CN107298652A - Propylene ether dihalide compound and its preparation and application - Google Patents
Propylene ether dihalide compound and its preparation and application Download PDFInfo
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- CN107298652A CN107298652A CN201610231967.XA CN201610231967A CN107298652A CN 107298652 A CN107298652 A CN 107298652A CN 201610231967 A CN201610231967 A CN 201610231967A CN 107298652 A CN107298652 A CN 107298652A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
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Abstract
The invention discloses the propylene ether dihalide compound shown in formula (I) and its preparation and application.Q, R, R in formula1、R2、R3、R4、R5, n, v have given in specification define.Formula (I) compound of the present invention has desinsection and/or sterilization bioactivity, especially has very high activity to insects such as mythimna separata, diamondback moths.
Description
Technical field
The invention belongs to desinsection, bactericide field, and in particular to the propylene ether dihalide with desinsection, sterilization bioactivity
Compound and preparation method thereof, the desinsection containing the compound, microbicide compositions and with these compounds control insect,
The purposes and method of harmful levels of pathogens.
Background technology
Insect, harmful levels of pathogens preventing and treating it is extremely important during high-efficiency agriculture is realized.Insect, harmful levels of pathogens simultaneously
Preventing and treating woods, herd, in the field such as secondary, fishing and public health it is also critically important.Although in the market prevent by many insects, harmful levels of pathogens
Medicament is controlled, but is due to continuous expansion, external insect and harmful levels of pathogens, insect, the resistance of harmful levels of pathogens, the medicine in market
The problems such as service life, economy of medicine and people to the pay attention to day by day of environment, it is necessary to scientists are constantly studied, and then
Develop compatible new efficient, safety, economy, environment and desinsection with the different modes of action, bactericide new varieties.
Propylene ether dihalide compound has insecticidal bioactivity, and SUMITOMO CHEMICAL company is in JP 09194418 and US
The propylene ether dihalide compound with insecticidal activity is disclosed in 5922880, and new killing of being therefrom found that shown in formula (i)
Worm agent-Pyridalyl.Pyridalyl has very high activity to most lepidoptera pest, can also be risen with various medicaments mixture
To synergistic effect.Studied by the structure-activity relationship to such compound, Sumitomo company draws the trifluoromethyl on pyridine ring
Be such compound have very well activity required for.
To obtain new and effective propylene halide class compound, we have designed and synthesized not according to early-stage Study result
See shown in the formula (I) of document report that there is insect, the propylene ether dihalide compound of harmful levels of pathogens activity, wherein some chemical combination
Thing not only has excellent insecticidal activity, but also with bactericidal activity.
The content of the invention
The invention provides the propylene ether dihalide chemical combination with bioactivity such as insect, harmful levels of pathogens shown in formula (I)
Thing and its isomers：
Wherein：
I.Q is selected from following group：
R ' is same or different, and represents hydrogen, halogen, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxy,
C1-C4Halogenated alkoxy；M represents 0,1,2,3 or 4；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, C1-C4Alkyl, C1-C4Alkyl halide
Base, C1-C4Alkoxy, C1-C4Halogenated alkoxy；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group,
C1-C6Alkylamino radical, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Chain
Alkenyl amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkyne
Base amido, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl
Amido, two C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkenyl, alkynyl group,
In phenyl hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen, C1-C6Alkane
Base, C1-C6Haloalkyl, C1-C6Alkyl oxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group；
IV.n represents 0,1,2 or 3；V represents 0 or 1；
In the definition of compound (I) given above, also it is used in compound word, represents no matter term used is used alone
Following substituent：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or undersaturated cycloalkyl；
Alkenyl；Refer to straight or branched and double bond can be there are on any position；
Alkynyl group；Refer to straight or branched and three keys can be there are on any position；
Halo：Refer to hydrogen moiety therein or can all be replaced by halogen atom.
Currently preferred compound is：In formula (I)：
I.Q is selected from Q1 or Q4, R ' it is same or different, and represent hydrogen, halogen, C1-C3Alkyl, C1-C3Alkyl halide
Base；M represents 0,1 or 2；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, methyl, trifluoromethyl；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group,
C1-C6Alkylamino radical, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Chain
Alkenyl amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkyne
Base amido, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl
Amido, two C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkenyl, alkynyl group,
In phenyl hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen, C1-C6Alkane
Base, C1-C6Haloalkyl, C1-C6Alkyl oxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group；
IV.n represents 0,1 or 2；V represents 0 or 1.
The further preferred compound of the present invention is：In formula (I)：
I.Q is selected from Q1 or Q4, R ' it is same or different, and represent hydrogen, halogen, methyl, trifluoromethyl；M represents 0,1
Or 2；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, methyl, trifluoromethyl；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group,
C1-C6Alkylamino radical, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkyne
Base, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy,
C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkene
In base, alkynyl group, phenyl hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen
Element, C1-C3Alkyl, C1-C3Haloalkyl, C1-C3Alkyl oxy, C1-C3Halogenated alkoxy；
IV.n represents 0,1 or 2；V represents 0 or 1.
