WO2021115195A1 - Complexe bimétallique cuivre-zinc dithiocarbamate, son procédé de préparation et son utilisation - Google Patents
Complexe bimétallique cuivre-zinc dithiocarbamate, son procédé de préparation et son utilisation Download PDFInfo
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- WO2021115195A1 WO2021115195A1 PCT/CN2020/133721 CN2020133721W WO2021115195A1 WO 2021115195 A1 WO2021115195 A1 WO 2021115195A1 CN 2020133721 W CN2020133721 W CN 2020133721W WO 2021115195 A1 WO2021115195 A1 WO 2021115195A1
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- Prior art keywords
- copper
- zinc
- complex
- dithiocarbamate
- bacteria
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/14—Dithiocarbamic acids; Derivatives thereof
- C07C333/16—Salts of dithiocarbamic acids
-
- 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
- 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
- A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—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, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
-
- 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
- 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
- A01N47/08—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 the carbon atom having one or more single bonds to nitrogen atoms
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the invention belongs to the field of agricultural fungicides, and specifically relates to the preparation and application of a copper-zinc dithiocarbamate complex.
- copper fungicides Due to the prohibition of agricultural antibiotics and the unstable efficacy of microbial preparations, copper fungicides have become the main force in the prevention and treatment of bacterial diseases at present, and are widely used in copper thiazide, copper thiamyth, copper hydroxide, quinolinone and so on. Copper fungicides play a certain role in the prevention and control of bacterial diseases and have obvious advantages. However, excessive copper ions can easily cause phytotoxicity to crops and have the disadvantages of easily inducing harmful mites.
- Dithiocarbamate fungicides are multi-action sites and protective fungicides discovered in the 1940s. They have the characteristics of low toxicity, low residue, easy degradation, and environmental friendliness. They have been in existence for more than 50 years, but so far No phytopathogenic fungi have been found to have obvious resistance to it.
- Zinc and Zinc are dithiocarbamate fungicides, which are widely used in the prevention and treatment of fungal diseases. Because they are easy to flocculate with copper preparations, they cannot be mixed with copper preparations for the prevention and control of bacterial diseases. This has seriously affected the convenience of farmers. The market urgently needs a compound of copper and zinc ions.
- One application can prevent fungal and bacterial diseases at the same time without causing mites.
- the introduction of metal zinc ions can interfere with the normal physiological activities of the pest’s nervous system, block the transmission of nerve signals, effectively inhibit the reproduction of pests, and can also supplement plants with trace elements, improve plant disease resistance, and overcome copper-induced mites Shortcomings.
- the invention solves the problem that the copper preparation cannot be compounded with the zinc preparation, and the two ions are complexed with the organic ligand at the same time in the production stage.
- the inventor also found that different dithiocarbamate ligands can be complexed with zinc ions, and then complexed with copper ions.
- the resulting copper-zinc dithiocarbamate complex also has better properties. The control effect of fungus and bacteria.
- the purpose of the present invention is to provide a new copper-zinc bimetallic complex and its application.
- the copper-zinc complex can effectively inhibit a variety of pathogens and harmful mites, especially for the application in the prevention and control of bacterial and fungal diseases of crops.
- the complex of copper-zinc bimetals solves the problem of copper preparations and zinc in agricultural production. The problem that the preparation cannot be compounded.
