CN110881476A - High-efficiency broad-spectrum low-toxicity environment-friendly agricultural new compound and composition thereof - Google Patents

High-efficiency broad-spectrum low-toxicity environment-friendly agricultural new compound and composition thereof Download PDF

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CN110881476A
CN110881476A CN201811050182.8A CN201811050182A CN110881476A CN 110881476 A CN110881476 A CN 110881476A CN 201811050182 A CN201811050182 A CN 201811050182A CN 110881476 A CN110881476 A CN 110881476A
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copper
compound
limited
sodium
bisultap
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刘力
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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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
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    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
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    • A—HUMAN NECESSITIES
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    • 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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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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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    • A01N47/12—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
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Abstract

The invention provides a bisultap α, β and omega-shaped crystal compound and an agricultural composition thereof, which have the advantages of lower energy consumption for preparation, easier preparation, greenness and environmental protection, lower hygroscopicity, better storage stability, better control effect and the like, and are suitable for preparing the compound containing the compound and the application in the fields of controlling various bacterial and fungal diseases on crops and/or promoting the health or growth and development of crops or medicaments for protecting industrial materials from being damaged by germs and the like.

Description

High-efficiency broad-spectrum low-toxicity environment-friendly agricultural new compound and composition thereof
Technical Field
The invention relates to the technical field of pesticides, and particularly provides a novel compound with better stability of high-efficiency broad-spectrum low-toxicity environment-friendly agricultural antibacterial agent bisultap, a composition of the novel compound and a preparation method and application of the novel compound.
Background
The chemical name of the copper bisilicon or the Thisen copper is N, N' -methylene-bis (2-amino-5-mercapto-1, 3, 4-thiadiazole) copper, and the molecular formula is C5H4N6S4Cu with molecular weight of 339.9 is thiazole organic copper broad-spectrum bactericide (document 1, pesticide for preventing and treating crop bacterial diseases CN00132657.0), and is mainly registered for preventing and treating bacterial leaf blight of rice, bacterial leaf streak, soft rot of Chinese cabbage and tomato bacterial wilt. The bactericide has the characteristics of high efficiency, broad spectrum, low toxicity, safety, environmental protection and no public hazard, has special effect on bacterial diseases, has high efficiency on fungal diseases, is stable under acidic conditions, can be mixed with other pesticides, is a novel pesticide which is produced and registered by a company Limited in east China of Zhejiang province chemical industry at present, belongs to a national torch plan project, is one of pesticide varieties which are mainly recommended by national center of agriculture technology of Ministry of agriculture, and is applied to large area in production [ reference 2, Zhang Chun Biao, Lidi Xing, Wang Xiang, He Yong Lin]World pesticide, 2007 (02): 53-54; document 3, Zhang Chun Bingqi, Lidi Yu, Wang physique, He Yonglin, creating a high-efficiency safe bactericide-Saisentong, 2006-11-22, twenty-second China plant protection information exchange and farm chemical trade meeting; literature 4, Yao, Wang Mei, Zhang Yong, etc., field efficacy study of 20% Saisentong suspending agent on rice bacterial diseases [ J]Modern agricultural technology, 2006 (10):67; literature 5, He Rong forest, Chen Jia Hua, Zhang Chun Bing, Chenjie, field test for controlling bacterial leaf blight of rice with 20% Thiessen copper suspension agent [ J]Modern pesticides, 2007 (02): 44-45.; document 6: study on efficacy and application technique of Chenzaihao, Zhujie, Linjizhong, Luqiong, 60% Thiessen copper WDG on bacterial streak disease of paddy rice [ J]Shanghai agricultural science, 2010 (01): 132-; document 7: experiment on Sacourage, Huilu, Saisentong for preventing and treating bacterial angular leaf spot of watermelon [ J]Zhejiang agricultural science, 2013 (11): 1406-; document 8: pharmacodynamic test of 20% Saisentong suspending agent and other medicaments for preventing and treating navel orange ulcer disease [ J]Botanic doctor, 2016, 29 (10): 51-53; document 9: measurement of Saisentong [ J ] on tobacco by high performance liquid chromatography]Jiangsu agricultural science, 2015, 43 (01): 284-286.]。
The action mechanism of the leaf bronze is as follows: the structure of the copper bisultap consists of 2 groups of thiazolyl and copper ions, and the thiazole group has poor bacterial inhibition in vitro of plants but is a high-efficiency therapeutic agent in vivo of plants. In the plant ductus porosa, bacteria are seriously damaged, and the cell wall becomes thin and then collapses, so that the bacteria die. And copper ions have the functions of killing bacteria and fungi. Copper ions in the medicament are exchanged with cations (H +, K +, and the like) on the surfaces of the cell membranes of pathogenic bacteria, so that proteins on the cell membranes of the pathogenic bacteria are coagulated to kill the pathogenic bacteria; part of the copper ions penetrate into the pathogenic bacteria cells, bind to certain enzymes, affect the activity of the pathogenic bacteria, cause dysfunction, and then the pathogenic bacteria die. Therefore, the Saisentong has good effect of preventing and treating crop bacterial diseases, the pesticide effect of the Saisentong is superior to that of common pesticides, and the Saisentong also has higher prevention effect on fungal diseases.
