CN105712916B - Aminodithioformic acid copper derivative and its preparation and application - Google Patents
Aminodithioformic acid copper derivative and its preparation and application Download PDFInfo
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- CN105712916B CN105712916B CN201610041347.XA CN201610041347A CN105712916B CN 105712916 B CN105712916 B CN 105712916B CN 201610041347 A CN201610041347 A CN 201610041347A CN 105712916 B CN105712916 B CN 105712916B
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- disease
- aminodithioformic acid
- acid copper
- powdery mildew
- canker
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- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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- 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
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Abstract
The present invention relates to aminodithioformic acid copper derivative (I) and preparation method, its preparation and purposes as disinfectant use in agriculture, the meaning of each group is shown in specification in formula.The aminodithioformic acid copper derivative of the present invention shows good bactericidal activity, it can suppress the pathogens such as pepper anthracnose, rice blast, wheat powdery mildew, powdery mildew of cucumber, especially have and suppress Valsa mali Miyabe et Yamada activity well, there is the prevention effect more excellent than asomate and thiophanate-methyl to apple tree, Fungus of Pear Canker Disease, can be used for preparing disinfectant use in agriculture prevention fruit tree putrefaction disease.
Description
Technical field
The present invention relates to aminodithioformic acid copper derivative and preparation method, its preparation and as agricultural bactericidal
The purposes of agent, belongs to technical field of pesticide.
Background technology
China is global maximum apple production state and exported country, and it is public that cultivated area of the apple in 2012 has developed to 2,300,000
Hectare, total output has broken through 38,000,000 tons, and area and total output have been occupied first of countries in the world.However, disease but seriously affects
The healthy and sustainable development of China's Apple Industry, particularly apple tree canker, are the one kind for endangering apple tree most serious in the world
Fungal disease, generally occurs in each Main Apple Varieties producing region in China and endangers serious.The major branch of the disease main harm apple tree, master
It is dry, and the skin portion of sprig, make cortex decay and necrosis, the title for having apple tree " cancer ".The pathogenic bacteria of apple tree canker
For Valsa ceratosperma, while the bacterium is also the pathogenic bacteria of Fungus of Pear Canker Disease, and Fungus of Pear Canker Disease equally has generating region
The characteristics of domain is wide, incidence is high, unmanageable.Infect the disease and cause that tree body disease scar is innumerable, limb is incomplete, or even ruin garden, seriously
Threaten the sound development of China's apple, pears industry.
At present, apple tree, the control measure of Fungus of Pear Canker Disease mainly have physical control and chemical control, due to the germ category
In weak parasite, germ is easily propagated, and has the reasons such as latent infection phenomenon, not only prevention effect is low but also recurrence rate for physical control
High, chemical control is still most important effective ways in actual production.Asomate, is prevention apple tree and Fungus of Pear Canker Disease
Unique special effect agent, have the characteristics that the lasting period is long, strong in the dead tissue site penetration of bark, have to rot disease trunk disease
Good preventive and therapeutic effect, thus be most widely used medicament in production of fruit trees.Due to asomate category moderate toxicity fungicide, according to
China's toxicity of pesticide analysis, its length of arsenic pollution lasting period to orchard, scope are wide, and not only poisonous to people, animal, having to skin stimulates
Property, also environment structure can potentially be threatened, asomate is forbidden using by country.The slightly lower thiophanate-methyl of prevention effect is made
For the substitute species of asomate, have become the product for most registering application extensively in the Ministry of Agriculture.Research is waited to find however, Huang is beautiful
Thiophanate-methyl suppresses the activity reduction of scab and pathogen conidia germination and mycelial growth, may with the long-term frequency in orchard
Numerous sensitiveness for using related, causing pathogen reduces (Plant Pathology, 2009,39 (5), 549~554.).Therefore, seek
New efficient pesticide control is looked for become urgent problem to be solved in current fruit tree putrefaction disease preventing and controlling.
The content of the invention
The object of the present invention is to provide aminodithioformic acid copper derivative and preparation method, its preparation and as
The purposes of disinfectant use in agriculture.The aminodithioformic acid copper derivative of the present invention shows good bactericidal activity, can suppress
The pathogens such as pepper anthracnose, rice blast, wheat powdery mildew, powdery mildew of cucumber, especially have and suppress apple tree well
Rot disease germ activity, has the prevention effect more excellent than asomate and thiophanate-methyl to apple tree, Fungus of Pear Canker Disease, can
For preparing disinfectant use in agriculture prevention fruit tree putrefaction disease.
The aminodithioformic acid copper derivative of the present invention is the compound for having structure shown in below formula (I)：
The aminodithioformic acid copper derivative (I) of the present invention can be prepared as follows (route one)：Copper chloride, or
Copper bromide, or copper sulphate, or the cupric salt such as cupric oxide react to obtain aminodithioformic acid copper with nabam
Derivative (I)；
Route one：
The aminodithioformic acid copper derivative (I) of the present invention can be prepared as follows (route two)：Copper chloride, or
Copper bromide, or copper sulphate, or the cupric salt such as cupric oxide and secondary amine R1R2NH and carbon disulfide react to obtain dithiocarbamates first
Sour copper derivative (I)；
Route two：
Above in each general formula：
R1、R2It is identical or different, it is respectively selected from hydrogen, cyano group, amino, C1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alcoxyl
Base, halo C1-C12Alkoxy, C3-C12Cycloalkyl, cyano group C1-C12Alkyl, C1-C12Alkyl amine group, C2-C12Dialkyl amino,
C1-C12Alkyl-carbonyl, C1-C12Alkoxy C1-C12Alkyl, C1-C12Alkoxy carbonyl, C1-C12Alkoxy carbonyl methylene, C1-
C12It is alkane sulfonyl, unsubstituted or phenylcarbonyl group, benzyloxycarbonyl group, the benzene that following group is further substituted with are independently selected from by 1-5
Oxygen carbonyl, benzyloxycarbonyl group, phenyl amino, phenyl amino carbonyl, phenyl, benzyl, pyridine radicals, thiazolyl or benzothiazolyl：Halogen
Element, nitro, cyano group, C1-C12Alkyl, C1-C12Alkoxy；
Or NR1R2Form morpholine, piperidines, nafoxidine, azetidine, Ethylenimine, piperazine or N methyl piperazine
Ring.
