kg of water, stirred for 5 minutes, filtered, and collected with 2.5kg of filter residue (the content of trichloropyridinol sodium is 45.1%, and the content of chlorpyrifos is 43.7%). The phase of the filtrate is separated, and the separated oil phase is dehydrated in vacuum to obtain 155.9kg of chlorpyrifos finished product (with the purity of 99.2%).
Example 6:
putting 90.0kg of ethyl chloride into a reaction kettle, stirring, adding 111.1kg of uniformly mixed sodium trichloropyridinol (90%), 1.5kg of sodium hydroxide, 0.53kg of benzyltriethylammonium chloride and 0.28kg of 4-dimethylaminopyridine, reacting for 2 hours at 44 ℃, adding 188.9kg of water, stirring for 5 minutes, filtering, and collecting 2.4kg of filter residue (the content of the sodium trichloropyridinol is 40.3%, and the content of the chlorpyrifos is 41.6%). The phase of the filtrate is separated, and the separated oil phase is dehydrated in vacuum to obtain 156.1kg of chlorpyrifos finished product (with the purity of 99.3%).
Claims (7)
1. A method for preparing chlorpyrifos in a condensed state is characterized by comprising the following steps: the trichloropyridine sodium alcoholate and the ethyl chloride are taken as raw materials and are subjected to condensation reaction under the action of a catalyst and alkali to prepare the trichloropyridine sodium alcoholate.
2. The condensed state chlorpyrifos preparation method according to claim 1, characterized in that: the condensation reaction temperature is 44-55 ℃, and the reaction time is 1-3 hours.
3. The condensed state chlorpyrifos preparation method according to claim 1, characterized in that: the molar ratio of the trichloropyridinol sodium to the ethyl chloride is 1: 1-1: 1.1.
4. The condensed state chlorpyrifos preparation method according to claim 1, 2 or 3, characterized in that: the catalyst is one or more of polyether, cyclic crown ether, quaternary ammonium salt, tertiary amine, quaternary ammonium base and quaternary phosphonium salt, and the dosage of the catalyst is 1-10 per mill of the total molar amount of the trichloropyridine sodium alcoholate and the ethyl chloride.
5. The condensed state chlorpyrifos preparation method according to claim 1, 2 or 3, characterized in that: the dosage of the alkali is 0.5-2% of the mass of the trichloropyridinol sodium.
6. The condensed state chlorpyrifos preparation method according to claim 1, 2 or 3, characterized in that: after the condensation reaction, washing with water, filtering, collecting filter residues, splitting phases of the filtrate, and carrying out vacuum dehydration on the oil phase to obtain a chlorpyrifos finished product.
7. The condensed state chlorpyrifos preparation method according to claim 6, characterized in that: the amount of the washing water is 0.72-2 times of the mass of the trichloropyridinol sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434403.7A CN113121597A (en) | 2021-04-22 | 2021-04-22 | Method for preparing chlorpyrifos in condensed state |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110434403.7A CN113121597A (en) | 2021-04-22 | 2021-04-22 | Method for preparing chlorpyrifos in condensed state |
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| Publication Number | Publication Date |
|---|---|
| CN113121597A true CN113121597A (en) | 2021-07-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110434403.7A Pending CN113121597A (en) | 2021-04-22 | 2021-04-22 | Method for preparing chlorpyrifos in condensed state |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262346A (en) * | 2021-12-17 | 2022-04-01 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532195A (en) * | 2011-12-23 | 2012-07-04 | 湖北犇星农化有限责任公司 | Method for synthesis of chlorpyrifos |
| CN102993236A (en) * | 2012-06-05 | 2013-03-27 | 湖北仙隆化工股份有限公司 | Synthesizing method of active compound of chlorpyrifos |
| CN104592299A (en) * | 2015-01-13 | 2015-05-06 | 安徽国星生物化学有限公司 | New process for treating synthesized chlorpyrifos |
| CN109320549A (en) * | 2018-12-20 | 2019-02-12 | 重庆华歌生物化学有限公司 | A kind of method of high―temperature nuclei chlopyrifos |
-
2021
- 2021-04-22 CN CN202110434403.7A patent/CN113121597A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532195A (en) * | 2011-12-23 | 2012-07-04 | 湖北犇星农化有限责任公司 | Method for synthesis of chlorpyrifos |
| CN102993236A (en) * | 2012-06-05 | 2013-03-27 | 湖北仙隆化工股份有限公司 | Synthesizing method of active compound of chlorpyrifos |
| CN104592299A (en) * | 2015-01-13 | 2015-05-06 | 安徽国星生物化学有限公司 | New process for treating synthesized chlorpyrifos |
| CN109320549A (en) * | 2018-12-20 | 2019-02-12 | 重庆华歌生物化学有限公司 | A kind of method of high―temperature nuclei chlopyrifos |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114262346A (en) * | 2021-12-17 | 2022-04-01 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
| CN114262346B (en) * | 2021-12-17 | 2023-11-28 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
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Application publication date: 20210716 |