CN115894398B - Fluothiazole amide-containing insecticidal acaricide - Google Patents
Fluothiazole amide-containing insecticidal acaricide Download PDFInfo
- Publication number
- CN115894398B CN115894398B CN202211535668.7A CN202211535668A CN115894398B CN 115894398 B CN115894398 B CN 115894398B CN 202211535668 A CN202211535668 A CN 202211535668A CN 115894398 B CN115894398 B CN 115894398B
- Authority
- CN
- China
- Prior art keywords
- compound
- general formula
- mites
- amide
- fluorine
- 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
- 230000000895 acaricidal effect Effects 0.000 title claims abstract description 15
- 239000000642 acaricide Substances 0.000 title claims abstract description 8
- 230000000749 insecticidal effect Effects 0.000 title claims description 11
- 150000001408 amides Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 241000238876 Acari Species 0.000 claims abstract description 13
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 9
- -1 thiazole amide compound Chemical class 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims 1
- 230000002147 killing effect Effects 0.000 abstract description 15
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 241000500437 Plutella xylostella Species 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 241000344246 Tetranychus cinnabarinus Species 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 150000003557 thiazoles Chemical class 0.000 description 2
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 1
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 1
- VBLXCTYLWZJBKA-UHFFFAOYSA-N 2-(trifluoromethyl)aniline Chemical compound NC1=CC=CC=C1C(F)(F)F VBLXCTYLWZJBKA-UHFFFAOYSA-N 0.000 description 1
- PGOOBECODWQEAB-FIBGUPNXSA-N 2-[(2-chloro-1,3-thiazol-5-yl)methyl]-1-nitro-3-(trideuteriomethyl)guanidine Chemical compound [2H]C([2H])([2H])NC(N[N+]([O-])=O)=NCC1=CN=C(Cl)S1 PGOOBECODWQEAB-FIBGUPNXSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000011301 Brassica oleracea var capitata Nutrition 0.000 description 1
- 235000001169 Brassica oleracea var oleracea Nutrition 0.000 description 1
- 239000005888 Clothianidin Substances 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005940 Thiacloprid Substances 0.000 description 1
- 239000005941 Thiamethoxam Substances 0.000 description 1
- 240000006677 Vicia faba Species 0.000 description 1
- 235000010749 Vicia faba Nutrition 0.000 description 1
- 235000002098 Vicia faba var. major Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000447 pesticide residue Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- NWWZPOKUUAIXIW-FLIBITNWSA-N thiamethoxam Chemical compound [O-][N+](=O)\N=C/1N(C)COCN\1CC1=CN=C(Cl)S1 NWWZPOKUUAIXIW-FLIBITNWSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention provides a fluorine-containing thiazole amide compound, which has a structure shown in a general formula I:wherein R is:
Description
The invention belongs to the field of pesticides and acaricides in pesticides, and relates to a fluorine-containing thiazole amide type pesticide and acaricide for controlling pest mites in agriculture or forestry.
Background art the increasingly serious drug resistance of pest mites in agriculture causes that the control efficiency of the conventional pesticides is lower and lower, the duration is shortened, and a series of problems of larger and larger dosage, rising pesticide residues and the like are brought. Therefore, the development of novel insecticidal and acaricidal agents has necessity and urgency. Thiazole compounds have various biological activities, thiazole compounds are important insecticidal active compound types in the field of pesticide development, and common pesticides such as clothianidin, thiacloprid, thiamethoxam and the like are typical representatives of thiazole pesticides. In addition, fluorine atoms in pesticide molecules can obviously improve the fat solubility of the compound, reduce the hydrophilicity, further change the physicochemical property of the compound, and obviously change the electron distribution in the molecular structure, thereby influencing the structure-activity relationship of the compound and changing the biological activity of the compound. The compound is a series of fluorine-containing thiazole amide compounds which are formed by splicing fluorine-containing aromatic rings and thiazole rings, and the compound shown in the general formula I and the application thereof as agricultural insecticidal acaricide in the prior art are not disclosed. The invention aims to provide an insecticidal and acaricidal agent which has novel structure, simple and convenient synthesis method, safety and high efficiency and can be used for preventing and controlling agricultural or forestry pest mites.
The technical scheme of the invention is as follows:
a fluorine-containing thiazole amide compound has a structure shown in a general formula I:
wherein R is:
the compounds of the general formula I according to the invention can be prepared by the following processes:
wherein R is as defined above.
The specific preparation method is shown in the synthetic example of the invention. Table 1 shows the structure and appearance of the compounds of formula I.
