CN108794462A - A kind of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class insecticidal bactericides - Google Patents
A kind of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class insecticidal bactericides Download PDFInfo
- Publication number
- CN108794462A CN108794462A CN201810755325.9A CN201810755325A CN108794462A CN 108794462 A CN108794462 A CN 108794462A CN 201810755325 A CN201810755325 A CN 201810755325A CN 108794462 A CN108794462 A CN 108794462A
- Authority
- CN
- China
- Prior art keywords
- formula
- thiazolidine
- compound
- fluorine
- substitution
- 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.)
- Granted
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 12
- 230000000749 insecticidal effect Effects 0.000 title claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 9
- 239000011737 fluorine Substances 0.000 title claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 title claims abstract description 8
- 150000004866 oxadiazoles Chemical class 0.000 title abstract description 7
- 239000003899 bactericide agent Substances 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- -1 oxadiazole class compounds Chemical class 0.000 claims description 11
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 claims description 6
- 150000002466 imines Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 230000000855 fungicidal effect Effects 0.000 claims description 2
- 239000000417 fungicide Substances 0.000 claims description 2
- 239000000575 pesticide Substances 0.000 claims description 2
- 241000256247 Spodoptera exigua Species 0.000 abstract description 9
- 241000500437 Plutella xylostella Species 0.000 abstract description 8
- 241000607479 Yersinia pestis Species 0.000 abstract description 5
- 241000223195 Fusarium graminearum Species 0.000 abstract description 4
- 241000222201 Colletotrichum capsici Species 0.000 abstract description 3
- 241000233866 Fungi Species 0.000 abstract description 3
- 241001281805 Pseudoperonospora cubensis Species 0.000 abstract description 3
- 241000813090 Rhizoctonia solani Species 0.000 abstract description 3
- 235000000664 Rosa chinensis Nutrition 0.000 abstract description 3
- 241000238631 Hexapoda Species 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 241000196324 Embryophyta Species 0.000 abstract 1
- 240000008254 Rosa chinensis Species 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000003814 drug Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HOKKPVIRMVDYPB-UVTDQMKNSA-N (Z)-thiacloprid Chemical compound C1=NC(Cl)=CC=C1CN1C(=N/C#N)/SCC1 HOKKPVIRMVDYPB-UVTDQMKNSA-N 0.000 description 3
- RQWSZANLCIPBIY-UHFFFAOYSA-N 2-(2,2-difluoroethoxy)benzonitrile Chemical compound FC(F)COC1=CC=CC=C1C#N RQWSZANLCIPBIY-UHFFFAOYSA-N 0.000 description 3
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000005940 Thiacloprid Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000857 drug effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- MMNYBVHUMNYQNA-UHFFFAOYSA-N 5-(chloromethyl)-3-[2-(2,2-difluoroethoxy)phenyl]-1,2,4-oxadiazole Chemical compound ClCC1=NC(=NO1)C1=C(C=CC=C1)OCC(F)F MMNYBVHUMNYQNA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 244000284380 Hibiscus rosa sinensis Species 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical compound NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 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 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000009036 growth inhibition Effects 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000005645 nematicide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000000126 substance Substances 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
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005071 1,2,4-oxadiazoles Chemical class 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- 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
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical class ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 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
- 241000244206 Nematoda Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 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
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 239000000284 extract 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
- 239000005457 ice water Substances 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
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 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
- 239000003208 petroleum Substances 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
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 210000003705 ribosome Anatomy 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
-
- 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
Landscapes
- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The present invention provides a kind of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class insecticidal bactericides, 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 fluorine-containing cyanogen imines thiazole
Alkane replaces oxadiazole class insecticidal bactericides.