Formula (I) compound specifically preferred according to the invention is compound as follows：
The compound of the present invention can the forms of one or more isomers exist.Isomers includes enantiomter, non-
Enantiomter, geometric isomer.Compound as shown in formula (I) of the present invention, because carbon therein-carbon double bond connection is different
Substituent and geometric isomer (different configurations is represented with Z and E respectively) can be formed, the present invention include Z-type isomers and E
The mixture of type isomers and their any ratios.Compound shown in formula (I) of the present invention, due to one of carbon atom
Upper to connect four different substituents and form stereoisomer (representing different configurations respectively with R and S), the present invention includes R
The mixture of type isomers and S types isomers and their any ratios.
The invention further relates to a kind of pest control, formula (I) compound containing biologic effective dose of harmful levels of pathogens and at least
A kind of other composition selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of pest control, formula (I) compound containing biologic effective dose of harmful levels of pathogens and effectively
At least one other bioactive compound of amount or the composition of preparation.
The invention further relates to a kind of method of pest control, harmful levels of pathogens, including by formula (I) compound of biologic effective dose
Contact insect, harmful levels of pathogens or its environment.Also relate to such a insect, harmful levels of pathogens prevention and controls, insect, have and fall ill
Formula (I) compound of bacterium or its environment biologic effective dose or at least one containing formula (I) compound and biologic effective dose are another
Outer compound or the mixture of preparation, which are contacted, comes pest control, harmful levels of pathogens.
Formula (I) compound of the present invention has broad spectrum of activity：Some compounds can be used for pest control, it may also be used for preventing and treating
Harmful levels of pathogens；And the compound having has very high bioactivity to some target pests so that under very low dosage just
Good effect can be obtained.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent
The method for selecting compound.
The part formula (I) compound listed below with table 1 further illustrates the present invention, but does not limit the present invention.This
Fusing point is not calibrated given in invention, and when formula (I) compound synthesized by the present invention is viscous solid, some viscous solids are put
Non-tacky solids can be cured as by postponing, when formula (I) compound synthesized by the present invention is viscous liquid, and some viscous liquids are placed
After can solidify, all compounds are considerable in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD) in table 1
Observe its molecular ion peak.Compound in table 11H NMR (Varian INOVA-300 spectrometer) with
Tetramethylsilane (TMS) makees internal standard, deuterochloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1
Compound shown in formula (I) of the present invention can be obtained by reaction equation 1 (1-1 or 1-2) shown below；Reaction equation
(II) and (IV) in 1 can be obtained by reaction equation 2 shown below；(III) in reaction equation 1 can pass through reaction equation 3
Obtain；L of the reaction equation 1 into reaction equation 3 is leaving group, and such as chlorine, bromine, sulphonic acid ester, other substituents are outer unless specified otherwise
Limited as before.
Reaction equation 1-1：
Reaction equation 1-2：
Reaction equation 2：
Reaction equation 3：
Formula (I) compound can be prepared so：In a suitable solvent as N,N-dimethylformamide, tetrahydrofuran,
Dichloromethane, chloroform, dichloroethanes, toluene, normal hexane or petroleum ether etc., in 0 DEG C~system reflux temperature, with formula (II)
Compound and formula (III) compound react formula (I) compound, add suitable catalyst such as triphenylphosphine etc. and azo
Two acid diesters such as diisopropyl azodiformate etc. can promote to react or accelerate to react (reaction equation 1-1).
Formula (I) compound is it is also possible that to prepare：In a suitable solvent such as N,N-dimethylformamide, tetrahydrochysene furan
Mutter, dichloromethane, chloroform, dichloroethanes, toluene, normal hexane or petroleum ether etc., in the presence of suitable alkali as triethylamine,
Pyridine, sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate etc., in 0 DEG C~system reflux temperature, with formula (IV) compound
With the compound of formula (III) react formula (I) compound (reaction equation 1-2).
The compound of formula (II) can be prepared so (reaction equation 2)：In a suitable solvent such as methanol, ethanol, N, N-
Dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, dichloroethanes or toluene etc., in room temperature to solvent reflux temperature, are used
The appropriate base such as processing formula such as potassium carbonate, potassium hydroxide, sodium acid carbonate, sodium carbonate, sodium hydride and/or sodium hydroxide (V) and (VI)
Compound obtain formula (VII) compound；Then such as benzene, toluene or carbon tetrachloride in a suitable solvent again, in room temperature extremely
Solvent reflux temperature, in the presence of catalyst such as triethylamine or pyridine, with halide reagent such as sulfonic acid chloride, chlorine, bromine or secondary
Hydracid tert-butyl ester etc. carries out halogenation to the compound of formula (VII) and obtains formula (VIII R1,R2=halogen) compound；Finally
In a suitable solvent as methanol, ethanol, N,N-dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, dichloroethanes or
Toluene etc., in room temperature to solvent reflux temperature, with appropriate base such as potassium carbonate, potassium hydroxide, sodium acid carbonate, sodium carbonate, sodium hydride
And/or the processing formula (VIII) such as sodium hydroxide and the compound of (IX) obtain formula (II) compound.
