CN108794462B - Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent - Google Patents
Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent Download PDFInfo
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- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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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
- A01N43/82—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 three ring hetero atoms
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Abstract
The invention provides an oxadiazole insecticidal bactericide containing fluorine cyanimide thiazolidine, which has a structure shown as a formula I:
Description
The invention belongs to the field of pesticide and bactericide, and particularly relates to an oxadiazole insecticidal bactericide substituted by fluorine-containing cyanimine thiazolidine.
Background Art in 2013, Monsanta developed a New and highly effective Nematicide, thiophene and phenyl substituted oxadiazole compounds, Tioxazafen (Compound II), which had a completely New mechanism of action and exerted its potency by interfering with the activity of nematode ribosomes (Slomczynska U, South M S, Bunkers G J, et al.Tioxazafen: A New Broad-Spectrum Seed Treatment New [ M ], Discovery and Synthesis of Crop Protection Products, 2015.). Thiacloprid (Thiacloprid) (compound III) is a novel chloronicotinyl insecticide developed by the cooperation of germany bayer agrichemical and japan bayer agrichemical. According to the invention, an active group cyanoimine thiazolidine is introduced to the 5-position of 1,2, 4-oxadiazole and difluoroethoxyphenyl is introduced to the 3-position of 1,2, 4-oxadiazole through an active group splicing technology to obtain a compound with a structure shown in a formula I.
The invention aims to provide the fluorine-containing cyanoimine thiazolidine substituted oxadiazole insecticidal bactericide which is novel in structure, efficient, safe and low in prevention and treatment cost.
The technical scheme of the invention is as follows:
a fluorine-containing cyanoimine thiazolidine substituted oxadiazole compound has a structure shown as I:
the compounds of formula I can be prepared by the following reaction:
and heating the intermediate compound shown in the formula IV and the compound shown in the formula V in DMF by taking potassium carbonate as an acid-binding agent to 80 ℃, and reacting for 4 hours to obtain the compound shown in the formula I. The specific preparation method is shown in the synthesis example of the specification.
The compound of the formula I has excellent insecticidal effect on asparagus caterpillars and diamond back moths and has good inhibition effect on rice sheath blight bacteria, pepper anthracnose bacteria, wheat scab bacteria and Chinese rose downy mildew bacteria through insecticidal tests, so the invention also comprises the application of the compound of the formula I in preventing and treating the pests and the bacterial damage of agriculture and forestry.
The invention has the advantages and positive effects that:
the compound of the invention is a pyrazole substituted 1,2, 4-oxadiazole compound with a brand new structure, the structure of the compound contains oxadiazole, cyanoimine thiazolidine and difluoroethoxyphenyl structures, and the molecule contains oxadiazole and cyanoimine thiazolidine structures simultaneously, so that the compound has insecticidal and bactericidal effects at the same time, has dual-purpose efficacy as one medicine, introduces heterocyclic pharmacophores such as oxadiazole and cyanoimine thiazolidine and the like, increases the action sites, is beneficial to increasing the efficacy and the broad spectrum, has small influence on pest resistance,the insecticidal composition shows unexpected ultrahigh killing activity to pests with strong resistance to asparagus caterpillars and diamond back moths; because the compound of the invention contains-OCH2CHF2The group increases fat solubility and permeability, and remarkably improves the suction conduction effect, thereby improving the drug effect. The compound has the advantages of easily obtained synthetic raw materials, simple synthetic process, no need of high temperature and high pressure and special equipment, less generation of three wastes in production, higher yield and low production cost. The compound of the invention is a nitrogen heterocyclic compound, has the characteristics of low toxicity to people, livestock and beneficial organisms, easy degradation and good environmental compatibility, and has the industrialization prospect and the commercialization potential as a new variety of creative insecticides.
The invention also comprises the insecticidal and bactericidal composition with the compound shown in the formula I as an active component, and the composition also comprises an agriculturally acceptable carrier.
The compound of the invention can be used alone or in combination with other active compounds when preventing and controlling insect pests and bacterial pests, so as to be beneficial to improving the comprehensive prevention and control performance of the product.
The compound composition can be prepared into a reagent for application, and the compound of the invention is taken as an active component to be dispersed or dissolved in a carrier or a solvent, and is added with a proper surfactant to be prepared into a suspending agent, a microemulsion, missible oil, an aqueous emulsion and the like.
It should be understood that various changes and modifications may be made within the scope of the present invention as defined by the claims.
The specific implementation mode is as follows:
the following synthetic examples and results of biological tests are provided to further illustrate the invention, but are not meant to limit the invention.
Synthesis examples
Example 1 preparation of Compounds of formula I
(1) Synthesis of 2- (2, 2-difluoroethoxy) benzonitrile
A250 mL three-necked flask was charged with 0.1mol (11.9g) of salicylanitrile, 0.105mol (14.49g) of potassium carbonate, and 100mL of DMF as a solvent. After stirring and warming to 80 ℃, 0.12mol (19.2g) of 2, 2-difluoroethanol methylsulfonate was slowly added dropwise to the flask via a 50mL dropping funnel, and the mixture was stirred for 4 hours. The reaction solution was poured into a 500mL flask, 100mL of 1% sodium hydroxide solution was added and washed, a small amount of unreacted salicylaldehyde was washed away, 100mL of ethyl acetate was added to extract the product, the organic phase was separated and retained, and then washed with 3 × 100mL of saturated brine, separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 17.1g of 2- (2, 2-difluoroethoxy) benzonitrile as a pale yellow oily liquid in 93.4% yield (based on the salicylaldehyde).
(2) Synthesis of intermediate 2- (2, 2-difluoroethoxy) -N' -hydroxybenzamidine
Adding 0.19mol (13.21g) of hydroxylamine hydrochloride, 0.2mol (20.2g) of triethylamine and 100mL of ethanol as a solvent into a 250mL three-necked flask, heating and refluxing for half an hour, adding 0.1mol (18.3g) of 2- (2, 2-difluoroethoxy) benzonitrile, stirring and refluxing for four hours, detecting that the 2- (2, 2-difluoroethoxy) benzonitrile has disappeared by TLC (thin layer chromatography), evaporating the ethanol to dryness, adding 200mL of ethyl acetate, extracting the product into an organic phase, performing suction filtration to remove the triethylamine, performing rotary pressure reduction on the filtrate to remove the ethyl acetate to obtain an oily product, recrystallizing with petroleum ether and ethyl acetate 10:1 to obtain an off-white crystal of 18.59g of 2- (2, 2-difluoroethoxy) -N' -hydroxybenzamidine, wherein the yield is 85.6%, and the melting point is 89-92 ℃.
(3) Synthesis of N' - (2-chloroacetyloxy) -2- (2, 2-difluoroethoxy) benzamidine
A250 mL three-necked flask was charged with 0.02mol (4.32g) of 2- (2, 2-difluoroethoxy) -N' -hydroxybenzamidine, 50mL of ethyl acetate as a solvent, and 0.022mol (2.2g) of triethylamine as an acid-binding agent, the flask was placed in an ice-water bath, stirred, 0.02mol (2.24g) of acetyl chloride was diluted with 50mL of ethyl acetate, and slowly dropped with a 100mL dropping funnel, and reacted for 2 hours after completion of dropping. TLC tracking till the point of 2-ethoxy-N-hydroxy-benzamidine disappears, suction filtering, collecting filtrate, evaporating filtrate to dryness by rotation to obtain oily product, and recrystallizing to obtain 5.5g of N' - (2-chloroethanoyloxy) -2- (2, 2-difluoroethoxy) benzamidine, wherein the yield is 94.1%, and the melting point is 81-84 ℃.
(4) Synthesis of 5- (chloromethyl) -3- (2- (2, 2-difluoroethoxy) phenyl) -1,2, 4-oxadiazole
0.02mol (5.85g) of N' - (2-chloroethanoyloxy) -2- (2, 2-difluoroethoxy) benzamidine and 100mL of toluene are added into a 250mL three-neck flask as a solvent, the mixture is heated to reflux, reacted for 2h, TLC (thin layer chromatography) is tracked until the raw material point disappears, the toluene solvent is evaporated under reduced pressure to obtain 6.4g of brown yellow oily matter, a small amount of methanol is added for recrystallization to obtain 5.03g of white solid 5- (chloromethyl) -3- (2- (2, 2-difluoroethoxy) phenyl) -1,2, 4-oxadiazole, the yield is 91.6%, and the melting point is 80-83 ℃.
(5) Synthesis of Compounds of formula I
Adding 0.01mol (1.28g) of 2-cyanoimino-1, 3-thiazolidine into a 250mL three-necked bottle, taking 100mL DMF as a solvent, taking 0.011mol (1.52g) of potassium carbonate as an acid-binding agent, heating to 80 ℃, stirring for half an hour, adding 0.01mol (2.73g) of 5- (chloromethyl) -3- (2- (2, 2-difluoroethoxy) phenyl) -1,2, 4-oxadiazole, keeping the temperature for reaction for 4 hours, tracking by TLC until the raw material point disappears, cooling to room temperature, adding 100mL of water, continuing stirring, separating out a solid, performing suction filtration to obtain a crude product, recrystallizing by using methanol to obtain a compound [5- ((2-cyanoimino-1, 3-thiazolyl) methyl) -3- (2- (2, 2-difluoroethoxy) phenyl-1 of the formula I, 2, 4-oxadiazoles]3.0g, yield 82.1% and melting point 168-171 ℃.1H NMR(500MHz，DMSO-d6)，δ(ppm)：3.42～3.45(t，2H)，4.16～4.18(t，2H)，4.21～4.27(m，2H)，5.06(s，2H)，6.20～6.41(m，1H)，7.21～7.23(t，1H)，7.34～7.37(d，1H)，7.50～7.53(m，1H)，7.87～7.89(d，1H).
Biological activity assay
(1) Preparing a medicament:
dissolving the compound of the formula I in dimethyl sulfoxide, diluting with 1 ‰ tween 80 water solution to obtain 50ml of solution to be tested with required concentration, wherein the content of dimethyl sulfoxide in the total solution is not more than 10%.
(2) Determination of insecticidal Activity
The biological activity of the compounds synthesized herein was determined using the leaf-invasion method. Diamondback moth (Plutella xylostella Linnaeus) and Beet armyworm (Beet armyworm) were used as test subjects, and divided into two groups, and blank controls were set. Soaking cabbage leaves with consistent growth in the prepared medicament for 10s, taking out the liquid medicament by using tweezers, and spreading the liquid medicament on a clean flat plate in sequence. After air drying, the leaves are transferred to culture dishes which are well sorted and contain moisturizing filter paper, 30 heads of 2-year-old beet armyworms with similar growth conditions are planted in each culture dish, the culture dishes are placed in a constant-temperature incubator (25 +/-1 ℃) for breeding, the death condition of the beet armyworms is checked after 48 hours when the photoperiod L: D is 16:8 and the relative humidity is 60%, and the death number is recorded. The experiment was repeated 3 times, and the corrected mortality was calculated by taking the average, as shown in equation (1):
in the formula: p1Mortality in percent (%); k-represents dead number of insects; n-represents the total number of insects treated.
The efficacy test of the diamondback moth is carried out by the same 2-year-old moth, and the experimental method is the same as the steps. The results of the test are given in Table 1, using Compound III as a control.
TABLE 1 biological Activity data of Compounds of formula I against beet armyworm and diamondback moth
As can be seen from the data in Table 1, the compound of formula I shows ultrahigh killing activity to beet armyworm and diamondback moth, which is superior to the control drug thiacloprid.