The present invention is preferably as follows the aminodithioformic acid copper derivative (I) of chemical structural formula：
The aminodithioformic acid copper derivative (I) of the present invention shows good bactericidal activity, can suppress capsicum charcoal
The pathogens such as subcutaneous ulcer disease, rice blast, wheat powdery mildew, powdery mildew of cucumber, especially have and suppress apple tree canker well
Germ activity, to Valsa mali Miyabe et Yamada active effect when test concentrations are 10mg/L, inhibitory activity is part of compounds
100%, hence it is evident that higher than comparison medicament asomate, thiophanate-methyl, Xinjunan acetate, Tebuconazole, benziothiazolinone, pyrazoles ether bacterium
Ester, humic copper sulphate, coumoxystrobin, zinc dimethyl dithiocarbamate.The aminodithioformic acid copper of the present invention derives
Thing (I) can be used for preparing disinfectant use in agriculture prevention fruit tree putrefaction disease.
1 (the chemical name of aminodithioformic acid copper derivative of the present invention：Cupric dimethyldithio carbamate, code name：
Yy-2014) prevention apple tree canker results of field plot shows it with good prevention effect, and promotes sick scar to be cured
The width of conjunction is all significantly better than comparison medicament asomate and thiophanate-methyl, and no poisoning occurs.
1 (the chemical name of aminodithioformic acid copper derivative of the present invention：Cupric dimethyldithio carbamate, code name：
Yy-2014) prevention wheat rust results of field plot shows it with good prevention effect, hence it is evident that is better than comparison medicament
Triazolone, and to wheat safety.
1 (the chemical name of aminodithioformic acid copper derivative of the present invention：Cupric dimethyldithio carbamate, code name：
Yy-2014) prevention wheat powdery mildew results of field plot shows it with good prevention effect, hence it is evident that is better than comparison medicine
Agent triazolone, no poisoning occur.
In addition the purposes of aminodithioformic acid copper derivative (I) of the present invention also has：One kind is with dithiocarbamates
Copper formate derivative (I) is the bactericidal composition of active component, in the composition aminodithioformic acid copper derivative (I) activity
The percentage by weight of component is 0.1-99%.
The application form of the present composition can be pulvis, wettable powder, missible oil, emulsifiable concentrate and microemulsion, suspension
Agent, suspension emulsion, granule, finish, water dispersible granules etc..The specific type selection of composition is decided by answering in actual production
With.
The present composition is to be prepared by known methods, such as under the conditions of existing for optional auxiliary agent, by scattered
Agent, stabilizer and/or solid diluent directly dissolve active material.
Selectable liquid diluent also has：As aromatic organic solvent (toluene, dimethylbenzene or alkylbenzene mixture,
Chlorobenzene etc.), alcohols (methanol, propyl alcohol, isoamyl alcohol, glycerine, butanol, octanol), esters (isobutyl acetate, ethyl acetate etc.), acyl
Amine (N, N- dimethylformamide, 1-methyl-2-pyrrolidinone etc.), ketone (cyclohexanone, acetophenone, acetone etc.), water.
Selectable solid diluent or carrier have：Such as clay, clay, kaolin, diatomite, pyrophyllite, talcum
Powder, silica, magnesia, calcium carbonate etc..
Selectable surfactant has：Such as polyoxyethanyl fatty acid ester, polyoxyethanyl sorbierite oleic acid or stearic acid
Ester, aliphatic acid polyglycerol esters, phosphoric acid esters wedding agents, alkyl polyoxyethyl ether and more aromatic core base polyoxyethyl ethers etc..
The present composition can also be based on specific purpose and add special material, such as sticker such as carboxymethyl cellulose
Element, polyethylene butyl ether, polyvinyl alcohol etc..
The concentration of the active component of the present composition can according to application target, use environment, preparation type and certain
In the range of change.The concentration range of usual active component is 1%-90%, and preferable scope is 1%-70%.
According to the actual requirements, can suitably add in the composition can be compatible with aminodithioformic acid copper derivative (I)
Other active components, for example, other kinds of fungicide for example pyraoxystrobin, carbendazim, thiophanate-methyl, benziothiazolinone, coumoxystrobin,
Fluazinam, pyraclostrobin, propiconazole, Xinjunan acetate, humic acid, copper sulphate, network ammonia copper, Tebuconazole, ambam, suppression are mould
Azoles etc., can also be with insecticidal/acaricidal agent, plant growth regulator such as methyl α-naphthyl acetate, herbicide, antibiosis to realize synergy or delaying drug resistance
Element is used together as active component, or in the form of medicine fertilizer.Therefore, aminodithioformic acid copper derivative of the invention
(I) purposes also have a kind of binary or multicomponent reactive component containing aminodithioformic acid copper derivative (I) sterilization or/and
Weeding, plant tune, insecticide acaricide composition.
Present invention firstly discloses the compound shown in aminodithioformic acid copper derivative (I), and preparation method thereof, kill
Bacterium activity and the purposes as disinfectant use in agriculture.Preparation method provided by the invention is easy to operate, raw material is easy to get, cleaning is given birth to
Production, high income.
The more existing disinfectant use in agriculture used of aminodithioformic acid copper derivative (I) of the present invention, has very big excellent
Gesture：Chemical constitution is simple, and chemical property is stablized, and bactericidal activity is notable.The present invention establishes to formulate new, efficient disinfectant use in agriculture
Determine basis, possess good creativeness.
Brief description of the drawings
Fig. 1 is that present invention prevention apple tree canker promotes sick scar healing -2014 years autumns-Liaoning Xingcheng；
Fig. 2 is that present invention prevention apple tree canker promotes sick scar healing -2015 years spring-Liaoning Xingcheng；
Fig. 3 is that present invention prevention apple tree canker promotes sick scar -2014 years autumns of healing-Tianjin west blue or green；
Fig. 4 is that present invention prevention apple tree canker promotes sick scar -2015 years spring of healing-Tianjin west blue or green；
Fig. 5 is that present invention prevention apple tree canker promotes sick scar healing -2015 years autumns-Liaoning Xingcheng；
Fig. 6 is that present invention prevention apple tree canker promotes sick scar -2015 years autumns of healing-Tianjin west blue or green；
Fig. 7 is that present invention prevention apple tree canker promotes sick scar healing -2015 years autumns-Yangling Shaanxi；
Fig. 8 is that present invention prevention apple tree canker promotes sick scar healing -2015 years autumns-Taian Shandong；
Fig. 9 is that present invention prevention apple tree canker promotes sick scar healing -2015 years autumns-Taiyuan, Shanxi.
