CN109997865A - A kind of Synergistic bactericidal composition and application containing difenoconazole - Google Patents
A kind of Synergistic bactericidal composition and application containing difenoconazole Download PDFInfo
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- CN109997865A CN109997865A CN201910352103.7A CN201910352103A CN109997865A CN 109997865 A CN109997865 A CN 109997865A CN 201910352103 A CN201910352103 A CN 201910352103A CN 109997865 A CN109997865 A CN 109997865A
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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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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Abstract
The invention discloses a kind of Synergistic sterilizing composition pesticides, with difenoconazole and (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-6-1) is effective component, it is collectively constituted with acceptable auxiliary element in pesticide, wherein difenoconazole and MIPO-6-1 weight ratio are that 1:1 to 30:1 has synergistic effect, wherein having significant synergistic effect in 1:1 to 10:1, CTC is all larger than 200.Synergistic effect is formed after two kinds of combination of active principles, and without antagonism, while crop safety is improved, sterilized especially suitable for industrial crops such as rice, cucumber, watermelon, citrus, capsicum, cotton, tobaccos.
Description
Technical field
The present invention relates to a kind of bactericidal composition, corresponding sterilization pesticide and its applications, especially a kind of to contain phenyl ether methyl cyclic
The bactericidal composition of azoles, corresponding sterilization pesticide and its application.
Background technique
Difenoconazole (molecular formula: C19H17Cl2N3O3；Molecular weight 406.26；No. CAS: 119446-68-3；Chemical name
Claim: suitable, the trans- chloro- 4- of 3- [4- methyl -2- (1H-1,2,4- triazol-1-yl methyl) -1,3- dioxolane -2- base] phenyl 4-
Chlorphenyl ether；English abbreviation: Cis, Trans-3-chloro-4- [4-methyl-2- (1h-1,2,4-triazole-1-
Methyl) -1,3-dioxylpentane-2-] ph- enyl-4-chlorophenyl ether, English abbreviation:
Difenoconazole, structure are as shown in Equation 1) it is the novel low-toxicity absorbability triazole that the Syngenta Co., Ltd of Switzerland researchs and develops
Class fungicide suffers from extensive usage degree in America, Europe and Asia.Difenoconazole technical material sterling is white solid,
75-76 DEG C of fusing point, industrial goods fusing point is generally 73~76 DEG C due to production technology and product purity difference, fusing point.Difficulty is dissolved in
Water (20 DEG C, 3.3g/L), is easily soluble in intensive polar solvent in acetone, ethyl alcohol, toluene, chloroform, methylene chloride etc., but in low pole
Solubility is relatively small in property organic solvent, such as n-hexane, petroleum ether.It is nonflammable, it does not explode, it is non-corrosive.Phenyl ether methyl cyclic
Azoles sales volume was once reaching annual 200000000 dollars or more, even up to the 3rd of triazole pesticide sales list.Difenoconazole
It is that safety is relatively high in triazole bactericidal agent, is widely used in the crops such as fruit tree, vegetables, effectively prevents scab, hemorrhagic black smallpox
Disease, white rot, spot defoliation, powdery mildew, brown spot, rust, stripe rust, head blight etc..Difenoconazole wide sterilization spectrum is right
Ascomycetes, Basidiomycetes and including Alternaria, Ascochyta, Cercospora, Colletotrichum, ball Cuo Pseudomonas, Phoma,
Disease is partly known including Ramularia, Septoria, Venturia, and Erysiphaceae, Uredinales and certain Seedborne pathogens have persistently
Protection and therapeutic effect.It is also fine to bitter rot or anthracnose of grape, white rot effect.Leaf is mainly used as in difenoconazole application method
The yield and guaranteed quality of crop can be improved in surface treatment and seed treatment.Difenoconazole toxicity is lower, rat LD50(oral)
1453 milligrams/KG, rabbit LD50It is (percutaneous) to be greater than 2010 milligrams/KG.Wild duck LD50It is (oral) to be greater than 2150 milligrams/KG.Rat LC50
(Acute inhalation；4 hours) it is greater than 0.045 mg/litre.Trout LC50(96 hours) 0.8 mg/litre.To rabbit skin and eyes spinosity
Effect is swashed, to cavy without skin allergy.It is nontoxic to honeybee.Domestic goods title: Cisco, generation are high, it approves journey at home at present
It spends higher and higher, and very big amount can be occupied in the sale of fungicide at home.The factory of country's difenoconazole at present
Family is more, and production capacity is more sufficient, and the synthesis technology mainly used is similar.Difenoconazole synthesizes method master reported in the literature
There are three routes: route one: using m-dichlorobenzene as raw material, through 2,4 dichloro benzene second is prepared with acetyl chlorine acylation
Ketone, 2,4- dichloroacetophenones and parachlorophenol carry out etherification reaction under potassium carbonate catalysis and obtain 4- (4- chlorophenoxy) -2- chlorine
Acetophenone intermediate, 4- (4- chlorophenoxy) -2- chloro-acetophenone intermediate and 1, it is chloro- that the progress condensation reaction of bis- propyl alcohol of 2- obtains 3-
4-(2,4-dimethyl-1,3-dioxin-pentane-2-yl) phenyl-4 '-chlorphenyl ether intermediates；3- chloro- 4-(2,
4-dimethyl-1,3-dioxin-pentane-2-yl) phenyl-4 '-chlorphenyl ether intermediate and bromine carry out bromo-reaction preparation
Obtain the chloro- 4- of 3- (4- methyl -2- bromomethyl -1,3- dioxin-pentane -2- base) phenyl -4 '-chlorphenyl ether intermediate, the chloro- 4- of 3-
(4- methyl -2- bromomethyl -1,3- dioxin-pentane -2- base) phenyl -4 '-chlorphenyl ether intermediate under potassium iodide catalysis with 1,2,
4- 1-Sodium-1,2,4-Triazole carries out condensation reaction and obtains difenoconazole.Route two: using m-dichlorobenzene as raw material, through acylated anti-with chloroacetic chloride
2,4- dichloroacetophenone, 2,4- dichloroacetophenones and parachlorophenol the progress etherification reaction under potassium carbonate catalysis should be prepared to obtain
To 4- (4- chlorophenoxy) -2- chloro-acetophenone intermediate, 4- (4- chlorophenoxy) -2- chloro-acetophenone intermediate and bromine carry out bromine
4- (4 '-chlorophenoxy) -2- chlorphenyl bromomethyl ketone intermediate, 4- (4 '-chlorophenoxy) -2- chlorobenzene is prepared in generation reaction
Bis- propyl alcohol of bromide methyl ketone intermediate 1,2- carries out condensation reaction and obtains the chloro- 4- of the 3- (evil of 4- methyl -2- bromomethyl -1,3- two penta
Alkane -2- base) the chloro- 4- of phenyl -4 '-chlorphenyl ether intermediate 3- (4- methyl -2- bromomethyl -1,3- dioxin-pentane -2- base) phenyl -
4 '-chlorphenyl ether intermediates carry out condensation reaction with 1,2,4- 1-Sodium-1,2,4-Triazole under potassium iodide catalysis and obtain difenoconazole.Route
Three: m-dichlorobenzene and parachlorophenol carry out etherification reaction under potassium carbonate catalysis and obtain 3-4 '-dichloro-diphenyl ether intermediate, intermediate
Body 3-4 '-dichloro-diphenyl ether and bromoacetyl chlorine carry out a pair gram acylation reaction and obtain 4- (4 '-chlorophenoxy) -2- chlorobenzene bromide first
Base ketone intermediate, 4- (4 '-chlorophenoxy) -2- chlorphenyl bromomethyl ketone intermediate 1, bis- propyl alcohol of 2- carry out condensation reaction and obtain 3-
Chloro- 4- (4- methyl -2- bromomethyl -1,3- dioxin-pentane -2- base) phenyl -4 '-chlorphenyl ether intermediate 3- chloro- 4- (4- methyl -
2- bromomethyl -1,3- dioxin-pentane -2- base) phenyl -4 '-chlorphenyl ether intermediate potassium iodide catalysis under with 1,2,4- 1-Sodium-1,2,4-Triazole
It carries out condensation reaction and obtains difenoconazole.Synthesized in three synthetic routes in above-mentioned difenoconazole, Article 3 route with 3,
4 '-dichloro-diphenyl ethers are raw material, use this raw material that is expensive, being not easy to obtain of bromoacetyl chlorine, therefore this technique remains in reality
Test the stage.Using 4- (4 '-chlorophenoxy) -2- chloro-acetophenone as starting material in synthetic route one, two, the first bromine of route one
Change, then is cyclized；Route two is first cyclized, then bromination, finally carries out nucleophilic substitution with 1,2,4-triazoles salt.Raw material is easy to get, reaction
Mildly, easy to industrialized production.Two lines technique slightly has difference, and product purity difference is little.Difenoconazole commonly uses agent
Type has: 10% water dispersible granules, 25% missible oil, 37% water dispersible granules, 3% suspension seed-coating agent, 30% suspending agent, 10% wettable powder
Agent.Although difenoconazole has more advantages, there are some disadvantages points for attention in other words in use:
(1) difenoconazole should not be mixed with copper agent.Because copper agent can reduce its sterilizing ability, if needs and copper really
Preparation is mixed, then to increase the dosage of 10% or more difenoconazole.Though difenoconazole has absorbability, transporting can be passed through
Tissue is transmitted to plant whole body, but in order to ensure control efficiency, has to abundance in spraying hourly water consumption, it is desirable that fruit tree complete stool is equal
Even spray；(2) though difenoconazole has protection and treatment double effects to answer to mitigate loss caused by disease as far as possible
Its protective effect is given full play to, therefore spraying time is urgent, it is best effect of spraying pesticide should to be carried out at the initial stage of a disease；(3) exist
Plant is used with caution when the florescence, is used with caution before fruit area does not have bagging.In addition, though domestic and international market is often used difenoconazole and third
The mixture of ring azoles, but should be noted that actually difenoconazole and propiconazole have no synergistic effect.