The inorganic copper preparation has poor pesticide effect, needs to increase the dosage to improve the effect, often causes pesticide damage due to improper use, and is forbidden to be used in the flowering period and the young fruit period of crops due to too high copper content. The Saisentong copper belongs to organic copper, has low copper content, overcomes the defects, can be used in each growth period of crops, is safe and does not generate phytotoxicity.
The Saisentong has strong systemic conductivity, has treatment and protection effects, and is used for preventing and treating diseases. The Saisentong can achieve good effects by adopting application methods such as spraying, seed dressing, seed soaking, root irrigation, soil mixing and broadcasting, soil disinfection and the like. The Saisentong can be mixed with various pesticides. Most inorganic copper formulations, because of their basicity, are often not compounded or mixed with most other insecticides, acaricides and fungicides. Besides strong alkaline pesticides, the thiasen copper can be mixed or blended with other various pesticides.
Spraying: generally, the crops are sprayed with 500-700 times of fine spray, and the leaf surfaces are preferably sprayed with wet. Root irrigation: the root diseases are roughly sprayed or poured on the roots by 700-900 times. Seed dressing or seed soaking: and (3) seed dressing or seed soaking treatment is carried out on the seeds by 500 times.
Soil disinfection: and (3) spraying 700-900 times of liquid to the soil.
For example, the control object: (1) rice: bacterial leaf blight, bacterial leaf streak, stem base rot, seedling rot, bacterial brown spot, etc. (2) Orange: ulcer, scab, anthracnose, and sand skin disease. (3) Tropical fruits: banana leaf spot, anthracnose, longan leaf spot, pineapple stem rot, heart rot, litchi anthracnose, mango anthracnose, scab and the like. (4) Cruciferous vegetables: soft rot, bacterial black rot, bacterial blight, etc. (5) Cucumber: bacterial angular leaf spot, blight, bacterial blight, and the like. (6) Bean cutting: bacterial peronophytosis, bacterial angular leaf spot, etc. (7) peanut: bacterial wilt, leaf spot, root rot, etc. (8) Taro plants: soft rot, ginger blast (rot ). (9) Shallot and ginger: bacterial soft rot of onion and bacterial blast of ginger (rot and rot). (10) Cotton: blight, bacterial perisporium, anthracnose, etc. (11) Tobacco: bacterial wilt, wild fire, soft rot (hollow stem disease) and the like. (12) Soybean: bacterial burn and spot disease. (13) medicinal materials, flowers and seedlings: ulcer, root rot, basal rot, leaf spot.
Can be applied by spraying, root dipping, seed soaking, root irrigation, rough watering, rough spraying and the like. The common crop is diluted by 500-600 times, and the foliage spray is suitable. The root diseases are roughly sprayed or poured on the base by 500-900 times of diluent. The dilution factor is increased (decreased) seriously. The control is continuously carried out for 2-3 times at an interval of 7-12 days.
At present, the literature reports that the copper folinate or the Saisentong (C)5H4N6S4Cu, molecular weight: 339.9) [ reference 10, pesticides for controlling bacterial diseases of crops, CN: 1109500]The preparation method of (1).
