CN108069905B - Pyrazole amide compound and application thereof - Google Patents
Pyrazole amide compound and application thereof Download PDFInfo
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- CN108069905B CN108069905B CN201610983987.2A CN201610983987A CN108069905B CN 108069905 B CN108069905 B CN 108069905B CN 201610983987 A CN201610983987 A CN 201610983987A CN 108069905 B CN108069905 B CN 108069905B
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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
- C07D231/14—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
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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
Abstract
The invention belongs to the field of bactericides, and particularly relates to a pyrazole amide compound and application thereof. Pyrazole amide compounds, represented by general formula I:
Description
Technical Field
The invention belongs to the field of bactericides, and particularly relates to a pyrazole amide compound and application thereof.
Background
Since fungicides are resistant to diseases after a period of use, there is a continuing need to invent new and improved compounds and compositions with bactericidal activity.
The bactericidal activity of pyrazole amide compounds has been reported, for example, JP62249975A discloses a compound KC (compound 4 in the patent) and its bactericidal activity.
In the prior art, pyrazole amide compounds with the structure shown in the general formula I are not reported.
Disclosure of Invention
The invention aims to provide a pyrazole amide compound with better bactericidal activity, which can be applied to the prevention and control of diseases in agriculture, forestry or sanitation.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a pyrazole amide compound characterized by: the compound is shown in a general formula I:
in the formula:
r1 is selected from C1-C6 alkyl or C3-C12 cycloalkyl;
r2 is selected from C3-C8 alkyl, C3-C8 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C3-C6 cycloalkyl-C3-C6 cycloalkyl. Wherein "-" means "and" - "means" for C3-C6 cycloalkyl-C3-C6 cycloalkyl.
Preferred compounds of the invention are those of the general formula I: r1 is selected from C1-C3 alkyl or C3-C6 cycloalkyl;
r2 is selected from C3-C8 alkyl or C3-C6 cycloalkyl.
Further preferred compounds of the invention are of the general formula I: r1 is selected from C1-C3 alkyl; r2 is selected from C3-C8 alkyl or C3-C6 cycloalkyl.
More preferred compounds of the invention are of the general formula I: r1 is selected from methyl, ethyl or isopropyl;
r2 is selected from (1-methyl) ethyl, (1-methyl) propyl, (1-ethyl) ethyl, (1-ethyl) pentyl, (2-methyl) propyl, (2-methyl) butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
An application of pyrazole amide compounds, and an application of the compounds in the general formula I in preparing medicines for controlling plant diseases of non-treatment-purpose agriculture or forestry.
A sterilization composition takes a compound shown as a general formula I as an active component, and the weight content of the active component in the composition is 1-99%.
A method for controlling plant diseases by applying a fungicidal composition at an effective dose of 10g to 1000 g per hectare to a target disease or a medium in which the target disease is growing.
The compounds of the general formula I according to the invention can be prepared by the following processes, in which the radicals are as defined above, unless otherwise indicated.
The compound of the general formula II and the compound of the general formula III react in a proper solvent and in the presence of a proper alkali at the temperature of-10 ℃ to the boiling point of the reaction solvent for 0.5 to 48 hours to prepare the target compound I.
Suitable solvents are selected from dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N-dimethylformamide or dimethyl sulfoxide, and the like.
Suitable bases include hydrogen compounds of alkali metals such as lithium, sodium or potassium, such as sodium hydride, hydroxides of alkali metals such as lithium, sodium or potassium, such as sodium hydroxide, and also carbonates of alkali metals such as sodium carbonate, and also organic bases such as triethylamine, sodium tert-butoxide, etc.
For compounds of general formula II, reference may be made to Han' guk Nonghwa Hakhoechi (1992), 35 (5): the description of the preparation method in the 382-charge 388 document.
Reference is made to Bioorganic & Medicinal Chemistry, 2012, 20 (3): 1213-1221; pesticide, 2007, 45 (5): 307-309, the methods described therein.
Table 1 lists the structure and physical properties of some of the compounds of formula I.
