CN109535143B - Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof - Google Patents
Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof Download PDFInfo
- Publication number
- CN109535143B CN109535143B CN201811558361.2A CN201811558361A CN109535143B CN 109535143 B CN109535143 B CN 109535143B CN 201811558361 A CN201811558361 A CN 201811558361A CN 109535143 B CN109535143 B CN 109535143B
- Authority
- CN
- China
- Prior art keywords
- pyrazole amide
- compound
- preparation
- aryl
- amide derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a pyrazole amide derivative (I) containing a 5-aryl oxazole structure, and a preparation method and application thereof. Is obtained by condensing pyrazole formyl chloride (II) and 5-aryl oxazole-2-methylamine (III). The pyrazole amide derivative containing the 5-aryl oxazole structure has an effective control effect on harmful insects, and can be used for preparing pesticides in the fields of agriculture, horticulture and the like.
Description
Technical Field
The invention relates to the field of chemical pesticides, and particularly relates to a pyrazole amide derivative containing a 5-aryl oxazole structure, and a preparation method and application thereof.
Background
The prevention and control of pests are always the core field of pesticide science research, and the wide use of pesticides enables most pests to be effectively treated. However, with the continuous expansion of the application scale of the pesticide, the problem of drug resistance of the traditional pesticide varieties becomes more and more prominent, and the continuous research and development of new pesticides become necessary choices due to the continuous emergence of new plant diseases and insect pests.
Pyrazole rings are widely applied in agricultural production, pyrazole compounds have excellent insecticidal and acaricidal activities, and pyrazole heterocycles are widely introduced into pesticide compound molecules, such as pyraclostrobin, tebufenpyrad and tolfenpyrad, and have excellent killing activities on mites, aphids and the like (Biochim. Biophys. acta 1998,1364, 236-244).
Oxazole is also an important nitrogen-containing heterocycle, and oxazole derivatives play an important role in the insecticidal aspect in the field of pesticides.
Therefore, in order to further search for a compound with excellent biological activity from the pyrazole amide derivatives, the pyrazole amide group and the oxazole unit are reasonably linked together by adopting an active group splicing method, and the invention discloses a pyrazole amide derivative containing a 5-aryl oxazole structure and having agricultural insecticidal application value.
Disclosure of Invention
The invention aims to provide a pyrazole amide compound containing a 5-aryl oxazole structure, which has an excellent control effect on various pests, is efficient, safe and environment-friendly, and meets the requirement of crop protection on efficient pesticides.
It is a further object of the present invention to provide the use of the above compounds in the preparation of insecticides.
Another object of the present invention is to provide a process for the preparation of the above compounds.
In order to solve the technical problems, the invention provides a pyrazole amide derivative containing a 5-aryl oxazole structure, which has a structure shown in a general formula I,
wherein R is1＝2,4-F2C6H3,CH3,C2H5,n-C3H7
R2＝H,4-F,4-Cl。
Preferably, the pyrazole amide derivative containing the 5-aryl oxazole structure has the following structure:
the second aspect of the present invention provides a preparation method of the pyrazole amide derivative containing the 5-aryl oxazole structure, which comprises the following steps:
dissolving a compound III in an organic solvent, adding an acid-binding agent, adding an intermediate II, reacting for a period of time, carrying out suction filtration on a reaction solution, carrying out reduced pressure concentration on a mother solution, separating and purifying an obtained residue to obtain a target compound,
wherein R is1＝2,4-F2C6H3,CH3,C2H5,n-C3H7
R2＝H,4-F,4-Cl
Preferably, the acid scavenger is selected from pyridine, triethylamine, N-diisopropylethylamine, sodium bicarbonate, and the solvent is selected from DMF, acetonitrile, dichloromethane, chloroform, and THF. The heating reaction temperature is 0-85 ℃, and the reaction time is 6-28 hours.
Preferably, the pyrazole amide derivative containing the 5-aryl oxazole structure is prepared by the following method:
wherein, the 5-aryl oxazole-2-methylamine intermediate III can be synthesized by a method of reference documents (Molecules 2017,22, 1925); pyrazole formyl chloride intermediates II were synthesized according to the methods described in J.Agric.food chem.2013,61, 8730-8736.
