CN108794461A - One kind oxadiazole containing fluorobenzene connects pyrazoles insecticidal bactericide - Google Patents
One kind oxadiazole containing fluorobenzene connects pyrazoles insecticidal bactericide Download PDFInfo
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- CN108794461A CN108794461A CN201810754684.2A CN201810754684A CN108794461A CN 108794461 A CN108794461 A CN 108794461A CN 201810754684 A CN201810754684 A CN 201810754684A CN 108794461 A CN108794461 A CN 108794461A
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- pyrazoles
- oxadiazole
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- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 13
- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 13
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 150000003217 pyrazoles Chemical class 0.000 title abstract description 8
- 239000003899 bactericide agent Substances 0.000 title abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- -1 pyrazole compound Chemical class 0.000 claims description 11
- 230000000855 fungicidal effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000417 fungicide Substances 0.000 claims description 3
- 239000000575 pesticide Substances 0.000 claims description 2
- 241000607479 Yersinia pestis Species 0.000 abstract description 4
- 241000233866 Fungi Species 0.000 abstract description 3
- 241000238631 Hexapoda Species 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 241000894006 Bacteria Species 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 241000256247 Spodoptera exigua Species 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 3
- 241000223195 Fusarium graminearum Species 0.000 description 3
- 244000284380 Hibiscus rosa sinensis Species 0.000 description 3
- 241001281805 Pseudoperonospora cubensis Species 0.000 description 3
- 235000000664 Rosa chinensis Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000008359 benzonitriles Chemical class 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000857 drug effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000005645 nematicide Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- HOKWHGYUNYFNTP-UHFFFAOYSA-N 2,2-difluoroethoxybenzene Chemical compound FC(F)COC1=CC=CC=C1 HOKWHGYUNYFNTP-UHFFFAOYSA-N 0.000 description 2
- 241000222201 Colletotrichum capsici Species 0.000 description 2
- 241000813090 Rhizoctonia solani Species 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- IHNSIFFSNUQGQN-UHFFFAOYSA-N tioxazafen Chemical compound C1=CSC(C=2ON=C(N=2)C=2C=CC=CC=2)=C1 IHNSIFFSNUQGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GRRIYLZJLGTQJX-UHFFFAOYSA-N 1,2-dibenzoylhydrazine Chemical compound C=1C=CC=CC=1C(=O)NNC(=O)C1=CC=CC=C1 GRRIYLZJLGTQJX-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical class OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 description 1
- RQWSZANLCIPBIY-UHFFFAOYSA-N 2-(2,2-difluoroethoxy)benzonitrile Chemical compound FC(F)COC1=CC=CC=C1C#N RQWSZANLCIPBIY-UHFFFAOYSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 241000193738 Bacillus anthracis Species 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
- 0 CCc1n[n](C)c(-c2nc(-c3ccccc3*)n[o]2)c1Cl Chemical compound CCc1n[n](C)c(-c2nc(-c3ccccc3*)n[o]2)c1Cl 0.000 description 1
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 1
- 241000255581 Drosophila <fruit fly, genus> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 241000244206 Nematoda Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 241001503951 Phoma Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 210000003705 ribosome Anatomy 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
- C07D413/04—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 directly linked by a ring-member-to-ring-member bond
-
- 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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- 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)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention provides one kind oxadiazole containing fluorobenzene and connects pyrazoles insecticidal bactericide, and structure is shown in formula I：
Description
The invention belongs to agricultural chemical insecticides and fungicide field for technical field, and in particular to a kind of oxadiazole containing fluorobenzene
Even pyrazoles insecticidal bactericide.