The compound of formula (IV) can be prepared so (reaction equation 2)：In a suitable solvent such as methanol, ethanol, N, N-
Dimethylformamide, tetrahydrofuran, dichloromethane, chloroform, dichloroethanes or toluene etc., in 0 DEG C~system reflux temperature, use formula
(II) chloride reagent such as compound and phosgene, triphosgene or oxalyl chloride react formula (IV) compound (reaction equation 2).
The compound of formula (III) can be prepared so (reaction equation 3)：Such as potassium carbonate, hydrogen-oxygen in the presence of suitable alkali
Change potassium, sodium acid carbonate, sodium hydride, triethylamine, pyridine, sodium carbonate and/or sodium hydroxide etc., in a suitable solvent such as N, N- bis-
NMF, tetrahydrofuran, ethanol, methanol, dichloromethane, chloroform, dichloroethanes or toluene etc., in the backflow of 0 DEG C~system
Temperature, with the compound of formula (X) and the compound of formula (XI) react formula (III) compound (reaction equation 3).
Specific synthetic method has more detailed elaboration in the following embodiments.
Formula (I) compound that the present invention is provided under 15~2250 grams of active ingredients/hectare consumption there is broad-spectrum biological to live
Property, it can be not only used for preventing and treating harmful insect, it may also be used for preventing and treating harmful levels of pathogens.There is some compounds good control of insect to make
With being obtained with good effect under very low dosage.
Formula (I) compound that the present invention is provided, with bioactivity and the compound that has has good bioactivity special
It is not to show activity in terms of agricultural, gardening, flowers and sanitary insect pest, the preventing and treating of germ.Harmful organism bag described here
Include, but be not limited only to this：
Harmful insect：Lepidoptera such as oriental armyworm, prodenia litura, diamondback moth, beet armyworm, cabbage looper, cabbage caterpillar, directly
Wing mesh such as blattaria, Thysanoptera such as cotton thrips, rice thripses, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, Hymenoptera such as sawfly children
Worm, Diptera such as yellow-fever mosquito, culex, fly；Acarina such as Jie-Li enzyme-SQ, cotton spider mites, T.urticae Koch；
Harmful pathogen：Phytophthora species, white powder belongs to species, Gibberella species, Venturia species, Sclerotinia kind
Class, Rhizoctonia species, Botrytis species, Pyricularia Sacc. species, such as Fusarium species, rice blast (Pyricularia
oryzae)；Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust
Disease；Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust；Barley
With wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew
(Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar)；Wheat sharp eyespot and
Glume blight (Septoria nodorum).The compacted spore of length, mouth spore on cereal are mould, Septoria is sick, caryosphere shell Pseudomonas disease,
Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).Peanut
Brown spot (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata)；Apple wheel
Line germ (Botryosphaeria berengriana f.sp piricola), Valsa mali (Cytospora sp.)；
Its Cercospora disease on beet, soybean and paddy.Tomato, cucumber, grape grey mould (Botrytis cinerea).Vegetables
Hinge spore category disease on (such as cucumber).Anthracnose on cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, potato
With the epidemic disease on tomato, list bacterium Thanatephorus cucumeris and other hosts such as wheat and barley on paddy,
Other rhizoctonias on vegetables；Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)；Wheat scab (Gibberella
zeae)；Phytophthora capsici disease (Phytophythora capsici).
It is effective to control insect, germ, they can also be with it when formula (I) compound of the present invention is used alone
Allogene chemical substance is used together, and these biochemicals include other insecticides, nematicide, acaricide and sterilization
Agent.
(I) compound provided with the present invention, as the Agrotechnical formulation of effective ingredient, can be made desired any one
Kind of formulation as dry compression particle, easily flowing intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate,
Pulvis, powdery concentrate, microemulsion, suspending agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable helps
Agent includes carrier (diluent) and other adjuvants such as spreader-sticker, emulsifying agent, wetting agent, dispersant, sticker and distintegrant.This
Contain the compound that the present invention is mixed with the acceptable solid of inert, pharmacology or liquid diluent in a little preparations.
Desired any formulation such as dry compression particle, easily flowing can also be made in the composition example of the present invention
Intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery concentrate, microemulsion, suspension
Agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent include carrier (diluent) and other auxiliary
Auxiliary agent such as spreader-sticker, emulsifying agent, wetting agent, dispersant, sticker and distintegrant.Contain in these preparations with inert, pharmacology
Learn acceptable solid or liquid diluent is mixed with the compound of the present invention.
The invention will be further described with reference to embodiments, and the yield in embodiment is not optimized, the present invention its
Its compound is referred to following embodiments and prepared by pertinent literature.
Embodiment
Embodiment 1 this example demonstrates that in table 1 compound 01 preparation method
The chloropropanes (0.5mol) of 1,1,3- tri chloropropenes 1,1,1,3- tetra- and Iron dichloride tetrahydrate (1.5mmol) are in 90
After~100 DEG C of reactions 10-15 hours (h), air-distillation collects 95~110 DEG C of fractions, obtains l, l, 3- tri chloropropene 56g, content
95% (GC), refrigerator preserves stand-by.
