CN104628568A - Method for producing bifenthrin with clean synthesizing process - Google Patents
Method for producing bifenthrin with clean synthesizing process Download PDFInfo
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- 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
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Abstract
The invention relates to a method for producing bifenthrin with a clean synthesizing process. Lambda-cyhalothric acid and 2-methyl-3-biphenylmethanol are adopted to react in a high-pressure kettle in the presence of a water-borne organic solvent and a catalyst, water generated in the reaction is moved out by the water-borne organic solvent, and a direct esterification reaction is carried out to obtain bifenthrin. The production method has the characteristics of high conversion rate of 2-biphenylmethanol, easily separated and recycled catalyst, small amount of three wastes in the synthesizing process and the like, and can meet the requirement of clean production.
Description
Technical field
The present invention relates to a kind of synthetic method of compound, be specifically related to the production method of bifenthrin.
Background technology
Chrysanthemum ester insecticide is one of the pillar product in hygienic insecticide market, the world today, and have the features such as efficient, wide spectrum, low toxicity, low residue, its quick-acting is good, power of knocking down is strong, use safety.Due to the stand-in that chrysanthemum ester insecticide is natural product, easily decompose at nature, not easily contaminate environment after using, easily metabolism, does not have cumulative function, can not pass through bioconcentration enrichment yet in animal body, affects less on the ecosystem.
Bifenthrin, also known as Uranus, the spirit of worm mite, Bi Fenning etc., is a kind of pyrethroid insecticides, miticide efficiently, is mainly used in preventing and treating each Species of Lepidopterous Larvae, aleyrodid, aphid, phytophagy tetranychid etc. more than 20 and plants insect.It is fast that bifenthrin knocks down speed; the residual effect time is long, and insecticidal spectrum is wide, has good preventive effect to mite; formulation relates to former medicine, missible oil, water and milk, micro emulsion, granule etc., and propagation and employment is in controls such as tea tree, cotton, tomato protecting field, apple tree, citrus trees widely.
United States Patent (USP) (US4341796) adopts 2-methyl-3-chloromethyl biphenyl in acid binding agent and suitable solvent, with lanbda-cyhalothric acid (chemical name: Z-3-(2-chloro-3,3, the fluoro-1-propenyl of 3-tri-)-2,2-dimethyl cyclopropane carboxylic acid) carry out chemical reaction, generate bifenthrin, but yield is low, waste water is many.CN201310098947.6 describes and adopts lanbda-cyhalothric acid first to carry out Lipase absobed with methyl alcohol, then carry out transesterify with 2-methyl-3-phenyl benzil alcohol again and obtain bifenthrin, carry out in Lipase absobed process at lanbda-cyhalothric acid and methyl alcohol, because water generation reaction relies on methyl alcohol to take out of, methanol usage and methyl alcohol cycle for the treatment of amount are very large, long reaction time.Carrying out in Exchange Ester Process with 2-methyl diphenyl benzylalcohol, usually require that 2-methyl-3-phenyl benzil alcohol is excessive, reaction process transformation efficiency only 95%, residual reactants easily has an impact for bifenthrin quality.
The invention provides the bifenthrin production method that a kind of building-up process is clean, the transformation efficiency that the method has 2-methyl diphenyl benzylalcohol is high, and the features such as catalyzer is easy to Separation and Recovery, and building-up process quantity of three wastes is little, meet the requirement of cleaner production.
Summary of the invention
The object of the invention is to: provide the bifenthrin production method that a kind of building-up process is clean, the transformation efficiency with 2-methyl diphenyl benzylalcohol is high, and the features such as catalyzer is easy to Separation and Recovery, and building-up process quantity of three wastes is little, meet the requirement of cleaner production.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
The bifenthrin production method that a kind of building-up process is clean is provided, adopt lanbda-cyhalothric acid and 2-methyl-3-phenyl benzil alcohol under being with water organic solvent and catalyzer to exist, react in autoclave, water generation reaction shifts out by band water organic solvent, direct esterification is obtained by reacting bifenthrin, and reaction equation is as follows:
In preferred embodiments of the present invention, lanbda-cyhalothric acid and 2-methyl-3-phenyl benzil alcohol, solvent, catalyzer are dropped in the autoclave with condenser and oily-water seperating equipment, be warmed up to 150 ~ 165 DEG C, reaction zone water is carried out under 0.25 ~ 0.35MPa pressure, after reaction to anhydrous taking out of, by reaction mixture cooling, filtering catalyst, then obtain bifenthrin crude oil through alkali cleaning, washing, precipitation, namely bifenthrin crude oil solubilizing agent recrystallization obtains the former powder of bifenthrin.