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.).Thiacloprid (Thiacloprid) (compound III) is by Bayer Bitterfeld GmbH agro-chemical companies
With the novel chloro nicotinic insecticide of Japanese Bayer agro-chemical companies cooperative development.The present invention by active group splicing,
Active group cyanogen imines thiazolidine is introduced on 1,2, the 4- positions oxadiazole 5-, difluoroethoxy phenyl is introduced into 1,2,4- oxadiazoles
On the positions 3-, structure compound as shown in formula I is obtained, in the prior art, compound of formula I as representative of the present invention is used as agriculture and forestry
Insecticidal bactericide is not disclosed.
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
Fluorine-containing cyanogen imines thiazolidine replaces oxadiazole class insecticidal bactericides.
Technical scheme is as follows：
A kind of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole compounds, structure is as shown in I：
Compound of formula I can be by reacting preparation as follows：
Intermediate formula IV compound is warming up to 80 DEG C in DMF with Formula V compound by acid binding agent of potassium carbonate, reacts 4h systems
Obtain compound of formula I.Specific preparation method is shown in that this specification synthesizes example.
Formula Compound I has beet armyworm and diamondback moth excellent insecticidal effect through insecticidal test, 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, cyanogen imines thiazolidine, difluoro ethoxyphenyl structure, due in molecule simultaneously Han You oxadiazoles and cyanogen imines thiazolidine knot
Structure so that the compound has desinsection and bactericidal effect simultaneously, plays the dual-purpose effect of a medicine, while drawing sub- into oxadiazole and cyanogen
The heterocycles pharmacophoric group such as amine thiazolidine, increases action site, is beneficial to increase drug effect and broad spectrum activity, be influenced by pest resistance
It is small, unexpected superelevation killing activity is shown to the pest of beet armyworm and diamondback moth resistance；Due to chemical combination of the present invention
Contain-OCH in object2CHF2Group increases fat-soluble and permeability, significantly improves its uptake and translocation effect, to improve
Its drug effect.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, is produced in production
Raw " three wastes " are few, and yield is higher, and production cost is low.The compounds of this invention is heterocyclic nitrogen compound, is had to people, animal and beneficial
Biological hypotoxicity, feature degradable, Environmental compatibility is good, have as initiative property insecticide new varieties industrialization foreground with
The potentiality of commercialization.
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) benzonitrile
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 intermediate 2- (2,2- difluoroethoxies)-N'- hydroxyl benzenecarboximidamides
The hydroxylamine hydrochloride of addition 0.19mol (13.21g) into the three-necked flask of 250mL, 0.2mol (20.2g) triethylamine,
100mL ethyl alcohol makees solvent, is heated to reflux half an hour, adds 0.1mol (18.3g) 2- (2,2- difluoroethoxy) benzonitrile, stirring
Reflux four hours, TLC detects that 2- (2,2- difluoroethoxy) benzonitrile point disappears, ethyl alcohol is evaporated, and 200mL acetic acid second is added
Ester extracts product in organic phase, filters removal triethylamine, and filtrate decompression rotates ethyl acetate, obtains oil product, uses
Petroleum ether:Ethyl acetate 10:1 recrystallization, obtains beige crystals 2- (2,2- difluoroethoxy)-N'- hydroxyl benzenecarboximidamides
18.59g, yield 85.6%, 89~92 DEG C of fusing point.
(3) synthesis of N'- (2- chloroethenes acyloxy) -2- (2,2- difluoroethoxies) benzenecarboximidamide
0.02mol (4.32g) 2- (2,2- difluoroethoxies)-N'- hydroxy benzenes first is added into the three-necked flask of 250mL
Amidine, 50mL ethyl acetate make solvent, and 0.022mol (2.2g) triethylamine does acid binding agent, reaction bulb is placed in ice-water bath, stirring,
0.02mol (2.24g) chloroacetic chlorides 50mL ethyl acetate is diluted, is slowly instilled with the dropping funel of 100mL, after dripping off
React 2h.The point that TLC tracks to 2- ethyoxyl-N- hydroxy-benzamidines disappears, and filters, and collects filtrate revolving and does, obtains oily production
Object is recrystallized to give N'- (2- chloroethenes acyloxy) -2- (2,2- difluoroethoxy) benzenecarboximidamide 5.5g, yield 94.1%, fusing point 81
~84 DEG C.