In the current agricultural field, due to single administration and other unscientific administration modes, part of bacterial and fungal diseases generate drug resistance to a plurality of medicaments, and the method becomes a great problem in the agricultural sterilization process. Due to the generation of resistance of pathogenic bacteria, the pesticide is applied in an indiscriminate way in agriculture, frequently applied, mixed with pesticides randomly, even extremely toxic and highly toxic pesticides are used, so that the application cost is increased, the environmental pollution is aggravated, the residual risk is increased, and the food safety is seriously challenged. Even highly effective novel pesticides, if used alone for a long time, are also at risk of developing resistance to drugs. The development of new pesticides has high investment risk, and the requirements on environmental protection and food safety are increased, so that the restriction is increased, and the development period is longer. The scientific and reasonable pesticide compounding can improve the control effect, increase the quick-acting property, prolong the lasting period, expand the control spectrum, reduce the dosage, reduce the cost, or improve the multifunction of one-time pesticide application, and the like, can overcome or delay the generation or development of the resistance of pests, prolong the service life of the pesticide, reduce the environmental pollution, protect natural enemies, maintain the biological diversity, keep the ecological balance or be convenient to use, reduce the working hours, and the like. The method has important value in the aspects of protecting the high yield and high quality of crops in the research and application of the efficient, safe, low-drug-resistance and convenient-to-use pesticide composition. Due to the limited bactericidal capacity of thiasen copper, the currently published chinese patent documents report the combination or combination of thiasen copper, such as the following documents [ chinese patent: a bactericidal composition containing carbendazim and Saisentong, which is disclosed as CN: 108271798, respectively; a bactericidal composition containing phenylthioimidazole and copper preparation, CN: 108244128, respectively; the bactericidal composition containing the amisulbrom and the organic copper compound has the following publication numbers: 104886075, respectively; a compound composition containing isolongifolene ketoxime lactam and thieson copper, CN: 107711854, respectively; a bactericidal composition containing pyraclostrobin and Saisentong, CN: 107361074, respectively; a bactericidal composition containing Saisentong and kasugamycin, CN: 107333775, respectively; an agricultural bactericide containing kasugamycin and thiasentong and application thereof are disclosed in the specification, wherein CN: 107156127, respectively; a bactericidal composition containing oxathiapiprolin, CN: 106719710, respectively; a pesticide composition containing Dufulin and thiazole bactericide and the bactericide thereof are disclosed, wherein CN: 105052996, respectively; a bactericidal composition containing benziothiazolinone and copper thiessense, CN: 106342830, respectively; a compound pesticide containing zhongshengmycin and Saisentong and application thereof are disclosed in the publication number CN: 105941482, respectively; a compound composition containing methylsulfonylconazole and Saisentong, CN: 104488903, respectively; an agricultural bactericidal composition containing Saisentong, CN: 105638683, respectively; a compound pesticide containing Saisentong and application thereof, CN: 103798270, respectively; agricultural bactericidal composition containing Saisentong, CN: 104222116, respectively; a compound pesticide containing triazolone and Saisentong and application thereof are disclosed, wherein CN: 103798251, respectively; ].
The stability of the original drug is the basis for ensuring the stability and good preparation performance of the pharmaceutical preparation, and is the basis for maintaining the effectiveness of the drug, the most stable form of the raw drug is continuously pursued in pharmacology, the pharmacology is an experimental science, the molecular form with good stability is unpredictable in advance, a plurality of cases are provided in the development history of the European and American drugs to clarify the value of searching the molecular form of the drug with good stability, and the continuous development and progress of the pharmacology are objectively promoted. It is not known to many professionals that some bulk drugs produced industrially for years have different stability of different batches of raw materials fed into the same batch of raw materials in the same workshop and the same equipment under the same process flow, some bulk drugs can only keep the stability of about 3 months even under the specified conditions, and some quality control indexes have different obvious changes, which causes the problem of confusion or trouble. From the actual situation, although the copper bisulphite (Saisen copper) has been on the market for many years, the stability of the copper bisulphite anhydride still has some problems, such as large hygroscopicity, reduced storage period content or excessive increase of related substances, and the like, and the problems can not be solved for many years, so that the solution for solving the compound stability problem is sought. Although valuable results are expected to be obtained by some experiments to obtain crystal form changes on the basis of unchanged compound molecular formula, no obvious improvement is obtained, and various problems still exist.
The situation is not an individual phenomenon, and according to the media disclosure, the quality problem of the pesticide product in China is relatively serious, and the quality difference of the raw pesticide is large due to various factors (documents: the quality difference of the raw pesticide is large due to various factors-the current situation and the main problem of the quality of the pesticide product in China are analyzed, a Chinese quality news network 2008-03-26,http：//www.cqn.com.cn/news/cpkkxbg/199443. html). This focus is reflected in:
1. quality difference between products of the same variety and the same enterprise!
There may also be differences in quality, even large, between products of the same variety produced by the same enterprise. The following two cases are mainly included: firstly, the product quality is unstable due to the immature production process, and the product quality of different production batches is different, which mainly exists in some small and medium-sized enterprises and some new products which are developed shortly; and secondly, part of production enterprises produce high-content products meeting export requirements through a traditional refining and purifying process, and as a result, low-content products containing a large amount of impurities are produced, and the products are partially self-digested and processed into preparation products by the production enterprises and partially pushed to domestic markets in a way of being mixed with fish eyes, so that the phenomenon is not lost even in some large and medium-sized enterprises.
2. Most raw medicine products have no control or not strict control on impurity content
At present, most of raw medicine products lack control indexes for the content of toxic and harmful impurities, and the impurity content of part of raw medicine products is obviously higher. Although it is required to provide an analysis report of the product at the time of product registration, the impurity content does not appear in the quality control index of the corresponding product (crude drug and its preparation) for most products. High impurity content of the original drug product may cause various adverse effects, some impurities have high toxicity, some impurities bring difficulty to preparation processing, and some impurities reduce the stability of active ingredients. With the use of preparation products, the impurities may also affect the environmental and ecological safety and even cause large-area crop phytotoxicity.
So far, no published literature at home and abroad reports the novel biscopper folinate compound of the invention with better stability, such as biscopper folinate α, β and omega-type crystal compounds (Thiessen copper α, β and omega-type crystal compounds), namely a novel biscopper folinate crystal hydrate with different molecular formulas or different crystal forms, and a preparation method and application thereof.