TABLE 1 Structure and appearance of Compounds of general formula I
The invention has the advantages and positive effects that:
the compound (formula I) of the invention is used as agricultural insecticide and acaricide, and has the advantages of novel structure, simple synthesis, high efficacy and control of mites. The compound has good inhibiting and killing effects on plutella xylostella and tetranychus cinnabarinus, and can achieve the excellent effect of simultaneously controlling insect pest mites of agriculture and forestry. The compound has killing activity on plutella xylostella, wherein the killing rate of I-1, I-2 and I-3 reaches 100% and the killing rate of I-4 reaches 97% at the concentration of 100mg/L (see table 2). The compound has good inhibition and killing effect on tetranychus cinnabarinus, wherein the I-4 inhibition and killing effect is the best, and the killing rate reaches 100% at the concentration of 100mg/L (see table 3). The compound disclosed by the invention is a fluorine-containing thiazole amide compound, has the characteristics of high activity, low toxicity and good biocompatibility, is particularly suitable for preventing and controlling pesticide-resistant agricultural pest mites commonly existing at present, and has good development and application prospects as a novel variety of pesticides with the functions of killing insects and mites.
The compound can be used singly or in combination with other active substances to improve the comprehensive performance of the product when being used for preventing and controlling agricultural pests or mites.
The invention also comprises an insecticidal and acaricidal composition taking the compound shown in the general formula I as an active component, wherein the mass percentage of the active component in the composition is 1-99%. The insecticidal and acaricidal composition also comprises an agriculturally or forestry acceptable carrier.
It should be understood that various changes and modifications can be made within the scope of the present invention as defined in the appended claims.
Detailed Description
The following synthetic examples, green test results, are useful for further illustration of the invention and are not meant to limit the invention.
Synthesis example
Example 1 preparation of Compound I-1:
(1) Synthesis of intermediate 2- (2, 6-difluorophenyl) -4, 5-dihydro-1, 3-thiazole-4-carboxylic acid:
13.9g (0.1 mol) of 2, 6-difluorobenzonitrile, 18.15g (0.15 mol) of cysteine, 12.6g of sodium bicarbonate and 50g of ethanol are respectively added into a 250mL three-neck flask, the temperature is raised to reflux, the reaction is carried out for 4 hours, after the TLC monitoring reaction is finished, the solvent is removed, 100g of water is added, dilute hydrochloric acid is slowly added dropwise, the pH is regulated to about 5, and the white solid 23.5g is obtained through suction filtration and drying.
(2) Synthesis of I-1:
into a 500mL four-necked flask equipped with a mechanical stirring device, 24.3g (0.1 mol) of 2- (2, 6-difluorophenyl) -4, 5-dihydro-1, 3-thiazole-4-carboxylic acid, 14.8g (0.1 mol) of o-trifluoromethylaniline and 15.8g of pyridine were charged, and 150mL of acetonitrile was further added as a solvent to stir. Slowly dropwise adding 12.6g of methylsulfonyl chloride into a reaction system at room temperature, reacting for 4h at room temperature, monitoring by TLC (developing agent V (petroleum ether): V (ethyl acetate) =1:1), adding 100g of water after the reaction is complete, carrying out suction filtration, washing a filter cake with 20mL of deionized water for three times, and drying to obtain 37.9g of white solid, wherein the crude product yield is 98.2%.
I-2, I-3, I-4 were prepared in a similar manner.
Biological Activity test
Example 2 insecticidal Activity assay
(1) Plutella xylostella killing Activity assay
The specific implementation method is as follows: the test samples are mixed liquid medicine with the concentration of 500mg/L prepared by the compound and DMF, and then the mixed liquid medicine is diluted into liquid medicine with different concentration gradients by using 0.1% Tween-80. Cutting cabbage leaves into discs with uniform size and shape, soaking the discs into the prepared medicinal liquid with gradient concentration for 15-20s, taking out, repeating each concentration for three times, airing, and placing the leaves on filter paper wetted in a culture dish. And (3) placing 30 plutella xylostella larvae with the same growth state in a culture dish, controlling the temperature in the culture dish to 25 ℃, controlling the relative humidity to 60%, controlling the photoperiod to LD=16:8, and observing and recording the growth state of plutella xylostella. And when the culture time is 72 hours, counting the death number of the plutella xylostella larvae, wherein the result is the average value of three groups of experiments.
TABLE 2 results of Plutella xylostella killing Activity test of Compounds of general formula I
The test result shows that the compound has good killing activity on plutella xylostella, wherein the killing rate of I-1, I-2 and I-3 reaches 100% and the killing rate of I-4 reaches 97% at the concentration of 100 mg/L.
Example 3 acaricidal Activity assay
The mite killing activity test is carried out on the compound, the test method is a spray method, the test object is tetranychus cinnabarinus, and the specific operation method is as follows:
diluting the prepared 500mg/L medicinal liquid with 0.1% Tween-80 to obtain samples with different concentrations, adding into a Potter spray tower, and setting pressure to 1.47×10 5 And (5) MPa. 30 mites are inoculated on round broad bean leaves with the diameter of 5cm, and three groups are arranged for each concentration. Then placing the leaf blade with the mite in a Potter spray tower, spraying 1mL of liquid medicine, placing in a constant temperature incubator at 25 ℃ for culturing for 48 hours after spray treatment, observing and recording the death number of the tetranychus cinnabarinus, and calculating the death rate of the mites according to a formula.