Background technology Monsanto in 2013 develops new and effective nematicide thiophene and phenyl substitution oxadiazole classes
Object Tioxazafen (compound II) is closed, with the completely new mechanism of action, is played by interfering by nematode is ribosomal active
Drug effect (Slomczynska U, South M S, Bunkers G J, et al.Tioxazafen:A New Broad-
Spectrum Seed Treatment Nematicide [M], Discovery and Synthesis of Crop
Protection Products, 2015.).1988, Idoux et al. proposed a series of Evil bis- containing halogenated alkoxyl phenyl
Azole compounds, such as 2- (2,4- dichlorophenyl) -5- (4- (1,1,2,2- tetrafluoro ethyoxyl) phenyl) -1,3,4- oxadiazoles (are changed
Close object III) have insecticidal action, when Drug level be 100mg/L when, kill drosophila activity value be 100% [Idoux J P,
Gibbsrein K S,Gupton J T,et al.Synthesis and insecticidal activity of some 2,
5-(fluoroalkoxyphenyl)-1,3,4-oxadiazoles and their N,N'-dibenzoyl hydrazine
precursors[J].Journal of Chemical&Engineering Data,1988,33(3):385-388.].Document
[Wang,Wen-yan,Nankai University.Syntheses of 1,3,4-Thia(oxa)diazole-
Substituted Pyrazole Derivatives and Their Fungicidal Activities [J] institutions of higher education
Chemical research (English edition), 2004,20 (5):543-547] report the oxadiazole class compound of pyrazoles substitution to day phoma hibernica
Bacterium has certain inhibiting effect.The present invention introduces 1,2,4- by active group splicing, by active group substituted pyrazolecarboxylic base
On the positions oxadiazole 5-, difluoroethoxy benzene is introduced on 1,2, the 4- positions oxadiazole 3-, structure compound as shown in formula I is obtained,
In the prior art, it is not disclosed to be used as agriculture and forestry nematicide for compound of formula I as representative of the present invention.
The purpose of the present invention is to provide the low one kind of a kind of structure novel, efficient, safety, cost accounting for invention content
Oxadiazole containing fluorobenzene connects pyrazoles agricultural insecticidal fungicide.
Technical scheme is as follows：
One kind oxadiazole containing fluorobenzene connects pyrazole compound, and structure is as shown in I：
Compound of formula I can be by reacting preparation as follows：
Compound 4 (adjacent difluoroethoxy cyanophenyl) reacted with hydroxylamine hydrochloride generate compound 3, compound 3 again with compound 5
(the chloro- 5- pyrazol formyl chlorides of 1- methyl -3- ethyls -4-) reaction generates compound 2, and Formulas I is made in reflux in toluene in compound 2
Close object.Specific preparation method is shown in that this specification synthesizes example.
Formula Compound I has good insecticidal effect through insecticidal test, to beet armyworm and diamondback moth, to rice line
Blight bacterium, Colletotrichum capsici, fusarium graminearum and Chinese rose Pseudoperonospora cubensis have a good inhibiting effect, therefore the invention also includes
Type I compound is used for the purposes of agriculture and forestry insect pest fungus damage prevention.
Advantages of the present invention and good effect：
The compounds of this invention is a kind of pyrazoles 1,2,4- oxadiazole compounds of substitution of brand new, is contained in its structure
Oxadiazole, pyrazoles, difluoro ethoxyphenyl structure, due to containing-OCH in the compounds of this invention2CHF2Group increases fat-soluble
And permeability, its uptake and translocation effect is significantly improved, to improve its drug effect；Due in molecule simultaneously Han You oxadiazoles and
Pyrrazole structure so that the compound has desinsection and bactericidal effect simultaneously, plays the dual-purpose effect of a medicine, while drawing into oxadiazole
With the heterocycles pharmacophoric group such as pyrazoles, action site is increased, is beneficial to increase drug effect and broad spectrum activity, be influenced by pest resistance small.
The compounds of this invention synthesis material is easy to get, and synthesis technology is simple, is not necessarily to high temperature and pressure and special installation, and " three wastes " are generated in production
Few, yield is higher, and production cost is low.The compounds of this invention is heterocyclic nitrogen compound, is had to people, animal and beneficial organism low toxicity
Property, feature degradable, Environmental compatibility is good, have as formulating property insecticidal bactericide new varieties industrialization foreground and commodity
The potentiality of change.
Insecticidal and bactericidal composition the invention also includes compound of formula I as active component further includes agriculture in the composition
Acceptable carrier in industry.
The compounds of this invention can be used alone in pest control fungus damage, can also be used with other active compounds,
In favor of improving the integrated control performance of this product.
The composition of the compounds of this invention can be made reagent application, the compounds of this invention be scattered in as active component or
It is dissolved in carrier or solvent, adds suitable surfactant that suspending agent, microemulsion, missible oil and aqueous emulsion etc. is made.
It should be appreciated that in the limited range of claim of the present invention, various changes and transformation can be carried out.
Specific implementation mode：
It synthesizes example below and raw test result can be used to further illustrate the present invention, but be not intended to limit this hair
It is bright.