In preferred embodiments of the present invention, react that the catalyzer that uses is sodium pyrosulfate, HZSM-5 molecular sieve or both mixtures.
In preferred embodiments of the present invention, the described preferred toluene of organic band water solvent.
In production method of the present invention, the mol ratio of lanbda-cyhalothric acid and 2-methyl-3-phenyl benzil alcohol preferably 0.98 ~ 1.02; Catalyst levels is preferably 3% ~ 10% of the weight of 2-methyl-3-phenyl benzil alcohol; The weight ratio of solvent and 2-methyl-3-phenyl benzil alcohol is preferably 3 ~ 5:1.
Described HZSM-5 molecular sieve is commercially available prod, and its leading indicator meets the requirement as following table 1:
Table 1
The transformation efficiency that method of the present invention has 2-methyl diphenyl benzylalcohol is high, and the features such as catalyzer is easy to Separation and Recovery, and building-up process quantity of three wastes is little, meet the requirement of cleaner production.
Embodiment
Embodiment 1:
To 2000L, stirring is housed, drops into lanbda-cyhalothric acid 242.5KG in the autoclave of prolong and oily-water seperating equipment, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 594Kg, sodium pyrosulfate 6.7KG, stir and heat up.Control temperature 165 DEG C, pressure 0.35MPa, high pressure zone water.Band water after 6 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 400.1KG, content 98.2%, to 2-methyl diphenyl yield 93.10%.
Embodiment 2:
To 2000L, stirring is housed, drops into lanbda-cyhalothric acid 242.5KG in the autoclave of prolong and oily-water seperating equipment, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 594Kg, sodium pyrosulfate 4Kg, HZSM-5 molecular sieve (si/Al=25) 10kg, stir and heat up.Control temperature 150 DEG C, pressure 0.25MPa, high pressure zone water.Band water after 8 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 402.1KG, content 98.4%, to 2-methyl diphenyl yield 93.76%.
Embodiment 3:
To 2000L, stirring is housed, drops into lanbda-cyhalothric acid 242.5KG in the autoclave of prolong and oily-water seperating equipment, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 990Kg, HZSM-5 molecular sieve (si/Al=100) 20kg, stir and heat up.Control temperature 165 DEG C, pressure 0.35MPa, high pressure zone water.Band water after 6 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 401.1KG, content 98.3%, to 2-methyl diphenyl yield 93.43%.
Embodiment 4:
To 2000L, stirring is housed, drops into lanbda-cyhalothric acid 242.5KG in the autoclave of prolong and oily-water seperating equipment, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 594Kg, the sodium bisulfate catalysis agent 8.5KG reclaimed in reaction, stir and heat up.Control temperature 165 DEG C, pressure 0.35MPa, high pressure zone water.Band water after 6 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 401.9KG, content 98.3%, to 2-methyl diphenyl yield 93.61%.
Embodiment 5:
To 2000L, stirring is housed, lanbda-cyhalothric acid 242.5KG is dropped into, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 594Kg in the autoclave of prolong and oily-water seperating equipment, HZSM-5 molecular sieve (si/Al=25) the catalyzer 18.6kg reclaimed in reaction, stirs and heats up.Control temperature 150 DEG C, pressure 0.25MPa, high pressure zone water.Band water after 8 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 403.1KG, content 98.1%, to 2-methyl diphenyl yield 93.71%.
Embodiment 6:
To 2000L, stirring is housed, drops into lanbda-cyhalothric acid 242.5KG in the autoclave of prolong and oily-water seperating equipment, 2-methyl-3-phenyl benzil alcohol 198Kg, toluene 990Kg, HZSM-5 molecular sieve (si/Al=25) 18.6kg reclaimed in reaction, stir and heat up.Control temperature 165 DEG C, pressure 0.35MPa, high pressure zone water.Band water after 6 hours, by fraction water device water-dividing, after confirming that water trap is anhydrous and continuing to take out of, cools to less than 60 DEG C releases, enters in aftertreatment still after filter recovery catalyzer.