Polymorphism of chemical drugs plays an important role in drug research, and is suitable for better drug requirements. Thermal analysis methods have important value and status in material science, chemistry or pharmaceutical analysis, etc., and can be used alone to detect polymorphic forms of a compound or changes in the crystalline form during the process (lee, thermal analysis, university of qinghua press, first edition 8 months 1987). Differential Thermal Analysis (DTA) is a relatively common analytical method used for both qualitative and quantitative identification of substances, and is used by Barta et al to identify unknown compounds as early as the second international conference on thermal analysis in 1968. The pharmacopoeia of many foreign countries has already collected the differential thermal analysis method, and over a decade ago, the differential thermal analysis method has been widely applied to chemical and pharmaceutical systems.
Disclosure of Invention
It is well recognized in the chemical arts that the presence or absence of a specific solvent compound for a compound is unpredictable, cannot be defined in advance by the markush formula, and that some solvent compounds are highly toxic, some are highly hygroscopic, and some are easily weathered. The invention relates to a new compound with better stability of copper cycloulnar, namely a crystal hydrate of N, N' -methylene-bis (2-amino-5-mercapto-1, 3, 4-thiadiazole) copper, and the molecular formula is C5H4N6S4Cu·nH2O, wherein n is 1, 1.25, 1.5, i.e. thiasen copper or bismeresulphos α, β, omega type crystal compounds and compositions containing the same, methods of making and uses thereof.
In the process of completing the invention, unexpectedly, it is found that although the current literature reports that the thiason copper anhydride is used as a pesticide, the study also finds that the stability of the thiason copper is not the best choice in pharmacology or pesticides, the thermal stability of the thiason copper is not good enough, and the thiason copper can cause the content of raw material medicines to be reduced or unqualified or the content of the pesticide preparation to be inaccurate in subpackaging under unexpected conditions, or can cause the thiason copper to be easily replaced or not used by more pesticide preparations due to high impurity content or has high impurity content, so that the environmental and ecological safety can be affected, even large-area crop phytotoxicity can be caused, adverse effects in multiple aspects can be caused, or adverse effects can be caused when the thiason copper anhydride is further applied to the fields of sensitive purity or high-grade materials and the like. Moreover, the present study found that the more stable thiesencopper hydrate is better accessible than thiesencopper anhydrate, which has long been overlooked by those skilled in the art.
Moreover, the present invention also finds the advantages of the novel compound of the present invention in the manufacturing process or the environment-friendly disposal process, and the drying temperature of the embodiment of preparing Saisentong anhydrous copper of the prior art in reference 10 (pesticide for preventing and treating bacterial diseases of crops, China CN: 1109500) is about 100 ℃, which inevitably consumes more energy, is not beneficial to constructing energy-saving production, increases total impurities, is not beneficial to the storage stability of raw materials, and the problems are ignored for a long time, but no professional can do simple and easy work to improve. The stability of the Thisen copper 1 hydrate, the Thisen copper 1.25 hydrate and the Thisen copper 1.5 hydrate can meet the requirement of pharmacy. This reflects that the tiarsen copper hydrate with better stability in different degrees has better availability and lower energy consumption advantage in the production process, and simultaneously shows that the material of the invention has more production convenience and better industrial value. This also reflects from another perspective that the availability of the thiason copper anhydrate production preparation is somewhat poor, and has been overlooked for a long time.
The Thiessen copper compound entity with the novel molecular structure obtained by the invention has the advantages that the Thiessen copper with the crystal water has far lower hygroscopicity than the Thiessen copper without the crystal water, the deliquescence of an anhydrate ensures that air is isolated to prevent adhesion and the like during treatment, the hydrate has good sliding property, so that the operability of a pesticide preparation is improved, the substance containing the crystal water can exist more stably than the Thiessen copper without the crystal water, the storage and the transportation are convenient, the manufacturing cost and the cost are reduced, and the preparation of the pesticide preparation is also facilitated. In addition, the stability of the anhydrous thiesenne copper during storage is low at present. The Thiessen copper crystal hydrate with different novel molecular formulas and novel molecular structures has different advantages in the aspects of stability and the like. Furthermore, the invention finds that the new Saisentong compound has better industrial value or pesticide value than Saisentong anhydride.
Surprisingly, the hydrates of the present invention characteristically have a corresponding endothermic peak at the weight loss plateau (under the weight loss curve before about 168 ℃) of the thermogram (TG-DSC or TG-DTA) showing the entities of the biscuprum compound, biscuprum α, β, omega-type crystalline compound-biscuprum hydrate (C) of novel structure5H4N6S4Cu·H2O, etc.) and the like. Even if different crystal forms of the same compound are prepared or obtained, the actual or potential or future significance or value can be realized in pharmacology, and the actual or potential or future significance or value can be realized in pharmacology by obtaining different crystal hydrates of the same drug.