Chinese patent (application number CN 2016108040631,2016 dates of application September 6th, the Granted publication date 2017 12
Months 22 days) in report the general formula of the artificial Xihua Univ of patent application (inventor Yang Weiqing, Li Hongyang etc.) be containing for MIPO
1- methyl -5- methylene imine base-piperazine -2- ketone derivatives class compound (formula 2) of two chiral centres is (represented by formula M IPO
For a kind of compound: containing 1 phenyl ring, 1 pyrrole ring, 1 piperidine ring, 1 piperazine azacyclo- in the structure of MIPO.In MIPO
Precursor structure in, R1Indicate aryl, substituted aryl, heterocyclic aryl, substituted heterocycle aryl；R2Indicate hydrogen or alkyl, cycloalkanes
Base；R3Indicate hydrogen or alkyl, naphthenic base；* represent chirality) synthetic method and its purposes as fungicide.Such sterilization
Agent all has significantly bacterium of downy mildew of cucumber, bacterial blight of rice, cotton curve leaf disease virus, tobacco mosaic virus (TMV), wheat scab
Effect.In 1- methyl -5- methylene imine base-piperazine -2- ketone derivatives class containing two chiral centres that numerous general formulas are MIPO
MIPO-6-1(formula 3 in compound) (and other 3 isomers), MIPO-8-1(formula 4) (and other 3 isomerisms
Body), MIPO-18-1(formula 5) (and other 3 isomers) have good bactericidal effect (refer to aforementioned Chinese patent: Shen
Please number CN 2016108040631,2016 dates of application September 6 days).Chinese patent (application number CN 2017106849171, Shen
Please 2017 dates August 11 days) in report the artificial Xihua Univ of patent application (inventor Yang Weiqing, Yang Zixuan etc.) to logical
Formula is chiral using novel three teeth to the key intermediate (1- aryl -1H- pyridine [3,4-b] indole -3-carboxylic acid methyl ester) of MIPO
The catalyst that ligand and four isopropyl oxygen titaniums are formed carries out asymmetric syntheses, obtains very good effect.Almost simultaneously, Chinese patent (Shen
Please number CN 2017107102476,2017 dates of application August 18 days) in report the artificial Xihua Univ of patent application (invention
Artificial Yang Weiqing, Yang Zixuan, She Minghu etc.) mutual-through type is key intermediate (1- aryl -1H- pyridine [3,4-b] Yin to MIPO
Diindyl -3- carboxylate methyl ester) using the progress asymmetric syntheses of novelty Salen-Mn catalyst, also obtain very good effect.Later, the project
Group further discloses at September 4th 2017 CN 2017107863918(dates of application of Chinese patent；Inventor Yang Weiqing, poplar
Zi Xuan, in committee east etc.) and March 7 2018 CN 2018101865806(date of application of Chinese patent；Inventor Yang Weiqing,
Liu Xiaoyu, Tian Zongyou etc.) mutual-through type be MIPO 1- methyl -5- methylene imine base-piperazine -2- ketone containing two chiral centres spread out
The method of two kinds of biological species compound progress chiral resolutions.Meanwhile MIPO(formula 2) production cost relative to currently on the market
For most of fungicide kinds, synthesis technology is more complex, and production cost is slightly higher, economically considers, also it is necessary to
Other effective fungicide carry out interworking use；For the resistance angle of fungicide kind, fungicide MIPO is also required to and it
He uses breed combination.
The viroses of plant have the title of " plant cancer ", for a long time, worldwide to cereal crops, garden crop,
The yield and quality of medicinal material etc. constitutes a serious threat, it is annual caused by the underproduction up to 10%~30%, annual global economy loss surpasses 200
Hundred million dollars.
Bacterial blight of rice (Rice Bacterial Leaf Blight) be it is a kind of endanger more serious rice disease, disease
Strain blade tip and edge are come into being yellow green spot, after along vein develop sickly, the long streak of yellowish-brown, last graying white and it is withered
Extremely.Diseased plant easily lodges, and the not firm rate of spike of rice increases.Germ overwintering propagation on seed and ill straw.Tillering stage disease starts to send out
Exhibition.High temperature and humidity, storm, rice field are conducive to plant disease epidemic when excessive by flood and nitrogenous fertilizer.Major rice region has generation in the world,
Have become the important disease of Asia and Pacific Ocean rice region at present.There is generation in overwhelming majority province, China, area.After rice is aggrieved,
Blade is withered, and shrivelled kernel increases, and rice matter is crisp, and dry granular weight reduces, generally can the underproduction 10 ~ 20%, it is serious can 40% or more the underproduction,
Even No kernels or seeds are gathered, as in a year of scarcity.
Tobacco mosaic virus (TMV) (Tobacco mosaic virus；It TMV), is a kind of single strand RNA virus, special infection is planted
Object, especially tobacco and other plants of Solanaceae can make these infected blades are apparently mottled to be stained, and hence obtain one's name (mosaic
For mosaic, that is, the meaning pieced together).Tobacco mosaic disease and masaic of tomato are early generally to be understood.The late 19th century people
It has been known that there is the diseases that certain threatens tobacco plants existence, but just know the presence of this virus until nineteen thirty.Tobacco mosaic disease etc.
Pathogen, belong to Tobamovirus groups.Occurs flower leaf paresthesia on leaf, defective mode is sunk into growth, and leaf is often in deformity.Tobacco
After plant catches an illness, young leaflet tablet lateral vein and offshoot tissue are translucent shape, i.e., bright arteries and veins.Vein two sides mesophyll tissue is gradually in pale green
Color.Virus is largely proliferated in leaf tissue, and part mesophyll cell is made to increase or increase, and it is irregular blade thin and thick occur, and color is yellow
It is green alternate, it is in floral leaf shape.The mottled degree of floral leaf increases afterwards, and shows large area dark brown necrotic plaque, and middle and lower part old leaf more so, is fallen ill
The leaf-shrinkage of weight, malformation and distortion.The plant shortened internodes of early stage morbidity, serious to downgrade, slow growth cannot normally bloom
Solid and easy to fall off, developable shade fruit is small and shrinkage, grain weight are few and small, cannot mostly germinate.Tobacco mosaic virus (TMV) is entire
Breeding time can occur, and after cigarette strain is susceptible, under High temperature, just show symptom within 5-7 days.Tobacco mosaic virus (TMV) host is wide
It is general, in addition to tobacco, also tomato, potato, eggplant, capsicum, black nightshade etc. the plants of Solanaceae often encroached under field conditions (factors),
Host can up to 300 kinds or more plants.Tobacco mosaic virus (TMV) Field diseases 5-15%.Seedling Stage infection or the sense of crop field initial stage
Dye, loss can be to 30% or more.