Table 1 structural and physical properties of some compounds of formula I
The 1H NMR data for some of the compounds are as follows:
compound 1: 1H NMR (300MHz, CDCl3) (ppm): 7.72(s, 1H), 7.60(d, 1H), 7.16(t, 1H), 6.68(d, 1H), 3.85(s, 3H), 3.73(d, 2H), 2.52(s, 3H), 2.22(s, 3H), 2.08-2.12(m, 1H), 1.04(d, 6H).
Compound 4: 1H NMR (400MHz, CDCl3) (ppm): 7.72(s, 1H), 7.59(d, 1H), 7.14-7.19(m, 1H), 6.71(d, 1H), 3.85(s, 3H), 3.73(d, 2H), 2.52(s, 3H), 2.21(s, 3H), 1.72-1.76(m, 1H), 1.33-1.57(m, 8H), 0.92(d, 6H).
Compound 8: 1H NMR (300MHz, CDCl3) (ppm): 7.70(s, 1H), 7.45(d, 1H), 7.17(s, 1H), 7.14(t, 1H), 6.68(d, 1H), 3.87(s, 3H), 3.73(d, 2H), 3.46-3.53(m, 1H), 2.18(s, 3H), 2.08-2.15(m, 1H), 1.35(d, 6H), 1.04(d, 6H).
Compound 15: 1H NMR (300MHz, CDCl3) (ppm): 7.86(s, 1H), 7.62(d, 1H), 7.17(t, 1H), 6.69(d, 1H), 3.81(s, 3H), 3.74(d, 2H), 2.43(s, 3H), 0.90-1.06(m, 11H).
Compound 17: 1H NMR (300MHz, CDCl3) (ppm): 7.74(s, 1H), 7.62(d, 1H), 7.13-7.18(m, 1H), 6.68(d, 1H), 3.85(s, 3H), 3.82(d, 2H), 2.52(s, 3H), 2.23(s, 3H), 1.25-1.28(m, 1H), 0.58-0.62(m, 2H), 0.32-0.38(m, 2H).
Compound 20: 1H NMR (300MHz, CDCl3) (ppm): 7.73(s, 1H), 7.59(d, 1H), 7.16-7.19(m, 1H), 6.69(d, 1H), 3.85(s, 3H), 3.76(d, 2H), 2.52(s, 3H), 2.21(s, 3H), 1.66-1.89(m, 6H), 1.06-1.33(m, 4H).
The pyrazole amide-based compounds of the present invention have higher fungicidal activity than known pyrazole amide-based compounds. The invention therefore also comprises the use of compounds of the general formula I for controlling plant diseases.
The invention also comprises a bactericidal composition which takes the compound in the general formula I as an active component. The weight percentage of the compound of the general formula I as an active component in the bactericidal composition is between 1 and 99 percent. The bactericidal composition also comprises an agriculturally or forestry acceptable carrier.
The compositions of the present invention may be administered in the form of a formulation. The compounds of formula I are dissolved or dispersed as active ingredients in carriers or formulated so as to be more easily dispersed for use as fungicides. For example: these chemicals can be formulated as wettable powders or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and when necessary, a suitable surfactant may be added.
The technical scheme of the invention also comprises a method for preventing and controlling the bacterial damage: the sterilization composition of the invention is applied to the harmful bacteria or the growth medium thereof. Preferably, an effective amount of 10 to 1000 grams per hectare is generally selected, with an effective amount of 20 to 500 grams per hectare being preferred.
For certain applications, for example in agriculture, one or more other insecticides, fungicides, herbicides, plant growth regulators or fertilizers and the like may be added to the fungicidal compositions of the present invention, thereby providing additional advantages and effects.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
Detailed Description
The following synthetic examples, biological test results, are provided to further illustrate the invention, but are not meant to limit the invention.