Embodiment
The present invention is described in further detail by the following examples, but the present invention is not limited to these Examples.
Embodiment 1：The synthesis of cupric dimethyldithio carbamate (1)
6.72g (0.05moL) copper chloride, 100mL H are added in 1L four-hole bottles2O, stirring and dissolving, at 10-20 DEG C slowly
The aqueous solution of 14.32g (0.1moL) sodium dimethyl dithiocarbamate is added dropwise, about 1.5 drip off when small, continue 30 points of stirring
Clock, there is brown solid generation, filters, washing, dry 12.77g cupric dimethyldithio carbamates (1), yield 84%.Palm fibre
Color solid, 300 DEG C of fusing point ＞.Anal.Calcd for C6H12CuN2S4(M.W.) 303.98g/mol, %：C, 23.24；H,
3.90；N, 8.89；S, 40.75.Found, %：C, 23.18；H, 4.01；N, 9.00；S, 40.51.HRMS (ESI) calcd for
C6H12CuN2S4[M+H]+302.9179, found 302.9172.IR (KBr pressed disc methods)：2961；2920；1552；1516；
1499；1479；1464；1435；1399；1384；1154；1142；1125；1119；980.1H NMR(DMSO-d6, δ)：3.52
(12H, br., CH3N)。
Embodiment 2：The synthesis of compound 2-26
Compound 2-26's is synthesized by completing the step of repeating cupric dimethyldithio carbamate (1).
Compound 2, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C10H20CuN2S4[M
+H]+358.9805 found 358.9803.
Compound 3, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C14H28CuN2S4[M
+H]+415.0431 found 415.0431.
Compound 4, yield 82%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C14H28CuN2S4[M
+H]+415.0431 found 415.0430.
Compound 5, yield 82%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C18H36CuN2S4[M
+H]+471.1057 found 471.1052.
Compound 6, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C8H16CuN2S4[M+
H]+330.9492 found 330.9490.
Compound 7, yield 82%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C10H20CuN2S4[M
+H]+358.9805 found 358.9803.
Compound 8, yield 81%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C10H20CuN2S4[M
+H]+358.9805 found 358.9801.
Compound 9, yield 82%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C12H24CuN2S4[M
+H]+387.0118 found 387.0114.
Compound 10, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C6H12CuN2O2S4
[M+H]+334.9078 found 334.9077.
Compound 11, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C12H20CuN2S4
[M+H]+382.9805 found 382.9806.
Compound 12, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C10H16CuN2S4
[M+H]+354.9492 found 354.9495.
Compound 13, yield 83%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C8H12CuN2S4[M
+H]+326.9179 found 326.9176.
Compound 14, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C6H8CuN2S4[M
+H]+298.8866 found 298.8863.
Compound 15, yield 84%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for
C10H16CuN2O2S4[M+H]+386.9391 found 386.9392.
Compound 16, yield 76%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C10H18CuN4S4
[M+H]+384.9710 found 384.9710.
Compound 17, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C12H22CuN4S4
[M+H]+413.0023 found 413.0020.
Compound 18, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C16H28CuN2S4
[M+H]+439.0431 found 439.0434.
Compound 19, yield 77%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C16H16CuN2S4
[M+H]+426.9492 found 426.9493.
Compound 20, yield 75%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C14H14CuN4S4
[M+H]+428.9397 found 428.9394.
Compound 21, yield 75%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C14H14CuN4S4
[M+H]+428.9397 found 428.9392.
Compound 22, yield 78%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C18H14CuN4S6
[M+H]+540.8839 found 540.8836.
Compound 23, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for
C10H16CuN2O4S4[M+H]+418.9289 found 418.9285.
Compound 24, yield 80%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for
C12H20CuN2O4S4[M+H]+446.9602 found 446.9600.
Compound 25, yield 74%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for C8H12CuN2O4S4
[M+H]+390.8976 found 390.8973.
Compound 26, yield 74%.Brown solid, 300 DEG C of fusing point ＞.HRMS(ESI)calcd for
C10H16CuN2O4S4[M+H]+418.9289 found 418.9286.
Embodiment 3：The synthesis of cupric dimethyldithio carbamate (1)
7.98g (0.05moL) copper sulphate, 100mL H are added in 1L four-hole bottles2O, stirring and dissolving, at 10-20 DEG C slowly
The aqueous solution of 14.32g (0.1moL) sodium dimethyl dithiocarbamate is added dropwise, about 1.5 drip off when small, continue 30 points of stirring
Clock, there is brown solid generation, filters, washing, dry 12.51g cupric dimethyldithio carbamates (1), yield 82%.
Embodiment 4：The synthesis of cupric dimethyldithio carbamate (1)
The dimethylamine agueous solution of 11.27g (0.1moL) 40%, 6.72g (0.05moL) chlorination are added in 1L four-hole bottles
Copper, 80mL H2O, stirring and dissolving, 7.61g (0.1moL) carbon disulfide is slowly added dropwise at 10-20 DEG C, continues stirring 60 after dripping off
Minute, there is brown solid generation, filter, washing, dry 14.78g cupric dimethyldithio carbamates (1), yield 97%.
Embodiment 5：The synthesis of cupric dimethyldithio carbamate (1)
The dimethylamine agueous solution of 11.27g (0.1moL) 40%, 7.98g (0.05moL) sulfuric acid are added in 1L four-hole bottles
Copper, 80mL H2O, stirring and dissolving, 7.61g (0.1moL) carbon disulfide is slowly added dropwise at 10-20 DEG C, continues stirring 60 after dripping off
Minute, there is brown solid generation, filter, washing, dry 14.75g cupric dimethyldithio carbamates (1), yield 97%.
Embodiment 6：The synthesis of cupric dimethyldithio carbamate (1)
The dimethylamine agueous solution of 11.27g (0.1moL) 40%, 3.98g (0.05moL) oxidations are added in 1L four-hole bottles
Copper, 80mL H2O, 7.61g (0.1moL) carbon disulfide is slowly added dropwise at 10-20 DEG C, and 30-40 DEG C of stirring 60 is warming up to after dripping off
Minute, there is brown solid generation, filter, washing, dry 14.91g cupric dimethyldithio carbamates (1), yield 98%.