The compound of the general formula I has excellent control activity on insects, so that the compound can be used for preparing pesticides to protect plants in agriculture, horticulture and the like. The insects comprise lepidoptera pests such as cotton bollworms, asparagus caterpillars, diamond back moths, cabbage caterpillars, rice leaf rollers, chilo suppressalis and the like; homoptera pests such as leafhopper, plant hopper, vermin, whitefly, coccid of psyllidae, etc.; dipteran pests such as houseflies, leaf miner, mosquitoes, etc.; locusts of the order orthoptera, pests of the order Coleoptera, longicorn beetles, scarab beetles, weevils, and the like; stinkbugs of the order hemiptera, and the like. Of course, the pests which the compounds of the invention can control are not limited to the above exemplified ranges.
When the compound of the invention represented by the general formula I is used as an insecticide in the fields of agriculture, horticulture and the like, the compound can be used alone or in the form of an insecticidal composition, for example, the compound is prepared into an aqueous emulsion, a suspending agent, a water dispersible granule, an emulsion and the like by taking the formula I as an active ingredient and adding pesticide auxiliaries commonly used in the field.
Commonly used pesticide adjuvants include liquid carriers such as water; organic solvents such as toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, animal and vegetable oils and fatty acids; common surfactants such as emulsifiers and dispersants, including anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants; other adjuvants, such as wetting agents, thickeners, and the like.
When the compound of the present invention represented by the general formula I is used as an active ingredient in an insecticide, the content in the insecticide is selected in the range of 0.1% to 99.5%, and an appropriate content of the active ingredient may be determined according to the formulation form and the application method. In general, the aqueous emulsion contains 5% to 50% (by weight, the same applies hereinafter) of the active ingredient, preferably 10% to 40%; the suspension concentrate contains 5% to 50% of active ingredient, preferably 5% to 40%.
For the use of the insecticide of the present invention, a commonly used application method such as stem and leaf spraying, water surface application, soil treatment, seed treatment, and the like can be selected. For example, when spray application from stems and leaves is employed, the compounds represented by the general formula I as active ingredients can be used in the form of aqueous emulsions, suspensions, water-dispersible granules, emulsifiable concentrates in the concentration range of 1 to 1000. mu.g/mL, preferably in the concentration range of 1 to 500. mu.g/mL.
The pyrazole amide derivative containing the 5-aryl oxazole structure disclosed by the invention has excellent control effect on harmful insects, so that the pyrazole amide derivative can be used for preparing pesticides used in the fields of agriculture, horticulture and the like.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1:
5mmol of compound IIIa are dissolved in 25mL of chloroform and 30mmol of sodium bicarbonate are added. 6mmol of intermediate IIa is added at room temperature, and after the addition, the mixture is heated and refluxed for 6 hours. The reaction was stopped, the solvent was removed under reduced pressure and the residue was passed through a columnAnd (5) carrying out chromatographic separation and purification to obtain the target compound Ia.1H NMR(400MHz,CDCl3):δ7.64(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).
Example 2:
4mmol of compound IIIb are dissolved in 25mL of acetonitrile, followed by addition of 30mmol of triethylamine. 6mmol of intermediate IIb is added at room temperature, and after the addition, the mixture is heated and refluxed for 12 hours. The reaction was stopped, the solvent was removed under reduced pressure, and the resulting residue was purified by column chromatography to give the target compound Ib.1H NMR(400MHz,CDCl3):δ7.56(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).
Example 3:
3mmol of compound IIIc are dissolved in 35mL of DMF, and 12mmol of DIEPA (N, N-diisopropylethylamine) are subsequently added. The intermediate IIc 3mmol was added thereto under ice-bath conditions, and after the addition was completed, the mixture was heated to 85 ℃ to react for 28 hours. Stopping the reaction, carrying out reduced pressure rotary evaporation to dryness, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ic.1H NMR(400MHz,CDCl3):δ7.59～7.62(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).
Example 4:
6mmol of compound IIIa are dissolved in 30mL of THF, followed by addition of 20mmol of pyridine. And adding 7mmol of intermediate IIc under ice bath condition, and continuing stirring for 15 hours in ice bath after the addition is finished. Stopping the reaction, carrying out reduced pressure rotary evaporation to dryness, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Id.1H NMR(400MHz,CDCl3):δ7.62(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).