(4) synthesis of 5- (chloromethyl) -3- (2- (2,2- difluoroethoxies) phenyl) -1,2,4- oxadiazoles
0.02mol (5.85g) N'- (2- chloroethenes acyloxy) -2- (2,2- difluoro second is added into the three-necked flask of 250mL
Oxygroup) benzenecarboximidamide, 100mL toluene makees solvent, is heated to flowing back, and reacts 2h, and TLC tracks to raw material point disappearance, and vacuum rotary steam is dry
Toluene solvant obtains pale tan oil 6.4g, and a small amount of recrystallizing methanol is added, and obtains white solid 5- (chloromethyl) -3- (2-
(2,2- difluoroethoxy) phenyl) -1,2,4- oxadiazole 5.03g, yield 91.6%, 80~83 DEG C of fusing point.
(5) synthesis of compound of formula I
0.01mol (1.28g) 2- cyanoiminos -1,3-thiazoles alkane, 100mL DMF are added into the there-necked flask of 250mL
Solvent is made, 0.011mol (1.52g) potassium carbonate does acid binding agent, is warming up to 80 DEG C, stirs half an hour, adds 0.01mol
(2.73g) 5- (chloromethyl) -3- (2- (2,2- difluoroethoxy) phenyl) -1,2,4- oxadiazoles, insulation reaction 4h, TLC tracking
It disappears, is cooled to room temperature to raw material point, 100mL water is added and continues to stir, there is solid precipitation, filters, crude product is obtained, with methanol weight
Crystallization, obtains compound of formula I [5- ((2- cyanoiminos -1,3-thiazoles base) methyl) -3- (2- (2,2- difluoroethoxy) phenyl -
1,2,4- oxadiazole] 3.0g, yield 82.1%, 168~171 DEG C of fusing point.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 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
As seen from the data in Table 1, compound of formula I shows superelevation killing activity to beet armyworm and diamondback moth, better than control
Medicine thiacloprid.
(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.
Claims (4)
1. a kind of fluorine-containing cyanogen imines thiazolidine replaces oxadiazole class compounds, structure shown in formula I：
2. a kind of purposes of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class compounds according to claim 1, special
Sign is that compound of formula I is used as agricultural or pesticide for forestry.
3. a kind of purposes of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class compounds according to claim 1, special
Sign is that compound of formula I 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810755325.9A CN108794462B (en) | 2018-07-11 | 2018-07-11 | Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810755325.9A CN108794462B (en) | 2018-07-11 | 2018-07-11 | Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108794462A true CN108794462A (en) | 2018-11-13 |
| CN108794462B CN108794462B (en) | 2021-02-19 |
Family
ID=64074775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810755325.9A Active CN108794462B (en) | 2018-07-11 | 2018-07-11 | Oxadiazole insecticidal bactericide containing fluorine cyanimine thiazolidine substituent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108794462B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635397A (en) * | 2020-06-23 | 2020-09-08 | 南通大学 | Preparation and application of 3- (4-trifluoromethylphenyl) -1,2, 4-oxadiazole derivative containing five-membered nitrogen heterocycle |
| CN111675704A (en) * | 2020-06-23 | 2020-09-18 | 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 |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-07-11 CN CN201810755325.9A patent/CN108794462B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| LIU SHAO-HUA ET AL.: ""Synthesis, Bioactivities and CrystalStructure of (Z)-N-(3-((2-(4-chlorophenyl)-oxazol-4-yl)methyl)thiazolidin-2-ylidene)cyanamide"", 《CHINESE J. STRUCT. CHEM.》 * |
| 刘少华 等: ""新型取代苯基噁唑类化合物的设计、合成及生物活性"", 《高等学校化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635397A (en) * | 2020-06-23 | 2020-09-08 | 南通大学 | Preparation and application of 3- (4-trifluoromethylphenyl) -1,2, 4-oxadiazole derivative containing five-membered nitrogen heterocycle |