4- (chloroallyloxyaminos of 3,3- bis-) phenol hydroquinones (0.21mol), potassium carbonate (0.22mol) and N, N- diformazan
The DMF (30mL) of 1,1,3- tri chloropropenes (0.19mol) is added dropwise in being stirred under normal temperature after 0.5h in base formamide (DMF 100mL)
Solution, reacts 6-8h, adds water, and ethyl acetate extraction, point liquid, washing, anhydrous sodium sulfate drying, decompression precipitation obtain crude product, pass through
Petroleum ether and ethyl acetate (V/V=10:1) column chromatography purification process, obtains title compound 26.2g.
The chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenol 4- (chloroallyloxyaminos of 3,3- bis-) phenol (0.12mol),
Triethylamine (7mmol) and toluene (150mL), stirring are warming up to 90-100 DEG C, and sulfonic acid chloride (0.26mol) is added dropwise, and drop continues after finishing
8-10h is reacted, is added water, ethyl acetate extraction, washing, anhydrous sodium sulfate drying depressurize precipitation, obtain title compound 32.7g.
Chloro- 4- (the 3,3- dichloro allyls of 3- [the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-)] phenoxypropanol 2,6- bis-
Epoxide) phenol (0.123mol), potassium carbonate (0.174mol) and DMF (150mL), stir after 0.5h, 3- bromopropyl alcohols are added dropwise
DMF (15mL) solution of (0.174mol), after drop finishes, 20-30 DEG C is continued to react 20-30h, stops reaction.Reaction solution is poured into
In frozen water, it is sufficiently stirred for, ethyl acetate extraction, washing, anhydrous sodium sulfate drying, precipitation.Title thing is purified to obtain through column chromatography
17.5g
2- (4- hydroxyphenoxies) -5- nitropyridines in ice-water bath cooling and stirring condition under, to sodium hydride (60%,
THF (40mL) solution of hydroquinones (0.10mmol) 0.12mol) and in the mixture of tetrahydrofuran (THF 80mL) is added dropwise.
After insulated and stirred reaction 0.5h, it is added dropwise after THF (40mL) solution of 2- chloro-5-nitropyridines (0.10mol), completion of dropping and continues
0.5h is reacted, reaction 4-6h is warmed to room temperature.Reactant mixture is poured into frozen water, ethyl acetate extraction, anhydrous sodium sulfate drying
Organic layer, filtering, precipitation obtains 22.8g crude products.Crude product purifies [v (petroleum ether) through column chromatography：V (ethyl acetate)=10:
1], faint yellow solid title thing 19.30g is obtained.
The chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenyl 3- (5- nitro -2- pyridine radicals phenoxies base) propyl ether (table
Compound 01 in 1) under ice bath cooling and stirring condition, to 3- [2,6- bis- chloro- 4- (3,3- bis- chloroallyloxyamino)] phenoxy group
Propyl alcohol (4.68mmol), 2- (4- hydroxyphenoxies) -5- nitropyridines (4.68mmol), triphenylphosphine (5.15mmol) and anhydrous
In the mixture of tetrahydrofuran (30mL), diisopropyl azodiformate (5.15mmol), insulation reaction after drop finishes is slowly added dropwise
0.5h, reacts at room temperature 20h.Reactant mixture is poured into frozen water, organic phase is washed in ethyl acetate extraction, and anhydrous sodium sulfate is done
Dry, filtering, decompression precipitation obtains crude product, and crude product purifies (V through column chromatographyPetroleum ether/VEthyl acetate=200:1) faint yellow sticky liquid is obtained
Body, placement solidify afterwards are yellow solid title thing 1.22g, content 96.5%, fusing point：67.1-68.4℃.1H NMR(CDCl3)
2.289-2.329(m,2H,CH2), 4.148 (t, J=6.0Hz, 2H, CH2), 4.262 (t, J=6.3Hz, 2H, CH2),4.576
(d, J=6.6Hz, 2H, CH2), 6.094 (t, J=6.0Hz, 1H, CH), 6.845 (s, 2H, Ph H), 6.977 (d, J=
9.3Hz, 1H, Py H), 6.980-7.098 (m, 4H, Ph H), 8.436 (dd, J=9.3,3.0Hz, 1H, Py H), 9.050
(dd, J=2.1Hz, 0.6Hz, 1H, Py H)；(the 85%M of LC-MS (APCI, Pos) (m/z) 559++ 1), 561 (100%M++1+
2), 563 (50%M++1+4).
Embodiment 2 this example demonstrates that in table 1 compound 141 preparation method
3- (the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenoxy group) chloroformate is cooled down and stirred in ice bath
Under the conditions of, be slowly added dropwise into the mixture of triphosgene (1.82mmol) and dichloromethane (25mL) 3- [2,6- bis- chloro- 4- (3,
The chloroallyloxyaminos of 3- bis-)] dichloromethane (10mL) solution of phenoxypropanol (3.6mmol).After reaction solution insulation reaction 2-4h,
Be concentrated under reduced pressure to obtain yellow liquid title thing 1.62g.