- the general formula of the copper-zinc dithiocarbamate bimetallic complex is:
- a in the complex of general formula I of the present invention is selected from the group consisting of C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 2 -C 5 alkene Group, C 2 -C 5 alkenyloxy, C 2 -C 5 alkynyl, C 2 -C 5 alkynyloxy, C 2 -C 6 heteroalkyl, C 2 -C 6 heteroalkoxy, Or selected from including C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C 6 cycloalkylthio, C 3 -C 6 cycloalkenyl, C 3 -C 6 cycloalkenyloxy Group of cyclic hydrocarbons, or selected from including C 2 -C 4 alkenyl, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyl, C 2 -C 4 alkynyl
- R 1 , R 2 , R 3 and R 4 in the complex of general formula I of the present invention are the same or different, and are independently selected from hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, ring Alkenyl, heterocyclic, hydroxy, alkoxy, cycloalkoxy, alkoxyalkyl, heterocyclooxy, alkylthio, heterocyclic thio, N,N-alkylamino, cycloalkylamino , Alkylamide group, alkylsulfonyl group, alkylsulfinyl group, sulfonamide group, alkylsulfonamide group, cycloalkylsulfonamide group, alkylcarbonyl group, alkoxycarbonyl group, cycloalkylcarbonyl group, carboxyl group, Formyl, cyano, nitro.
- Alkyl straight or branched chain alkyl, such as methyl, ethyl, propyl, isopropyl and the like.
- Cycloalkyl substituted or unsubstituted cyclic alkyl, such as cyclopropyl, cyclopentyl or cyclohexyl.
- Alkoxy straight or branched chain alkyl, connected via an oxygen atom, such as CH 3 O-.
- Alkylthio straight or branched chain alkyl, connected via a sulfur atom, such as CH 3 S-.
- Alkenyl linear or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1,2-propadienyl and the like.
- Alkynyl straight-chain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and different butynyl groups.
- Alkynyloxy straight or branched chain alkynyl, connected via an oxygen atom, for example HC ⁇ CCH 2 O-.
- Alkoxyalkyl alkyl-O-alkyl-, for example: CH 3 OCH 2-
- Alkylthioalkyl alkyl-S-alkyl-, for example: CH 3 SCH 2-
- Alkylsulfinyl straight or branched chain alkyl is connected via sulfinyl (-SO-), such as methylsulfinyl.
- Alkylsulfonyl A straight or branched chain alkyl group is connected via a sulfonyl group (-SO 2 -), such as a methylsulfonyl group.
- Alkylcarbonyl The alkyl group is connected via a carbonyl group, such as CH 3 CO-, CH 3 CH 2 CO-.
- Alkylcarbonyloxy The alkylcarbonyl group is connected via an oxygen atom, such as CH 3 COO-.
- Alkoxycarbonyl The alkoxy is connected via a carbonyl group, such as CH 3 OCO-.
- Heteroalkyl The heteroalkyl referred to in the present invention is a five-membered or six-membered saturated heteroalkyl containing one or more N, O, S heteroatoms, such as tetrahydropyrrole, N-methyltetra Hydropyrrole, tetrahydrofuran, tetrahydrothiophene, piperidine, N-methylpiperidine, tetrahydropyran, cyclopentane sulfide, piperazine, 1,4-dimethylpiperazine, N-methylpiperazine, 1 ,3-dioxane, 1,4-dioxane, etc.
- N, O, S heteroatoms such as tetrahydropyrrole, N-methyltetra Hydropyrrole, tetrahydrofuran, tetrahydrothiophene, piperidine, N-methylpiperidine, tetrahydropyran, cyclopentane sulf
- Table 1 shows that R 1 , R 2 , R 3 , and R 4 in the general formula I may be the same or different, and are selected from the specific groups in the table.
- Table 2 shows the specific groups in the A part of the general formula I, but they are not It is not limited to these groups.
- the ratio of m:n in the present invention ranges from 1:0.01 to 1:1; preferably, the ratio of m:n ranges from 1:0.05 to 1:0.5; more preferably, the ratio of m:n is between 1:0.05 and 1:0.5. The range is from 1:0.09 to 1:0.11.
- the complex of the present invention is prepared according to the following method, and the reaction formula is as follows:
- preparation method of the complex of general formula I includes the following steps:
- the substituted diamine and carbon disulfide are stirred and reacted in a solvent under alkaline conditions to obtain Intermediate 1 solution, and then the X salt solution is added to the reaction.