The preparation of the novel biscopper phthalocyanine crystal hydrate comprises but is not limited to the following methods:
adding the bisultap into a reaction vessel, adding water and/or an organic solvent C1-C6Is selected from low molecular alcohol (such as methanol, ethanol, isopropanol, n-butanol, etc.), C2-C8Low molecular ether (selected from but not limited to diethyl ether, tetrahydrofuran, isopropyl ether, etc.), C2-C6Dissolving one or more of the low molecular nitriles in water or organic solvent solution of alkali selected from but not limited to sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide and sodium isooctanoate, stirring, adding copper salt selected from but not limited to copper sulfate, copper sulfate pentahydrate, copper chloride dihydrate, copper acetate monohydrate, copper nitrate or aqueous solution thereof, stirring, fully precipitating solid, filtering, adding water and C1-C6Low molecular alcohol of (2), C2-C8Low molecular ether of (2), C3-C8Low molecular ketone of (2), C2-C6Low molecular nitrile of (2), C1-C6Low molecular halogenated hydrocarbon of C2-C8Washing one or more of the low molecular weight esters once to several times, filtering, and drying the obtained solid to obtain a novel phyllobis copper compound, namely a phyllobis copper crystalline hydrate;
wherein, the bismerthiazol used in the reaction: the equivalent ratio of one of alkali (selected from but not limited to one of sodium carbonate, sodium hydroxide, potassium hydroxide and sodium isooctanoate) is about 1: 1-1.1; the weight volume ratio of the leafy indigo (weight g) used in the reaction to water, or C1-C6 low molecular alcohol, or C2-C8 lower ether (selected from but not limited to diethyl ether, tetrahydrofuran, isopropyl ether, etc.), or C2-C6 lower nitrile (selected from but not limited to acetonitrile, propionitrile, etc.) is one or more of the following organic solvents: 1(g) to 3.5-60 (ml), preferably in the following ratio: 1(g) to 5-40 (m 1); the equivalent ratio of the bisultap to one or more of the copper salts is about 1: 0.98-1.05;
the solvent used in the synthesis process of the new phyllobicopper compound is selected from one or more of water, acetonitrile, tetrahydrofuran, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, ethyl formate, diethyl ether, tetrahydrofuran, isopropyl ether, dichloromethane, chloroform, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide) and the like; more preferably one or more of water, methanol, ethanol, isopropanol, tetrahydrofuran, ethyl acetate, isopropyl ether, dichloromethane, chloroform, DMF, and DMSO.
The carbon number of the organic solvent lower alcohol or low molecular alcohol in the present invention is defined as C1-C6 (i.e., alcohol of 1-6 carbon atoms), such as methanol, ethanol, isopropanol, etc.; the carbon atom number of the lower ether or low molecular ether is defined as C2-C8, such as diethyl ether, dibutyl ether, tetrahydrofuran, etc.; the lower halogenated hydrocarbon has carbon number defined as C1-C6, and includes dichloromethane, dichloroethane, chloroform, etc.; the number of carbon atoms of the lower ester is defined as C2-C8, and includes butyl acetate, ethyl formate, etc., unless otherwise specified as a lower ester of formic acid; the C3-C8 low molecular ketone is defined as ketone with 3-8 carbon atoms, including acetone, butanone, isohexanone, etc.; the labeling method for the number of carbon atoms of any of the compounds described as "lower or low molecular" appears once in the text, and the number of carbon atoms of any of the other unlabeled compounds of the same class described as "lower or low molecular" is consistent with the number already indicated herein.
The product of the present invention may be dried at various temperatures (e.g., between 20-70 c), drying times, or ambient conditions with other drying agents (including silica gel, phosphorus pentoxide, anhydrous calcium chloride, anhydrous sodium sulfate, etc.), or using atmospheric or reduced pressures. The drying temperature is preferably 35 to 60 ℃.
The anhydrate can be prepared by drying the final product at various temperatures (e.g., 90-100 ℃), drying times (up to several days), or in the presence of other drying agents (including silica gel, molecular sieves, phosphorus pentoxide, sodium hydroxide, soda lime, anhydrous sodium carbonate, anhydrous calcium chloride, anhydrous sodium sulfate, anhydrous magnesium sulfate, etc.), or by drying under atmospheric or reduced pressure, or by treating with anhydrous benzene for several days or distilling off the entrained water, and drying in conjunction with other drying methods described herein.