Compound 2-26 is synthesized by method of 6 synthesization of dimethyl disulfide of embodiment for carbamic acid copper (1), yield all exists
More than 98%.
Embodiment 7：(each component is weight percent to 30% aminodithioformic acid copper derivative 1-26 wettable powders
Content)
Each component of the present invention：Aminodithioformic acid copper derivative 1-2630%, lauryl sodium sulfate 1.8%, NNO
(naphthalene sulfonic acid formaldehyde condensation polymer) 1%, polyvinyl alcohol 1.3%, diatomite complements to 100%, said components is uniformly mixed, powder
It is broken, obtain the aminodithioformic acid copper derivative 1-26 wettable powders containing active ingredient 30%.
Embodiment 8：40% yy-2014 wettable powders (each component is weight percentage)
Each component of the present invention：Yy-2014 40%, nekal 1.43%, sodium lignin sulfonate 1.05%, carboxylic
Methylcellulose 1.29%, clay complements to 100%, and said components are uniformly mixed, and crushes, obtains containing active ingredient 40%
Yy-2014 wettable powders.
Embodiment 9：(each component is that weight percent contains to 25% aminodithioformic acid copper derivative 1-26 suspending agents
Amount)
Each component of the present invention：Aminodithioformic acid copper derivative 1-26 25%, neopelex 0.8%, wood
Quality sodium sulfonate 2%, Magnesiumaluminumsilicate 4%, propane diols 6%, bentonite 3%, dimethyl silicone polymer 2%, water complements to
100%, said components are uniformly mixed, are stirred, high speed dispersion obtains the aminodithioformic acid copper containing active ingredient 25% and spreads out
Biological 1-26 suspending agents.
Embodiment 10：30% yy-2014 suspending agents (each component is weight percentage)
Each component of the present invention：Yy-2014 30%, ethylene glycol 5%, diisooctyl maleate sulfonate 2%, alkyl
Aryl polyoxyethylene polyoxypropylene ether 2%, calcium dodecyl benzene sulfonate 1%, carboxymethyl cellulose 0.4%, sodium lignin sulfonate
1%, Tween 80 0.2%, water complements to 100%, and said components are uniformly mixed, and stirring, high speed dispersion obtains containing active ingredient
30% yy-2014 suspending agents.
Embodiment 11：25% yy-2014 thiophanate-methyl suspending agents
Each component of the present invention：Yy-2014 22%, thiophanate-methyl 3%, amber platinum sodium dioctyl sulfo 0.9%, polyoxy
Ethene polyoxypropylene block copolymers 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer 2%,
Water complements to 100%, and said components are uniformly mixed, and stirring, high speed dispersion obtains the yy-2014 first containing active ingredient 25%
Base thiophanate suspending agent.
Embodiment 12：30% yy-2014 Xinjunan acetate suspending agents
Each component of the present invention：Yy-2014 28.2%, Xinjunan acetate 1.8%, neopelex 0.9%,
Polyoxyethylene polyoxypropylene block copolymer 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer
2%, water complements to 100%, and said components are uniformly mixed, and stirring, high speed dispersion obtains the yy- containing active ingredient 30%
2014 Xinjunan acetate suspending agents.
Embodiment 13：30% yy-2014 pyraclostrobin suspending agents
Each component of the present invention：Yy-2014 20%, pyraclostrobin 10%, neopelex 0.9%, polyoxy second
Alkene polyoxypropylene block copolymers 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer 2%, water
100% is complemented to, said components are uniformly mixed, is stirred, high speed dispersion obtains the yy-2014 pyrazoles containing active ingredient 30%
Kresoxim-methyl suspending agent.
Embodiment 14：30% yy-2014 humic acid suspending agents
Each component of the present invention：Yy-2014 28%, humic acid 2%, neopelex 0.9%, polyoxyethylene gathers
Oxypropylene block copolymer 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer 2%, water is supplied
To 100%, said components are uniformly mixed, are stirred, high speed dispersion obtains the yy-2014 humic acid containing active ingredient 30% and hangs
Floating agent.
Embodiment 15：30% yy-2014 copper sulphate suspending agents
Each component of the present invention：Yy-2014 29.6%, copper sulphate 0.4%, neopelex 0.9%, polyoxy second
Alkene polyoxypropylene block copolymers 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer 2%, water
100% is complemented to, said components are uniformly mixed, is stirred, high speed dispersion obtains the yy-2014 sulfuric acid containing active ingredient 30%
Copper suspending agent.
Embodiment 16：30% yy-2014 methyl α-naphthyl acetate suspending agents
Each component of the present invention：Yy-2014 29.98%, methyl α-naphthyl acetate 0.02%, neopelex 0.9%, polyoxy
Ethene polyoxypropylene block copolymers 2%, polyvinyl alcohol 4%, ethylene glycol 5%, white carbon 3%, dimethyl silicone polymer 2%,
Water complements to 100%, and said components are uniformly mixed, and stirring, high speed dispersion obtains the yy-2014 naphthalenes containing active ingredient 30%
Acetic acid suspending agent.
Embodiment 17：35% yy-2014 benziothiazolinone suspension emulsions
Each component of the present invention：Yy-2014 34.2%, benziothiazolinone 0.8%, calcium dodecyl benzene sulfonate 3%, oleic acid first ammonia
Base ethylsulfonic acid sodium 4%, Sodium Polyacrylate 2%, diethylene glycol (DEG) 5%, sodium benzoate 3%, dimethyl silicone polymer 3%, water is supplied
To 100%, said components are uniformly mixed, are stirred, high speed dispersion obtains the yy-2014 benziothiazolinone containing active ingredient 35% and hangs
Emulsion.