- the Intermediate 2 is obtained by suction filtration; the Intermediate 2 is suspended in the solvent , Adding Y salt, carrying out a complex reaction at a temperature of 20-100° C., and then filtering and drying to obtain the complex of the general formula I.
- the dithiocarbamate ligand is first combined with the X metal ion through an ionic bond, and then combined with the Y metal ion through a coordinate bond to finally form a complex of general formula I.
- Suitable bases can be selected from, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, ammonia, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, sodium or potassium tert-butoxide, and the like.
- the solvent can be selected from, for example, methanol, ethanol, water or a mixed solvent thereof.
- Substituted diamines are commercially available.
- the copper salt is selected from copper chloride, copper sulfate, copper bromide, copper acetate, etc.,
- the zinc salt is selected from zinc chloride, zinc sulfate, zinc bromide, zinc acetate and the like.
- the complexation reaction temperature can be between room temperature and the boiling temperature of the solvent, and is usually 20-100°C.
- the complexation reaction time is 30 minutes to 20 hours, usually 1-10 hours.
- the diversification of the structure of the general formula I complex and the morphology and binding form of the metal ion in the present invention enable the copper-zinc complex of the present invention to have better bactericidal and/or acaricidal activity, and has a novel structure. It is easy to synthesize and has wide practical application prospects.
- the copper-zinc bimetallic complex in the general formula I of the present invention shows excellent activity against a variety of pathogens in agriculture and forestry, and also shows an inhibitory effect on pest mites, which can solve the problem of sterilization of similar copper preparations. Cause the problem of mite damage.
- the technical scheme of the present invention also includes the use of the copper-zinc complex of the general formula I in the production of fungicides and acaricide drugs in agriculture, forestry, and health: the general formula I complex is used in the yellow list Bacteria, Acidophilus Bacteria, Burkholderia Bacteria, Ralstonia Bacteria, Pseudomonas Bacteria, Pantoea Bacteria, Dicchiella Bacteria, Pectobacterium Bacteria, Rods Uses of bacteria of the genus Bacteroides, bacteria of the genus Streptomyces, bacteria of the class Oomycetes, deuteromycetes, basidiomycetes, and ascomycetes, as well as for the elimination of diseases caused by the genus Woo's bee mites, mango bud mites and spiny skin mites Species, use of the mites of the tomato spiny skin gall mite.
- the general formula I complex is used in the yellow list Bacteria,
- the complex in the general formula I can be used to prevent and control the following diseases: Xanthomonas bacteria (Xanthomonas) cause diseases (rice bacterial leaf blight, rice bacterial streak, cassava bacterial wilt, sugarcane gum disease, Mango black spot, banana bacterial wilt, banana necrosis stripe, cassava bacterial leaf spot, strawberry angular leaf spot, sugarcane white stripe, pepper leaf spot, citrus canker, hyacinth yellow rot fungus, poplar Bacterial canker, black rot, etc.); diseases caused by Acidovorax (melon fruit spot, orchid brown spot, oat brown streak, konjac bacterial leaf spot, etc.); Burke Diseases caused by Burkholderia bacteria (carnation wilt, onion rot, rice bacterial ear blight, etc.); diseases caused by Ralstonia bacteria (bacterial wilt, etc.); false bills Diseases caused by Pseudomonas (corn bacterial brown
- the copper-zinc complex in general formula I can be used to control the following mites:
- Acarina (mite and tick): Acarapsis woodi (Tracheal mite of honeybee); Acarus spp. ( Food mites); Acarus siro (grain mite); Aceria mangiferae (mango budmite); Aculops spp.; Tomato thorn skin gall Aculops lycopersici (tomato russet mite); Aculus pelekassi; Aculus pointedendali (Apple rust mite); Amblyomma amcricanum ( lone star tick; Boophilus spp.