Aftertreatment still enters precipitation still precipitation, final temperature 135 DEG C/3mmhg after adding 5% liquid caustic soda alkali cleaning, washing.Precipitation still cover water for cooling, to 50 DEG C, adds recrystallization after 700KG n-hexane dissolution, holding temperature 0 ~ 5 DEG C, and after insulation 6hr, blowing is centrifugal, dries and obtains bifenthrin 401.5KG, content 98.3%, to 2-methyl diphenyl yield 93.52%.
Claims (7)
1. the bifenthrin production method that a building-up process is clean, it is characterized in that: adopt lanbda-cyhalothric acid and 2-methyl-3-phenyl benzil alcohol under being with water organic solvent and catalyzer to exist, react in autoclave, water generation reaction shifts out by band water organic solvent, direct esterification is obtained by reacting bifenthrin, and reaction equation is as follows:
2. method according to claim 1, it is characterized in that: lanbda-cyhalothric acid, 2-methyl-3-phenyl benzil alcohol, band water organic solvent, catalyzer are dropped in the autoclave with condenser and oily-water seperating equipment, be warmed up to 150 ~ 165 DEG C, reaction zone water is carried out under 0.25 ~ 0.35MPa pressure, after reaction to anhydrous taking out of, by reaction mixture cooling, filtering catalyst, then obtain bifenthrin crude oil through alkali cleaning, washing, precipitation, namely bifenthrin crude oil solubilizing agent recrystallization obtains the former powder of bifenthrin.
3. any one method described in claim 1 or 2, is characterized in that: described catalyzer is sodium pyrosulfate, HZSM-5 molecular sieve or both mixtures.
4. any one method described in claim 1 or 2, is characterized in that: described organic band water solvent is toluene.
5. any one method described in claim 1 or 2, is characterized in that: the mol ratio of described lanbda-cyhalothric acid and 2-methyl-3-phenyl benzil alcohol is 0.98 ~ 1.02.
6. any one method described in claim 1 or 2, is characterized in that: described catalyst levels is 3% ~ 10% of the weight of 2-methyl-3-phenyl benzil alcohol.
7. any one method described in claim 1 or 2, is characterized in that: described band water organic solvent and the weight ratio of 2-methyl-3-phenyl benzil alcohol are 3 ~ 5:1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485564A (en) * | 2018-11-28 | 2019-03-19 | 赵学迅 | A kind of new method preparing Biphenthrin |
| CN111348985A (en) * | 2015-12-31 | 2020-06-30 | 江苏扬农化工股份有限公司 | Synthesis method of cis-trifluoro-chloro-chrysanthemic acid |
| CN113788754A (en) * | 2021-10-20 | 2021-12-14 | 北京怡力生物科技有限公司 | Preparation method of bifenthrin |
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| CN101234971A (en) * | 2008-02-29 | 2008-08-06 | 中国烟草总公司郑州烟草研究院 | Method for synthesizing phenylacetic acid ester derivatives and application for products thereof |
| CN102070454A (en) * | 2011-01-29 | 2011-05-25 | 常州吉恩化工有限公司 | Method for preparing bifenthrin |
| CN102807491A (en) * | 2012-08-22 | 2012-12-05 | 中国林业科学研究院林产化学工业研究所 | Method for preparing terephthalic acid ester plasticizer with pressurization method |
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- 2013-11-15 CN CN201310571360.2A patent/CN104628568A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101234971A (en) * | 2008-02-29 | 2008-08-06 | 中国烟草总公司郑州烟草研究院 | Method for synthesizing phenylacetic acid ester derivatives and application for products thereof |
| CN102070454A (en) * | 2011-01-29 | 2011-05-25 | 常州吉恩化工有限公司 | Method for preparing bifenthrin |
| CN102807491A (en) * | 2012-08-22 | 2012-12-05 | 中国林业科学研究院林产化学工业研究所 | Method for preparing terephthalic acid ester plasticizer with pressurization method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348985A (en) * | 2015-12-31 | 2020-06-30 | 江苏扬农化工股份有限公司 | Synthesis method of cis-trifluoro-chloro-chrysanthemic acid |
| CN111348985B (en) * | 2015-12-31 | 2022-05-27 | 江苏扬农化工股份有限公司 | Synthesis method of cis-trifluoro-chloro-chrysanthemic acid |
| CN109485564A (en) * | 2018-11-28 | 2019-03-19 | 赵学迅 | A kind of new method preparing Biphenthrin |
| CN113788754A (en) * | 2021-10-20 | 2021-12-14 | 北京怡力生物科技有限公司 | Preparation method of bifenthrin |
| 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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Application publication date: 20150520 |