Embodiment 18：Indoor bactericidal activity：
A. in vitro sterilization test, biomass growth rate determination method (Plating)：
Precise testing compound, aseptically, by testing compound, comparison medicament water or/and organic molten
Dilution agent dilutes spare into 20mg/L or as needed.Draw 1mL liquids to be transferred in the culture dish of 9cm, then add 9mL's
Culture medium, which shakes up, to be allowed to be uniformly mixed with liquid, is positioned to containing tablet, and by sterile water containing 1mL and the tablet of 9mL culture mediums
As control treatment group.Bacterium disk is taken to be transferred on culture medium flat plate using the card punch of a diameter of 4mm.Each processing is repeated 3 times,
Be placed on temperature in constant incubator and be arranged to 24 ± 1 DEG C, 72 it is small when after investigate the diameter of each bacterium disk extension, wherein apple tree
Rot disease and Fungus of Pear Canker Disease are same pathogen, are investigated after 5 days, bactericidal activity inhibiting rate is tried to achieve as follows：
I=(D1-D2)/D1*100%
I is bacteriostasis rate, and D1 represents the diameter of blank control group extension bacterium disk, and D2 is that chemicals treatment group extends the straight of bacterium disk
Footpath.
The in vitro bactericidal activity measurement result of table 1
(note：- represent not test)
The aminodithioformic acid copper derivative (I) of indoor in vitro bactericidal activity result (being shown in Table 1) the display present invention and its
Preparation has good bactericidal activity, particularly has extraordinary activity to apple rot pathogen.Wherein compound 16,
17th, 25,26 under the concentration of 20mg/L to the inhibitory activity of Colletotrichum capsici and rice blast fungus all more than 70%, change
2,3,4,6,7,8,9,10,15,16,18,19,22,25,26 suppression under the concentration of 10mg/L to Valsa mali of compound
Activity is 100%, 40% yy-2014 wettable powders, 30% yy-2014 suspending agents, 25% yy-2014 methyl sulphur
Bacterium spirit suspending agent, 30% yy-2014 Xinjunan acetates suspending agent, 30% yy-2014 pyraclostrobins suspending agent,
30% yy-2014 humic acid suspending agent, 30% yy-2014 copper sulphate suspending agent, 30% yy-2014 methyl α-naphthyl acetates
Suspending agent and 35% yy-2014 benziothiazolinone suspension emulsions, to the inhibitory activity of Valsa mali under the concentration of 10mg/L
Respectively 71.4%, 72.6%, 78.3%, 74.2%, 76.1%, 74.8%, 73.4%, 72.9% and 75.3%, and it is lived
Property component composition 1 inhibitory activity be 60.1%, hence it is evident that be better than comparison medicament asomate, thiophanate-methyl, octyl trichlamide acetic acid
Salt, Tebuconazole, benziothiazolinone, pyraclostrobin, humic copper sulphate, coumoxystrobin, zinc dimethyl dithiocarbamate.
B. live body sterilization test：
Wheat powdery mildew：It is spare that 24 small caused Powdery Mildew Fresh spores on morbidity wheat leaf blade are collected first, it is accurate
Really weigh testing compound, aseptically, by testing compound, comparison medicament water or/and organic solvent diluting into
20mg/L or dilute as needed it is spare, using spray-on process dispenser.Then Fresh spores are uniformly inoculated at 2-3 leaf phase medicaments
On potted plant wheat seedling after reason.
Leaves infected stage division is as follows：Disease-free spot is 0 grade；It is 1 grade below 5% that the area of scab, which accounts for whole leaf area,；
Lesion area accounts for whole below leaf area 6%-10% as 3 grades；Spot area accounts for whole below leaf area 11%-25% as 5 grades；Disease
Spot area accounts for whole below leaf area 26%-50% as 7 grades；Lesion area accounts for whole leaf area more than 50% as 9 grades.
The computational methods of disease index and prevention effect are：
Disease index=[∑ (the typical value number of the disease numbers of blade at different levels × opposite series) ÷ (total leaf numbers × highest series
Typical value)] × 100；
Preventive effect (%)=[(control group be averaged disease index-processing be averaged disease index) ÷ control groups be averaged disease index]
×100。
Powdery mildew of cucumber：Planted using 1 leaf, the 2 heart stage cucumber seedling of hot-house culture as the experiment host of powdery mildew of cucumber
Thing.Using spray-on process dispenser, the medicine liquid spray prepared is dried in the shade naturally in host plant cauline leaf, the test material after processing,
24 it is small when after be inoculated with pathogen and moisturizing 24 it is small when.
Leaves infected stage division is as follows：Disease-free spot is 0 grade；It is 1 grade below 5% that the area of scab, which accounts for whole leaf area,；
Lesion area accounts for whole below leaf area 6%-10% as 3 grades；Spot area accounts for whole below leaf area 11%-25% as 5 grades；Disease
Spot area accounts for whole below leaf area 26%-50% as 7 grades；Lesion area accounts for whole leaf area more than 50% as 9 grades.
The computational methods of disease index and prevention effect are：
Disease index=[∑ (the typical value number of the disease numbers of blade at different levels × opposite series) ÷ (total leaf numbers × highest series
Typical value)] × 100；
Preventive effect (%)=[(control group be averaged disease index-processing be averaged disease index) ÷ control groups be averaged disease index]
×100。
Apple tree canker：By testing compound, comparison medicament water or/and organic solvent diluting into needing concentration standby
With the apple tree branch of clip 35cm long, is punched using diameter 1cm card punch on apple tree branch, then by diameter 1cm's
Valsa mali Miyabe et Yamada bacterium piece is placed at apple tree branch punching, and it is that bacterium piece is fixed on branch to be wound with preservative film at punching
On.Branch is positioned in incubator and is cultivated 3 days under the conditions of 25 DEG C.Supply in reagent liquid to soak prepared after removing bacterium piece
10 seconds, 15 days investigation prevention effects are cultivated under the conditions of being placed on 25 DEG C, are calculated as follows.
Sick scar recurrence rate=[sick scar adds up to recur the sick scar total block data of disease block number ÷ investigation] × 100.
Prevent (%)=[(blank control group disease scar recurrence rate-chemicals treatment group disease scar recurrence rate) ÷ blank control groups disease
Scar recurrence rate] × 100.
Fungus of Pear Canker Disease：By testing compound, comparison medicament water or/and organic solvent diluting into needing concentration spare,
The pear tree branch of clip 25cm long, is punched using diameter 1cm card punch on pear tree branch, then that the pear tree of diameter 1cm is rotten
Rotten disease germ bacterium piece is placed at pear tree branch punching, and it is that bacterium piece is fixed on branch to be wound with preservative film at punching.Branch is put
It is placed in incubator and is cultivated 3 days under the conditions of 25 DEG C.Supply in reagent liquid to soak 10 seconds prepared after removing bacterium piece, be placed on
15 days investigation prevention effects are cultivated under the conditions of 25 DEG C, are calculated as follows.