- ticks ticks
- Brevipalpus obovatus privet mite
- Brevipalpus phoenicis red and black mite
- Lip flat tick Genus and species Demodex spp.) (mange mites); Dermacentora spp. (Ixodes); American dog tick (Dermacentor variabilis) (american dog tick); House dust mite (Dermatophagoides pteronnyssinus) (housedust mite) ; Eotetranycus spp. (Eotetranychus carpini (yellow spider mite)); Epitimerus spp.; Epitimerus spp.
- the amount of copper-zinc complex in the general formula I varies due to various factors, such as the copper-zinc complex in the general formula I used, pre-protected crops, types of pests, degree of infection, and climatic conditions , Application method, dosage form used.
- the present invention also includes a bactericidal and acaricidal composition using the copper-zinc complex compound of the general formula I as the active component.
- the weight percentage of the active ingredient in the bactericidal and acaricidal composition is 1-99%.
- the bactericidal and acaricidal composition also includes agricultural, forestry, and sanitary acceptable carriers.
- the bactericidal and acaricidal composition of the present invention can be applied in the form of a formulation.
- the copper-zinc complex in the general formula I is used as an active component to be dissolved or dispersed in a solvent or formulated into other preparations for easier dispersion during use.
- the bactericidal and acaricidal composition is made into wettable powder, water suspension, oil suspension, granules and the like.
- at least one liquid or solid carrier is added, and when necessary, suitable surfactants, stabilizers and/or dispersants can be added.
- one or more other fungicides, acaricides, herbicides, insecticides, plant growth regulators can be added to the fungicidal and acaricidal composition of the present invention Or fertilizer, etc., which can produce additional advantages and effects.
- the technical scheme of the present invention also includes a method for preventing and controlling pathogens and harmful mites: applying the composition of the present invention to the above-mentioned pathogens or growth media.
- the most suitable dosage is usually 10g to 2000g per hectare, and the preferred effective dosage is 20g to 1000g per hectare.
- the complex of the present invention shows good activity against a variety of pathogens in the agricultural field, and also shows a certain inhibitory effect against harmful mites.
- the compound of the present invention is used to test the obtained sample against plant pathogenic fungi and bacteria in vitro antibacterial activity or in vivo protection effect.
- the results of the bactericidal activity measurement are shown in the following examples.
- the determination method is as follows: inoculate the bacteria strains that have been continuously cultured for 3 to 4 times in PDA medium, and cultivate in a thermostat at 25°C for 3 days. Prepare a spore suspension, check the number of spores under a microscope (10 ⁇ 10 times), and average 40-60 spores per field of view. Then different copper-zinc complexes were diluted to a corresponding design concentration of 2mL and 2mL of spore suspension mixed, and 2mL of carbendazim and 2mL of spore suspension were mixed as positive control.
- the spore germination method was used, placed in a 24 °C thermostat, 15 hours later, the germination rate was investigated, the mixed drug solution was stirred, and 1 drop of the mixed drug solution was taken on a glass slide, covered with a cover glass, and 10 samples were randomly observed under a microscope Visual field, randomly inspect 10 sporangia (100) per field, record the number of sporangia: the number of sporangia germinated and the number of sporangia not germinated. The spore germ tube exceeds the short radius of the spore as the germination state. Repeat the test three times, and the spore germination rate is above 80% as an effective test, and then the relative inhibition rate is calculated. According to the logarithm of the concentration of the agent and the probability value of the relative inhibition rate, the EC 50 of the complex for inhibiting spore germination of the tested fungus was calculated. The results are shown in Table 3.
- microdilution method was used to determine the inhibitory effects of different copper-zinc complexes on the three test bacteria Pseudomonas solanacearum, Xanthomonas zingiberi and Erwina carorovora. Bacterial activity.
- the plate coating method was used for verification, the test tube was taken out and 10 ⁇ l was sucked onto the beef extract medium for coating, and it was placed in an incubator at 35° C. for 24 hours.
- the sterile growth on the culture medium is the negative tube
- the bacteria growth on the culture medium is the positive tube
- the minimum complex concentration corresponding to the positive tube with bacterial growth is the lowest inhibitory concentration.