1- (5- nitropyridine -2- bases) piperazines are under room temperature and stirring condition, to 2- chloro-5-nitropyridines
The ethanol of piperazine (0.042mol) is added dropwise in (0.04mol), Anhydrous potassium carbonate (0.04mol) and ethanol (80mL) mixture
(10mL) solution.After reaction solution stirring reaction 2-4h, it is poured into water, ethyl acetate extraction, through anhydrous slufuric acid after organic layer washing
Sodium is dried, and removed under reduced pressure solvent obtains yellow solid title thing 9.10g.
3- (the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenoxy group) propyl group 4- (5- nitropyridine -2- bases) piperazine -1-
Formic acid esters (compound 141 in table 1) is under ice bath cooling and stirring condition, to 1- (5- nitropyridine -2- bases) piperazine
3- is slowly added dropwise in the mixture of (2.85mmol), triethylamine (3.60mmol) and anhydrous tetrahydro furan (25mL), and (2,6- bis- is chloro-
4- (chloroallyloxyaminos of 3,3- bis-) phenoxy group) chloroformate (3.60mmol).Reactant mixture ice bath cools down insulation reaction
After 0.5h, it is slowly increased to room temperature and continues to react 4-5h.Reactant mixture is poured into frozen water, ethyl acetate extraction, organic phase water
After washing, through anhydrous sodium sulfate drying, filtering, decompression precipitation obtains crude product, and crude product purifies (V through column chromatographyPetroleum ether/VEthyl acetate=
30:1) faint yellow viscous solid is obtained, placement solidify afterwards are faint yellow solid title thing 0.51g, content 97.0%, fusing point：91.8-
93.5℃。1H NMR(CDCl3)2.167-2.207(m,2H,CH2),3.629-3.663(m,4H,2CH2),3.789-3.882
(m,4H,2CH2), 4.056 (t, J=6.3Hz, 2H, CH2), 4.414 (t, J=6.3Hz, 2H, CH2), 4.578 (d, J=
6.3Hz,2H,CH2), 6.096 (t, J=6.3Hz, 1H, CH), 6.584 (d, J=9.3Hz, 1H, Py H), 6.845 (s, 2H, Ph
), H 8.224 (dd, J=9.6,3.0Hz, 1H, Py H), 9.042 (dd, J=2.4Hz, 0.6Hz, 1H, Py H)；LC-MS
(APCI, Pos) (m/z) 579 (75%M++ 1), 581 (100%M++ 1+2), 583 (45%M++1+4).
Embodiment 3 this example demonstrates that in table 1 compound 168 preparation method
1- (3- chloro-5-nitropyridine -2- bases) piperazine is with reference to 1- (5- nitropyridine -2- bases) piperazine in above-described embodiment
Preparation method, replace 2- chloro-5-nitropyridines with the chloro-5-nitropyridines of 2,3- bis-, prepare 1- (3- chloro-5-nitropyridines -2-
Base) piperazine.
3- (the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenoxy group) propyl group 4- (3- chloro-5-nitropyridine -2- bases) piperazine
Piperazine -1- formic acid esters (compound 168 in table 1) is with reference to 3- (the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) in above-described embodiment
Phenoxy group) propyl group 4- (5- nitropyridine -2- bases) piperazine -1- formic acid esters (compound 141 in table 1) preparation method, with 1- (3-
Chloro-5-nitropyridine -2- bases) piperazine replace 1- (5- nitropyridine -2- bases) piperazine, be prepared into faint yellow solid title thing
0.55g, content 96.1%, fusing point：99.6-101.2℃.1H NMR(CDCl3)2.164-2.205(m,2H,CH2),3.644-
3.677(m,8H,4CH2), 4.038 (t, J=6.3Hz, 2H, CH2), 4.408 (t, J=6.3Hz, 2H, CH2), 4.579 (d, J
=6.3Hz, 2H, CH2), 6.097 (t, J=6.3Hz, 1H, CH), 6.584 (d, J=9.3Hz, 1H, Py H), 6.848 (s, 2H,
Ph H), 8.355 (d, J=2.7Hz, 1H, Py H), 8.980 (d, J=2.7Hz, 1H, Py H)；LC-MS(APCI,Pos)(m/
Z) 613 (70%M++ 1), 615 (100%M++ 1+2), 617 (75%M++1+4).
