CN109553577A - A kind of pyrazole compound and preparation method and application - Google Patents
A kind of pyrazole compound and preparation method and application Download PDFInfo
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- CN109553577A CN109553577A CN201811562054.1A CN201811562054A CN109553577A CN 109553577 A CN109553577 A CN 109553577A CN 201811562054 A CN201811562054 A CN 201811562054A CN 109553577 A CN109553577 A CN 109553577A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of pyrazole compound and preparation method and application, shown in the compound structure such as formula (I):
Description
Technical field
The present invention relates to a kind of pyrazole compound and applications, belong to pesticide acaricide.
Background technique
In recent years, heterocyclic compound occupies highly important status due to good bioactivity in New pesticides discovery.
Wherein, for pyrazole derivatives as an important branch in heterocyclic compound, application range is extremely extensive, such as desinsection/kill
The fields such as mite, sterilization, weeding, such as acaricide Fipronil, insecticide fenpyroximate (Fenpyroximate), Rynaxypyr
(Chlorantraniliprole), nitrile insect amide (Cyantraniliprole), herbicide azimsulfuron
(Azimsulfuron), pyrrole chlorine grass amine (Nipyraclofen) and fungicide pyrazoles Fluoxastrobin (Pyraclostrobin) etc..
In addition, unsaturated hydro carbons substructure unit also tends to have good bioactivity, have in terms of New pesticides discovery extensive
Research and important application.
In view of above-mentioned background, principle is spliced using active substructure, pyrazoles and active substructure unsaturated olefin are had
Effect splicing, to obtain the pesticide candidate variety or lead compound with pesticide activity especially acaricidal activity, undoubtedly works as
One of the hot spot of modern New pesticides discovery.It should also be noted that due to existing acaricidal long-term a large amount of uses, pest population
The sensibility of pesticide is reduced, so that the resistance problem that current many insecticide varieties face also becomes increasingly conspicuous, and is developed more
The acaricide kind of more structure novels just becomes an important channel for solving resistance problem.
Summary of the invention
There is excellent control efficiency for various harmful mites the object of the present invention is to provide a kind of, there is high activity, low dose
A kind of compound for the features such as amount and safety are good is passed through thus with meeting crop protection to the acaricidal requirement of highly effective and safe
Cross research, it was found that pyrazole class compound and preparation method thereof and using such compound as the control agent of active constituent.Institute
Belonging to compound has structure feature shown in general formula (I), and wherein R is ethyl, difluoromethyl and trifluoromethyl；The system of the compound
Preparation Method be under alkaline condition, in organic solvent under the conditions of 60 DEG C to 120 DEG C, pyrazoles acid esters with it is anti-to tert-butyl benzene acetonitrile
It answers, obtains intermediate, then react, be made (I) with pivaloyl chloride under alkali metal compound effect；The compound, which can be used as, to kill
Mite agent has efficiently, low dosage and the good feature of safety.
The purpose of the present invention is achieved by the following measures:
General formula (I) indicates pyrazole compound:
Wherein R is ethyl, difluoromethyl and trifluoromethyl
Logical formula (I) of the invention indicates pyrazole compound, can be made by following equation:
According to above-mentioned reaction equation, synthetic method the following steps are included:
(1) to tert-butyl benzene acetonitrile and pyrazoles acid methyl esters in solvent A in 60~120 DEG C, alkali effect under react, react
Intermediate (II) is obtained after complete.
(2) by intermediate (II) and pivaloyl chloride in solvent B in 90~120 DEG C, it is anti-under alkali metal compound effect
It answers, water washing is added after having reacted, layering is evaporated off solvent crystallization and obtains target product (I).
Other technical characteristics of the invention are as follows:
Tert-butyl in above-mentioned steps (1) is 1:1~2:1~2 to the molar ratio of benzene acetonitrile, pyrazoles acid methyl esters and alkali.
Mass volume ratio 1g:3~the 10ml of tert-butyl in above-mentioned steps (1) to benzene acetonitrile and solvent A.
Alkali in above-mentioned steps (1) is sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Solvent A n-hexane, normal heptane, hexamethylene, ether, ethylene glycol monoethyl ether, glycol dinitrate in above-mentioned steps (1)
Ether, isopropyl ether, dichloroethanes, methylene chloride chloroform carbon tetrachloride, DMF, DEF, toluene, dimethylbenzene, acetonitrile and dimethyl sulfoxide
A combination of one or more.
Tert-butyl in above-mentioned steps to the molar ratio of benzene acetonitrile, pivaloyl chloride and alkali metal compound be 1:1~2:1~
2。
Tert-butyl in above-mentioned steps is 1g:3~10ml to benzene acetonitrile and solvent the B mass volume ratio for being.
Organic solvent described in above-mentioned steps (2) be one or both of benzene,toluene,xylene, methanol and ethyl alcohol with
On combination.
The alkali metal compound of above-mentioned steps (2) is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride.
The post-processing of above-mentioned steps (2), which is followed successively by, to be cooled to room temperature plus water washing, layering, saturated common salt water washing, anhydrous
Magnesium sulfate is dry, and decompression steams solvent, filtration drying.
Acarid control agent of the pyrazole compound as active constituent:
The compound that logical formula (I) indicates can be used as acaricidal work to the prevention and treatment activity that mite is excellent, the compound of the present invention
Property ingredient.
When the compound that logical formula (I) indicates is as acaricide, it can be used alone, common pesticide in pesticide can also be used and help
Missible oil, pulvis, wettable powder, suspending agent, granule, water dispersible granules and aqueous emulsion etc. are processed into agent.
When the compound that logical formula (I) indicates is as acaricidal active constituent, acaricide effective component can be arrived 0.1%
It is selected in the range of 99.5%, and active component content appropriate is determined according to mechanism type and method of administration, usually 0.1%
To between 40%, preferably 10% to 20%.
It is spraying using cauline leaf to acaricide of the invention, it the use of concentration is 1ppm to 1000ppm, preferred concentration 1ppm
To 500ppm.
Beneficial effects of the present invention: the pyrazole compound that logical formula (I) of the invention indicates is as acaricide, in experiment item
Under part, processing to adult mite, killing rate are 100% after 72h, have excellent control efficiency.
Specific embodiment
It is the embodiment that invention provides below, to be further explained explanation to technical solution of the present invention.
Embodiment 1:
1) solid sodium methylate 11.0g (0.2mol), toluene 200ml are added in four mouthfuls of reaction flasks, is warming up to 100 DEG C, delays
Slow be added dropwise 31.5g (0.18mol) is to tert-butyl benzene acetonitrile, 1- methyl -3- ethylpyrazol -5- methyl formate 30.8g (0.18mol)
With the mixed liquor of 50ml toluene, about 1~2h is added dropwise to complete.After completion of dropwise addition, it is warming up to reflux 6h, liquid phase is detected to tert-butyl benzene
It after ethane nitrile content is less than 1%, cools to 100~105 DEG C and obtains the sodium salt toluene suspension liquid of intermediate hydroxyl acrylonitrile, directly use
In in next step.
2) it at 100~105 DEG C, walks 24.4g (0.2mol) pivaloyl chloride is added dropwise in reaction mixture upwards, 10~
20min is added dropwise to complete.Reaction 1h is stirred for after completion of dropwise addition.It is down to room temperature after reaction, washes 2 times, each 100ml, point
Water-yielding stratum, organic layer removed under reduced pressure toluene, kettle raffinate are recrystallized to give through methanol-water (80:20), obtain white solid after dry
55.0g, content 99.0%, yield 77.2%.
1H NMR (δ ppm): 7.55 (2H, d), 7.48 (2H, d), 6.45 (1H, s), 4.17 (2H, q), 2.22 (3H, s),
1.43 (3H, t), 1.29 (9H, s), 1.08 (9H, s).
Embodiment 2:
1) solid sodium methylate 11.0g (0.2mol), methanol 200ml are added in four mouthfuls of reaction flasks, is warming up to 70 DEG C, slowly
31.5g (0.18mol) is added dropwise to tert-butyl benzene acetonitrile, 1- methyl -3- difluoromethyl pyrazole -5- methyl formate 34.2g
The mixed liquor of (0.18mol) and 50ml methanol, about 1~2h are added dropwise to complete.After completion of dropwise addition, it is warming up to reflux 6h, liquid phase detection
To tert-butyl benzene ethane nitrile content less than 1% after, distillating carbinol, cooling is added after water is acidified with hydrochloric acid, and filtration drying obtains intermediate
Hydroxy nitrile is in next step.