Example 5:
8mmol of compound IIIc are dissolved in 25mL of dichloromethane, followed by addition of 30mmol of triethylamine and addition of 10mmol of intermediate IId thereto under ice-bath conditions. After the addition, stirring in ice bath was continued for 10 hours. Stopping the reaction, carrying out rotary evaporation on the reaction liquid under reduced pressure until the reaction liquid is dried, and carrying out column chromatography separation and purification on the obtained residue to obtain the target compound Ie.1H NMR(400MHz,CDCl3):δ7.59～7.62(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).
Example 6:
insecticidal activity screening of samples against armyworm
The leaf soaking method proposed by the International Resistance Action Committee (IRAC) was adopted: the target for testing is armyworm, namely, a proper amount of corn leaves are fully soaked in prepared liquid medicine and then naturally dried in the shade, the corn leaves are placed into a culture dish filled with filter paper, 10 heads/dish of armyworm larvae in the 3-instar middle stage are connected, the corn leaves are placed into an observation room for culture at 24-27 ℃, and the result is investigated after 48 hours. If the body of the insect is touched by a brush pen, no response is regarded as dead insect. The test concentration was 500. mu.g/mL (other concentrations of drug solution could be diluted with 500. mu.g/mL).
The insecticidal activity test result shows that all the compounds have insecticidal activity. At the tested dose of 500. mu.g/mL (Table 1), the insecticidal activity of the compounds Ia, Ib, ic, id and ie against armyworm was all better, with the kill rates of 100%, 100%, 100% and 100%, respectively.
TABLE 1 Primary insecticidal Activity data for Ia-Ie
The experimental data show that the novel compound obtained by reasonably combining the substituted oxazole structure and the pyrazole amide active units shows good biological activity, and the experimental data also provide important structure selection modes and theoretical bases for continuing to carry out molecular design, synthesis and biological activity research of novel pyrazole amide derivatives in the future.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited by the foregoing examples, which are provided to illustrate the principles of the invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention, which is also intended to be covered by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A pyrazole amide derivative I containing a 5-aryl oxazole structure is characterized by having a structure as follows:
2. the process for preparing pyrazole amide derivatives I containing 5-aryloxazole structures according to claim 1, which comprises the following steps:
3. the use of pyrazole amide derivatives I containing 5-aryl oxazole structures according to claim 1 for the preparation of a medicament for killing armyworms, wherein: the compound is used alone; or the compound I is used as an active ingredient, and is added with pesticide auxiliary agents to be processed into an aqueous emulsion, a suspending agent, a water dispersible granule and an emulsifiable solution, wherein the pesticide auxiliary agents are water, toluene, xylene, cyclohexanol, methanol, butanol, ethylene glycol, acetone, dimethylformamide, acetic acid, dimethyl sulfoxide, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a wetting agent and a thickening agent.
4. The use of pyrazole amide derivatives I containing 5-aryl oxazole structures according to claim 3 for the preparation of a medicament for killing armyworm, wherein: when compound I is used as an active ingredient of an anti-myxocidal drug, the content in the anti-myxocidal drug is selected in the range of 0.1% to 99.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811558361.2A CN109535143B (en) | 2018-12-19 | 2018-12-19 | Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811558361.2A CN109535143B (en) | 2018-12-19 | 2018-12-19 | Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109535143A CN109535143A (en) | 2019-03-29 |
| CN109535143B true CN109535143B (en) | 2021-12-10 |
Family
ID=65855838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811558361.2A Active CN109535143B (en) | 2018-12-19 | 2018-12-19 | Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109535143B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106432216A (en) * | 2016-08-01 | 2017-02-22 | 南通大学 | Preparation method and application of pyrazol amide compound containing 5-aryl isoxazole structure |
| 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 |