Cotton curve leaf disease virus (Cottoneleafcurlvirus) is a kind of single stranded circle DNA with twin particle shape
Plant virus belongs to geminivirus infection section (Geminiviridae) Begomovirus (Begomovirus).The virus by
Aleyrodid is propagated, and the various crops such as infringement cotton, the rose of Sharon, gumbo, tobacco, tomato and French pea cause very big economic loss.It is early
This virus is found on Pakistani cotton in late 1960s, eruption and prevalence in 1987, at subsequent more than 10 years, which existed
Pakistan and West India prevalence are caused disaster, and bring heavy losses to Cotton Production.According to statistics, 1991-1992, Pakistan
Output of cotton is wrapped up to 12,820,000.After this disease outburst, 1992-1993, Pakistani output of cotton reduces to 9,050,000 packets；1993-
1994, Pakistani injured area reached 900000hm2, output of cotton only have 7,100,000 packet.It is passed through caused by between 1992-1995
Ji loss is more than 5,000,000,000 dollars.Currently, the virus is mainly distributed on Pakistan, India, the Sudan, Egypt, Nigeria, horse traction
The areas such as peacekeeping South Africa.There has been no infecting Cotton in China on a large scale to report, it is listed in inward plant quarantine harmful organism
List.China is that Cotton Production and consumption big country, the diseases state such as Pakistan adjoin Xinjiang of China cotton production areas, and biography in the world
The aleyrodid for contaminating this virus has spread each cotton region in China, once the incoming China's consequence of this virus will be hardly imaginable.Therefore, we are necessary
Numerous studies are carried out to cotton curve leaf disease virus prevention and control, are prevented trouble before it happens.
Citrus bacterial canker disease (Citrus Canker) is distributed in each citrus producing region at present.Citrus bacterial canker disease is domestic and international
Plant quarantine object.The disease pathogen is a kind of bacterium of ecliptic pole hair bacillus.Thallus rod-short, two terminal circle, one end have one
Flagellum, can move, and have a pod membrane, no gemma, and Gram-negative reaction is aerobic.On culture medium, bacterium colony is in bright orange
Color, round, surface is smooth, around there is narrow leukorrhea.On beef broth peptone culture medium, bacterium colony is round, and wax yellow has light
Pool, full edge, micro- protuberance are sticky.Be critically ill harmful Citrus leaf, branch and the fruit.Nursery stock and the aggrieved especially severe of treelet will cause
Fallen leaves, spike top, influence tree vigo(u)r；The aggrieved severe one shedding of fruit, less serious case with ill scar, do not rot by storage tolerance, generation, substantially reduces fruit
Real commodity value, increases orchard worker by insect pest preventing and controlling cost, and economic benefit is impaired.First occurs pinhead-sized dense Huang on plant leaf blade
Color grease stain shape round spot, then leave dual sides are swelled, and in spongy, subsequent disease portion central rupture, suberification is in canescence volcano
Mouth shape.Scab is mostly subcircular, often has wheel line or shape of threads, around there is the greasy outer ring of a crineous and yellow halo.Fruit
It is similar on blade with the scab on branch, but the suberification degree of scab is even more serious, more significant, the branch of mountain pass shape cracking
The tip is aggrieved to cause leaf abscission with summer shoot most serious when serious, branch is withered.
Pepper ralstonia solanacearum is a kind of bacterial disease of soil-borne, and the main route of entry of germ is to pass through crop root
Wound infection.Germ enters vascular bundle after invading crop, and by proliferation blocking conducting system, moisture is made not can enter cauline leaf
And cause green withered.Germ is difficult to remove once entering vascular bundle, therefore, bacterial wilt is prevented and treated in production, prevention is crucial.It is peppery
Green pepper bacterial wilt shows the radicula brown stain first that symptom is plant, starts to decay and disappears soon.Cut the disease close to surface location
Stem it can be found that vascular bundle is micro- brown stain, and secrets out of white casse dirt juice from the position.Bacterial wilt is tomato, eggplant, peppery
The Major Diseases of the solanaceous vegetables such as green pepper, potato.Cardinal symptom is that plant wilts rapidly, is withered, and cauline leaf still keeps green.Sick stem
Brown stain position squeezed with hand, have milky bacterium solution discharge.In high temperature and humidity, continuous cropping continuous cropping, geodepression soil is glutinous, field ponding, soil
When earth meta-acid, inclined nitrogen fertilizer application, which is easy to happen.Pepper ralstonia solanacearum is generally from discovery performance symptom to complete stool dead 7
It or so.Therefore, pepper ralstonia solanacearum is to the very harmful of capsicum.Since fungicide easily generates resistance, it is therefore desirable to constantly push away
New type bactericide and microbicide compositions out.
Summary of the invention
For above situation, it can solve the above problem present invention firstly provides one kind and have significant synergistic effect containing benzene
The bactericidal composition of ether methyl cyclic-azole, and the sterilization pesticide using the bactericidal composition as effective component is further provided for, and its wrapping
Include prevention and treatment rice sheath blight disease, bacterial blight of rice, bacterium of downy mildew of cucumber, pear scab, pepper anthracnose, apple spot fallen leaves
Disease, bitter rot or anthracnose of grape, grapevine anthracnose, citrus scab, watermelon grafting, powdery mildew of strawberry, early blight of tomato, cotton Qu Ye
Downy mildew, mosaic virus, powdery mildew, the epidemic disease of the crops such as virus, tobacco mosaic virus (TMV), wheat scab and other fruit/vegetables
Etc. application in terms of diseases reduce control cost, and delay the generation of drug resistance to effectively improve the control efficiency to disease.
Bactericidal composition of the present invention is with Chinese for (6R,12aR) -2,3,6,7,12,12a- hexahydro -4- methyl imido
Base -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (present invention in
Be referred to as MIPO-6-1 down, structural formula is as shown in Equation 3) and Chinese be difenoconazole (No. CAS: 119446-68-3；
Molecular formula: C19H17Cl2N3O3；Chemical name: suitable, the trans- chloro- 4- of 3- [4- methyl -2- (1H-1,2,4- triazol-1-yl first
Base) -1,3- dioxolane -2- base] phenyl 4- chlorphenyl ether；English abbreviation: Difenoconazole, structure such as 1 institute of formula
Show) it collectively constitutes；The present invention is using the compound of MIPO-6-1 and difenoconazole as acceptable in effective component, with pesticide
Auxiliary element collectively constitutes.
Bactericidal composition of the present invention can also be with Chinese for (6R,12aR) -2,3,6,7,12,12a- hexahydro -4- methyl
Imino group -2- methyl -6- (2,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles is (in the present invention
Hereinafter referred to as MIPO-8-1, structural formula are as shown in Equation 4) and Chinese be difenoconazole (No. CAS: 119446-68-
3；Molecular formula: C19H17Cl2N3O3；Chemical name: suitable, the trans- chloro- 4- of 3- [4- methyl -2- (1H-1,2,4- triazol-1-yl first
Base) -1,3- dioxolane -2- base] phenyl 4- chlorphenyl ether；English abbreviation: Difenoconazole, structure such as 1 institute of formula
Show) it collectively constitutes；The present invention is using the compound of MIPO-6-1 and difenoconazole as acceptable in effective component, with pesticide
Auxiliary element collectively constitutes.
Bactericidal composition of the present invention can be with Chinese for (6R,12aR) -2,3,6,7,12,12a- hexahydro -4- methyl
Imino group -2- methyl -6- (4- fluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles is (following in the present invention
Referred to as MIPO-18-1, structural formula are as shown in Equation 5) and Chinese be difenoconazole (No. CAS: 119446-68-3；Point
Minor: C19H17Cl2N3O3；Chemical name: suitable, the trans- chloro- 4- of 3- [4- methyl -2- (1H-1,2,4- triazol-1-yl methyl) -
1,3- dioxolane -2- base] phenyl 4- chlorphenyl ether；English abbreviation: Difenoconazole, structure are as shown in Equation 1) altogether
With composition；The present invention is assisted using the compound of MIPO-6-1 and difenoconazole as acceptable in effective component, with pesticide
Ingredient collectively constitutes.
