CN109485564B - Novel method for preparing bifenthrin - Google Patents
Novel method for preparing bifenthrin Download PDFInfo
- Publication number
- CN109485564B CN109485564B CN201811434928.5A CN201811434928A CN109485564B CN 109485564 B CN109485564 B CN 109485564B CN 201811434928 A CN201811434928 A CN 201811434928A CN 109485564 B CN109485564 B CN 109485564B
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- Prior art keywords
- reaction
- bifenthrin
- preparing
- cyhalothrin
- content
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- 239000005874 Bifenthrin Substances 0.000 title claims abstract description 41
- OMFRMAHOUUJSGP-IRHGGOMRSA-N bifenthrin Chemical compound C1=CC=C(C=2C=CC=CC=2)C(C)=C1COC(=O)[C@@H]1[C@H](\C=C(/Cl)C(F)(F)F)C1(C)C OMFRMAHOUUJSGP-IRHGGOMRSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 25
- ZXQYGBMAQZUVMI-UNOMPAQXSA-N cyhalothrin Chemical compound CC1(C)C(\C=C(/Cl)C(F)(F)F)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-UNOMPAQXSA-N 0.000 claims abstract description 18
- 238000004128 high performance liquid chromatography Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- -1 trimethyl silane magnesium chloride Chemical compound 0.000 claims abstract description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract 3
- 235000010290 biphenyl Nutrition 0.000 claims abstract 3
- 239000004305 biphenyl Substances 0.000 claims abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- DWZSONOXRMCFDJ-UHFFFAOYSA-M [Cl-].C[Si](C)(C)[Mg+] Chemical compound [Cl-].C[Si](C)(C)[Mg+] DWZSONOXRMCFDJ-UHFFFAOYSA-M 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 4
- 238000004811 liquid chromatography Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229960002836 biphenylol Drugs 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a novel method for preparing bifenthrin, which is characterized in that trimethyl silane magnesium chloride is used as a catalyst, cyhalothrin acid and biphenyl alcohol are condensed to prepare bifenthrin, reaction liquid is sampled, and the reaction end point is the reaction end point by controlling and detecting that the content of the biphenyl alcohol in the reaction liquid is less than 0.1 percent through a high performance liquid chromatography. The invention adopts the catalysis of trimethyl silane magnesium chloride as an ultra-high efficiency liquid super-strong base catalyst, and the bifenthrin is prepared by directly condensing cyhalothrin and biphenol. The method has the advantages of reducing reaction steps, reducing the discharge amount of three wastes, improving the indexes such as the yield and the quality of the bifenthrin, and being a green and environment-friendly new method for preparing the bifenthrin.
Description
Technical Field
The invention belongs to a preparation method of bifenthrin, and particularly relates to a novel method for preparing bifenthrin.
Background
Bifenthrin is used as a high-efficiency pesticide, and the consumption of bifenthrin is gradually increased worldwide. At present, cyhalothrin is prepared by acylation of cyhalothrin acid with cyhalothrin acid chloride, and condensation of cyhalothrin acid chloride and biphenol in the presence of organic or inorganic base.
Disclosure of Invention
The invention aims to provide a novel method for preparing bifenthrin with high yield of bifenthrin.
According to one aspect of the invention, a novel method for preparing bifenthrin is provided, trimethyl silane magnesium chloride is used as a catalyst, cyhalothrin and biphenol are condensed to prepare bifenthrin,
sampling the reaction liquid, and detecting that the content of the diphenoxyl in the reaction liquid is less than 0.1 percent through high performance liquid chromatography as a reaction end point.
In some embodiments, the reaction is:
in some embodiments, toluene is pumped into a glass lining reaction kettle, the cyhalothrin acid, the diphenoxyl and the trimethylsilyl magnesium chloride are added under stirring, steam is introduced into a jacket of the glass lining reaction kettle, the temperature is raised, the reaction is carried out, and the reaction is finished when the content of the diphenoxyl in the reaction liquid is less than 0.1% through high liquid chromatography control detection.
In some embodiments, the trimethylsilylmagnesium chloride is present in an amount of 0.5% to 5.0% of the amount of the cyhaloacid.
In some embodiments, the reaction temperature is 30-100 ℃.
In some embodiments, the reaction time is 8 hours.
In some embodiments, after the reaction is finished, stirring the reaction solution, cooling to about 20 ℃, washing with water for two times to stratify, combining water phases to remove wastewater, allowing an organic phase toluene layer to enter a concentration kettle, concentrating under reduced pressure, recycling toluene for reuse to obtain bifenthrin, discharging, and packaging to obtain bifenthrin with the content of more than 99.0%.
The beneficial effects are as follows: the invention adopts the catalysis of trimethyl silane magnesium chloride as an ultra-high efficiency liquid super-strong base catalyst, and the bifenthrin is prepared by directly condensing cyhalothrin and biphenol. The method has the advantages of reducing reaction steps, reducing the discharge amount of three wastes, improving the indexes such as the yield and the quality of the bifenthrin, and being a green and environment-friendly new method for preparing the bifenthrin.