(3) Measurement of fungicidal Activity
The bactericidal effect of the compounds was determined by the plate method. Four hyphae of rice sheath blight (Rhizoctonia solani), pepper anthracnose (Colletotrichum capsicii), wheat gibberellic disease (Gibberella zeae) and Chinese rose downy mildew are taken as test objects and divided into four groups, and blank controls are set. Sucking 1mL of liquid medicine, injecting into a sterile conical flask in which a sterilized culture medium is melted in advance, shaking up sufficiently, then pouring into 3 culture dishes with the diameter of 9cm in equal amount to prepare a medicine-containing flat plate with the concentration of 50 mug/L, setting 3 times of repeated experiments, and using the same treatment without medicine as a blank control. The above cultured pathogenic bacteria are sterilized by a sterilizing perforator with diameter of 5mm under aseptic condition, the bacterial cake is cut from the edge of bacterial colony, inoculated to the center of the drug-containing plate by an inoculator, the hypha face is upward, the cover of the culture dish is closed, and the culture dish is placed in a constant temperature incubator at (24 +/-1) DEG C for culture. After 72h, the diameter of the colonies was measured with a caliper, and the average diameter was measured once for each diameter by the cross method. And (3) according to the experimental result, calculating the hypha growth inhibition rate of different medicaments on the target bacteria to be tested according to the formulas (1) and (2).
D＝D1-D2…………………………………………………(1)
In the formula: d, colony growing diameter; d1-colony diameter; d2-the diameter of the cake.
In the formula: i-hypha growth inhibition rate; d0-growing the diameter of the blank colony; dtMedicament-treated colonies grow in diameter.
The results are shown in Table 2.
TABLE 2 biological Activity data of the Compounds against four pathogens
As can be seen from the data in Table 2, the compounds of formula I have a fungicidal action.
Claims (4)
1. An oxadiazole compound substituted by thiazolidine containing fluorine cyanimide has a structure shown as a formula I:
2. use of a fluorochemical cyanimide thiazolidine substituted oxadiazole compound for non-disease therapeutic purposes according to claim 1 as an agricultural or forestry insecticide.
3. The use of a fluorochemical cyanoimine thiazolidine substituted oxadiazole compound for non-disease therapeutic purposes according to claim 1 wherein the compound of formula I is used as an agricultural or forestry fungicide.
4. An insecticidal and fungicidal composition comprising the compound of formula I as claimed in claim 1 as an active ingredient and an agriculturally or forestry acceptable carrier.
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| CN111675704B (en) * | 2020-06-23 | 2022-11-01 | 南通大学 | 2-substituent imidazole alkane compound containing oxadiazole heterocyclic structure and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010032874A1 (en) * | 2008-09-19 | 2010-03-25 | 住友化学株式会社 | Composition for agricultural use |
| CN103539716A (en) * | 2013-10-31 | 2014-01-29 | 青岛农业大学 | One group of 2-para chlorphenyl-4-substituted methyl-5- trifluoromethyl-3-cyanpyrrole compounds |
| CN107674070A (en) * | 2017-09-19 | 2018-02-09 | 华南农业大学 | A kind of cyano group imines thiazolidine furoyl amine compound and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010032874A1 (en) * | 2008-09-19 | 2010-03-25 | 住友化学株式会社 | Composition for agricultural use |
| CN103539716A (en) * | 2013-10-31 | 2014-01-29 | 青岛农业大学 | One group of 2-para chlorphenyl-4-substituted methyl-5- trifluoromethyl-3-cyanpyrrole compounds |
| CN107674070A (en) * | 2017-09-19 | 2018-02-09 | 华南农业大学 | A kind of cyano group imines thiazolidine furoyl amine compound and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "Synthesis, Bioactivities and CrystalStructure of (Z)-N-(3-((2-(4-chlorophenyl)-oxazol-4-yl)methyl)thiazolidin-2-ylidene)cyanamide";LIU Shao-Hua et al.;《Chinese J. Struct. Chem.》;20130630;第32卷(第6期);第931-935页 * |
| "新型取代苯基噁唑类化合物的设计、合成及生物活性";刘少华 等;《高等学校化学学报》;20140228;第35卷(第2期);第281-285页 * |
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