Bactericidal composition of the present invention containing difenoconazole, by difenoconazole and MIPO-6-1 be by weight 1:1 ~
30:1 composition.Further preferred embodiment with MIPO-6-1 is that 1:1 ~ 10:1 is formed by difenoconazole by weight.
Bactericidal composition of the present invention containing difenoconazole can also be 1 by difenoconazole and MIPO-8-1 by weight:
1 ~ 30:1 composition.Further preferred embodiment with MIPO-8-1 is that 1:1 ~ 10:1 is formed by difenoconazole by weight.
Bactericidal composition of the present invention containing difenoconazole can also be by weight with MIPO-18-1 by difenoconazole
1:1 ~ 30:1 composition.It is 1:1 ~ 10:1 group that further preferred embodiment is by difenoconazole and MIPO-18-1 by weight
At.
Any two kinds in tri- kinds of MIPO-6-1, MIPO-8-1, MIPO-18-1 first, the MIPO-II mixture of formation.
Bactericidal composition of the present invention containing difenoconazole, can also by difenoconazole and MIPO-II mixture, by weight for 1:1 ~
30:1 composition.It is 1:1 ~ 10:1 group that further preferred embodiment is by difenoconazole and MIPO-II mixture by weight
At.
Tri- kinds of MIPO-6-1, MIPO-8-1, MIPO-18-1 first form MIPO-III mixture according to different proportion.This
Bactericidal composition of the invention containing difenoconazole, can also by difenoconazole and MIPO-III mixture, by weight for 1:1 ~
30:1 composition.It is 1:1 ~ 10:1 group that further preferred embodiment is by difenoconazole and MIPO-III mixture by weight
At.
Additionally due to the compound that general formula is MIPO contains two chiral centres, therefore each compound is same there are four
Enantiomers.By taking MIPO-6 compound as an example, (6 are just existed simultaneouslyR,12aR) -2,3,6,7,12,12a- hexahydro -4- methyl Asia
Amino-2-methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles is (referred to as
MIPO-6-1) its structure is as shown in Equation 3), (6S,12aR) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -
6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-6-2) its structure such as formula 6
It is shown), (6R,12aS) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrrole
Piperazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-6-3) its structure is as shown in Equation 7), (6S,12aS)-2,3,
6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1]
Pyridine [3,4-b] indoles (MIPO-6-4) (its structure is as shown in Equation 8).
It is formed using above-mentioned bactericidal composition as acceptable auxiliary element in effective active composition, with pesticide.Institute
Say acceptable auxiliary element in pesticide, including at present in pesticide using, will not have an adverse effect it is all kinds of often
With solvent and/or inert filler and/or surfactant and/or preservative and/or antifreezing agent and/or anti-caking agent and/or disappear
Infusion and/or the corresponding adding ingredient such as cosolvent and/or stabilizer and/or thickener, and can be according to preparation shape produced
Formula does corresponding selection or adjustment.Such as the described formulations of pesticide composition and corresponding typical preparation method can be as following.
Agrochemical formulations generally comprise the Herbicidal combinations of the present invention of 0.1-99 weight %, especially 2-90 weight %.?
Herbicidal combinations concentration is in wettable powder (WP), such as the rest part in 10-90 weight %, 100 weight % is by routinely making
Agent auxiliary element composition.Herbicidal combinations concentration is in suspending agent (SC), such as 1-90 weight %, preferably 5-75 weight %, 100
Rest part in weight % is made of conventional formulation auxiliary element.Herbicidal combinations concentration is in suspoemulsion (SE), such as 1-
90 weight %, preferably 5-75 weight %, the rest part in 100 weight % are made of conventional formulation auxiliary element.In water dispersant
(WDG) Herbicidal combinations concentration is in, such as 1-95 weight %, preferably 10-70 weight %, and the rest part in 100 weight % is by normal
Regulation agent auxiliary element composition.The preparation of other powder types includes 1-40 weight % reactive compound, and preferably 5-20 weight % is living
Property compound, the rest part in 100 weight % are made of conventional formulation auxiliary element.
Herbicidal combinations of the present invention are needed according to different uses or application Huan Jing ∕ condition, raw by current conventional pesticide
Production mode is abundant for raw material to MIPO-6-1 effective component and corresponding auxiliary element by difenoconazole in the bactericidal composition
Mixing, is prepared into various forms of available corresponding dosage forms.Possible dosage form includes: microemulsion (ME), aqueous emulsion
(EW), microcapsule formulations, wettable powder, water dispersible granules, suspending agent, aqueous emulsion, suspoemulsion, microcapsule formulations etc..Such as it is several
Typical common dosage forms and preparation can be with:
Water dispersible granules (WDG) can fater disintegration in water, and can be uniformly dispersed in and form higher suspension dispersion in water
A kind of granular preparation.Present composition difenoconazole and MIPO-6-1 and auxiliary element one can be reinstated air-flow powder when preparation
Pure or ultra-fine grinding, is made wettable powder, this is dry method；It is to be situated between with water by the present composition, auxiliary agent, adjuvant etc.
Matter is ground in sand mill, and suspending agent is made, and then re-dry is granulated, this is wet process.
Wettable powder (WP), i.e., solid powder preparation that in water can be evenly dispersed.It, can be according to conventional side when preparation
Formula is firstly added the composition of difenoconazole and MIPO-6-1 of the present invention, then be added diatomite, clay, precipitated calcium carbonate,
The common diluent such as white carbon black or inert substance add other common auxiliary elements, such as alkylnaphthalene sulfonate, alkyl benzene sulphonate
Salt, aliphatic alcohol sulfate, alkyl bromination ammonium, alkyl ammomium chloride, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, sulfomethylated lignin
One of hydrochlorate, lignin, carboxymethyl cellulose, sodium carboxymethylcellulose, azone, thiophene ketone are several, and common steady
Determine the complementary auxiliary component such as agent, foam inhibitor, anticaking agent.
Microemulsion (ME) is that pesticide active ingredient and emulsifier, dispersing agent, antifreezing agent, stabilizer, cosolvent etc. help
Agent is evenly dispersed in substrate water, the transparent or corpus mamillare of formation.Microemulsion is the heating power that two kinds of non soluble liquids are formed
Learn stable mouth, isotropic, appearance transparent or translucent homogeneous dispersion system, it is microcosmic on by surfactant interface film
The droplets of stable one or two kinds of liquid constituted.The microemulsion of narrow sense is defined as by oil ingredient-water-surfactant structure
At transparent or semitransparent single_phase system, be the thermodynamically stable micelle dispersion to have swollen.Microemulsion is dispersed in water
In the partial size of effective component be 0.01~0.1 micron, thus the appearance of microemulsion is transparent or close to transparent.Its emulsifier
Dosage is generally twice of active material or more, and needs a certain amount of organic solvent and solubilizer.It is capable of processing into aqueous emulsion
Active material can theoretically be processed into microemulsion, but process concentration and be usually no more than 20%.The selection of emulsifier and solvent is non-
Otherwise crystallization and phase inversion easily occur for Chang Guanjian.Emulsifier in microemulsion, Chang Xuanyong HLB value 13 is with hydrophilic nonionic
Type surfactant and lipophilic back activating agent mixture.Nonionic surface active agent selection is to note: it is living to change surface
Property agent molecule ethylene oxide chain link (EO) mean adjusts amphipathic property；Shadow of the hydrophilic lipophilic group size to emulsifying effectiveness
It rings；The distribution of EO chain number is narrower in molecule, and threephase region is smaller, and the range for forming micro emulsion is bigger；Amphipathic property is temperature sensitive.