| CN111675704A (en) * | 2020-06-23 | 2020-09-18 | 南通大学 | 2-substituent imidazole alkane compound containing oxadiazole heterocyclic structure and preparation method and application thereof |
| CN111635397B (en) * | 2020-06-23 | 2022-10-25 | 南通大学 | Preparation and application of 3- (4-trifluoromethylphenyl) -1,2,4-oxadiazole derivative containing five-membered nitrogen heterocycle |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108794462B (en) | 2021-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| UA89546C2 (en) | N-thio-anthranilamid compounds, process for the preparation thereof, their use and method for control of parasites, method for plant protection, method for treatment of animals, composition and process for the preparation thereof | |
| CN101827817B (en) | Saturated and insaturated bi- or tricyclic aryloxyacetamide derivatives and their use as fungicides | |
| CN102276596B (en) | Thiadiazole compound as well as preparation and application thereof | |
| CN109320471B (en) | 3- (2, 6-difluorophenyl) -1,2, 4-oxadiazole compound and application thereof | |
| KR20020063277A (en) | Trifluoromethylpyrrole carboxamides and trifluoromethylpyrrolethioamides as fungicides | |
| CN108794462A (en) | A kind of fluorine-containing cyanogen imines thiazolidine substitution oxadiazole class insecticidal bactericides | |
| CN106432081B (en) | Preparation method and application of pyrazole oxime ether compound containing 4-chloro-3-ethyl-1-methylpyrazole structure | |
| CN108191786B (en) | 2, 5-substituent-1, 3, 4-oxadiazole disulfone derivative, preparation method and application thereof | |
| CN108341808A (en) | Yi Zhong oxadiazoles connect pyrazole compound and application thereof | |
| CN110372622A (en) | Phenyl acetanides containing chiral oxazoline and the purposes as disinfectant use in agriculture | |
| CN108794461B (en) | Fluorine-containing phenyl oxadiazole pyrazole insecticidal bactericide | |
| CN109232534B (en) | Heterocyclic diarylamine-containing pyrazole formamide compound and preparation method and application thereof | |
| CN107629012A (en) | The carboxylic acid bisamide class compound of azophenlyene 1 and its application | |
| CN108117528B (en) | 2, 5-substituent-1, 3, 4-oxadiazole sulfone derivative, preparation method and application thereof | |
| CN108912114A (en) | A kind of 1,2,4- oxadiazole insecticides of the base containing o-benzoic sulfimide | |
| CN104910092B (en) | The contraposition of 4 phenyl contains aldoxime ether structure oxazoline compounds and its preparation and the application in terms of worm mite Juncao is prevented and treated | |
| CN102002018B (en) | (2-oxo-benzothiazole)-3-diacetyl hydrazone compound as well as preparation method and application thereof | |
| JPS6117570A (en) | Pyridazinone derivative, its preparation and insecticidal, miticidal and bactericidal agent | |
| CN111187214B (en) | Fluorobenzene bishydrazide azole compound and application thereof | |
| EP0459660A2 (en) | Halopropargyl compounds and the use thereof as microbicides | |
| CN104557691B (en) | A kind of 3 amine acyl bishydrazide derivatives and its preparation method and application | |
| CN105153177B (en) | Furans and chroman oxime alkene/propargyl ether and preparation method and application | |
| CN111454202A (en) | Heteroaryl formanilide compound containing pentafluorothio and preparation method and application thereof | |
| CN111574507B (en) | Compound containing natural butenolide skeleton, preparation and application thereof | |
| CN114957123B (en) | 3- (difluoromethyl) -pyrazole-4-carboxylic ester derivative and preparation method 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 |