Synthesize example
The preparation of example 1, compound of formula I
(1) synthesis of 2- (2,2- difluoroethoxies) benzonitriles (compound 4)
Addition 0.1mol (11.9g) salicylonitrile into the three-necked flask of 250mL, 0.105mol (14.49g) potassium carbonate,
100mL DMF make solvent.Stirring, is warming up to 80 DEG C, with the dropping funel of 50mL by 0.12mol (19.2g) 2,2- difluoroethanols
Methanesulfonate ester slowly instills in reaction bulb in batches, is stirred to react 4h.Reaction solution is poured into 500mL flasks, 1% hydrogen is added
Sodium hydroxide solution 100mL washings, wash away the complete a small amount of salicylonitrile of unreacted, and 100mL ethyl acetate extraction product, liquid separation is added
Retain organic phase, then use 3 × 100mL saturated common salt water washings again, liquid separation dries organic phase with anhydrous sodium sulfate, decompression
Solvent is evaporated off, obtains pale yellowish oil liquid 2- (2,2- difluoroethoxy) benzonitrile 17.1g, yield 93.4% is (with salicylonitrile
Meter).
(2) synthesis of compound 3
100mL ethyl alcohol, three second of 13.8g (0.2mol) hydroxylamine hydrochlorides and 20g (0.2mol) are added into 250mL three-necked flasks
Amine is heated to 50-60 DEG C of reaction 1h, free hydrochloric acid azanol.4 (adjacent difluoroethoxy benzene of 22g compounds is added after 1h into flask
Nitrile), temperature rising reflux reacts 2h, and TLC detection compounds 4 disappear, and revolving removes ethyl alcohol, and 150mL water is added into flask, dissolve three second
Amine hydrochlorate, residue filter, and filter cake is compound 3, and white solid, yield 90% are obtained after drying.
(2) synthesis of compound 2
10.8g (0.05mol) compound 3 is added into 250mL round-bottomed flasks, 100mL ethyl acetate is added, room temperature is added dropwise
10.35g (0.05mol) compound 5 (the chloro- 5- pyrazol formyl chlorides of 1- methyl -3- ethyls -4-) after being added dropwise, reacts 3h, TLC
Detection compound 3 disappears, and vacuum distillation removes ethyl acetate, obtains faint yellow solid 2, yield 91%.
(3) synthesis of compound of formula I
3.87g (0.01mol) compound 2 is added into 250mL round-bottomed flasks, 80mL toluene is added, flow back 3h, TLC inspections
It surveys compound 2 to disappear, vacuum distillation removes toluene, obtains faint yellow solid compound of formula I, yield 90.5%.
The nuclear-magnetism and melting point data of compound of formula I：1H-NMR (500MHz, DMSO)：δ/ppm 1.21~1.24 (t, 3H),
2.63~2.68 (q, 2H), 4.22 (s, 3H), 4.45~4.52 (m, 2H), 6.31~6.54 (m, 1H), 7.22~7.25 (m,
1H), 7.34~7.36 (d, 1H), 7.60~7.64 (m, 1H), 8.00~8.02 (m, 1H).Fusing point：137~139 DEG C.
Biological activity determination
(1) medicament is prepared：
It by compound of formula I dmso solution, is then diluted, is configured to required dense with 1 ‰ Tween 80 aqueous solution
50 milliliters of the prepare liquid of degree, content of the dimethyl sulfoxide (DMSO) in total solution are no more than 10%.
(2) insecticidal activity assay
Using invade leaf method measure herein synthesize compound bioactivity.With diamondback moth (Plutella xylostella
Linnaeus), beet armyworm (Beet armyworm) is test object, is divided into two groups, and blank control is arranged.Choose growing way
Consistent cabbage leaves impregnate 10s in the medicament prepared, and drying liquid is taken out with tweezers, are put down successively in clean in sequence
It is spread out on plate.Blade is transferred in the ranked good culture dish containing moisturizing filter paper after drying, is implanted into each culture dish
The similar 2 age beet armyworm of upgrowth situation 30, and it is placed on raising, photoperiod L in constant incubator (25 ± 1 DEG C):D=
16:8, relative humidity 60% checks the death condition of beet armyworm after 48h, and records dead number.3 repeated experiments are made even
Mean value, calculates corrected mortality, and calculation formula (1) is as follows：
In formula：P1--- the death rate, unit are percentage (%)；K --- indicate dead borer population；N --- indicate that processing is total
Borer population.