Chloro- 4- (chloroallyloxyaminos of 3,3- bis-) the phenyl 3- (5- nitro -2- pyridine radicals phenoxies base) of 4 2,6- of embodiment bis-
The preparation of propyl ether (compound 01 in table 1) 10% oil slick
Weigh compound 01 in formula (I) the compound such as table 1 that the present invention of appropriate (by weight percentage 10%) is provided, fit
Cosolvent (such as ethyl acetate or acetone), appropriate agricultural chemicals used additives and the solvent (such as toluene) of amount are put into reactor, first add
Enter a certain amount of solvent (such as toluene) and defoamer stirs 10~30min, add appropriate stabilizer, synergist, penetrating agent
Etc. component, continue to stir 10~30min, adjust pH value, then the solvent of effective dose is put into kettle, blowing is produced after stirring
The missible oil of the chloro- 4- of 2,6- bis- (chloroallyloxyaminos of 3,3- bis-) phenyl 3- (5- nitro -2- pyridine radicals phenoxies base) propyl ether 10%.
It is raw to survey embodiment
Desinsection and bactericidal activity experiment are carried out to the compounds of this invention, part of test results is as follows.
Biological evaluation of the embodiment 5 to mythimna separata (Mythimna separata)
Potter spray-on processes：Appropriate the compounds of this invention is weighed, is dissolved with DMF, adds and tells on a small quantity
Warm 80 emulsifying agents, stir, and add quantitative clear water, are configured to required concentration, if clear water is control.Fresh and tender maize leaves are taken to cut
Into the fragment that size is basically identical, it is put into and is lined with advance in the culture dish of filter paper (Ф 90mm).Then the age of mythimna separata 3 is accessed in ware
Larva 10, is put under Potter spray towers and carries out metered dose, and spray liquid measure 1ml, per 3 repetitions of concentration.It is disposed, covers
Upper ware lid, is placed in culture in recovery room, and routine observation, in being checked after 72 hours and recording test worm death condition, calculates the death rate
(%), results averaged.Activity relative to blank control in percentage, is divided into A, B, C, D level Four, 100%≤death rate
≤ 90% is A grades.As a result showing the compound of the present invention has very high activity to mythimna separata, and partial test result is as follows, and i is represented
Commercialization insecticide Pyridalyl shown in formula (i).
Insecticidal activity of the part of compounds of table 2 under 500mg/L concentration to mythimna separata
| No. | 01 | 11 | 141 | 146 | 168 | i |
| Active (%) | A | A | A | A | A | A |
Insecticidal activity of the part of compounds of table 3 under 20mg/L concentration to mythimna separata
| No. | 01 | 141 | 168 | i |
| Active (%) | A | A | A | A |
Insecticidal activity of the part of compounds of table 4 under 10mg/L concentration to mythimna separata
| No. | 01 | 141 | 168 | i |
| Active (%) | 70 | 90 | 80 | _a |
aDo not test
Further to compare the insecticidal activity of the compounds of this invention and commercialization insecticide Pyridalyl, the selection present invention
Compound 01 is representative, while testing 01 and insecticidal activities of the Pyridalyl to mythimna separata.The result of table 5 shows chemical combination of the present invention
Thing 01 has the mythimna separate better than Pyridalyl.
The insecticidal activity of the compound 01 of table 5 and Pyridalyl to mythimna separata
| No. | Regression equation (y=ax+b) | Regression coefficient (r) | LC50(mg/L) |
| 01 | Y=3.6653X+2.1867 | 0.9550 | 4.05 |
| i | Y=2.8967+3.0826x | 0.9948 | 4.81 |
Bactericidal activity of the embodiment 6 to Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%Tween
The sterilized water of 80 emulsifying agents is diluted to required concentration；3mL decoctions are taken to add the potato for the 27mL for being cooled to 45 DEG C with pipette
Culture dish is poured into after shaking up in agar medium (PDA) and fully；Transfer needle is used after cooling from the germ colony edge of culture 7 days
6mm diameter mycelia blocks are taken, culture dish center is moved to, mycelia is face-down, while setting the blank without testing compound as control, often
Handle 4 repetitions；Culture dish is placed in 28 DEG C of constant temperature biochemical cultivation case after being disposed and cultivated, mycelia life is measured after 4 days
Long diameter, is analyzed using EXCEL statistical softwares and calculates mycelial growth inhibition rate (%).Activity relative to blank control with
Percentages, as a result showing the compound of the present invention has remarkable activity to Sclerotinia sclerotiorum, such as under 25mg/L concentration, changes
Compound 141,168 etc. has 90~100% activity to Sclerotinia sclerotiorum, and under same test condition, shown in formula (i)
Pyridalyl is 0 to the activity of Sclerotinia sclerotiorum.
Bactericidal activity (pot-culture method) of the embodiment 7 to wheat powdery mildew (Erisiphe griminis)
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%Tween
The sterilized water of 80 emulsifying agents is diluted to required concentration；Cut-off stem 15cm or so basin alms bowl, the full healthy and strong kind of wheat is sowed per alms bowl
Son 20, wait grow two leaves wholeheartedly afterwards be for experiment；Take ready wheat seedling plant through certain density reagent spray at
Reason, carries out germ inoculation after one day.3 repetitions are often handled, the blank without testing compound are separately set as control, the training of moisturizing thermophilic
Support to blank control morbidity, check lesion area, calculate pharmacy control efficacy.Activity is relative to blank control in percentage.Knot
Fruit shows that the compound of the present invention has prevention effect to wheat powdery mildew, such as under 500mg/L dosage, compound 141 and 168
Deng the prevention effect to powdery mildew up to 70%, but under same test condition, the Pyridalyl shown in formula (i) is to powdery mildew
Prevention effect is 0.