Synthesis examples
Example 1 preparation of compound 1:
3-isobutoxy-2-methylaniline (0.24g, 1.339mmol), dichloromethane (15m L) and triethylamine (0.163g, 1.607mmol) were added to a 100m L single-neck flask, a dichloromethane solution (15m L) of 5-chloro-1, 3-dimethyl-1H-pyrazole-4-carbonyl chloride (0.310g, 1.607mmol) was added dropwise with stirring at room temperature, the reaction was monitored at T L C, after 2 hours, dichloromethane (20m L) and water (50m L) were added to extract the mixture, and the organic layer was taken, washed with a saturated aqueous sodium bicarbonate solution and a saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
Example 2 preparation of compound 17:
to a 100m L single neck flask was added 3- (cyclopropylmethoxy) -2-methylaniline (0.16g, 0.903mmol), dichloromethane (15m L), triethylamine (0.110g, 1.083mmol), a dichloromethane solution (15m L) of 5-chloro-1, 3-dimethyl-1H-pyrazole-4-carbonyl chloride (0.209g, 1.083mmol) was added dropwise with stirring at room temperature, the reaction was monitored at T L C, after 2 hours, the reaction was terminated, dichloromethane (20m L) and water (50m L) were added and extraction was carried out, and the organic layer was taken, washed with a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
Other compounds of formula I of the present invention may be synthesized by reference to the methods described above.
Examples of biological Activity assays
EXAMPLE 3 measurement of fungicidal Activity
The compounds of the present invention obtained as described above were tested for various diseases of plants. The method of testing is as follows:
(1) in vivo protective Activity test
The test was performed using potted seedling assay. Selecting potted cucumber seedlings with consistent growth in two leaf stages as test host plants of cucumber downy mildew; selecting potted wheat seedlings with consistent growth in two leaf periods as test host plants of wheat powdery mildew, and selecting potted corn seedlings with consistent growth in two leaf periods as test host plants of corn rust. Foliar spray treatments were carried out with the compounds of the present invention at the designed concentrations. And additionally arranging a blank control sprayed with clear water, repeating for 3 times, and performing disease inoculation the next day after treatment. After inoculation, the plants are placed in a climatic chamber for humid cultivation (temperature: 25 ℃ day, 20 ℃ night, relative humidity: 95-99%). After the test material is cultured for 24h, the test material is moved to a greenhouse for culture, and plants which do not need to be subjected to moisture-preserving culture are directly inoculated and cultured in the greenhouse. The control is taken to evaluate the disease prevention effect of the compound after full disease (usually a week). The results were examined with reference to the American society for Plant Diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
Some of the test results are as follows:
prevention effect on cucumber downy mildew:
of some tested compounds, the following compounds have better control effect at a concentration of 400ppm, for example, the control effect of compounds 4, 8, 15 and 17 on cucumber downy mildew is more than or equal to 80%.
In accordance with the above procedure, compounds 8 and 17 were selected and tested in parallel with the known compound KC for controlling cucumber downy mildew activity. The test results are shown in Table 2.
Table 2: comparison of the Effect of Compounds 8 and 17 of the present invention on controlling cucumber downy mildew with KC
Note: "-", not tested.
The prevention effect on wheat powdery mildew is as follows:
according to the method, the compound 1 and a known compound KC are selected to perform parallel determination of the activity of preventing and treating wheat powdery mildew. The test results are shown in Table 3.
Table 3: comparison of the Effect of Compound 1 of the present invention on the prevention of wheat powdery mildew with KC
The prevention effect on the corn rust disease is as follows:
among some tested compounds, the following compounds have good control effect at the concentration of 400ppm, for example, the control effect of the compounds 1, 4, 8, 15, 17, 20 and the like on corn rust is more than or equal to 80%.
The control effect on cucumber anthracnose is as follows:
in some tested compounds, the following compounds have good control effect when the concentration is 400ppm, for example, the control effect of the compounds 4 and 17 on cucumber anthracnose is more than or equal to 80%.
(2) In vitro test for bacteriostatic activity
The measurement method is as follows: a high-throughput screening method is adopted, namely a compound sample to be detected is prepared into a liquid to be detected with required concentration by using a proper solvent (the type of the solvent is acetone, methanol, DMF, and the like, and is selected according to the dissolving capacity of the solvent to the sample). Under an ultraclean working environment, adding the solution to be tested into micropores of a 96-hole culture plate, adding the pathogen propagule suspension into the micropore, placing the treated culture plate in a constant-temperature incubator for culture, and investigating after 24 hours. During investigation, the germination or growth condition of the pathogen propagules is visually observed, and the bacteriostatic activity of the compound is evaluated according to the germination or growth condition of the control treatment.