| CN106866649A (en) * | 2017-02-13 | 2017-06-20 | 南通大学 | The preparation method and application of the pyrazol acid amide compounds containing the oxadiazole structure of 5 aryl 1,3,4 |
-
2018
- 2018-12-19 CN CN201811558361.2A patent/CN109535143B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN106432216A (en) * | 2016-08-01 | 2017-02-22 | 南通大学 | Preparation method and application of pyrazol amide compound containing 5-aryl isoxazole structure |
| CN106866649A (en) * | 2017-02-13 | 2017-06-20 | 南通大学 | The preparation method and application of the pyrazol acid amide compounds containing the oxadiazole structure of 5 aryl 1,3,4 |
Non-Patent Citations (3)
| Title |
|---|
| Design, Synthesis, DFT Study and Antifungal Activity of the Derivatives of Pyrazolecarboxamide Containing Thiazole or Oxazole Ring;Zhongzhong，等;《European journal of medicinal chemistry》;20180221;第149卷(第1期);170-181 * |
| Synthesis and insecticidal activities of novel 1H-pyrazole-5-carboxylic acid derivatives;Danling，等;《HETEROCYCLIC COMMUNICATIONS》;20171122;第23卷(第6期);第2页方案1,第3页表1,第4页右栏第3段 * |
| 新型含取代异噁唑结构的吡唑酰胺类衍生物的合成及其生物活性研究;戴红,等;《有机化学》;20170401(第37期);2165-2171 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109535143A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110092776B (en) | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof | |
| CN110407828B (en) | Pyrazole-5-amide derivative containing oxazole structure and preparation method and application thereof | |
| CN109678845B (en) | Pyrazole amide derivative containing benzotriazole structure and preparation method and application thereof | |
| CN110128409B (en) | Preparation and application of difluoromethylpyrazole oxime derivative containing pyridine bipyrazole structure | |
| CN109678846B (en) | Pyrazole amide compound containing 1,2, 3-triazole structure, and preparation method and application thereof | |
| CN110922397B (en) | Preparation method and application of 3- (pyrazole biphenyl methoxy) pyrazole derivative containing substituted isoxazole unit | |
| CN110407831B (en) | Preparation and application of pyrazole oxime ester derivative containing N- (3-chloropyridine-2-yl) pyrazole structure | |
| CN106946856B (en) | Pyrazole oxime derivative containing tetrazole biphenyl structure and preparation method and application thereof | |
| CN110845487B (en) | 3- (triazole biphenyl methoxyl) pyrazole amide compound containing isoxazole structure and preparation method and application thereof | |
| CN106243039B (en) | Preparation method and application of pyrazole oxime compound containing 1-methyl-3-ethyl-4-chloro-5-formylpyrazole structure | |
| CN109553605B (en) | Pyrazole amide compound containing tetrazole biphenyl structure and preparation method and application thereof | |
| CN109879867B (en) | Preparation and application of pyrazole oxime ether compound containing 5-aryl oxazole structure | |
| CN110437221B (en) | Pyrazole derivative containing aryloxy methyl oxadiazole unit and preparation method and application thereof | |
| CN110845488A (en) | Preparation method and application of 3- (benzotriazole benzyloxy) pyrazole derivative containing aryl isoxazole | |
| CN106432081B (en) | Preparation method and application of pyrazole oxime ether compound containing 4-chloro-3-ethyl-1-methylpyrazole structure | |
| CN110407813B (en) | Pyrazole oxime compound containing 1- (3-chloropyridine-2-yl) pyrazole structure and preparation method and application thereof | |
| CN110713460A (en) | Preparation method and application of pyrazole amide derivative containing pyrazole phenyl unit | |
| CN109535154B (en) | Pyrazole amide compound containing 4-arylthiazole structure and preparation method and application thereof | |
| CN109879868B (en) | Preparation and application of pyrazole amide compound containing 2-aryl oxazole structure | |
| CN112010836B (en) | 2-substituent imidazolidine derivative containing aryl bipyridyl oxygen structure and preparation method and application thereof | |
| CN110776463B (en) | Preparation and application of pyrazole oxime derivative containing 3-trifluoromethylpyrazole | |
| CN109535143B (en) | Pyrazole amide derivative containing 5-aryl oxazole structure and preparation method and application thereof | |
| CN110467599B (en) | Preparation and application of pyrazole amide containing substituted pyridine unit | |
| CN111592526B (en) | Preparation and application of 3- (chloropyridine methoxyaryl) -1-methylpyrazole compound containing azole heterocyclic structure | |
| CN109879866B (en) | Preparation and application of pyrazole oxime derivative containing oxazole biphenyl sulfenyl structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |