CN109535143A - The pyrazole amide analog derivative and its preparation method and application of the oxazole structure of aryl containing 5- - Google Patents
The pyrazole amide analog derivative and its preparation method and application of the oxazole structure of aryl containing 5- Download PDFInfo
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- CN109535143A CN109535143A CN201811558361.2A CN201811558361A CN109535143A CN 109535143 A CN109535143 A CN 109535143A CN 201811558361 A CN201811558361 A CN 201811558361A CN 109535143 A CN109535143 A CN 109535143A
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- oxazole
- aryl containing
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- insecticide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
Abstract
The present invention relates to pyrazole amide analog derivatives (I) of a kind of oxazole of aryl containing 5- structure and its preparation method and application.It is condensed to yield with pyrazoles formoxyl chlorine (II) and 5- aryl oxazole -2- methyl amine (III).The pyrazole amide analog derivative of the oxazole of aryl containing the 5- structure has effective control efficiency to harmful insect, which can be used for preparing the insecticide in the fields such as agricultural, gardening.
Description
Technical field
The present invention relates to chemical pesticide fields, and in particular to a kind of pyrazole amide analog derivative of the oxazole of aryl containing 5- structure
And its preparation method and application.
Background technique
The prevention and treatment of pest is the core realm of pesticide science research all the time, and insecticide is widely used so that most evils
Worm has obtained effective improvement.But with the continuous expansion of insecticide application scale, the resistance problems of traditional pesticide species are increasingly
It highlights, in addition the emergence of new pest and disease damage, so that the research and development that continues of novel pesticide becomes inevitable choice.
Pyrazole ring is widely used in terms of agricultural production, and pyrazole compound has excellent desinsection, mite killing isoreactivity, pyrrole
Azoles heterocycle is widely introduced into agricultural chemical compound molecule, right such as pyrazole amide insecticidal/acaricidal agent tebufenpyrad and Tolfenpyrad
Acarid, aphid etc. have excellent killing activity (Biochim.Biophys.Acta 1998,1364,236-244).
Oxazole is also a kind of important nitrogen-containing heterocycle, and oxazole analog derivative plays important in terms of the desinsection of pesticide field
Effect.
Therefore, it in order to further find the compound with excellent bioactivity from pyrazole amide analog derivative, uses
Pyrazole amide group and oxazole unit are reasonably engaged togather by active group joining method, and the invention discloses one kind to have
There is the pyrazole amide analog derivative of the oxazole structure of aryl containing 5- of agricultural insecticidal application value.
Summary of the invention
It is and efficient, safe, environmental-friendly the object of the present invention is to provide there is excellent control efficiency for various pests
The pyrazol acid amide compounds of one kind oxazole structure of aryl containing 5-, to meet crop protection to efficient pesticides demand.
A further object of the present invention is to provide purposes of the above compound in terms of preparing insecticide.
It is a further object of the present invention to provide the preparation methods of above compound.
In order to solve the above technical problems, the first aspect of the present invention provides a kind of pyrazole amide of the oxazole of aryl containing 5- structure
Analog derivative, with general formula I,
Wherein, R1=2,4-F2C6H3,CH3,C2H5,n-C3H7
R2=H, 4-F, 4-Cl.
Preferably, the pyrazole amide analog derivative of the oxazole of aryl containing the 5- structure has the following structure:
The second aspect of the present invention provides the preparation method of the pyrazole amide analog derivative of the above-mentioned oxazole of aryl containing 5- structure,
It includes the following steps:
Compound III is dissolved in organic solvent, acid binding agent is added, then in addition intermediate II, one section of final reaction
Between, reaction solution is filtered, mother liquor is concentrated under reduced pressure, and gained residue isolates and purifies to obtain target compound,
Wherein, R1=2,4-F2C6H3,CH3,C2H5,n-C3H7
R2=H, 4-F, 4-Cl
Preferably, the acid binding agent is selected from pyridine, triethylamine, n,N-diisopropylethylamine, sodium bicarbonate, the solvent choosing
From DMF, acetonitrile, methylene chloride, chloroform and THF.The heating reaction temperature is 0 DEG C -85 DEG C, and the reaction time is that 6-28 is small
When.
Preferably, the pyrazole amide analog derivative of the oxazole of aryl containing 5- structure the preparation method is as follows:
Wherein, 5- aryl oxazole -2- methylamine intermediate III can refer to document (Molecules 2017,22,1925)
Method synthesizes to obtain；Pyrazol formyl chloride intermediate II reference literature (J.Agric.Food Chem.2013,61,8730-8736)
Method synthesize to obtain.
Compound of Formula I has excellent prevention and treatment activity to insect, thus the compound of the present invention can be used as preparing desinsection
Agent, and then protect the plants such as agricultural, gardening.The insect include lepidoptera pest for example bollworm, beet armyworm, diamondback moth,
Cabbage caterpillar, rice leaf roller and striped rice borer etc.；Homoptera pest such as leafhopper, plant hopper, earthworm worm, aleyrodid, the scale insect of Psyllidae etc.；
Diptera pest such as housefly, Liriomyza, mosquito class etc.；The locust etc. of Orthoptera, longicorn, chafer, weevil, bean weevil of coleoptera etc.
Pest etc.；The stinkbug etc. of Semiptera.Certainly, the harmful organism that the compound of the present invention can prevent and treat is not limited to the range of the example above.
When the compound of the present invention indicated by general formula I is used as the insecticide in the fields such as agricultural, gardening, can individually make
With, or used in a manner of Pesticidal combination, such as using Formulas I as active constituent, in addition insecticides adjuvant commonly used in the art is processed into
Aqueous emulsion, suspending agent, water dispersion granule, missible oil etc..
Common insecticides adjuvant includes: liquid-carrier, such as water；Organic solvent such as toluene, dimethylbenzene, cyclohexanol, methanol, fourth
Alcohol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and plant oil and fatty acid；Common surface agent is such as
Emulsifier and dispersing agent, including anionic surfactant, cationic surfactant, nonionic surfactant and both sexes table
Face activating agent；Other auxiliary agents, such as wetting agent, thickener.
When being used as the active constituent in insecticide by the compound of the present invention that general formula I is indicated, in the insecticide
Content is selected in the range of 0.1% to 99.5%, and can determine activity appropriate according to dosage form and method of administration
Component content.In general, preferably it contains containing active constituent described in 5% to 50% (weight percent, similarly hereinafter) in aqueous emulsion
Amount is 10% to 40%；In suspending agent containing 5% to 50% active constituent, preferably its content be 5% to 40%.
Common application method may be selected in use for insecticide of the invention, as cauline leaf is spraying, used for ponds, native
Earth processing and seed treatment etc..For example, when spraying using cauline leaf, the compound indicated by general formula I as active constituent
Can be used concentration range be 1 to 1000 μ g/mL aqueous emulsion, suspending agent, water dispersion granule, missible oil, preferably its concentration be 1 to
500μg/mL。
The pyrazole amide analog derivative of the oxazole of aryl containing 5- structure disclosed by the invention prevents harmful insect with excellent
Effect is controlled, therefore can be used to prepare the insecticide for fields such as agricultural, gardening.
Specific embodiment
Above scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the invention.Implementation condition used in the examples can be done according to the condition of specific producer
Further adjustment, the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1:
5mmol compound III a is dissolved in 25mL chloroform, 30mmol sodium bicarbonate is then added.Under room temperature to
Intermediate II a 6mmol is wherein added, finishes, heating reflux reaction 6 hours.Stop reaction, solvent is removed under reduced pressure, gained is remaining
Object obtains target compound Ia through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3): δ 7.64 (d, J=1.2Hz, 2H,
), Ar-H 7.57 (s, 1H, NH), 7.41~7.52 (m, 3H, Ar-H), 7.35 (d, J=7.2Hz, 1H, Ar-H), 7.31 (s, 1H,
), Oxazole-H 6.92~7.00 (m, 2H, Ar-H), 4.87 (d, J=5.2Hz, 2H, CH2),4.26(s,3H,N-CH3).
Embodiment 2:
4mmol compound III b is dissolved in 25mL acetonitrile, 30mmol triethylamine is then added.Add thereto under room temperature
Enter intermediate II b 6mmol, finishes, heating reflux reaction 12 hours.Stop reaction, solvent, gained residue warp is removed under reduced pressure
Column chromatographic isolation and purification obtains target compound Ib.1H NMR(400MHz,CDCl3): δ 7.56 (d, J=8.4Hz, 2H, Ar-H),
7.45 (s, 1H, NH), 7.39 (d, J=8.4Hz, 2H, Ar-H), 7.29 (s, 1H, Oxazole-H), 4.82 (d, J=5.2Hz,
2H,CH2),4.14(s,3H,N-CH3),2.25(s,3H,N-CH3).
Embodiment 3:
3mmol compound III c is dissolved in 35mL DMF, 12mmol DIEPA (n,N-diisopropylethylamine) then is added.
Intermediate II c 3mmol is added under condition of ice bath thereto, finishes, is heated to 85 DEG C and reacts 28 hours.Stop reaction, decompression rotation
It steams to doing, gained residue obtains target compound Ic through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3): δ 7.59~
7.62 (m, 2H, Ar-H), 7.47 (s, 1H, NH), 7.24 (s, 1H, Oxazole-H), 7.10~7.14 (m, 2H, Ar-H), 4.82
(d, J=5.2Hz, 2H, CH2),4.14(s,3H,N-CH3), 2.66 (q, J=7.6Hz, 2H, CH2), 1.25 (t, J=7.6Hz,
3H,CH3).