Detailed Description
The invention is further described with reference to specific examples.
Example one
400 kg of toluene are pumped into a 1000 l glass lining reactor, and 97.1 kg of cyhalothrin acid, 79.3 kg of biphenol and 2 kg of trimethylsilylmagnesium chloride are added with stirring. And (3) introducing steam into a jacket, heating to 60 ℃, reacting for 8 hours, and performing control detection in a high liquid chromatography until the content of the diphenoxyl in the reaction liquid is less than 0.1%. And (3) discharging steam by a jacket, introducing cooling water, cooling to about 20 ℃ of the temperature of the reaction liquid, transferring the reaction liquid into a washing kettle, washing by 2 x 200 kg of water, layering for half an hour, combining lower-layer water, delivering wastewater for treatment, transferring an upper-layer toluene layer into a concentration kettle, concentrating under reduced pressure, and removing dryness to obtain 159 kg of bifenthrin, wherein the content of the bifenthrin is 99.5 percent by High Performance Liquid Chromatography (HPLC), and the yield is 94 percent.
Example two
400 kg of toluene was pumped into a 1000 kg glass lining reactor, and 97.1 kg of cyhalothrin acid, 79.3 kg of biphenol and 3 kg of trimethylsilylmagnesium chloride were added with stirring. Introducing steam into the jacket, heating to 60 ℃ for reaction for 8 hours, and performing high performance liquid chromatography hollow detection until the content of the diphenoxyl in the reaction liquid is less than 0.1%. The steam is discharged from the jacket, cooling water is introduced to the jacket, the temperature of the reaction liquid is reduced to about 20 ℃, then the reaction liquid is transferred into a washing kettle, 2 x 200 kg of water is stirred and washed for half an hour, the reaction liquid is kept stand and layered for half an hour, and the lower layer of water is merged and sent to wastewater treatment. Transferring the toluene layer on the upper layer into a concentration kettle, concentrating under reduced pressure to remove toluene to obtain 166.4 kg of bifenthrin, and detecting the content of the bifenthrin by high performance liquid chromatography to be 99.7 percent, wherein the yield is 98.4 percent.
EXAMPLE III
400 kg of toluene was pumped into a 1000 kg glass-lined reactor, and 97.1 kg of a cyhalothrin acid, 79.3 kg of a biphenylol and 4 kg of a trimethylsilylmagnesium chloride were added with stirring. Steam is introduced into a jacket, the temperature is raised to 60 ℃ for reaction for 8 hours, and the content of the diphenoxyl in the reaction liquid is controlled and detected to be less than 0.1 percent in the high performance liquid chromatography. The steam is discharged from the jacket, cooling water is introduced to cool the temperature of the reaction liquid to about 20 ℃, the reaction liquid is transferred into a washing kettle, 2 multiplied by 200 kilograms of water are stirred and respectively washed for half an hour, the reaction liquid is kept stand and layered for half an hour, and the lower layer of water is combined and sent to wastewater treatment. Transferring the toluene layer at the upper layer into a concentration kettle, distilling under reduced pressure to remove toluene to obtain 165.7 kg of bifenthrin, and detecting that the content of bifenthrin is 99.8% by high performance liquid chromatography and the yield is 98.0%.
Example four
400 kg of toluene are pumped into a 1000 l glass lining reactor, and 97.1 kg of cyhalothrin acid, 79.3 kg of biphenol and 3 kg of trimethylsilylmagnesium chloride are added with stirring. Introducing steam into a jacket, heating to 40 ℃, reacting for 10 hours, and performing control detection in a high performance liquid chromatography until the content of the diphenoxyl in the reaction liquid is less than 0.1%. And (3) discharging steam by a jacket, introducing cooling water, cooling to about 20 ℃, transferring the reaction liquid into a water washing kettle, stirring and washing for half an hour by 2 x 200 kg of water respectively, standing and layering for half an hour, combining lower-layer water and delivering the combined water to wastewater treatment, transferring an upper toluene layer into a concentration kettle, performing reduced pressure distillation to remove toluene to obtain 151.4 kg of bifenthrin, and detecting that the content of the bifenthrin is 99.3% by high performance liquid chromatography and the yield is 89.5%.
Example four
400 kg of toluene are pumped into a 1000 l glass lining reactor, and 97.1 kg of cyhalothrin acid, 79.3 kg of biphenol and 3 kg of trimethylsilylmagnesium chloride are added with stirring. Introducing steam into a jacket, heating to 40 ℃, reacting for 10 hours, performing controlled detection in high performance liquid chromatography until the content of the bifenthrin in a reaction solution is less than 0.1%, introducing cooling water into the jacket for stirring steam, cooling to about 20 ℃, transferring the reaction solution into a water washing kettle, stirring and washing for half an hour respectively by 2 x 200 kg of water, standing for layering for half an hour, combining lower-layer water, delivering the lower-layer water to wastewater treatment, transferring an upper-layer toluene layer into a concentration kettle, distilling with alkali liquor to remove toluene to obtain 151.4 kg of bifenthrin, detecting that the content of the bifenthrin is 99.3% by high performance liquid chromatography, and obtaining the yield of 89.5%.
EXAMPLE five
400 kg of toluene are pumped into a 1000 glass lining reaction kettle, and 97.1 kg of cyhalothrin acid, 79.3 kg of biphenol and 3 kg of trimethylsilyl magnesium chloride are added under stirring. Introducing steam into a jacket, heating to 80 ℃, reacting for 6 hours, and performing control detection in a high performance liquid chromatography until the content of the diphenoxyl in the reaction liquid is less than 0.1%. The steam is discharged from the jacket, cooling water is introduced to cool the temperature of the reaction liquid to about 20 ℃, the reaction liquid is transferred into a washing kettle, 2 multiplied by 200 kilograms of water are stirred and washed for half an hour respectively, the reaction liquid is kept stand and layered for half an hour, and the lower layer of water is combined and sent to wastewater treatment. Transferring the toluene layer on the upper layer into a concentration kettle, distilling under reduced pressure to remove dry toluene to obtain 158.6 kg of bifenthrin, and detecting that the content of bifenthrin is 99.1 percent by high performance liquid chromatography and the yield is 93.8 percent.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (7)
1. A method for preparing bifenthrin is characterized in that trimethyl silane magnesium chloride is used as a catalyst, cyhalothrin and biphenyl alcohol are condensed to prepare bifenthrin,
sampling the reaction liquid, and detecting that the content of the diphenoxyl in the reaction liquid is less than 0.1 percent through high performance liquid chromatography as a reaction end point.
2. The method of claim 1, wherein the reaction formula is:
3. the method for preparing bifenthrin according to claim 1, wherein toluene is pumped into a glass-lined reaction kettle, the cyhalothrin acid, the biphenol and the trimethylsilyl magnesium chloride are added while stirring, steam is introduced into a jacket of the glass-lined reaction kettle, the temperature is raised for reaction, and the reaction is finished after the reaction is controlled and detected by a high liquid chromatography until the content of the biphenol in the reaction liquid is less than 0.1%.
4. The method of claim 1, wherein the trimethylsilylmagnesium chloride is present in an amount of 0.5% to 5.0% of the amount of the cyhalothrin acid.
5. The method for preparing bifenthrin according to claim 1, wherein the reaction temperature is 30-100 ℃.
6. The method for preparing bifenthrin according to claim 1, wherein the reaction time is 8 hours.
7. The method for preparing bifenthrin according to claim 1, wherein after the reaction is finished, the reaction solution is stirred and cooled to 20 ℃, after the reaction solution is layered twice by washing, water phases are combined to remove wastewater for treatment, an organic phase toluene layer enters a concentration kettle, reduced pressure concentration is carried out, toluene is recycled and reused, bifenthrin is obtained, and discharging and packaging are carried out, so that bifenthrin with the content of more than 99.0% is obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811434928.5A CN109485564B (en) | 2018-11-28 | 2018-11-28 | Novel method for preparing bifenthrin |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811434928.5A CN109485564B (en) | 2018-11-28 | 2018-11-28 | Novel method for preparing bifenthrin |
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| CN109485564A CN109485564A (en) | 2019-03-19 |
| CN109485564B true CN109485564B (en) | 2021-08-27 |
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| CN113788754B (en) * | 2021-10-20 | 2023-10-24 | 北京怡力生物科技有限公司 | Preparation method of bifenthrin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| SE441179B (en) * | 1976-09-21 | 1985-09-16 | Roussel Uclaf | NEW CYCLOPROPANCARBOXYL ACIDS WITH POLYHALOGENATED SUBSTITUENT, SET FOR PREPARATION AND USE thereof IN PESTICIDE COMPOSITIONS |
| FR2642421B1 (en) * | 1989-01-30 | 1991-09-06 | Roussel Uclaf | NOVEL 2,2-DIMETHYL 3- (2-MONOHALOETHENYL) CYCLOPROPANE CARBOXYLIC ACID DERIVATIVES, PROCESS FOR THEIR PREPARATION AND THEIR USE AS MEDICAMENTS |
| CN102020564A (en) * | 2009-09-17 | 2011-04-20 | 上海生农生化制品有限公司 | Fluoro-containing cyclopropane carboxylate with acetylenic bond and preparation method and use thereof |
| CN103319345A (en) * | 2012-03-23 | 2013-09-25 | 英德广农康盛化工有限责任公司 | Method for preparing bifenthrin |
| CN103145558B (en) * | 2013-03-26 | 2014-04-30 | 盐城科菲特生化技术有限公司 | Three-waste-free preparation method for bifenthrin |
| CN104628568A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Method for producing bifenthrin with clean synthesizing process |
| CN104628569A (en) * | 2013-11-15 | 2015-05-20 | 江苏扬农化工股份有限公司 | Method for producing bifenthrin with clean synthesizing process |
| CN108218696B (en) * | 2016-12-21 | 2021-03-26 | 江苏优嘉植物保护有限公司 | Production process of bifenthrin |
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- 2018-11-28 CN CN201811434928.5A patent/CN109485564B/en not_active Expired - Fee Related
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