CN105859688B - The synthesis and its application of the pyridylpyrazole derivatives of the ring containing imidazolidine - Google Patents
The synthesis and its application of the pyridylpyrazole derivatives of the ring containing imidazolidine Download PDFInfo
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- CN105859688B CN105859688B CN201610263880.0A CN201610263880A CN105859688B CN 105859688 B CN105859688 B CN 105859688B CN 201610263880 A CN201610263880 A CN 201610263880A CN 105859688 B CN105859688 B CN 105859688B
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- Prior art keywords
- cucumber
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- ring containing
- imidazolidine
- pyridylpyrazole
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Classifications
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- 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
- C07D401/14—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 three or more hetero rings
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
-
- 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
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
Abstract
The present invention relates to the preparation and application as led to the pyridylpyrazole derivatives of the ring containing imidazolidine shown in formula (I), such compound represents a kind of insecticidal bactericide structure type of broad-spectrum high efficacy.The pyridylpyrazole derivatives of the ring containing imidazolidine are used as new type disinsection fungicide can prevent oriental armyworm, diamondback moth, beet armyworm well；Also perform well in preventing Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, cucumber fusarium axysporum, cucumber downy mildew, powdery mildew of cucumber, bacterial spot of tomato, rice sheath blight disease very much.R in formula1、R2、R3Meaning see specification.
Description
One, technical field
Answering in terms of the present invention relates to the pyridylpyrazole derivatives of the ring containing imidazolidine and its as insecticide and fungicide
With category technical field of pesticide.
Two, background technology
Anabasine insecticide is the desinsection that another major class is important after organophosphor, carbamate and pyrethroid
Agent.It acts on insect CNS, efficient, selective to mammalian safe, and between traditional pesticide not
There are cross resistances.The 1980s mid-term, Japanese pesticide and Beyer Co., Ltd have developed first anabasine insecticide
Imidacloprid, and be commercialized in 1991.Due to imidacloprid have the novel mode of action, high-efficiency broad spectrum, selectivity it is good, to environment
The features such as friendly, in the world some big pesticide companies focus onto the research of nicotinoids in succession, become desinsection
One big hot spot of agent exploitation.By to the transformation of such compound functional group and structure activity study, developing a series of tools in succession
There is the ultra high efficiency anabasine insecticide of new type heterocycle structure.The anabasine insecticide being commercialized at present has 7：Pyrrole worm
Quinoline (imidacloprid), Diacloden (thiamethoxam), thiacloprid (thiacloprid), dinotefuran
(dinotefuran), Acetamiprid (acetamiprid), Nitenpyram (nitenpyram), clothianidin (clothianidin).
In recent years, field of agrochemicals achieves breakthrough by the research and development of target insecticide of ryanodine receptor.
Japanese pesticide company, Beyer Co., Ltd and E.I.Du Pont Company are found that two class high activity insecticides-phthalic diamides and neighbour respectively
Formamido group benzamides, this is to find to act on the synthetic pesticide of target ryanodine receptor for the first time, it is by inducing elder brother
The activation of worm ryanodine receptor makes endogenous Ca store discharge, and then leads to insect death.This insecticides shows efficient, wide
Spectrum, to non-target organism safety and the features such as with conventional pesticides no interactions resistance.
Chlorantraniliprole (chlorantraniliprole), the bromo- N- of chemical name 3- [4- chloro-2-methyl -6- [(methylaminos
Formoxyl) benzene] -1- (3- chloropyridine -2- bases) -1H- pyrazoles -5- formamides, trade name health is wide (Ryanxypyr).It is the U.S.
A kind of Novel ortho formamido benzamide insecticides that E.I.Du Pont Company developed belong to insect ryanodine receptor inhibitor,
With tagging and stomach poison function, show efficiently, wide spectrum, novel holding effect and the mechanism of action the features such as, can be used for preventing each fruit scale
Wing mesh pest, control effect is substantially better than the other commercialization insecticide varieties used in current production, to other insecticides
There is no cross resistances, and to natural enemy insect safety, can be used for the crops such as vegetables, beet, cotton prevention beet armyworm, wild cabbage night
The various pests such as moth, diamondback moth, cabbage butterfly, bollworm have good control effect to each instar larvae.It is currently ryania
The hot spot of receptor insecticides research.
The ryanodine receptor insecticides being commercialized at present have with three：
Three, invention content
The object of the present invention is to provide the pyridylpyrazole derivatives of one kind ring containing imidazolidine and its application, such compounds
With excellent desinsection, bactericidal activity.
The present invention is the preparation and application of the pyridylpyrazole derivatives of the ring containing imidazolidine shown in logical formula (I)：
In formula, R1Represent nitro or cyano；R2Represent that hydrogen, halogen, 1-6 carbon alkyl, one or more are identical or different
Halogen atom substitution alkyl；R3Represent halogen, substituted or unsubstituted alkoxy, alkenyloxy group, alkynyloxy group, cycloalkyloxy.