Bactericidal activity (pot-culture method) of the embodiment 8 to corn rust
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%Tween
The sterilized water of 80 emulsifying agents is diluted to required concentration；Morbidity maize leaf is cut, fitted with containing 0.05%Tween 80 or other
The aqueous surfactant solution of conjunction washes lower spore, and with 2 layers~4 layers filtered through gauze, and it is 1 × 105 spore/mL's that concentration, which is made,
Suspension.After plant chemicals treatment 24h, spore suspension spray inoculation, moved to after inoculation moisturizing cabinet (relative humidity 95% with
On, 20~22 DEG C of temperature), (intensity of illumination 5000Lux~10000Lux) cultivates 15~24h under low light condition；Treat blank control
When sick leaf rate is up to more than 50%, the incidence of each processing of classification investigation calculates pharmacy control efficacy.3 repetitions are often handled, are separately set not
Blank containing testing compound is control.Activity relative to blank control in percentage, as a result shows the compounds of this invention pair
Corn rust is active.Such as under 500mg/L concentration, compound 141,168 etc. is to the prevention effect of corn rust up to 75%
More than.
Claims (10)
1. propylene ether dihalide compound and its preparation and application, it is characterised in that represent dichloro allyl ethers with logical formula (I)
Compound and its isomers：
Wherein：
I.Q is selected from following group：
R ' is same or different, and represents hydrogen, halogen, C1-C4Alkyl, C1-C4Haloalkyl, C1-C4Alkoxy, C1-C4Halogen
For alkoxy；M represents 0,1,2,3 or 4；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, C1-C4Alkyl, C1-C4Haloalkyl, C1-
C4Alkoxy, C1-C4Halogenated alkoxy；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C1-C6
Alkylamino radical, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl
Amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amine
Base, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amine
Base, two C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkenyl, alkynyl group, benzene
In base hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen, C1-C6Alkyl,
C1-C6Haloalkyl, C1-C6Alkyl oxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group；
IV.n represents 0,1,2 or 3；V represents 0 or 1；
In the definition of compound (I) given above, also it is used in compound word, represents as follows no matter term used is used alone
Substituent：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or undersaturated cycloalkyl；
Alkenyl；Refer to straight or branched and double bond can be there are on any position；
Alkynyl group；Refer to straight or branched and three keys can be there are on any position；
Halo：Refer to hydrogen moiety therein or can all be replaced by halogen atom.
2. dichloro allyl ether compound according to claim 1, it is characterised in that in compound shown in logical formula (I)：
I.Q is selected from Q1 or Q4, R ' it is same or different, and represent hydrogen, halogen, C1-C3Alkyl, C1-C3Haloalkyl；M generations
Table 0,1 or 2；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, methyl, trifluoromethyl；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C1-C6
Alkylamino radical, two (C1-C6) alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl
Amido, two C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amine
Base, two C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amine
Base, two C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkenyl, alkynyl group, benzene
In base hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen, C1-C6Alkyl,
C1-C6Haloalkyl, C1-C6Alkyl oxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Alkyl amine group；
IV.n represents 0,1 or 2；V represents 0 or 1.
3. dichloro allyl ether compound according to claim 1 or claim 2, it is characterised in that in compound shown in logical formula (I)：
I.Q is selected from Q1 or Q4, R ' it is same or different, and represent hydrogen, halogen, methyl, trifluoromethyl；M represents 0,1 or 2；
II.R1And R2, R3, R4, R5It is same or different, and represents hydrogen, halogen, methyl, trifluoromethyl；
III.R is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylthio group, C1-C6
Alkylamino radical, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkynyl group,
C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8
Cycloalkylsulfanyl, C3-C8Cycloalkyl amido, phenyl, phenoxy group, anilino-；And alkyl described in R, cycloalkyl, alkenyl, alkyne
In base, phenyl hydrogen moiety or can all be selected from it is following in identical or different substituent substitution：Hydrogen, halogen, C1-C3
Alkyl, C1-C3Haloalkyl, C1-C3Alkyl oxy, C1-C3Halogenated alkoxy；
IV.n represents 0,1 or 2；V represents 0 or 1.