TABLE 3 acaricidal Activity test results for Compounds of the general formula I
The test result shows that the compound has a good inhibition effect on tetranychus cinnabarinus, wherein the inhibition effect of I-4 is good and reaches 100% at the concentration of 100 mg/L.
Claims (3)
1. A fluorine-containing thiazole amide compound has a structure shown in a general formula I:
wherein R is: />
2. The use of a fluorine-containing thiazole amide compound according to claim 1, which is characterized in that the compound of the general formula I is used as an agricultural or forestry insecticidal acaricide and has a control effect on agricultural pest mites.
3. An insecticidal and acaricidal composition comprising a compound of the general formula i as defined in claim 1 as active ingredient and an agriculturally or forestry acceptable carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211535668.7A CN115894398B (en) | 2022-12-02 | 2022-12-02 | Fluothiazole amide-containing insecticidal acaricide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211535668.7A CN115894398B (en) | 2022-12-02 | 2022-12-02 | Fluothiazole amide-containing insecticidal acaricide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115894398A CN115894398A (en) | 2023-04-04 |
| CN115894398B true CN115894398B (en) | 2024-03-12 |
Family
ID=86483703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211535668.7A Active CN115894398B (en) | 2022-12-02 | 2022-12-02 | Fluothiazole amide-containing insecticidal acaricide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115894398B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143957A (en) * | 1994-01-24 | 1997-02-26 | 纳幕尔杜邦公司 | Arthropodicidal 2-oxa and thia-zolines |
| AU2005220705A1 (en) * | 2004-02-11 | 2005-09-22 | The Ohio State University Research Foundation | Analogs exhibiting inhibition of cell proliferation, methods of making, and uses thereof |
| CN114605298A (en) * | 2022-04-11 | 2022-06-10 | 青岛科技大学 | Fluorine-containing benzoyl thiourea insecticide and acaricide |
-
2022
- 2022-12-02 CN CN202211535668.7A patent/CN115894398B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143957A (en) * | 1994-01-24 | 1997-02-26 | 纳幕尔杜邦公司 | Arthropodicidal 2-oxa and thia-zolines |
| AU2005220705A1 (en) * | 2004-02-11 | 2005-09-22 | The Ohio State University Research Foundation | Analogs exhibiting inhibition of cell proliferation, methods of making, and uses thereof |
| CN114605298A (en) * | 2022-04-11 | 2022-06-10 | 青岛科技大学 | Fluorine-containing benzoyl thiourea insecticide and acaricide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115894398A (en) | 2023-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2692723B1 (en) | Aryloxy dihalopropenyl ether compound and use thereof | |
| CN109232550B (en) | 3-chloro-5-trifluoromethylpyridyl-1, 3, 4-oxadiazole-2-ketone compound and application thereof | |
| CN115894398B (en) | Fluothiazole amide-containing insecticidal acaricide | |
| CN108794462B (en) | Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent | |
| WO2017148226A1 (en) | Fluorobenzoxazole compound and use thereof | |
| HUT56053A (en) | Process for producing derivatives of butiric acid, and insecticide compositions containing them | |
| JP2884425B2 (en) | Insecticidal composition for agricultural use | |
| CN114656402B (en) | Fluorine-containing nicotinoyl urea compound and application thereof | |
| CN109988149B (en) | Pyrazole amide compound with insecticidal activity and application thereof | |
| CN108329263B (en) | 1, 8-naphthalimide amide compound and application thereof | |
| KR100574351B1 (en) | Fungicidal composition for agriculture and horticulture having a 4-quinolinone derivative | |
| CN114805197B (en) | Fluorinated pyridine acyl urea insecticide and acaricide | |
| CN111187214B (en) | Fluorobenzene bishydrazide azole compound and application thereof | |
| CN114644596B (en) | Fluoropyrimidine aromatic amine compound and application thereof | |
| JP2001172270A (en) | 5-carboxanilide-2,4-bis-trifluoromethyl-thiazole | |
| AU2021101116A4 (en) | Fluorobenzobishydrazide azole compound and use thereof | |
| KR100613690B1 (en) | 4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same | |
| WO2019128872A1 (en) | Pyrazole amide compound having pesticidal activity and use thereof | |
| CN108912114B (en) | 1,2, 4-oxadiazole insecticide containing o-benzoylsulfonylimido | |
| CN116589430A (en) | Fluorine-containing amide thiazolidine ester compound and application thereof | |
| CN108822082B (en) | Fluorine-containing pyridine piperazine amide compound and application thereof | |
| KR20090024394A (en) | Synthesis of new fluoroaromatic formamidines and their biological activity | |
| KR100613688B1 (en) | 2-amino-4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same | |
| CN115745878A (en) | Fluorine-containing pyridine bisamide insecticide and acaricide | |
| CN114773388A (en) | Novel isoxazole derivative and application thereof |
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 |