The pyridylpyrazole derivatives for the ring containing imidazolidine that the present invention narrates can be prepared as follows：Intermediate 3 and 5
It is prepared by ethylenediamine and the reaction of corresponding raw material 1 or 4.The intermediate 6 accordingly replaced is reacted with intermediate 3 or 5 is made mesh
Mark leads to the pyridylpyrazole derivatives of the ring containing imidazolidine of formula (I).
Compound 1,4 and 6 is commercially available or is prepared by known method.
The present invention can also be illustrated with the compound that table 1 is listed, but not limit the present invention.
There is the compound that the present invention leads to formula (I) excellent bactericidal and insecticidal activity can be used to prevent squama wing as insecticide
Mesh class, coleoptera class, Homoptera class, Diptera class and Orthoptera class pest；As fungicide, can be used to prevent cucumber foxiness
Disease, cucumber bacterial angular leaf spot, cucumber fusarium axysporum, cucumber downy mildew, powdery mildew of cucumber, bacterial spot of tomato, rice line
Blight.
The compound that the present invention leads to formula (I) can be used directly, can also be added the carrier agriculturally received and be used, also may be used
With with the bactericide compounded use of other types insecticide.
Four, specific implementation mode
It further illustrates the present invention with reference to embodiments：
Embodiment one：The synthesis of intermediate N nitro imido imidazolyl alkane
The synthesis of intermediate 3：Ethylenediamine (1.44g, 0.024mol) is dissolved in 2mL chloroforms, instill compound 1 (3.32g,
In chloroformic solution 0.02mol), 25-27 DEG C is maintained the temperature at, after 3h, remove most of solvent, obtain white solid, filter, use
Ether washs (2 × 5mL), dry N- nitro imido imidazolyl alkane 2.42g, yield 93.2%, m.p.215-217 DEG C,1H
NMR(DMSO-d6, 400MHz) δ：7.66 (s, br, 2H, NH), 3.42~3.49 (m, 4H, CH2CH2).
Embodiment two：The synthesis of intermediate N cyanoimino imidazolidine
The synthesis of intermediate 5：Ethylenediamine (1.44g, 0.024mol) is dissolved in 2mL chloroforms, instill compound 4 (2.92g,
In chloroformic solution 0.02mol), 25-27 DEG C is maintained the temperature at, after 3h, remove most of solvent, obtain white solid, filter, use
Ether washs (2 × 5mL), dry N- cyanoimino imidazolidine 2.17g, yield 98.9%, m.p.205-206 DEG C,1H
NMR(DMSO-d6, 400MHz) and δ：7.68 (s, br, 2H, NH), 3.46 (m, 4H, CH2CH2).
Embodiment three：Logical formula (I) compound synthesis
6 (1.0mmol) of acid are dissolved in 20mL dichloromethane, oxalyl chloride (0.38g, 3mmol) and two drop DMF is added.Reaction
Mixture removes solvent under reduced pressure and obtains crude acid chloride in room temperature reaction 3h.Intermediate 3 or 5 (1.0mmol) is dissolved in 20mL acetonitriles,
Anhydrous potassium carbonate 1.5mmol is added, stirs 10min at room temperature.Crude acid chloride is dissolved in 10mL acetonitriles, is slowly dropped into upper liquid, is dripped
Finish, is warming up to reflux, reacts and terminate after 5h, it is cooling, acetonitrile is removed, dichloromethane (80mL) is added, then respectively with saturation chlorine
Change sodium water solution (20mL) and water (50mL) washs organic layer, anhydrous Na2SO4Dry, filtering, filtrate concentration, residue is through silica gel
Chromatographic column reduced pressure chromatography, eluent are ethyl acetate and petroleum ether mixed solvent, obtain the compound of logical formula (I), specific chemical combination
Object is shown in Table 1.
Pyridylpyrazole derivatives (I) list of 1 ring containing imidazolidine of table
aThe value of HRMS[M+Na]+.