The results of the in vitro bacteriostatic activity (expressed as inhibition) test of some compounds are as follows:
rice blast germs:
among some tested compounds, the following compounds have better control effect at the concentration of 25ppm, for example, the inhibition rate of compound 15 and the like on rice blast germs is more than or equal to 80%.
Cucumber gray mold pathogen:
among some tested compounds, the following compounds have better control effect when the concentration is 25ppm, for example, the inhibition rate of the compound 15 and the like on the botrytis cinerea of cucumber is more than or equal to 80%.
The other compounds of the general formula I of the invention also have the corresponding action effects.
Claims (6)
1. A pyrazole amide compound characterized by: the compound is shown in a general formula I:
in the formula:
R1is selected from C1-C3Alkyl or C3-C6A cycloalkyl group;
R2is selected from C3-C8Alkyl or C3-C6A cycloalkyl group.
2. Pyrazole amide compounds according to claim 1, characterized in that: in the general formula I:
R1is selected from C1-C3An alkyl group;
R2is selected from C3-C8Alkyl or C3-C6A cycloalkyl group.
3. Pyrazole amide compounds according to claim 2, characterized in that: in the general formula I:
R1selected from methyl, ethyl or isopropyl;
R2selected from (1-methyl) ethyl, (1-methyl) propyl, (1-ethyl) ethyl, (1-ethyl) pentyl, (2-methyl) propyl, (2-methyl) butyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
4. Use of a pyrazole amide compound according to claim 1, wherein:
the application of the compound of the general formula I in preparing medicines for controlling plant diseases of non-treatment-purpose agriculture or forestry.
5. A germicidal composition, characterized by: the bactericidal composition takes the compound shown as the general formula I in claim 1 as an active component, and the weight content of the active component in the composition is 1-99%.
6. A method for controlling plant diseases by using the fungicidal composition according to claim 5, characterized in that: the fungicidal composition is applied to a target disease or a medium in which a target disease is growing at an effective dose of 10g to 1000 g per hectare.
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Citations (6)
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|---|---|---|---|---|
| JPS62249975A (en) * | 1986-04-22 | 1987-10-30 | Sumitomo Chem Co Ltd | Anilide derivative and germicide containing said derivative as active ingredient |
| CN101212899A (en) * | 2005-06-07 | 2008-07-02 | 拜尔农作物科学股份公司 | Carboxamides |
| CN103524418A (en) * | 2013-11-01 | 2014-01-22 | 青岛农业大学 | 3-methyl pyrazol compounds |
| CN104649973A (en) * | 2013-11-25 | 2015-05-27 | 中国中化股份有限公司 | Pyrazole amide compound and application thereof |
| CN105503727A (en) * | 2014-10-14 | 2016-04-20 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compounds and applications thereof |
| CN105646395A (en) * | 2014-12-02 | 2016-06-08 | 沈阳中化农药化工研发有限公司 | Thiazole amide compound and application thereof |
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- 2016-11-09 CN CN201610983987.2A patent/CN108069905B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62249975A (en) * | 1986-04-22 | 1987-10-30 | Sumitomo Chem Co Ltd | Anilide derivative and germicide containing said derivative as active ingredient |
| CN101212899A (en) * | 2005-06-07 | 2008-07-02 | 拜尔农作物科学股份公司 | Carboxamides |
| CN103524418A (en) * | 2013-11-01 | 2014-01-22 | 青岛农业大学 | 3-methyl pyrazol compounds |
| CN104649973A (en) * | 2013-11-25 | 2015-05-27 | 中国中化股份有限公司 | Pyrazole amide compound and application thereof |
| CN105503727A (en) * | 2014-10-14 | 2016-04-20 | 沈阳中化农药化工研发有限公司 | Pyrazole amide compounds and applications thereof |
| CN105646395A (en) * | 2014-12-02 | 2016-06-08 | 沈阳中化农药化工研发有限公司 | Thiazole amide compound and application thereof |
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