Preparation of bisbronze anhydrate referred to in this invention: a commercially available biscopper anhydrous substance or a biscopper sample prepared according to the method of the embodiment of the literature (pesticide for preventing and treating bacterial diseases of crops, China CN: 1109500) is taken, vacuum drying is carried out for about 4 hours in a vacuum drying oven at about 95 ℃, then a beaker containing enough solid sodium hydroxide and a beaker containing soda lime are placed in the vacuum drying oven, vacuumizing is carried out again (the reading of a vacuum meter is about 0.08 MPa), heating is stopped, vacuum drying is continuously carried out for 2 days at room temperature, and the biscopper anhydrous substance is obtained, wherein the water content of the biscopper anhydrous substance is lower than about 0.7 percent as measured by a Karl Fischer method.
The detection of the novel compound of the biscopper phyllinate (including HPLC method and the like) is generally carried out by a reference method. The moisture content of the biscopper phyllide new compound or the biscopper phyllide anhydrate and the like in the present invention is measured by the karl fischer method with reference to the first method a of chinese pharmacopoeia appendix VIII M, 2010, and the moisture content of the related compound and the like is measured by a specific karl fischer moisture content measuring instrument.
In one aspect of the invention, different specific crystalline hydrates or polymorphs of biscopper phyllinate are provided.
In another aspect of the invention, different crystalline hydrates are provided, as well as methods for their preparation.
In another aspect, the present invention provides a pharmaceutical composition comprising any one or more of the crystalline hydrates of tephronium prepared by the process of the present invention, and one or more pharmaceutically acceptable excipients.
The invention further provides a process for preparing a pharmaceutical formulation comprising combining any one or more of the tobermorite formulations prepared by the process of the invention or with at least one or pharmaceutically acceptable excipients.
The invention further provides an application of the bisultap crystal hydrate or the thiesenne copper crystal hydrate in preparing pesticide compositions for sterilization and the like.
Compared with the phyllobium copper, the phyllobium copper hydrate provided by the invention is beneficial to reducing energy consumption and reducing the operation cost of the medicine, and has positive significance.
The cost of the phyllobilanthus leaf crystal hydrate is not obviously increased compared with that of the phyllobilanthus leaf, and the preparation energy consumption is reduced.
The bisbronze hydrate of the invention is easier to prepare than bisbronze anhydrate.
Moreover, the present inventors have found that the drying temperature for preparing Saisen copper anhydrate in example 1 of prior art document 1 (CN: 001326570) is about 100 ℃, which consumes much energy, and the temperature raising and lowering process is long, which is not favorable for energy-saving production.
The drying in the preparation process of the Saisentong crystal hydrate only needs about 30-60 ℃, or the drying is carried out by utilizing natural wind and then the drying is carried out, so that the energy consumption is lower, and the product stability or pharmacodynamics research finds that the product can completely meet the requirements on pharmacology. This reflects that the tiarsen copper hydrate with better stability has better availability in the production process and has lower energy consumption advantage, and simultaneously, the material of the invention has more production convenience and better industrialization value. This also reflects the poor availability of the thieson copper anhydrate production preparation from another perspective. The Thixon copper 1 hydrate of the present invention is much easier to prepare than the Thixon copper anhydrate, and has been overlooked for a long time.
In the preparation of the anhydrous Saisen copper, the situation that the degradation of the Saisen copper is accelerated in the storage period is easy to occur, so that the original target product is unqualified, and the target product is not favorable for maintaining the sterilization effect of the target product.
The hygroscopicity of the drug is an important content for examining the stability of the drug, and is a necessary work in the research process of the drug, which is sometimes ignored. The advantage of the crystalline hydrate of kukoku according to the present invention was found by comparative studies such as a hygroscopicity test on the crystalline hydrate and an anhydrate.
1. Hygroscopicity test
The inventive bisbronze new compound and anhydrate samples were subjected to the hygroscopicity test: taking the bisultap anhydrous (the bisultap is dried in vacuum at 90-100 ℃ for 6 hours and then placed in a drying box containing solid sodium hydroxide and soda lime, drying in vacuum for one week at room temperature to obtain the bisultap anhydrous, measuring the water content of the bisultap anhydrous by a Karl Fischer method to be lower than 0.7%), placing about 5g of the bisultap anhydrous and the novel bisultap compound in a drying constant-weight watch glass, precisely weighing, respectively placing in an experiment box with the temperature of about 25 +/-2 ℃ and the relative humidity of about 55 +/-5%, respectively sampling in experiments for 0h and 8h, and calculating the percentage of moisture-attracting weight increase. The results are shown in Table 1.
TABLE 1 moisture wicking test results
Figure RE-GDA0001845365540000071
The results of the moisture absorption test show that the moisture absorption of the bisultap anhydrate is about 5 times or more higher than that of the novel bisultap compound of the present invention, and it can be seen that the deliquescence of the bisultap anhydrate is more severe, and the two have significant differences.