- the determination method is as follows: the live pot determination method is used, that is, the test complex sample is suspended or dissolved in water, diluted with 0.1% Tween 80 water, and prepared into the test solution of the required concentration. Spray the test solution on the plants to be infected by the crop sprayer (the plants to be infected are standard potted seedlings cultivated in the greenhouse), and then the disease inoculation is carried out 24 hours later.
- the diseased plants that require temperature control and moisturization are inoculated and then cultured in an artificial climate room. After the disease is infected, they are moved to the greenhouse for cultivation, and the diseased plants that do not need to be moisturized are directly inoculated and cultivated in the greenhouse.
- the disease prevention effect of the compound is evaluated after the control is fully onset.
- Example 1 has a higher activity on controlling cucumber downy mildew and cucumber bacterial angular leaf spot, and has a better protective activity in vivo.
- the compound of the present invention was used for the determination of acaricidal activity using Airbrush spray method.
- the pressure of Airbrush spray treatment was 0.7kg/cm 2
- the spray volume was 0.5 mL
- after treatment 2 ⁇ 3 Investigate the mortality rate of the target daily.
- Example 1 Complex 5 85% To 15 100%
- Example 2 Complex 5 85% To 15 100%
- Example 3 Complex 5 85% To 15 100%
- Example 4 Complex 5 85% To 15 100%
- Example 5 Complex 5 85% To 15 100%
- Example 6 Complex 5 85% To 15 100%
- Example 7 Complex 5 85% To 15 100%
- Example 8 Complex 5 85% To 15 100%
- Example 1 Complex 10 80% To 20 90%
- Example 2 Complex 10 80% To 20 90%
- Example 3 Complex 10 80% To 20 90%
- Example 4 Complex 10 80% To 20 90%
- Example 5 Complex 10 80% To 20 90%
- Example 6 Complex 10 80% To 20 90%
- Example 7 Complex 10 80% To 20 90%
- Example 8 Complex 10 80% To 20 90%
- Example 11 40% complex (Example 1 complex) granules
- Example 1 After the components are thoroughly mixed, they are pulverized by an ultrafine pulverizer, extruded to granulate, and dried to obtain a granule containing 40% of the complex of Example 1.
- Example 12 80% complex (Example 1 complex) granules
- Example 1 After mixing the components thoroughly, they are pulverized by an ultrafine pulverizer, extruded to granulate, and dried to obtain a granule containing 80% of the complex of Example 1.
- Example 13 70% complex (Example 4 complex) suspending agent
- Example 4 The components were added to a sand mill for grinding to prepare a suspension containing 70% of the complex of Example 4.
- Example 14 80% complex (Example 6 complex) wettable powder
- Example 6 After the components are thoroughly mixed, pulverized by a jet mill, and dried, a wettable powder containing 80% of the complex of Example 6 is obtained.
- Example 15 Greenhouse efficacy test of the insecticidal and acaricidal composition containing the complex represented by the general formula I against rice bacterial leaf spot pathogen
- the medicament used was the composition medicament prepared in Examples 9-12, and the control medicament was the purchased 45% prochloraz emulsion; the efficacy test was mainly completed in the plastic greenhouse of the rice greenhouse, and the rice bacterial leaf streak was inoculated first
- the efficacy test was mainly completed in the plastic greenhouse of the rice greenhouse, and the rice bacterial leaf streak was inoculated first
- the rice leaves appear yellow and wilt symptoms, apply the pesticide for the first time at the initial stage of the disease, and apply the pesticide every 7 days for a total of 3 sprays.
- Table 9 The efficacy test of the composition containing the complex represented by the general formula I in preventing and curing rice bacterial leaf spot
- composition containing the complex represented by the general formula I can effectively control the bacterial leaf spot of rice, and the control effect is better than that of the control agent 45% prochloraz water emulsion. long.