Sick scar recurrence rate=[sick scar adds up to recur the sick scar total block data of disease block number ÷ investigation] × 100.
Prevent (%)=[(blank control group disease scar recurrence rate-chemicals treatment group disease scar recurrence rate) ÷ blank control groups disease
Scar recurrence rate] × 100.
2 live body bacteriostatic activity test result of table
(note：- represent not test)
Indoor living bactericidal activity result (being shown in Table 2) display the present invention aminodithioformic acid copper derivative (I) and its
Preparation has good prevention effect to wheat powdery mildew and powdery mildew of cucumber, particularly rots to apple tree canker and pear tree
Disease has extraordinary preventive effect.Wherein compound 15,16,17,18,22,25,26 under the concentration of 100mg/L to wheat white powder
Disease and powdery mildew of cucumber prevention effect all more than 70%, compound 2,3,4,5,6,7,8,9,10,15,16,17,18,19,
22nd, 25,26 prevention effect to canker of apple fruit and Fungus of Pear Canker Disease under the concentration of 2g/L is 100%, 40% yy-2014
Wettable powder, 30% yy-2014 suspending agents, 25% yy-2014 thiophanate-methyls suspending agent, 30% yy-
2014 Xinjunan acetate suspending agents, 30% yy-2014 pyraclostrobins suspending agent, 30% yy-2014 humics
Sour suspending agent, 30% yy-2014 copper sulphate suspending agent, 30% yy-2014 methyl α-naphthyl acetates suspending agent and 35% yy-
2014 benziothiazolinone suspension emulsions, are respectively to the prevention effect of canker of apple fruit and Fungus of Pear Canker Disease under the concentration of 2g/L
88.8% and 88.5%, 90.2% and 89.8%, 95.8% and 96.2%, 91.8% and 91.5%, 94.3% and 94.1%,
92.6% and 92.4%, 92.1% and 91.9%, 89.9% and 90.1% and 93.3% and 93.5%, and its active component chemical combination
Thing 1 is respectively 84.2% and 83.7% to the prevention effect of canker of apple fruit and Fungus of Pear Canker Disease, hence it is evident that is better than comparison medicament good fortune
U.S. arsine, thiophanate-methyl, Xinjunan acetate, Tebuconazole, benziothiazolinone, pyraclostrobin, humic copper sulphate, coumoxystrobin,
Zinc dimethyl dithiocarbamate.
Embodiment 19：40%yy-2014 wettable powders prevent apple tree canker field plot trial：
According to the related request of " National Standard of the People's Republic of China's pesticide field trial criterion ", 2014 to 40%
40 times of yy-2014 wettable powders dilution agent, 80 times, 120 times of test process carry out the examination of prevention apple tree canker field plot
Test, control treatment is used as using 40% 50 times of asomate wettable powder dilution agent.Experiment is respectively in Liaoning Xingcheng Scientia Agricultura Sinica
Fruit tree research institute of institute and Tianjin Xi Qing Tianjin Plant Protection Institute carry out, and are experimental field apple tradition growing area.Liaoning is emerging
City trial zone is 21 years green apple trees, kind：Tianjin is light, by strain check mark disease scar and strikes off rotten position during experiment, every 8 pieces of diseases
Scar simultaneously records position as an experimental plot, random alignment, Unified number, and often processing is repeated 4 times, by each inorganic agent
Amount, blank control apply clear water, and coating 1 time in the range of rear sick scar and its surrounding 2cm is controlled to scraping.On the November 18th, 2014 of investigation one
Secondary, on April 10th, 2015 carries out prevention effect investigation, and measures disease scar healing width.Tianjin Xi Qing trial zones are 15 years raw apples
Fruit tree, kind：Red Star, by strain check mark disease scar and strikes off rotten position during experiment, every 10 pieces sick scars are small as an experiment
Area, random district's groups arrangement, Unified number simultaneously record position, and often processing is repeated 4 times, and is applied by each treatment dosage, blank control
Clear water, sprays 2 times, the date is respectively on June 12nd, 2014 and in August, 2014 to scraping to control in the range of rear sick scar and its surrounding 5cm
12, on October 20th, 2014 was investigated once, and on April 3rd, 2015 carries out prevention effect investigation.Field management is practised by local cultivation
It is used, complete unity management during all trial zones.
Drug effect computational methods：
Sick scar recurrence rate (%)=(the sick scar block number of sick scar recurrence block number ÷ investigation) × 100；
Prevention effect (%)=[(the blank control disease scar recurrence rate-sick scar recurrence rate of coating processing) ÷ blank control disease scars
Recurrence rate] × 100；
Unilateral healing width (the mm)=∑ of sick scar [every piece of sick unilateral healing width (mm) of scar] sick scar block number of ÷ measurements；
The sick scar of the coating processing width-blank control disease scar that averagely heals averagely heals width；
Promote healing effect (%)=[(the sick scar of the coating processing width-blank control disease scar that averagely heals averagely heals width
Degree) ÷ blank control disease scars averagely heal width] × 100.
Pilot survey and result
Liaoning Xingcheng：
On November 18th, 2014, investigation canker of apple fruit disease scar healing state is as shown in Figure 1,40%yy-2014 wettables
Pulvis has prevention apple tree canker effect well, and sick scar healing width is significantly better than comparison medicament asomate.
On April 10th, 2015, investigation canker of apple fruit disease scar healing state is as shown in Fig. 2, 40%yy-2014 wettable powders
Agent has prevention apple tree canker effect well, and disease recurrence rate is extremely low, and sick scar healing width is significantly better than comparison medicament
Asomate.
3 40%yy-2014 wettable powders of table prevent the result of the test of apple tree canker
According to cell preventive effect conversion value, significance test is carried out with DMRT methods.
By the field control effectiveness test (being shown in Table 3) of Fruit Institute, Chinese Academy of Agricultural Sciences in 2014,40%yy-2014 can
Wet powder has good prevention effect to the recurrence of apple tree canker scar, and no poisoning occurs, and has the sick scar Healing of promotion.