Stabilizer is commonly incorporated into microemulsion.Generally plus consistent dose is 0.5% ~ 30%, and common stabilizer has chloro- 1, the 2- epoxy chloropropionate of 3-
Alkane, phenyl glycidyl ether, butyl glycidyl ether, sorbierite and polyethylene.Ethyl glycol glycidol ether etc..In microemulsion
It is commonly incorporated into antifreezing agent agent.Generally plus antifreeze dosage is 5% ~ 10%, and common antifreezing agent has ethylene glycol, propylene glycol, glycerine, poly- second
Glycol, sorbierite etc..These alcohols have antifreeze effect, and the effect in adjustable system transparency temperature region.It commonly uses at present micro-
Emulsion kind has 10% efficient phenothrin, 5% cypermethrin, 30% binapacryl microemulsion, 8% fenvalerate, 5% efficient chlorine cyanogen
The commodity such as the microemulsions such as pyrethroids and 10% Feng Wei, 35% grass enemy.Microemulsion cost is generally higher than missible oil and emulsion (because wherein emulsifying
The dosage of agent and solvent is big).To develop this one dosage type low temperature, Ying Shouxian is promoted on the crop (such as veterinary antibiotics) of high added value to be made
With to improve the quality of veterinary antibiotics, then gradually expanding application range.
Aqueous emulsion (EW), the raw medicine liquid or raw medicine for being insoluble in water are dissolved in the resulting liquid of organic solvent not soluble in water
It is dispersed in water the liquid preparation to be formed.It can be by described active drug ingredient and including solvent, emulsifier, altogether emulsification when preparation
Auxiliary element including agent, antifreeze, defoaming agent, antimicrobial, pH adjusting agent, density adjuster, thickener etc., cuts through height
Emulsification is cut to be made.Solvent therein can choose in pesticide in benzene class, ketone or the alcohols equal solvent such as common toluene, dimethylbenzene
One or more;Emulsifier can choose as above-mentioned ethoxylated alkyl ether, ethoxyquin alkyl phenylate, alkylbenzene sulfonate,
Ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid ester, sorbitan alkyl ester, gathers alkyl phenol polyglycol ether
One or more of the poly- alkane alkene polyamine of oxygen alkane alkene, amides etc.;Co-emulsifier can choose such as butanol, isobutanol, dodecane
One or more of alkanes alcohols such as alcohol -1, tetradecanol -1, octadecanol -1;Antifreeze can choose such as above-mentioned chlorination
Sodium, urea, ammonium sulfate, ethylene glycol, one or more of polyalcohols such as 1,2- propylene glycol;Thickener and stabilizer can also select
One or more of such as above-mentioned xanthan gum (XG), polyvinyl alcohol (PVA), aluminum magnesium silicate are selected, and is used when necessary
PH adjusting agent and auxiliary agents such as defoaming agent etc..
Suspending agent (SC) i.e. agricultural chemicals suspension agent (SC) is water insoluble solids pesticide or not mixed liquid pesticidal in water or oil
Dispersion.When preparation, with water or oil for decentralized medium, by difenoconazole of the present invention and MIPO-6-1 composition and auxiliary
Ingredient (such as thickener, stabilizer, Ricinate, antifreezing agent, pH adjusting agent, defoaming agent) is through soybean dietary fiber (grinding)
It is made.Wherein Ricinate is phosphate polyethers, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl
Ammonium bromide, alkyl ammomium chloride, crown ether, quaternary alkylphosphonium salt, alkyl polyoxyethylene base ether sulfate, lignosulfonates, lignin, carboxylic first
One of base cellulose, sodium carboxymethylcellulose, azone, thiophene ketone are several；Thickener and stabilizer are polyvinyl alcohol, contracting
Close one of phosphate, xanthan gum, aluminum magnesium silicate etc. or several；Antifreezing agent is sodium chloride, urea, ammonium sulfate, second two
One of alcohol, glycerol etc. are several；PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, carbonic acid
One of potassium etc. is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
Suspoemulsion (SE) the i.e. hybrid dispersions of the insoluble pesticide of water in water, one such effective component is in suspension
State, other effective components are in emulsion state.When preparation can by the present composition and corresponding emulsion, Ricinate,
The auxiliary elements such as thickener, stabilizer, antifreezing agent, pH adjusting agent, defoaming agent, it is conventionally, mixed through soybean dietary fiber
It closes and is made.Wherein emulsifier is alkyl phenol polyoxyethylene ether class (agriculture breast 100#), alkylbenzene sulfonate (agriculture breast 500#), phenethyl
In phenol polyethenoxy ethers (agriculture breast 600#), alkyl phenol or aralkyl phenol polyethenoxy ether formaldehyde condensation species (Nongru-700 #) etc.
One or several kinds.Wherein Ricinate be lignosulfonates, lignin, phosphate polyethers, carboxymethyl cellulose,
Sodium carboxymethylcellulose, crown ether, alkylnaphthalene sulfonate, alkylbenzene sulfonate, aliphatic alcohol sulfate, alkyl ammonium halide, quaternary alkylphosphonium salt,
One of alkyl polyoxyethylene base ether sulfate, azone, thiophene ketone are several；Thickener and stabilizer are polyvinyl alcohol, contracting
Close one of phosphate, xanthan gum, aluminum magnesium silicate etc. or several；Antifreezing agent is sodium chloride, urea, ammonium sulfate, second two
One of alcohol, glycerol etc. are several；PH adjusting agent is potassium dihydrogen phosphate, dipotassium hydrogen phosphate, citric acid, sodium carbonate, carbonic acid
One of potassium etc. is several.Organosilicon is commonly used as defoaming agent and foam inhibitor.
It should be noted that specific dosage form mentioned above is the representative dosage form that the present composition can be prepared, enumerate not
It is limited to these above-mentioned dosage forms.
Concrete mode by the following examples is again described in further detail above content of the invention.But it does not answer
This range for being interpreted as the above-mentioned theme of the present invention is only limitted to example below by this.The above-mentioned technical idea feelings of the present invention are not being departed from
Under condition, the various replacements or change made according to ordinary skill knowledge and customary means, should all include of the invention
In range.Each material composition ratio is weight % in embodiment.
Specific embodiment
One, example of formulations
The MIPO-6-1 wettable powder (WP) of embodiment 1:30%
35 grams, 45 grams 300 grams of MIPO-6-1,35 grams of lignosulfonates calcium, pull powder Bx carboxymethyl celluloses are weighed respectively
Sodium, 70 grams of aluminum magnesium silicates, 40 grams of neopelexes, 25 grams of tetrabutylammonium bromide, 460 grams of kaolin, it is spare；Preparation:
Each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(1:1 of embodiment 2:20%) wettable powder (WP)
100 grams of difenoconazoles, 100 grams of MIPO-6-1,30 grams of tetrabutylammonium bromide, 30 grams, 40 grams of pull powder Bx are weighed respectively
Lignosulfonates calcium, 45 grams of sodium carboxymethylcelluloses, 35 grams of aluminum magnesium silicates, 30 grams of neopelexes, 590 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(3:1 of embodiment 3:20%) wettable powder (WP)
Weigh respectively 150 grams of difenoconazoles, 50 grams of MIPO-6-1,40 grams of neopelexes, 25 grams of pull powder Bx,
45 grams of lignosulfonates calcium, 35 grams of sodium carboxymethylcelluloses, 35 grams of aluminum magnesium silicates, 35 grams of tetrabutylammonium bromide, 585 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(9:1 of embodiment 4:20%) wettable powder (WP)
Weigh respectively 180 grams of difenoconazoles, 20 grams of MIPO-6-1,30 grams of neopelexes, 25 grams of pull powder Bx,
55 grams of lignosulfonates calcium, 45 grams of sodium carboxymethylcelluloses, 35 grams of aluminum magnesium silicates, 30 grams of tetrabutylammonium bromide, 580 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(1:3 of embodiment 5:20%) wettable powder (WP)
50 grams of difenoconazoles, 150 grams of MIPO-6-1,30 grams of tetrabutylammonium bromide, 50 grams of aluminum magnesium silicates, 40 gram ten are weighed respectively
Dialkyl benzene sulfonic acids sodium, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 560 grams of kaolin, pull powder Bx 30
Gram, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(4:1 of embodiment 6:25%) wettable powder (WP)
200 grams of difenoconazoles, 50 grams of MIPO-6-1,50 grams of lignosulfonates calcium, 25 grams of pull powder Bx, 45 are weighed respectively
Gram neopelex, 40 grams of sodium carboxymethylcelluloses, 30 grams of aluminum magnesium silicates, 30 grams of tetrabutylammonium bromide, 530 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-8-1(2.57:1 of embodiment 7:25%) wettable powder (WP)
Weigh respectively 180 grams of difenoconazoles, 70 grams of MIPO-8-1,30 grams, 45 grams neopelexes of pull powder Bx,
35 grams of tetrabutylammonium bromide, 40 grams of aluminum magnesium silicates, 35 grams of lignosulfonates calcium, 40 grams of sodium carboxymethylcelluloses, 525 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-8-1(1:3 of embodiment 8:20%) wettable powder (WP)
50 grams of difenoconazoles, 150 grams of MIPO-8-1,25 grams of tetrabutylammonium bromide, 50 grams of dodecyl benzene sulfonic acid are weighed respectively
Sodium, 40 grams of aluminum magnesium silicates, 40 grams of lignosulfonates calcium, 50 grams of sodium carboxymethylcelluloses, 565 grams of kaolin, pull powder Bx 30
Gram, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-8-1(4:1 of embodiment 9:25%) wettable powder (WP)
200 grams of difenoconazoles, 50 grams of MIPO-8-1,45 grams of lignosulfonates calcium, 25 grams of pull powder Bx, 35 are weighed respectively
Gram neopelex, 40 grams of sodium carboxymethylcelluloses, 45 grams of aluminum magnesium silicates, 30 grams of tetrabutylammonium bromide, 530 grams of kaolinites
Soil, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1(4:1 of embodiment 10:30%) water dispersible granules (WDG)
240 grams of difenoconazoles, 60 grams of MIPO-6-1,20 grams of dispersing agent D909S, 30 grams of 600C suspension aids, 35 are weighed respectively
Gram lignin, 35 grams of acrylic acid minor matters polymer, 35 grams of dodecyl sodium sulfates, 25 grams of polyethylene glycol, 520 grams of bentonites, it is standby
With；Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated, it is dry
Up to water dispersible granules.