Embodiment 4:
6mmol compound III a is dissolved in 30mL THF, 20mmol pyridine is then added.It is added thereto under condition of ice bath
Intermediate II c 7mmol, finishes, and continues ice bath stirring 15 hours.Stop reaction, vacuum rotary steam is to doing, and gained residue is through column
Chromatography purifies to obtain target compound Id.1H NMR(400MHz,CDCl3): δ 7.62 (d, J=7.2Hz, 2H, Ar-H),
7.40~7.47 (m, 3H, Ar-H and NH), 7.35 (d, J=7.2Hz, 1H, Ar-H), 7.30 (s, 1H, Oxazole-H),
4.83 (d, J=5.2Hz, 2H, CH2),4.15(s,3H,N-CH3), 2.66 (q, J=7.6Hz, 2H, CH2), 1.25 (t, J=
7.6Hz,3H,CH3).
Embodiment 5:
8mmol compound III c is dissolved in 25mL methylene chloride, then addition 30mmol triethylamine, to it under condition of ice bath
Middle addition intermediate II d 10mmol.It finishes, continues ice bath stirring 10 hours.Stop reaction, by reaction solution vacuum rotary steam to dry,
Gained residue obtains target compound Ie through column chromatographic isolation and purification.1H NMR(400MHz,CDCl3): δ 7.59~7.62 (m,
2H, Ar-H), 7.45 (s, 1H, NH), 7.24 (s, 1H, Oxazole-H), 7.10~7.14 (m, 2H, Ar-H), 4.82 (d, J=
5.2Hz,2H,CH2),4.15(s,3H,N-CH3), 2.60 (t, J=7.6Hz, 2H, CH2), 1.69 (t, J=7.6Hz, 2H,
CH2), 0.97 (t, J=7.6Hz, 3H, CH3).
Embodiment 6:
Sample screens the insecticidal activity of mythimna separata
The leaf dipping method for using international resistance Action Committee (IRAC) to propose: for examination target for mythimna separata, i.e., by appropriate corn
Leaf dries in the shade naturally after sufficiently infiltrating in the medical fluid prepared, is put into the culture dish for being lined with filter paper, connects mythimna separata 3 age mid-term larva 10
Head/ware is placed in 24-27 DEG C of observation ward and cultivates, investigation result after 48h.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Examination
Testing concentration is 500 μ g/mL (medical fluid of other concentration can be diluted by the medical fluid of 500 μ g/mL and be obtained).
Insecticidal activity test result shows that all compounds show insecticidal activity.It is 500 μ g/mL in proof load
When (table 1), chemical compounds I a, I b, I c, I d and I e are preferable to the insecticidal activity of mythimna separata, and killing rate are respectively 100%,
100%, 100%, 100% and 100%.
The preliminary insecticidal activity data of table 1.Ia-Ie
The above experimental data shows for substituted oxazoline structure and pyrazole amide activity unit to be reasonably combined, and obtains
New compound show good biological activity, these experimental datas are also that continue to be engaged in novel pyrazole amides from now on derivative
MOLECULE DESIGN, synthesis and the bioactivity research of object provide important structure choice mode and theoretical foundation.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel only illustrate the present invention it should be appreciated that the present invention is not limited by examples detailed above described in examples detailed above and specification
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its is equal
Object defines.
Claims (4)
1. a kind of pyrazol acid amide derivative I of the oxazole of aryl containing 5- structure, it is characterised in that structure are as follows:
2. a kind of preparation method of the pyrazol acid amide derivative I of the oxazole of aryl containing 5- structure as described in claim 1, special
Sign is that method is as follows:
3. the pyrazol acid amide derivative I of the oxazole of aryl containing 5- structure is in terms of preparing insecticide as described in claim 1
Purposes, it is characterised in that: the compound is used alone；Or used in a manner of Pesticidal combination, i.e., with compound I be activity at
Point, in addition insecticides adjuvant commonly used in the art is processed into aqueous emulsion, suspending agent, water dispersion granule, missible oil.
4. the pyrazol acid amide derivative I of the oxazole of aryl containing 5- structure is in terms of preparing insecticide as claimed in claim 3
Purposes, it is characterised in that: when compound I is used as the active constituent in insecticide, the content in the insecticide can be 0.1%
It is selected in the range of to 99.5%.
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|---|---|---|---|---|
| CN87107603A (en) * | 1986-11-06 | 1988-08-10 | 日产化学工业株式会社 | The preparation method of the amide derivatives that replaces and contain the bactericide of this compound |
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| CN106608873A (en) * | 2015-10-26 | 2017-05-03 | 湖南化工研究院有限公司 | Pyrazole amide compound, and preparation method and application thereof |
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2018
- 2018-12-19 CN CN201811558361.2A patent/CN109535143B/en active Active
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| CN87107603A (en) * | 1986-11-06 | 1988-08-10 | 日产化学工业株式会社 | The preparation method of the amide derivatives that replaces and contain the bactericide of this compound |
| JPH05255268A (en) * | 1992-03-17 | 1993-10-05 | Mitsubishi Kasei Corp | Pyrazolecarboxamides, insecticide, acaricide and agricultural and horticultural germicide comprising the same as active ingredient |
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