4. dichloro allyl ether compound according to claim 1 or 2, it is characterised in that leading to compound shown in formula (I) is
Compound as follows：
5. the preparation method of dichloro allyl ether compound according to claim 1 or 2, it is characterised in that shown in formula (I)
Compound prepared by reaction shown below,
Reaction equation 1-1：
Reaction equation 1-2：
Reaction equation 2：
Reaction equation 3：
Formula (I) compound can be prepared so (reaction equation 1-1)：In solvent N,N-dimethylformamide, tetrahydrofuran, dichloro
In methane, chloroform, dichloroethanes, toluene, normal hexane or petroleum ether, in 0 DEG C~system reflux temperature, with formula (II) change
The compound of compound and formula (III) react formula (I) compound, add catalyst triphenylphosphine and azoformic acid diisopropyl
Ester can promote to react or accelerate reaction；
Formula (I) compound is it is also possible that to prepare (reaction equation 1-2)：In solvent N,N-dimethylformamide, tetrahydrofuran, two
In chloromethanes, chloroform, dichloroethanes, toluene, normal hexane or petroleum ether, in alkali triethylamine, pyridine, sodium hydroxide, carbonic acid
In the presence of sodium, potassium hydroxide or potassium carbonate, in 0 DEG C~system reflux temperature, with the compound and the chemical combination of formula (III) of formula (IV)
Thing react formula (I) compound；
The compound of formula (II) can be prepared so (reaction equation 2)：In solvent methanol, ethanol, N,N-dimethylformamide, four
In hydrogen furans, dichloromethane, chloroform, dichloroethanes or toluene, in room temperature to solvent reflux temperature, with alkali potassium carbonate, hydroxide
Potassium, sodium acid carbonate, sodium carbonate, sodium hydride and/or naoh treatment formula (V) and the compound of (VI) obtain formula (VII) chemical combination
Thing；Then again in solvent benzol, toluene or carbon tetrachloride, in room temperature to solvent reflux temperature, in catalyst of triethylamine or pyridine
In the presence of, halogenation is carried out to the compound of formula (VII) with halide reagent sulfonic acid chloride, chlorine, bromine or the hypohalogenous acids tert-butyl ester and obtained
Formula (VIII R1,R2=halogen) compound；Finally in solvent methanol, ethanol, N,N-dimethylformamide, tetrahydrofuran, two
In chloromethanes, chloroform, dichloroethanes or toluene, in room temperature to solvent reflux temperature, with alkali potassium carbonate, potassium hydroxide, bicarbonate
Sodium, sodium carbonate, sodium hydride and/or naoh treatment formula (VIII) and the compound of (IX) obtain formula (II) compound；
The compound of formula (IV) can be prepared so (reaction equation 2)：In solvent methanol, ethanol, N,N-dimethylformamide, four
In hydrogen furans, dichloromethane, chloroform, dichloroethanes or toluene, in 0 DEG C~system reflux temperature, with the compound of formula (II) and
Chloride reagent phosgene, triphosgene or oxalyl chloride react formula (IV) compound；
The compound of formula (III) can be prepared so (reaction equation 3)：In alkali potassium carbonate, potassium hydroxide, sodium acid carbonate, hydrogenation
In the presence of sodium, triethylamine, pyridine, sodium carbonate and/or sodium hydroxide, in solvent DMF, tetrahydrofuran, second
In alcohol, methanol, dichloromethane, chloroform, dichloroethanes or toluene, in 0 DEG C~system reflux temperature, with the compound of formula (X) and
The compound of formula (XI) react formula (III) compound；
Q, R, R in formula1、R2、R3、R4、R5, n, v have given in claim 1 define, L be leaving group chlorine, bromine or sulphonic acid ester.
6. the purposes of the dichloro allyl ether compound according to claim 1 or 2,4, it is characterised in that 7.5~2250
There is insecticidal bioactivity under gram active ingredient/hectare consumption.
7. the purposes of the dichloro allyl ether compound according to claim 1 or 2,4, it is characterised in that 7.5~2250
There is sterilization bioactivity under gram active ingredient/hectare consumption.
8. the dichloro allyl ether compound according to claim 1 or 2,4 is used to prepare the medicine with insecticidal activity
Purposes.
9. the dichloro allyl ether compound according to claim 1 or 2,4 is used to prepare the medicine with bactericidal activity
Purposes.
10. a kind of desinsection or bactericidal composition, it is characterised in that：Containing as active component as described in claim 1 or 2,4
Dichloro allyl ether compound and acceptable carrier, the weight percentage of active component is 0.5~90% in composition.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464612A (en) * | 2010-11-19 | 2012-05-23 | 中国中化股份有限公司 | Dihalide propylene ether compound containing piperazine carbamic acid ester and application |
| CN102718701A (en) * | 2011-03-30 | 2012-10-10 | 中国中化股份有限公司 | Aryloxy dihalide propylene ether compound and application thereof |
| CN104738079A (en) * | 2013-12-26 | 2015-07-01 | 中国中化股份有限公司 | Binary insecticide composition and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464612A (en) * | 2010-11-19 | 2012-05-23 | 中国中化股份有限公司 | Dihalide propylene ether compound containing piperazine carbamic acid ester and application |
| CN102718701A (en) * | 2011-03-30 | 2012-10-10 | 中国中化股份有限公司 | Aryloxy dihalide propylene ether compound and application thereof |
| CN104738079A (en) * | 2013-12-26 | 2015-07-01 | 中国中化股份有限公司 | Binary insecticide composition and application thereof |
Non-Patent Citations (1)
| Title |
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| JI-CHUN YANG等: "Design, synthesis and insecticidal evaluation of aryloxy dihalopropene derivatives", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
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