CN110467599A - The preparation and application of the pyrazole amide of the unit containing substituted pyridines - Google Patents
The preparation and application of the pyrazole amide of the unit containing substituted pyridines Download PDFInfo
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- CN110467599A CN110467599A CN201910782020.1A CN201910782020A CN110467599A CN 110467599 A CN110467599 A CN 110467599A CN 201910782020 A CN201910782020 A CN 201910782020A CN 110467599 A CN110467599 A CN 110467599A
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- Prior art keywords
- substituted pyridines
- unit containing
- containing substituted
- pyrazole amide
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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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The present invention relates to the preparations and application of a kind of pyrazole amide of unit containing substituted pyridines.It is condensed to yield with pyrazole acyl chloride intermediate and substituent pyridine methyl amine.A kind of pyrazole amide of unit containing substituted pyridines shows effectively preventing effect 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 the preparation and application of the pyrazole amide of the unit containing substituted pyridines.
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, such as pyrazole amide insecticide Tolfenpyrad, is had to mythimna separata etc. excellent
Good killing activity (Biochim.Biophys.Acta 1998,1364,236-244).
Nitrogen-containing heterocycle compound is widely used in terms of agricultural production, and substituted pyridine compounds important contain as a kind of
Nitrogen heterocyclic has excellent desinsection isoreactivity, and wherein typicalness substituted pyridine compounds have sulfoxaflor, in agriculture
(US 20080108667) is played an important role in terms of the desinsection in medicine field.
Therefore, in order to find the compound with preferable bioactivity, reasonably by pyrazoles unit and substituted pyridines group
It is stitched together, is therefrom expected to obtain the noval chemical compound with insecticidal activity.
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 pyrazole amide of one kind unit containing substituted pyridines, to meet crop protection to efficient pesticides demand.
It is a further object of the present invention to provide the preparation methods of above compound.
A further object of the present invention is to provide purposes of the above compound in terms of mythimna separata and aphid agent are killed in preparation.
In order to solve the above technical problems, the first aspect of the present invention provides a kind of pyrazole amide of unit containing substituted pyridines,
It has the following structure:
The present invention provides the preparation method of the pyrazole amide of the above-mentioned unit containing substituted pyridines, it is characterised in that including walking as follows
It is rapid:
Wherein, intermediate pyrazole formoxyl chlorine can refer to document (J.Agric.Food Chem.2013,61,8730-
8736) method synthesizes to obtain；The conventional method of the synthesis reference literature report of intermediate substituent pyridine methyl amine
(Chemical Reagents 2004,26,99-100)。
Compound of Formula I has excellent prevention and treatment activity to mythimna separata and aphid, thus the compound of the present invention can be used as making
It is standby to kill mythimna separata and aphid agent, and then protect the plants such as agricultural, gardening.
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 of the unit disclosed by the invention containing substituted pyridines has excellent control efficiency to mythimna separata and aphid, because
This 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:
3mmol compound III a is dissolved in 15mL tetrahydrofuran, 12mmol pyridine is then added.Under condition of ice bath thereto
Intermediate II a 5mmol is added, finishes, continues to be stirred at room temperature 12 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, institute
It obtains residue and obtains target compound Ia through column chromatographic isolation and purification；1H NMR(400MHz,DMSO-d6):δ8.94(s,1H,
), NH 8.06 (d, J=2.0Hz, 1H, Py-H), 7.84~7.87 (m, 1H, Py-H), 7.13~7.45 (m, 4H, Py-H and
), Ar-H 4.44 (d, J=6.0Hz, 2H, CH2),3.82(s,3H,N-CH3),2.13(s,3H,CH3).
Embodiment 2:
6mmol compound III a is dissolved in 30mL acetonitrile, under room temperature thereto be added 10mmol intermediate II b and
18mmol sodium carbonate, finishes, and heating reflux reaction 16 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, gained residue
Target compound Ib is obtained through column chromatographic isolation and purification；1H NMR(400MHz,DMSO-d6):δ8.93(s,1H,NH),8.07(d,J
=2.0Hz, 1H, Py-H), 7.84~7.87 (m, 1H, Py-H), 7.12~7.46 (m, 4H, Py-H and Ar-H),
4.44 (d, J=6.0Hz, 2H, CH2),3.83(s,3H,N-CH3), 2.55 (q, J=8.0Hz, 2H, CH2),1.16
(t, J=7.6Hz, 3H, CH3).
Embodiment 3:
8mmol compound III b is dissolved in 30mL 1,7mmol intermediate is added in 2- dichloroethanes thereto under room temperature
II b and 16mmol sodium bicarbonate, finishes, and heating reflux reaction 20 hours.Stop reaction, by reaction solution vacuum rotary steam to dry, institute
It obtains residue and obtains target compound Ic through column chromatographic isolation and purification；1H NMR(400MHz,DMSO-d6):δ8.92(s,1H,
), NH 8.11 (d, J=2.0Hz, 1H, Py-H), 7.82~7.84 (m, 1H, Py-H), 7.02~7.26 (m, 5H, Py-H and
), Ar-H 4.44 (d, J=6.0Hz, 2H, CH2),3.83(s,3H,N-CH3), 2.55 (q, J=7.2Hz, 2H, CH2),1.16(t,
J=7.6Hz, 3H, CH3).
Embodiment 4:
Sample screens the insecticidal activity of aphid
The spray-on process for using international resistance Action Committee (IRAC) to propose: it for examination target for aphid, i.e., will be connected to respectively
The Broad Bean Leaves of aphid spraying treatment under Potter spray tower, aphid is placed in 20-22 DEG C of observation ward and cultivates after processing, after 2d
Investigation result.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Experimental concentration is that (medical fluid of other concentration can be by by 500 μ g/mL
The medical fluid of 500 μ g/mL is diluted and is obtained).
Embodiment 5:
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 2d.Polypide is touched with writing brush, it is reactionless to be considered as dead worm.Test
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 all have preferable insecticidal activity.It is 500 μ in test concentrations
When g/mL (table 1), the c of chemical compounds I a~I is respectively 100%, 100% and 100% to the killing effect of aphid；The c of chemical compounds I a~I
Insecticidal activity to mythimna separata is respectively 100%, 100% and 100%.Chemical compounds I a and I b test concentrations be 100 μ g/mL when pair
The killing effect of aphid is respectively 100% and 100%；Chemical compounds I a and I b kills mythimna separata when test concentrations are 100 μ g/mL
Deactivation is respectively 100% and 90%.In addition, chemical compounds I a and I b also show aphid when test concentrations are reduced to 20 μ g/mL
Excellent insecticidal effect out, killing rate are respectively 100% and 90%.
The insecticidal activity data of table 1.Ia-Ic
"-": undetermined is indicated
The above experimental data shows for substituted pyridines group to be organically engaged togather with pyrazol framework, obtains newcooperative medical system
It closes object and shows excellent insecticidal activity, the type compound is optional to be used as desinsection guide, and it is derivative and raw to make further structure
Object activity research.
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 (3)
1. a kind of pyrazole amide I of unit containing substituted pyridines, it is characterised in that structure are as follows:
2. a kind of preparation method of the pyrazole amide I of the unit containing substituted pyridines as described in claim 1, it is characterised in that method
It is as follows:
3. a kind of pyrazole amide I of the unit containing substituted pyridines as described in claim 1 kills mythimna separata and aphid drug side in preparation
The purposes in face.
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| CN201910782020.1A CN110467599B (en) | 2019-08-23 | 2019-08-23 | Preparation and application of pyrazole amide containing substituted pyridine unit |
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| CN201910782020.1A CN110467599B (en) | 2019-08-23 | 2019-08-23 | Preparation and application of pyrazole amide containing substituted pyridine unit |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925681A (en) * | 2022-04-22 | 2023-04-07 | 中国农业大学 | Pyrazole amide compounds, preparation thereof and application thereof as pesticides and bactericides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102427A (en) * | 1987-04-24 | 1988-11-09 | 三菱化成工业株式会社 | Pyrazole derivatives and insecticidal or acaricidal compositions containing them |
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
-
2019
- 2019-08-23 CN CN201910782020.1A patent/CN110467599B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN88102427A (en) * | 1987-04-24 | 1988-11-09 | 三菱化成工业株式会社 | Pyrazole derivatives and insecticidal or acaricidal compositions containing them |
| US5039693A (en) * | 1988-10-14 | 1991-08-13 | Mitsubishi Kasei Corporation | Pyrazole amides and insecticide and miticide containing them as active ingredient |
| CN103081916A (en) * | 2011-11-02 | 2013-05-08 | 中国中化股份有限公司 | Application of pyrazole amide compound as agricultural bactericide |
Non-Patent Citations (1)
| Title |
|---|
| 刘长令: "生物电子等排及其在新农药创制中的应用", 《农药》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925681A (en) * | 2022-04-22 | 2023-04-07 | 中国农业大学 | Pyrazole amide compounds, preparation thereof and application thereof as pesticides and bactericides |
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