Recommend for reagent prevention canker of apple fruit scar recurrence, to be advisable using 40 times -120 times or so.
Tianjin west is blue or green：
On October 20th, 2014, investigation canker of apple fruit disease scar healing state is as shown in figure 3,40%yy-2014 wettables
Pulvis has prevention apple tree canker effect well, and sick scar healing width is significantly better than comparison medicament asomate.
On 04 03rd, 2015, investigation canker of apple fruit disease scar healing state was as shown in figure 4,40%yy-2014 wettables
Pulvis has prevention apple tree canker effect well, and disease recurrence rate is extremely low, and sick scar healing width is significantly better than comparison medicine
Agent asomate.
4 40%yy-2014 wettable powders of table prevent the result of the test of apple tree canker scar
Arcsine conversion and variance analysis are carried out to the prevention effect of each cell, and is patted with SSR methods and prevented more everywhere
The significance of difference between effect.
By the field control effectiveness test (being shown in Table 4) of Tianjin Plant Protection Institute in 2014, for reagent 40%yy-2014
Wettable powder has good prevention effect to the recurrence of apple tree canker scar, and 40%yy-2014 wettable powders are in dilution 120
Processing under lowest dose level again is better than the prevention effect under the high dose of 40% 50 times of asomate wettable powder dilution agent.
Embodiment 20：40%yy-2014 wettable powders prevent wheat rust field plot trial：
According to the related request of " National Standard of the People's Republic of China's pesticide field trial criterion ", 2014 to 40%
400 times of yy-2014 wettable powders dilution agent, 600 times, 800 times of test process carry out prevention wheat rust field plot trial,
1000 times, which are diluted, using 15% trazodone wettable powder is used as control treatment.Experiment is in the western blue sky Jinshi City plant protection research in Tianjin
Carried out.
Investigation and drug effect computational methods
Leaf area ratio is accounted for according to scab, classification investigation is carried out to inoculation leaves infected situation, with the following method：It is disease-free
Spot is 0 grade；It is 1 grade below 5% that the area of scab, which accounts for whole leaf area,；Lesion area accounts for whole below leaf area 6%-25%
3 grades；Spot area accounts for whole below leaf area 26%-50% as 5 grades；Lesion area accounts for whole below leaf area 51%-75% as 7
Level；Lesion area accounts for whole leaf area more than 76% as 9 grades；
Disease index is calculated according to the sick series of investigation and prevention effect, computational methods are：
Disease index=[∑ (the disease number of blade × relative disease series at different levels) ÷ (investigation total leaf number × 9)] × 100；
Preventive effect (%)=[(blank control group disease index-processing disease index) ÷ blank control groups be averaged disease index]
×100。
5 40%yy-2014 wettable powders of table prevent the result of the test of wheat rust
Arcsine conversion and variance analysis are carried out to the prevention effect of each cell, and is patted with SSR methods and prevented more everywhere
The significance of difference between effect.
Result of the test shows and (is shown in Table 5), and each processing of 40%yy-2014 wettable powders has wheat rust pretty good
Prevention effect, the processing of 40%yy-2014 wettable powders 400 times of liquid of dilution agent are wettable significantly better than 15% triazolone of comparison medicament
Property pulvis, there was no significant difference with comparison medicament for prevention effect of the 40%yy-2014 wettable powders under middle dosage.
Embodiment 21：40%yy-2014 wettable powders prevent wheat powdery mildew field plot trial：
According to the related request of " National Standard of the People's Republic of China's pesticide field trial criterion ", 2014 to 40%
400 times of yy-2014 wettable powders dilution agent, 600 times, 800 times of test process carry out the examination of prevention wheat powdery mildew field plot
Test, diluting 1500 times using 15% triazolone missible oil is used as control treatment.Experiment is in Tianjin Xi Qing Tianjin Plant Protection Institute
Carry out.
Investigation and drug effect computational methods
Leaf area ratio is accounted for according to scab, classification investigation is carried out to inoculation leaves infected situation, with the following method：It is disease-free
Spot is 0 grade；It is 1 grade below 5% that the area of scab, which accounts for whole leaf area,；Lesion area accounts for whole below leaf area 6%-15%
3 grades；Spot area accounts for whole below leaf area 16%-25% as 5 grades；Lesion area accounts for whole below leaf area 26%-50% as 7
Level；Lesion area accounts for whole leaf area more than 50% as 9 grades；
Disease index is calculated according to the sick series of investigation and prevention effect, computational methods are：
Disease index=[∑ (the disease number of blade × relative disease series at different levels) ÷ (investigation total leaf number × 9)] × 100；
Preventive effect (%)=[1- (disease index after disease index × chemicals treatment district medicine before blank control group medicine) ÷ (blank
Disease index before disease index × chemicals treatment district medicine after control group medicine) × 100].
6 40%yy-2014 wettable powders of table prevent the result of the test of wheat powdery mildew
Arcsine conversion and variance analysis are carried out to the prevention effect of each cell, and is patted with SSR methods and prevented more everywhere
The significance of difference between effect.
Result of the test shows and (is shown in Table 6), and each processing of 40%yy-2014 wettable powders has wheat powdery mildew pretty good
Prevention effect, there was no significant difference with comparison medicament for the prevention effect of 40%yy-2014 wettable powders 400 times of liquid of dilution agent.
Embodiment 22：30%yy-2014 suspending agents prevent apple tree canker field plot trial：
According to the related request of " National Standard of the People's Republic of China's pesticide field trial criterion ", 2015 respectively in the Liao Dynasty
Peaceful Xingcheng Fruit Institute, Chinese Academy of Agricultural Sciences, Tianjin Xi Qing Tianjin Plant Protection Institute carry out, Yangling Shaanxi northwest
Plant protection institute of agriculture and forestry science and technology university, Taian Shandong Shandong Fruit-tree Inst., Taiyuan, Shanxi Shanxi Shanxi Academy of Agricultural Sciences plant
Thing Protective strategy institute, it is rotten to carry out prevention apple tree to 30 times of 30%yy-2014 suspensions dilution agent, 60 times, 90 times of test process
Rotten disease field plot trial, dilutes 10 times of (the Liao Dynasty with 40% 50 times of asomate wettable powder dilution agent, 3% thiophanate-methyl paste
Peaceful Xingcheng) control treatment is used as, it is experimental field apple tradition growing area.By strain check mark disease scar and rotten portion is struck off during experiment
Position, experimental plot random alignment, Unified number simultaneously record position, and often processing is repeated 4 times, by each treatment dosage, blank pair
According to clear water is applied, coating 1 time in the range of rear sick scar and its surrounding 2cm is controlled to scraping.Field management is accustomed to by local cultivation, all experiments
Management is completely unified during area.