2) 200ml toluene, upper step intermediate and 27.3g potassium carbonate are added in 500ml four-hole bottle, are warming up to 100~105
DEG C, it walks 24.4g (0.2mol) pivaloyl chloride is added dropwise in reaction mixture upwards, 10~20min is added dropwise to complete.After completion of dropwise addition again
It is stirred to react 1h.It is down to room temperature after reaction, washes 2 times, each 100ml, separate water layer, organic layer removed under reduced pressure toluene,
Kettle raffinate is recrystallized to give through methanol-water (80:20), obtains white solid 61.5g, content 99.3%, yield after dry
82.0%.
1H NMR (δ ppm): 7.31 (2H, d), 7.24 (2H, d), 6.45 (1H, s), 6.34 (1H, s), 3.71 (3H, s),
1.35 (9H, s), 1.24 (9H, s).
Embodiment 3:
1) addition solid sodium methylate 11.0g (0.2mol), DMF200ml in four mouthfuls of reaction flasks is being filled, is being warming up to 100 DEG C, delays
Slow be added dropwise 31.5g (0.18mol) is to tert-butyl benzene acetonitrile, 1- methyl-3-trifluoromethyl pyrazol -5- methyl formate 37.4g
The mixed liquor of (0.18mol) and 50mlDMF, about 1~2h are added dropwise to complete.After completion of dropwise addition, insulation reaction 6h, liquid phase is detected to uncle
After butyl benzene ethane nitrile content is less than 1%, the sodium salt suspension of intermediate hydroxyl acrylonitrile is obtained, is directly used in next step.
2) it at 100~105 DEG C, walks 24.4g (0.2mol) pivaloyl chloride is added dropwise in reaction mixture upwards, 10~
20min is added dropwise to complete.Reaction 1h is stirred for after completion of dropwise addition.It is evaporated under reduced pressure DMF after reaction, is down to room temperature, water is added
Then 200ml, filtering are recrystallized with methanol-water (80:20), obtain white solid 66.3g, content 99.0%, yield after dry
85.0%.
1H NMR (δ ppm): 7.31 (2H, d), 7.24 (2H, d), 6.35 (1H, s), 3.71 (3H, s), 1.37 (9H, s),
1.25 (9H, s).
The preparation example using the compounds of this invention as active constituent will be described below, but embodiments of the present invention are not limited to
The following contents.
Embodiment 4:
10 parts of the compound of the present invention are dissolved in the solvent of 50 parts of solvent naphthas and 25 parts of dimethylformamides composition, then
Be added 15 parts of TX-10 emulsifier, stir and be uniformly mixed obtain 10% missible oil.
Embodiment 5:
By 20 parts of the compound of the present invention, 10 parts of neopelex, 10 parts of ethylene glycol, 1 part of xanthan gum, silicic acid are mould
4 parts and 55 parts water of aluminium, are ground with ball mill, obtain 20% suspending agent.
It is described below using the compounds of this invention as the acaricidal test example of active constituent, still, test side of the invention
Formula is not limited to the following contents.
The application test of pyrazole compound of the invention:
The Tetranychus cinnabarinus adult mite continuously raised using interior carries out miticidal effect test as subjects, using infusion process.
According to example of formulations 5, the compound of three compounds (embodiment 1,2 and 3) meaning of the invention is made respectively
At acaricide 1,2 and 3, it is diluted to the medical fluid of 500ml/L with pure water, adult mite is handled according to pesticide test code requirement, after 72h
It checks life or death borer population, counts the death rate (stiff for death standard with adult mite).
The death rate of the compound 1,2 and 3 at 500ppm is 100%.
| Compound number | Death rate % after 72h |
| 1 | 100 |
| 2 | 100 |
| 3 | 100 |
Claims (5)
1. a kind of pyrazole compound, shown in structural formula such as formula (I):
Wherein R is ethyl, difluoromethyl or trifluoromethyl.