The novel compound of the invention has no efflorescence phenomenon, but has good sliding property, the novel compound of the invention is different from the deliquescence of anhydrous substances, so that air is isolated to prevent adhesion and the like during treatment, the operability of the preparation in the subpackaging process is improved, and the novel compound of the invention can better and stably respond to the change of drying temperature, humidity and the like, and is more beneficial to stable storage. The dosage is more accurate in the preparation process, the yield of the production of the raw material medicines or the pesticide preparations is improved, the phenomenon that the dosage is insufficient due to the difference of the loading amount caused by moisture absorption is avoided, the product is unqualified, the scrapping loss is caused in the production process, and the like is avoided, and the accuracy and the effectiveness of application and administration are facilitated. The pharmacodynamics always tends to select a medicine form with better stability from the raw material medicines, namely the always tends to select a compound with better stability as the raw material medicines.
2. Stability test
The inventive biscuprite crystalline hydrate samples (samples prepared by the methods of example 1, example 2, example 3 and example 5, respectively) and biscuprite anhydrate were sealed in vials under light-tight conditions at RH65 ± 5% and 25 ± 2 ℃ for a stability test for 12 months, and changes in appearance and color were observed, and the substances before and after the test were measured. The related substances are determined by HPLC method and are prepared by Phenomenex C18(4.6 mm. times.250 mm, 4.6 μm) chromatography column, column temperature 25 ℃, detection wavelength 313nm, mobile phase: acetonitrile-0.1% acetic acid water (17.5: 82.5, volume ratio), method references methods [ document 9: measurement of Saisentong [ J ] on tobacco by high performance liquid chromatography]Jiangsu agricultural science, 2015, 43 (01): 284-286.]And (4) determining the total related substances outside the main peak in the HPLC (in the invention, the content of the copper bisultap crystal hydrate or the Thisenon copper is determined by qualitative analysis) of the copper bisultap in the tested sample.
The experimental result shows that the change of the appearance color is not obvious, the related substances of the samples in the examples are increased slightly, and the increase of the related substances of the Saisen copper anhydride is increased slightly. The experimental results show that the biscopper leaf crystal hydrate has good room temperature storage stability (the results are shown in table 2).
TABLE 2 stability test results
Figure RE-GDA0001845365540000072
Figure RE-GDA0001845365540000081
3. Experimental result of germination rate research after seed soaking
The rice seeds carry a plurality of pathogenic bacteria, and can show various disease symptoms at different periods and stages of rice plant growth. After the seed-borne diseases occur, the growth, development, yield and quality of rice plants are affected to different degrees. In addition, since the rice seed-carrying bacteria (diseases) are the initial (initial) infection source causing the disease of the rice plant, the re-infection, generation, spread and damage of the disease can be caused in the growing season. Some diseases have great threat to rice production, generally cause the yield reduction of rice by 10-20 percent, and reduce the yield by more than 50 percent when the disease is serious. For the prevention and treatment of seed-borne diseases, people always adopt bactericides to treat seeds before sowing. The germination of rice seeds is a respiratory metabolic process from water absorption expansion to germination and then to germination, and if a medicine is in a problem, the germination rate of the rice seeds can be influenced. The influence of the new leaf-bronze compound group and the leaf-bronze anhydrous substance on the germination rate of rice after seed soaking is researched in a grouping way.
The samples of the biscuprum folicum new compound group (divided into three groups: the sample group of example 1 method, the sample group of example 3 method, the sample group of example 4 method) and the sample of the biscuprum folicum anhydrate (the sample group of biscuprum folicum anhydrate) were each placed in the air for 6 hours to absorb moisture, then the samples of the biscuprum folicum new compound group were each dried at 60 ℃ for 6 hours, the samples of the biscuprum folicum anhydrate were dried at 99 ℃ for 6 hours, then sealed in glass bottles and kept at 60 ℃ for two weeks, purified water was added to make the solid concentration 30%, the solid water mixture was shaken on a shaker every day for 3 hours, then placed in the dark, thus the solid water mixture was sealed for one week, then the above-mentioned liquid medicine was taken out to 20 + -1 ℃ to soak rice seeds (Zhengzao No. 6 rice seeds, 2016 years), 4 repeated experiments were carried out for each treatment, each 100 repeated experiments, and the liquid medicine was used to soak rice seeds for, after treatment, the seeds are placed in a culture dish with double layers of filter paper, heat preservation and germination acceleration are carried out at the temperature of 25 +/-1 ℃, the germination conditions of the treatment are observed and recorded every day in the germination acceleration and statistical analysis is carried out, the germination standard of the rice seeds is regarded as the seed exposure, the germination rate is tested, and the experimental result is shown in table 3.
TABLE 3 influence of different chemical seed soaking on the germination rate of Zhengzao No. 6 rice seeds
Number of seeds Germination rate
Saisentong copper anhydrate group 100 granules 90.3％
EXAMPLE 1 method set 100 granules 94.8％
EXAMPLE 3 method set 100 granules 95.8％
Example 4 method set 100 granules 95.3％
The experimental results show that the leaching solutions of the leaf bronze new compound group (the sample group obtained by the method of example 1, the sample group obtained by the method of example 3 and the sample group obtained by the method of example 4) and the leaf bronze anhydride (the leaf bronze anhydride group) have a significant influence on the germination rate of rice seeds, and the germination rate of the leaf bronze anhydride group is significantly lower than that of the leaf bronze new compound group, which indicates that the seed soaking after the treatment of the leaf bronze anhydride is not favorable for the germination of rice seeds.