Pilot survey：
In November, 2015, to Liaoning Xingcheng, the western green grass or young crops in Tianjin, Yangling Shaanxi, Taian Shandong, Taiyuan, Shanxi 5 experimental field
Field efficacy carries out first time investigation.
Liaoning Xingcheng：
Canker of apple fruit disease scar healing state is as shown in figure 5,30%yy-2014 suspending agents have prevention apple tree well
Rot disease effect, sick scar healing width is good, and is significantly better than 40% asomate wettable powder of comparison medicament and 3% methyl
Thiophanate paste.
Tianjin west is blue or green：
Canker of apple fruit disease scar healing state is as shown in fig. 6,30%yy-2014 suspending agents have prevention apple tree well
Rot disease effect, sick scar healing width are significantly better than 40% asomate wettable powder of comparison medicament.
Yangling Shaanxi：
Canker of apple fruit disease scar healing state is as shown in fig. 7,30%yy-2014 suspending agents have prevention apple tree well
Rot disease effect, sick scar healing width are significantly better than 40% asomate wettable powder of comparison medicament.
Taian Shandong：
Canker of apple fruit disease scar healing state is as shown in figure 8,30%yy-2014 suspending agents have prevention apple tree well
Rot disease effect, sick scar healing width are significantly better than 40% asomate wettable powder of comparison medicament.
Taiyuan, Shanxi：
Canker of apple fruit disease scar healing state is as shown in figure 9,30%yy-2014 suspending agents have prevention apple tree well
Rot disease effect, sick scar healing width are significantly better than 40% asomate wettable powder of comparison medicament.
Claims (11)
1. the aminodithioformic acid copper derivative of structure shown in below formula (I)
It selects following compound：
2. purposes of the following aminodithioformic acid copper compound as disinfectant use in agriculture,
It is characterized in that suppress pepper anthracnose, rice blast, wheat powdery mildew, powdery mildew of cucumber, apple tree canker disease
Opportunistic pathogen.
3. purposes of the aminodithioformic acid copper derivative described in accordance with the claim 1 as disinfectant use in agriculture, its feature exist
In suppression pepper anthracnose, rice blast, wheat powdery mildew, powdery mildew of cucumber, Pathogen of Apple Canker.
4. according to purposes of the aminodithioformic acid copper derivative as disinfectant use in agriculture described in claim 1 or 2, its feature
In them in prevention apple tree canker, Fungus of Pear Canker Disease, wheat rust, wheat powdery mildew, the application in powdery mildew of cucumber.
5. according to purposes of the aminodithioformic acid copper derivative as disinfectant use in agriculture described in claim 4, its feature exists
Fruit tree putrefaction disease is prevented in being used to prepare disinfectant use in agriculture.
6. according to purposes of the aminodithioformic acid copper derivative as disinfectant use in agriculture described in claim 4, its feature exists
In cupric dimethyldithio carbamate in prevention apple tree canker, Fungus of Pear Canker Disease, wheat rust, wheat powdery mildew, Huang
Application in melon powdery mildew.
7. the purposes of aminodithioformic acid copper derivative, it is characterised in that with the aminodithioformic acid described in claim 1
Copper derivative (I) is the bactericidal composition of active component, in the composition aminodithioformic acid copper derivative (I) active component
Percentage by weight be 0.1-99%.
8. according to the purposes described in claim 7, it is characterised in that the composition is configured to pulvis, wettable powder, breast
Oil, emulsifiable concentrate, microemulsion, suspending agent, suspension emulsion, granule, finish, water dispersible granules.
9. the purposes of aminodithioformic acid copper derivative, it is characterised in that contain the dithiocarbamates first described in claim 1
The sterilization or/and weeding of the binary or ternary active component of sour copper derivative (I), plant tune, insecticide acaricide composition.
10. according to the purposes described in claim 9, it is characterised in that contain the aminodithioformic acid copper described in claim 1
In the binary composition of derivative (I) another active component be selected from thiophanate-methyl, Xinjunan acetate, pyraclostrobin,
Humic acid, copper sulphate, methyl α-naphthyl acetate, benziothiazolinone.
11. rot according to the bactericidal composition described in any one in claim 8-10 in prevention apple tree canker, pear tree
Application in disease, wheat rust, wheat powdery mildew, powdery mildew of cucumber.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037041A (en) * | 1959-10-26 | 1962-05-29 | Roussel Uclaf | Copper complex of dimethyl dithiocarbamic acid and preparation thereof |
| CN1014239B (en) * | 1985-12-30 | 1991-10-09 | 苏联科学院西伯利亚分院伊尔库茨克有机化学研究所 | Pesticide of n-(vinal oxyethyl) dithio-carbamate |
| CN1846494A (en) * | 2006-04-17 | 2006-10-18 | 曾立雄 | New type of copper salt for killing pests and bacteria in water area |
| CN104858968A (en) * | 2014-12-22 | 2015-08-26 | 王玉燕 | Environmental protection wood preservative |
-
2016
- 2016-01-22 CN CN201610041347.XA patent/CN105712916B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037041A (en) * | 1959-10-26 | 1962-05-29 | Roussel Uclaf | Copper complex of dimethyl dithiocarbamic acid and preparation thereof |
| CN1014239B (en) * | 1985-12-30 | 1991-10-09 | 苏联科学院西伯利亚分院伊尔库茨克有机化学研究所 | Pesticide of n-(vinal oxyethyl) dithio-carbamate |
| CN1846494A (en) * | 2006-04-17 | 2006-10-18 | 曾立雄 | New type of copper salt for killing pests and bacteria in water area |
| CN104858968A (en) * | 2014-12-22 | 2015-08-26 | 王玉燕 | Environmental protection wood preservative |
Non-Patent Citations (1)
| Title |
|---|
| 化合物的RN;CA公司;《CA》;20090818 * |
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