2. the preparation method of pyrazole compound as described in claim 1, which comprises the following steps: make in alkali
In 60 DEG C~120 DEG C under, in organic solvent A, pyrazoles acid esters obtains intermediate, then with to tert-butyl benzene acetonitrile reaction
Under 90 DEG C~120 DEG C, alkali metal compound effect, is reacted in solvent B with pivaloyl chloride and formula (I) compound is made；Wherein
Tert-butyl is 1:1~2:1~2:1~2 to the molar ratio of benzene acetonitrile, pyrazoles acid methyl esters, pivaloyl chloride and alkali；Tert-butyl is to benzene second
Mass volume ratio 1g:3~10ml of nitrile and solvent A；Mass volume ratio 1g:3~10ml of the tert-butyl to benzene acetonitrile and solvent B；
Organic solvent A is n-hexane, normal heptane, hexamethylene ether, ethylene glycol monoethyl ether, glycol dimethyl ether, isopropyl ether, two chloroethenes
Alkane, methylene chloride, chloroform, carbon tetrachloride, DMF, DEF, toluene, dimethylbenzene, acetonitrile and dimethyl sulfoxide it is one or two kinds of with
On combination；Solvent B is the combination of one or more of benzene,toluene,xylene, methanol and ethyl alcohol.
3. the preparation method of pyrazole compound as claimed in claim 2, it is characterised in that the alkali is sodium methoxide, ethyl alcohol
Sodium, sodium tert-butoxide or potassium tert-butoxide；Alkali metal compound is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride.
4. the preparation method of pyrazole compound as claimed in claim 2, it is characterised in that the organic solvent A is first
The combination of one or more of benzene, dimethylbenzene, DMF, methanol and ethyl alcohol；Organic solvent B be benzene,toluene,xylene and
The combination of one or more of DMF.
5. the pyrazole compound that general formula (I) as described in claim 1 indicates is used as pesticide acaricide as active constituent.
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| CN201811562054.1A CN109553577A (en) | 2018-12-20 | 2018-12-20 | A kind of pyrazole compound and preparation method and application |
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| CN201811562054.1A CN109553577A (en) | 2018-12-20 | 2018-12-20 | A kind of pyrazole compound and preparation method and application |
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Citations (7)
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|---|---|---|---|---|
| JP2003201280A (en) * | 2001-10-24 | 2003-07-18 | Nissan Chem Ind Ltd | Acrylonitrile compound |
| JP2003206281A (en) * | 2002-01-10 | 2003-07-22 | Nissan Chem Ind Ltd | Acrylonitrile compound |
| JP2004155693A (en) * | 2002-11-06 | 2004-06-03 | Nissan Chem Ind Ltd | Insecticidal, acaricidal, nematicidal, fungicidal or bactericidal composition, and method for controlling disease and insect pest |
| CN101367784A (en) * | 2008-09-28 | 2009-02-18 | 江苏省农药研究所股份有限公司 | Vinyl cyanide compounds, preparation and application thereof |
| CN101817784A (en) * | 1996-04-25 | 2010-09-01 | 日产化学工业株式会社 | Ethene derivatives and the pesticides that contains this derivative |
| CN101875633A (en) * | 2009-04-29 | 2010-11-03 | 中国中化股份有限公司 | Pyrazolyl acrylonitrile compound and application thereof |
| CN105801484A (en) * | 2014-12-29 | 2016-07-27 | 沈阳中化农药化工研发有限公司 | Preparation method of pyrazolyl acrylonitrile compound |
-
2018
- 2018-12-20 CN CN201811562054.1A patent/CN109553577A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817784A (en) * | 1996-04-25 | 2010-09-01 | 日产化学工业株式会社 | Ethene derivatives and the pesticides that contains this derivative |
| JP2003201280A (en) * | 2001-10-24 | 2003-07-18 | Nissan Chem Ind Ltd | Acrylonitrile compound |
| JP2003206281A (en) * | 2002-01-10 | 2003-07-22 | Nissan Chem Ind Ltd | Acrylonitrile compound |
| JP2004155693A (en) * | 2002-11-06 | 2004-06-03 | Nissan Chem Ind Ltd | Insecticidal, acaricidal, nematicidal, fungicidal or bactericidal composition, and method for controlling disease and insect pest |
| CN101367784A (en) * | 2008-09-28 | 2009-02-18 | 江苏省农药研究所股份有限公司 | Vinyl cyanide compounds, preparation and application thereof |
| CN101875633A (en) * | 2009-04-29 | 2010-11-03 | 中国中化股份有限公司 | Pyrazolyl acrylonitrile compound and application thereof |
| WO2010124617A1 (en) * | 2009-04-29 | 2010-11-04 | 中国中化股份有限公司 | Pyrazolyl acrylonitrile compounds and uses thereof |
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