The bactericidal composition difenoconazole MIPO-8-1(2:1 of embodiment 11:30%) water dispersible granules (WDG)
200 grams of difenoconazoles, 100 grams of MIPO-8-1,40 grams of polyethylene glycol, 35 grams of dispersing agent D909S, 30 grams of wood are weighed respectively
Quality, 50 grams of acrylic acid minor matters polymer, 50 grams of dodecyl sodium sulfates, 35 grams of 600C suspension aids, 460 grams of bentonites, it is standby
With；Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated, it is dry
Up to water dispersible granules.
The bactericidal composition difenoconazole MIPO-6-1(7:1 of embodiment 12:40%) water dispersible granules (WDG)
350 grams of MIPO-6-1,50 grams of difenoconazoles, 40 grams of dispersing agent D909S, 20 grams of lignin, 30 grams of propylene are weighed respectively
Sour minor matters polymer, 50 grams of dodecyl sodium sulfates, 50 grams of polyethylene glycol, 30 grams of 600C suspension aids, 380 grams of bentonites, it is standby
With；Each material is sequentially added in reaction kettle, is uniformly mixed, is then ground in sand mill, suitable quantity of water is added, is granulated, it is dry
Up to water dispersible granules.
The bactericidal composition difenoconazole MIPO-6-1MIPO-8-1 water dispersible granules (WDG) of embodiment 13:30%
200 grams of difenoconazoles, 50 grams of MIPO-6-1,50 grams of MIPO-8-1,35 grams of 600C suspension aids, 50 grams of wood are weighed respectively
Quality, 50 grams of acrylic acid minor matters polymer, 25 grams of dodecyl sodium sulfates, 40 grams of polyethylene glycol, 500 grams of bentonites, it is spare；It will
Each material sequentially adds in reaction kettle, is uniformly mixed, then grinds in sand mill, and suitable quantity of water is added, and is granulated, is drying to obtain water
Dispersible granule.
The bactericidal composition difenoconazole MIPO-6-1MIPO-8-1 water dispersible granules (WDG) of embodiment 14:35%
310 grams of difenoconazoles, 20 grams of MIPO-6-1,20 grams of MIPO-8-1,25 grams of acrylic acid minor matters polymer, 55 are weighed respectively
Gram polyethylene glycol, 55 grams of dodecyl sodium sulfates, 25 grams of lignin, 30 grams of 600C suspension aids, 460 grams of bentonites, it is spare；It will
Each material sequentially adds in reaction kettle, is uniformly mixed, then grinds in sand mill, and suitable quantity of water is added, and is granulated, is drying to obtain water
Dispersible granule.
The bactericidal composition difenoconazole MIPO-6-1(9:1 of embodiment 15:30%) microemulsion (ME)
270 grams of difenoconazoles, 30 grams of MIPO-6-1,60 grams of cyclohexanone, 55 grams of isopropanols, 75 grams of alkyl phenol polyoxies are weighed respectively
Ethylene ether phosphate, 65 grams of polyoxyethylene alkyl ethers, 65 grams of sorbit fatty acid esters, 180 grams of dimethylbenzene, 200 grams of water, it is spare.It adopts
With conventional method, raw medicine, solvent mixed dissolution under stirring, are added water to mixed after emulsifier, co-emulsifier mixing is added
It closes uniformly, microemulsion is made.
The bactericidal composition difenoconazole MIPO-6-1(1:1 of embodiment 16:30%) microemulsion (ME)
150 grams of MIPO-6-1,150 grams of difenoconazoles, 70 grams of alkyl phenol polyoxyethylene ether phosphates, 85 grams of hexamethylenes are weighed respectively
Ketone, 65 grams of isopropanols, 70 grams of polyoxyethylene alkyl ethers, 60 grams of sorbit fatty acid esters, 160 grams of dimethylbenzene, 190 grams of water, it is spare.It adopts
With conventional method, raw medicine, solvent mixed dissolution under stirring, are added water to mixed after emulsifier, co-emulsifier mixing is added
It closes uniformly, microemulsion is made.
The bactericidal composition difenoconazole MIPO-6-1(1:5 of embodiment 17:30%) microemulsion (ME)
250 grams of MIPO-6-1,50 grams of difenoconazoles, 80 grams of cyclohexanone, 55 grams of isopropanols, 85 grams of alkyl phenol polyoxies are weighed respectively
Ethylene ether phosphate, 65 grams of polyoxyethylene alkyl ethers, 65 grams of sorbit fatty acid esters, 150 grams of dimethylbenzene, 200 grams of water, it is spare.It adopts
With conventional method, raw medicine, solvent mixed dissolution under stirring, are added water to mixed after emulsifier, co-emulsifier mixing is added
It closes uniformly, microemulsion is made.
The bactericidal composition difenoconazole MIPO-6-1(2:1 of embodiment 18:30%) suspending agent (SC)
Weigh respectively 200 grams of difenoconazoles, 100 grams of MIPO-6-1,35 grams of neopelexes, 45 grams of polyethylene glycol,
35 grams of lignosulfonates calcium, 20 grams, 25 grams sodium carboxymethylcelluloses of tetrabutylammonium bromide, 20 grams of aluminum magnesium silicates, 520 grams of water,
It is spare.Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, has then been ground in sand mill
Grain diameter of components is imitated at 2~5 μm.
The bactericidal composition difenoconazole MIPO-6-1(4:1 of embodiment 19:20%) suspending agent (SC)
160 grams of difenoconazoles, 40 grams of MIPO-6-1,45 grams of polyethylene glycol, 35 grams of aluminum magnesium silicates, 35 grams of lignin are weighed respectively
Sulfonate calcium, 30 grams, 40 grams sodium carboxymethylcelluloses of tetrabutylammonium bromide, 35 grams of neopelexes, 580 grams of water, it is standby
With.Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill effectively
Grain diameter of components is at 2~5 μm.