Example IV：Biological activity test
It is tested, is verified to pest biological evaluation using derivative provided by the invention (I-1~I-28)：
Any derivative (I-1~I-28) provided by the invention is dissolved in solvent, water and surfactant, is mixed into
Uniform water phase, when use, are diluted with water to any desired concentration, and test object and test method are as follows：
1) to the biological evaluation of oriental armyworm：It is oriental armyworm (Mythimna separata for examination insect
Walker), the normal population of indoor maize leaves raising.Using leaf dipping method, dipping Maize Seedling leaf is in configured good solution
In, it is put into after drying in diameter 7cm culture dishes, accesses 4 instar larvaes, each concentration is repeated 3 times；Control acetone soln impregnates beautiful
Rice leaf breeding grub；Test result is observed after 24 hours, 48 hours, 72 hours；
2) to the biological evaluation of diamondback moth：It is 2 instar larvae of diamondback moth (Plutella xylostella for examination insect
(L.)), it is the indoor normal population normally raised；Using leaf dipping method, cabbage leaves are impregnated in configured good solution with tweezers
In, time 2--3 second, get rid of extraction raffinate；1 tablet once, totally 3, each sample；After liquid is dry, it is put into the straight type test tube of 10cm long
It is interior, 2 age diamondback moth larvaes are accessed, nozzle is covered with gauze；Test process is placed in standard process chamber, 24 hours, 48 hours,
Test result is observed after 72 hours；
3) to the biological evaluation of beet armyworm：It is 3 instar larvae of beet armyworm (Laphygma exigua for examination insect
Hubner), it is the indoor normal population normally raised；Using leaf dipping method, with tweezers dipping cabbage leaves in configured good molten
In liquid, time 2--3 second, extraction raffinate is got rid of；1 tablet once, totally 3, each sample；After liquid is dry, it is put into diameter 7cm culture dishes
In, 3 instar larvae of beet armyworm is accessed, test process is placed in standard process chamber, is observed after 24 hours, 48 hours, 72 hours
Test result；
The results are shown in Table 2 for the partial test of above-mentioned experiment.
Table 2
Mortality levels in table：A grades are 100%-90%；B grades are 90%-70%；C grades are 70%-50%；D grades are
50%-0%.
Embodiment seven：Prevent the experiment of vegetable disease live body microscreen
2 cotyledon period cucumber seedlings are selected, Cucumber Target Leaf Spot, powdery mildew, downy mildew use spore suspension spray inoculation, yellow
Melon bacterial angular leaf spot, bacterial spot of tomato use bacteria suspension spray inoculation, cucumber fusarium axysporum disease to be connect using radicle seed soaking
Kind method, rice sheath blight disease use mycelia spray inoculation method.Reagent agent and comparison medicament are uniformly sprayed in the fine day morning
In cucumber cotyledons, pathogen, moisturizing culture are inoculated with after 2 hours.Wait for that control fully after the onset according to grade scale, investigates the state of an illness,
Calculate disease index and preventive effect.Table 3 is the test result of part of compounds.
3 part of compounds of table prevents vegetable disease live body microscreen test result (500mg kg-1)
Claims (3)
1. a kind of pyridylpyrazole derivatives of ring containing imidazolidine, it is characterised in that it has structure shown in logical formula (I) as follows：
In formula, R1For nitro or cyano；R2For hydrogen, chlorine；R3For chlorine, bromine, methoxyl group, ethyoxyl, isopropoxy, allyloxy, alkynes
Propoxyl group, trifluoro ethoxy.
2. the application of the pyridylpyrazole derivatives of the ring according to claim 1 containing imidazolidine, it is characterised in that its conduct
Insecticide can be used to prevent Lepidoptera class, coleoptera class, Homoptera class, Diptera class and Orthoptera class pest.
3. the application of the pyridylpyrazole derivatives of the ring according to claim 1 containing imidazolidine, it is characterised in that its conduct
Fungicide can be used to prevent Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, cucumber fusarium axysporum, cucumber downy mildew, cucumber white powder
Disease, bacterial spot of tomato, rice sheath blight disease.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742060A (en) * | 1985-02-04 | 1988-05-03 | Nihon Tokushu Noyaku Seizo K. K. | Heterocyclic compounds |
| US4880933A (en) * | 1986-12-19 | 1989-11-14 | Nihon Tokushu Noyaku Seizo K.K. | Nitro- or cyano-derivatives of 2-imino-imidazolines and 2-imino-tetrahydropyrimidines |
| CN103172613A (en) * | 2013-01-05 | 2013-06-26 | 南开大学 | O-formylamino benzamide derivative containing N-cyano sulfone(sulfur) imine and preparation method and use thereof |
-
2016
- 2016-04-21 CN CN201610263880.0A patent/CN105859688B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742060A (en) * | 1985-02-04 | 1988-05-03 | Nihon Tokushu Noyaku Seizo K. K. | Heterocyclic compounds |
| US4880933A (en) * | 1986-12-19 | 1989-11-14 | Nihon Tokushu Noyaku Seizo K.K. | Nitro- or cyano-derivatives of 2-imino-imidazolines and 2-imino-tetrahydropyrimidines |
| CN103172613A (en) * | 2013-01-05 | 2013-06-26 | 南开大学 | O-formylamino benzamide derivative containing N-cyano sulfone(sulfur) imine and preparation method and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| (反)-β-法尼烯类似物的电子结构及构效关系;龚珍奇等;《农药》;20090228;102-104,15 * |
| 基于Ugi 反应的新型鱼尼丁受体杀虫剂的设计、合成及生物活性;刘鹏飞等;《高等学校化学学报》;20120430;738-743 * |
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