What it is to the implantation of the test of pesticide effectiveness of diamondback moth is both 2 instars, and experimental method is identical as above-mentioned steps.With compound III
As a contrast, test result is listed in table 1.
Biologically active data of 1 compound of formula I of table to beet armyworm and diamondback moth
(3) bactericidal activity measures
The bactericidal effect of compound is measured using Plating.With Rhizoctonia solani Kuhn (Rhizoctonia solani), peppery
Green pepper anthrax bacteria (Colletotrichum capsici), fusarium graminearum (Gibberella zeae), Chinese rose Pseudoperonospora cubensis
Four kinds of mycelia are test object, are divided into four groups, and blank control is arranged.1mL liquids are drawn, sterilizing culture has been melted in injection in advance
It in the sterile conical flask of base, fully shakes up, then equivalent is poured into the culture dish of 3 a diameter of 9cm, and a concentration of 50 μ g/L are made
Drug containing tablet, be arranged 3 times repetition test, that no medicament is used in combination does same treatment as blank control.It will be above cultured
Pathogen aseptically uses the sterilization punchers of diameter 5mm, cuts bacteria cake from colony edge, be inoculated in and contained with inoculator
Medicine tablet center, mycelia is face-up, covers culture ware lid, culture dish is put in the constant incubator of (24 ± 1) DEG C and is trained
It supports.Calliper colony diameter is used after 72h, is respectively measured once using crossing method diameter, is surveyed its average diameter.According to experiment
As a result, calculating different agents to the mycelial growth inhibition rate for trying target bacterium by formula (1), (2).
D=D1-D2··················(1)
In formula：D-bacterium colony increases diameter；D1--- colony diameter；D2--- bacteria cake diameter.
In formula：I --- mycelial growth inhibition rate；D0--- blank control bacterium colony increases diameter；Dt--- chemicals treatment bacterium colony
Increase diameter.
As a result it is listed in table 2.
The biologically active data of 2 four kinds of germs of compound pair of table
As seen from the data in Table 2, compound of formula I has bactericidal effect, especially excellent to Chinese rose Pseudoperonospora cubensis bactericidal effect.
Claims (4)
1. a kind of oxadiazole containing fluorobenzene connects pyrazole compound, structure is shown in formula I：
2. a kind of oxadiazole containing fluorobenzene according to claim 1 connects the purposes of pyrazole compound, it is characterised in that Formulas I
Compound is used as agricultural or pesticide for forestry.
3. a kind of oxadiazole containing fluorobenzene according to claim 1 connects the purposes of pyrazole compound, it is characterised in that Formulas I
Compound is used as agricultural or forestry fungicide.
4. a kind of insecticidal and bactericidal composition is in active component and agricultural or forestry containing compound of formula I described in claim 1
Acceptable carrier.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114920734A (en) * | 2022-06-02 | 2022-08-19 | 浙江工业大学 | 5- (pyrazole-5-yl) -1,2, 4-oxadiazole substituted benzamide compounds and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| WO2017012970A2 (en) * | 2015-07-17 | 2017-01-26 | Syngenta Participations Ag | Pesticidally active pyrazole derivatives |
| CN106459000A (en) * | 2014-04-02 | 2017-02-22 | 拜耳作物科学股份公司 | Novel 3-[(pyrazol-5-yl)-heteroaryl]-benzamide derivatives |
| CN107056773A (en) * | 2017-04-24 | 2017-08-18 | 贵州大学 | Pyrazoles Lian Evil containing pyridiniujm（Thiophene）Diazoles compound and preparation method and application |
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| CN106459000A (en) * | 2014-04-02 | 2017-02-22 | 拜耳作物科学股份公司 | Novel 3-[(pyrazol-5-yl)-heteroaryl]-benzamide derivatives |
| WO2017012970A2 (en) * | 2015-07-17 | 2017-01-26 | Syngenta Participations Ag | Pesticidally active pyrazole derivatives |
| CN107056773A (en) * | 2017-04-24 | 2017-08-18 | 贵州大学 | Pyrazoles Lian Evil containing pyridiniujm（Thiophene）Diazoles compound and preparation method and application |
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| CN114920734A (en) * | 2022-06-02 | 2022-08-19 | 浙江工业大学 | 5- (pyrazole-5-yl) -1,2, 4-oxadiazole substituted benzamide compounds and preparation method and application thereof |
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