The bactericidal composition difenoconazole MIPO-6-1(2:1 of embodiment 20:30%) suspending agent (SC)
200 grams of difenoconazoles, 100 grams of MIPO-6-1,35 grams of neopelexes, 30 grams of lignin sulfonic acids are weighed respectively
Salt calcium, 35 grams, 40 grams sodium carboxymethylcelluloses of tetrabutylammonium bromide, 20 grams of aluminum magnesium silicates, 90 grams of polyethylene glycol, 450 grams of water, it is standby
With.Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill effectively
Grain diameter of components is at 2~5 μm.
The bactericidal composition difenoconazole MIPO-8-1 suspending agent (SC) of embodiment 21:30%
90 grams of difenoconazoles, 210 grams of MIPO-8-1,20 grams of aluminum magnesium silicates, 65 grams of polyethylene glycol, tetrabutyl phosphonium bromides are weighed respectively
35 grams, 25 grams sodium carboxymethylcelluloses of ammonium, 30 grams of lignosulfonates calcium, 25 grams of neopelexes, 500 grams of water, it is standby
With.Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill effectively
Grain diameter of components is at 2~5 μm.
The bactericidal composition difenoconazole MIPO-8-1 suspending agent (SC) of embodiment 22:30%
250 grams of difenoconazoles, 50 grams of MIPO-8-1,40 grams of neopelexes, 25 grams of lignin sulfonic acids are weighed respectively
Salt calcium, 20 grams, 20 grams sodium carboxymethylcelluloses of tetrabutylammonium bromide, 25 grams of aluminum magnesium silicates, 70 grams of polyethylene glycol, 500 grams of water, it is standby
With.Each material is sequentially added in reaction kettle, just dispersion is carried out using high-speed shearing machine, is then ground in sand mill effectively
Grain diameter of components is at 2~5 μm.
The micro-emulsion of phenyl ether methyl cyclic-azole (ME) of embodiment 23:30%
300 grams of difenoconazoles, 100 grams of dimethylbenzene, 95 grams of cyclohexanone, 55 grams of isopropanols, 70 grams of alkyl phenol polyoxies are weighed respectively
Ethylene ether phosphate, 60 grams of polyoxyethylene alkyl ethers, 60 grams of sorbit fatty acid esters, 260 grams of water, it is spare.It, will using conventional method
Raw medicine, solvent mixed dissolution under stirring, are added water to uniformly mixed, are made micro- after emulsifier, co-emulsifier mixing is added
Emulsion.
The MIPO-6-1 microemulsion (ME) of embodiment 24:30%
300 grams of MIPO-6-1,55 grams of polyoxyethylene alkyl ethers, 85 grams of methylene chloride, 80 grams of isopropanols, 120 grams of alkane are weighed respectively
Base phenol polyethenoxy ether phosphate, 85 grams of sorbit fatty acid esters, 80 grams of dimethylbenzene, 195 grams of water, it is spare.It, will using conventional method
Raw medicine, solvent mixed dissolution under stirring, are added water to uniformly mixed, are made micro- after emulsifier, co-emulsifier mixing is added
Emulsion.
The difenoconazole wettable powder (WP) of embodiment 25:10%
100 grams of difenoconazoles, 80 grams of aluminum magnesium silicates, pull powder Bx 35 grams, 65 grams lignosulfonates calcium, 25 are weighed respectively
Gram tetrabutylammonium bromide, 55 grams of sodium carboxymethylcelluloses, 55 grams of neopelexes, 635 grams of kaolin, it is spare；Preparation:
Each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
The MIPO-6-1 wettable powder (WP) of embodiment 26:15%
150 grams of MIPO-6-1,70 grams of aluminum magnesium silicates, 35 grams, 55 grams lignosulfonates calcium of pull powder Bx, 25 grams are weighed respectively
Tetrabutylammonium bromide, 45 grams of sodium carboxymethylcelluloses, 55 grams of neopelexes, 565 grams of kaolin, it is spare；Preparation: will
Each material sequentially adds in reaction kettle, and stirring mixes them thoroughly, and is crushed to 5~20 μm.
The bactericidal composition difenoconazole MIPO-6-1 wettable powder (WP) of embodiment 27:35%
Weigh respectively 300 grams of difenoconazoles, 50 grams of MIPO-6-1,40 grams of tetrabutylammonium bromide, 40 grams of lignosulfonates calcium,
40 grams of sodium carboxymethylcelluloses, 30 grams of aluminum magnesium silicates, 30 grams of neopelexes, 390 grams of kaolin, pull powder Bx 30
Gram, it is spare；Preparation: each material is sequentially added in reaction kettle, stirring mixes them thoroughly, and is crushed to 5~20 μm.
Following test results shows synergistic function possessed by composition pesticide of the present invention and positive prevention and treatment
Effect.
Two, indoor sterilization is tested
Embodiment 28: difenoconazole and MIPO-6-1 composite formula screening experiment
Reagent agent (A difenoconazole in following reagents；B represents MIPO-6-1)
A agent: 10% difenoconazole wettable powder (WP) (being prepared by the method for embodiment 25)
B agent: 15% MIPO-6-1 wettable powder (WP) (being prepared by the method for embodiment 26)
Reagent agent AB1: difenoconazole MIPO-6-1(A:B=1:40)
Reagent agent AB2: difenoconazole MIPO-6-1(A:B=1:30)
Reagent agent AB3: difenoconazole MIPO-6-1(A:B=1:20)
Reagent agent AB4: difenoconazole MIPO-6-1(A:B=1:10)
Reagent agent AB5: difenoconazole MIPO-6-1(A:B=1:1)
Reagent agent AB6: difenoconazole MIPO-6-1(A:B=10:1)
Reagent agent AB7: difenoconazole MIPO-6-1(A:B=20:1)
Reagent agent AB8: difenoconazole MIPO-6-1(A:B=30:1)
Reagent agent AB9: difenoconazole MIPO-6-1(A:B=40:1)
Test method:
Using rice sheath blight disease as subjects, the evaluation of pesticide effectiveness of the present composition is carried out using indoor pot method.Referring in
Magnificent people's republic's farm-chemical indoor determination test rule YC/T-1996 is carried out.It is rice susceptible variety, vernalization for studying object
Every basin sows 1 afterwards, and wherein the consistent plant of growing way is spare in 1 heart stage of 2 leaf for selection.On the basis of preliminary experiment, according to medicine
Agent activity, is arranged 5 ~ 7 series mass concentration.Medical fluid is uniformly sprayed on to blade face to whole wettings, is advisable with not dripping, to medicine
Liquid natural air drying is spare.10 basin per treatment.And it sets and makees blank without the processing of effective component containing only solution and surfactant
Control.Inoculation is moved back to greenhouse, and 20 ~ 25 DEG C are cultivated 14 days, and a situation arises for investigation virus.
Drug effect calculation method:
1, disease index calculation method: obtaining disease index according to the viral situation of investigation first, and disease index calculation method is
It is as follows: disease index (%)=[∑ (this grade of typical value number of disease number of sheets * at different levels)/(investigation total number of sheets * superlative degree typical value)] * 100.
2, control efficiency calculation method: according to disease index data are obtained, control efficiency is further calculated.Control efficiency
(%)=[(control disease index-processing disease index)/control disease index] * 100.
3, virulence equation and EC50Calculation method: it is vertical sit that the control efficiency of every kind of reagent, which is converted to corresponding probability value (y),
Mark, and using the logarithm lgx of the various concentration of various reagents as abscissa, using least square method, obtain virulence equation (y=a+
Blgx coefficient a, b in).According to virulence equation, as y=5.000 (probability value when inhibiting rate is 50%), the reagent is calculated
Concentration EC in inhibition50。
4, (bibliography: Tan Genjia, wishing Jianping etc. to CTC calculation method, " fungicide bioassay calculation method and answers
With ", Anhui agronomy notification, 1998,4(1), 27-28): the co-toxicity coefficient of confection is calculated using Sun Yunpei equation
(CTC).Survey toxicity index (ATI)=(standard agent EC50/ reagent agent EC50)×100；Theoretical toxicity index (TTT)=(A
The percentage composition of A in medicament toxicity index × mixture)+(percentage composition of A in A medicament toxicity index × mixture)；Co-toxicity coefficient
(CTC)=[mixture surveys toxicity index (ATI)/mixtures theoretical toxicity index (TTI)] × 100.It is calculated using Sun Yunpei equation
CTC value out, China are generally acknowledged that (wherein: CTC is greater than 200, and there is CTC significant synergy to make with synergistic effect greater than 150
With), CTC is summation action 80~150, and CTC is antagonism less than 80.To rice sheath blight disease indoor toxicity test experimental drug
Result is imitated referring to table 1.The weight ratio of difenoconazole and MIPO-6-1 are malicious altogether within the scope of 30:1-1:1 in the present composition
Coefficient is all larger than 150, i.e. the composition shows as synergistic effect to the bioactivity of rice sheath blight disease, especially in 10:1-
The composition shows as significant synergistic effect to the bioactivity of rice sheath blight disease within the scope of 1:1 (CTC is greater than 200).