- Example 16 Suspension concentrate of 50% complex of Example 1 + 20% difenoconazole
- the components are added to a sand mill for grinding to prepare a suspension.
- Example 17 Suspension concentrate of 60% complex of Example 4 + 20% cymoxanil
- the components are added to a sand mill for grinding to prepare a suspension.
- Example 18 55% Example 6 complex + 25% difenoconazole wettable powder
- Example 19 Greenhouse efficacy test of the combination of the bactericidal and acaricidal composition of the present invention and other bactericides for the prevention and control of bacterial leaf leaf spot on rice
- the medicament used is the composition prepared in Examples 16-17.
- the control medicament is the purchased 45% cymoxanil granules and 30% difenoconazole suspension; the efficacy test is mainly in the plastic greenhouse of the rice greenhouse.
- Table 10 The efficacy test of the bactericidal and acaricidal composition of the present invention and other bactericides to prevent and treat rice bacterial leaf spot
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Abstract
L'invention concerne un complexe bimétallique cuivre-zinc dithiocarbamate. Le complexe bimétallique cuivre-zinc dithiocarbamate a la formule générale suivante : (I) comprenant : un ligand dithiocarbamate, un ion métallique X et un ion métallique Y ; lorsque X est le cuivre, Y est le zinc, et lorsque X est le zinc, Y est le cuivre ; et l'ion métallique X et l'ion métallique Y ont un rapport molaire de m : n. Le complexe bimétallique cuivre-zinc dithiocarbamate a un bon effet régulateur dans la prévention et le traitement de maladies fongiques et bactériennes ainsi que d'un dommage lié aux acariens dans des cultures agricoles, n'est pas susceptible d'induire une résistance aux médicaments des agents pathogènes et de provoquer une phytotoxicité pour les cultures agricoles, est facilement dégradable, est sans danger pour l'homme, le bétail et la vie aquatique, est facile à synthétiser, est peu coûteux en utilisation, résout le problème de la production agricole selon lequel une préparation de cuivre ne peut pas être mélangée avec une préparation de zinc, et présente de larges applications en agriculture et en sylviculture.
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|---|---|---|---|
| CN201911260218.X | 2019-12-10 | ||
| CN201911260218.XA CN110885303A (zh) | 2019-12-10 | 2019-12-10 | 二硫代氨基甲酸酯铜锌双金属络合物、制备方法及其应用 |
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| WO (1) | WO2021115195A1 (fr) |
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|---|---|---|---|---|
| DE1235287B (de) * | 1963-11-29 | 1967-03-02 | Bayer Ag | Verfahren zur Herstellung von fungizid wirksamen Dodecylamin-Metallsalz-Komplexverbindungen der mono- und bis-Dithiocarbamidsaeuren |
| CN1846494A (zh) * | 2006-04-17 | 2006-10-18 | 曾立雄 | 水域杀虫杀菌消毒的新型铜盐 |
| CN107118142A (zh) * | 2017-04-26 | 2017-09-01 | 利民化工股份有限公司 | 代森锰铜化合物及其制备方法与应用 |
| CN110885303A (zh) * | 2019-12-10 | 2020-03-17 | 利民化学有限责任公司 | 二硫代氨基甲酸酯铜锌双金属络合物、制备方法及其应用 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2095263B (en) * | 1981-03-23 | 1985-05-30 | Nippon Oils & Fats Co Ltd | Anti-fouling composition |
| CN1695449A (zh) * | 2005-04-08 | 2005-11-16 | 许惠朝 | 代森锰锌制备工艺 |
| CN104725433B (zh) * | 2015-02-09 | 2017-11-28 | 北京化工大学 | 一种二乙基二硫代氨基甲酸基双金属配合物硫化促进剂 |
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2019
- 2019-12-10 CN CN201911260218.XA patent/CN110885303A/zh active Pending
-
2020
- 2020-12-04 WO PCT/CN2020/133721 patent/WO2021115195A1/fr not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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