Table 1: to rice sheath blight disease The Toxicity Determination result
Three, field trial
1, prevention and treatment cucumber downy mildew test
A, test process: test is carried out referring to People's Republic of China's standard (pesticide field efficacy medicine test criterion).This investigational agent
Agent dosage sets three concentration for the treatment of according to the difference of each ingredient respectively, comparison medicament be respectively 10% difenoconazole it is wettable
Property pulvis (WP) (by embodiment 25 method prepare) and 15% MIPO-6-1 wettable powder (WP) (by the side of embodiment 26
Method preparation) and blank clean water experiment.Experiment reagent is respectively by the bactericidal composition difenoconazole MIPO- of embodiment 2:20%
6-1(1:1) the bactericidal composition difenoconazole MIPO-6-1(3:1 of wettable powder (WP), embodiment 3:20%) wettable
The bactericidal composition difenoconazole MIPO-6-1(9:1 of pulvis (WP), embodiment 4:20%) 3 kinds of wettable powder (WP) etc.
Experiment reagent composition.
B, test method: each plot area is 50m2, it is repeated 4 times, the inspection drug effect side after investigating and prevent and treat before being administered
Method are as follows: every cell chooses 10 plants, accounts for the percentage of entire leaf area with the lesion area on every plant of every a piece of leaf to be classified.Examination
Test that the results are shown in Table 2.
C, experimental result: table 2 the results show that pesticide of the present invention has good control efficiency, prevention and treatment to cucumber downy mildew
Effect is better than single dose kind.By taking after medicine 10 days as an example embodiment 2,3,4 it is different amounts of be significantly higher than 10% difenoconazole it is wettable
Property pulvis and 15% MIPO-6-1 wettable powder effect.14 days after medicine, embodiment 2,3,4 is different amounts of significant also the same
Difenoconazole wettable powder higher than 10% and 15% MIPO-6-1 wettable powder effect.
Table 2: the mutual pairing cucumber downy mildew field test effect of difenoconazole and MIPO-6-1
Claims (10)
1. bactericidal pesticide composition, with difenoconazole and (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- methyl imido
Base -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (referred to as MIPO-6-
1) it is collectively constituted for acceptable auxiliary element in effective component, with pesticide, wherein difenoconazole and (6R, 12aR) -2,
3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1]
Pyridine [3,4-b] indoles (referred to as MIPO-6-1) weight ratio is 1:100 to 100:1.
2. bactericidal pesticide composition as claimed in claim, it is characterized in that difenoconazole and (6R, 12aR) -2,3,6,7,
12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,
4-b] indoles (referred to as MIPO-6-1) weight ratio be 1:1 to 30:1.
3. bactericidal pesticide composition as claimed in claim, it is characterized in that difenoconazole and (6R, 12aR) -2,3,6,7,
12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,
4-b] indoles (referred to as MIPO-6-1) weight ratio be 1:1 to 10:1.
4. microbicide compositions as described in claim 1, it is characterized in that being prepared into not by current conventional pesticide production method
(referred to as with the available microemulsion (ME) of form, missible oil (abbreviation EC), water dispersible granules (abbreviation WDG), microcapsule formulations
CJ), the preparation formulations such as suspending agent (abbreviation SC), aqueous emulsion (abbreviation EW), suspoemulsion (abbreviation SE), wettable powder (abbreviation WP)
In any dosage form.
5. microbicide compositions as described in claim 1, it is characterized in that for rice, cucumber, watermelon, citrus, capsicum, cotton,
The sterilization of the industrial crops such as tobacco.
6. microbicide compositions as described in claim 1, it is characterized in that being used for rice sheath blight disease (Rice Sheath Blight
Disease), watermelon anthrax (Watermelon Anthracnose), cucumber downy mildew (Cucumber Downy
Mildew), bacterial blight of rice (Rice Bacterial Leaf Blight), citrus citrus bacterial canker disease (Citrus
Canker), pepper ralstonia solanacearum (Pepper Bacterial Wilt), cotton cotton curve leaf disease
(Cottoneleafcurlvirus), the bacteria-treatings such as tobacco mosaic virus (TMV) (Tobacco Mosaic Virus).
7. in microbicide compositions as described in claim 1, it is characterized in that for the sterilization of the bare places such as meadow, beach, forest.
8. in microbicide compositions as described in claim 1, it is characterized in that for banded sclerotial blight, bacterial leaf spot on industrial crops rice
The various preventions and cure of viruses such as disease, pythium rot, mould white disease, damping-off.
9. as in claim 1 microbiocidal agent composition, it is characterized in that (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- first
Base imino group -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles is (referred to as
MIPO-6-1) can by with (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- bis-
Fluorophenyl)-similar the compound (6R, 12aR) -2,3,6 of pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indole structure,
7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (2,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine
[3,4-b] indoles (abbreviation MIPO-8-1), (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -
6- (4- fluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (abbreviation MIPO-18-1) etc. replaces.
10. as in claim 1 microbicide compositions, it is characterized in that (6R, 12aR) -2,3,6,7,12,12a- hexahydro -4- first
Base imino group -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles is (referred to as
It MIPO-6-1) can be by isomer compound (6S, 12aR) -2,3,6,7,12,12a- hexahydro -4- first of MIPO-6-1
Base imino group -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-
6-2)；(6R, 12aS) -2,3,6,7,12,12a- hexahydro -4- methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -
1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-6-3)；(6S, 12aS) -2,3,6,7,12,12a- hexahydro -4-
Methyl-imino -2- methyl -6- (3,5- difluorophenyl)-pyrazine -1- ketone-[6,1:2,1] pyridine [3,4-b] indoles (MIPO-
6-4) etc. replace.
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| CN101524074A (en) * | 2009-04-23 | 2009-09-09 | 浙江林学院 | Composite bactericide and usage thereof |
| CN102057923A (en) * | 2011-01-06 | 2011-05-18 | 北京燕化永乐农药有限公司 | Germicide composition |
| CN104744460A (en) * | 2013-12-30 | 2015-07-01 | 南开大学 | B-carboline, dihydro-B-carboline and tetrahydro-B-carboline alkaloid derivative as well as preparation method and application in aspects of plant virus prevention and cure, sterilization and insecticide |
| CN106432237A (en) * | 2016-09-06 | 2017-02-22 | 西华大学 | Synthesis and purpose of amidine compound containing two chiral centers |
| CN107439566A (en) * | 2017-07-20 | 2017-12-08 | 中国检验检疫科学研究院 | A kind of medicament of Antiphytoviral |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101524074A (en) * | 2009-04-23 | 2009-09-09 | 浙江林学院 | Composite bactericide and usage thereof |
| CN102057923A (en) * | 2011-01-06 | 2011-05-18 | 北京燕化永乐农药有限公司 | Germicide composition |
| CN104744460A (en) * | 2013-12-30 | 2015-07-01 | 南开大学 | B-carboline, dihydro-B-carboline and tetrahydro-B-carboline alkaloid derivative as well as preparation method and application in aspects of plant virus prevention and cure, sterilization and insecticide |
| CN106432237A (en) * | 2016-09-06 | 2017-02-22 | 西华大学 | Synthesis and purpose of amidine compound containing two chiral centers |
| CN107439566A (en) * | 2017-07-20 | 2017-12-08 | 中国检验检疫科学研究院 | A kind of medicament of Antiphytoviral |
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