The invention not only prepares a more stable new compound of the phyllidium bicolor, but also provides a composition of the new compound, the bactericidal active compound composition contains the new compound A of the phyllidium bicolor and any one of other known bactericidal active or antiviral drug compounds B, and the compound is applied to the control of diseases caused by plant fungi, bacteria and viruses. The bactericidal active compound composition has the activity of a synergistic bactericidal or antiviral drug and improves the compatibility with plants, thereby meeting the requirements of agricultural production.
The novel bisultap copper compound is used for preparing a pharmaceutical composition or a pesticide composition which comprises the novel bisultap copper compound and an effective dose of bactericidal drugs or antibacterial drugs or antiviral drugs andor plant growth regulators, and other pharmaceutically acceptable auxiliary materials to prepare pharmaceutically acceptable pesticide preparations; namely, preparing a new pharmaceutical composition or a pesticide composition from an effective dose of the new compound of the active ingredient A, namely the bisultap and an effective dose of the active ingredient B; wherein the weight ratio of active ingredient A to active ingredient B is 180: 1-1: 100 (calculated by weight of anhydrous or hydrous substance); wherein the weight ratio of the active component A to the active component B is preferably 100: 1 to 1: 100 (the weight can be calculated by the anhydrous substance or the hydrous substance); wherein the weight ratio of the active component A to the active component B is preferably from 80: 1 to 1: 80 (calculated as the weight of the anhydrous or hydrous product); the active ingredient B is selected from any one or more of B.1) -B.13) and pharmaceutically acceptable salts or solvent compounds thereof (reference A: liu Chang Ling, Chaibaoshan Master eds, "creation and Synthesis of New pesticides," chemical industry Press, 2013, Beijing; document B: grandfather, qijunshan, a modern pesticide application technology series: volume of fungicides, chemical industry publishers, 2017, beijing);
b.1) a strobilurin fungicide or an antiviral agent selected from one of, but not limited to, azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, enestroburin, fluoxastrobin, picoxystrobin, kresoxim-methyl, enestroburin or metominostrobin, phenamacril, Picarbitraconazole, orysastrobin, pyraclostrobin, coumoxystrobin, closterin, pyraclostrobin, UBF307, KZ165, probenazole, diclorocyanid and the like;
b.2) triazole fungicide selected from but not limited to difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, hexaconazole, myclobutanil, penconazole, propiconazole, tetraconazole, triadimenol, triadimefon, metconazole, ipconazole, prothioconazole, imazazole, triticonazole, cyproconazole, mefentriflumizole mefentrafluconazole, ipriflurazole, ipfenflurrifluconazole, bromuconazole, fenbuconazole, fluquinconazole and the like;
b.3) an amide fungicide selected from one of, but not limited to, metalaxyl-M, flutolanil, mandipropamid, boscalid, fluopyram, carboxin, Bixafen, penflufen, epoxiconazole, Fluxapyroxad, penthiopyrad, thifluzamide, fluopicolide and isopyrazam, fluofen, fluoxafen, cycloflusulfamide, methiavalicarb, benalaxyl-m, thifluzamide, tiadinil, ethaboxam, silthiopham, cyflufenamid, fluopyram, zoxamide, fenhexamid, cyprodinil, flusulfamide, metosulam, oryzamide, Bixafen, Fluxapyroxad, Sedaxane and the like;
b.4) one of imidazole bactericides which is selected from one of cyazofamid, triflumizole, imazalil, fenamidone, oxpoconazole, albendazole, phenylthioimidazole and the like;
b.5) dicarboximide bactericides selected from but not limited to one of procymidone, iprodione, vinclozolin, captan, dimethachlon, tolclofos-methyl and the like;
b.6) carbamate bactericide which is selected from but not limited to one of propamocarb hydrochloride, diethofencarb, benomyl, carbendazim, thiophanate-methyl, iprovalicarb, benthiavalicarb and the like;
b.7) antibiotic bactericide or antiviral agent selected from, but not limited to, validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshengmycin, pesticide 120, aureonucleomycin, Changchuan mould, tetramycin, etc.;
b.8) oxazole based fungicide selected from but not limited to oxadixyl, hymexazol, famoxadone, pyrisoxazole, fluorothiazolepyrietone, benfurazolesulfone, dichloroazole and methanesulfonylazole;
b.9) morpholine bactericide or antiviral drug, which is selected from one of tridemorph, dimethomorph, flumorph, moroxydine hydrochloride and the like;
b.10) a pyrimidine fungicide selected from but not limited to one of cyprodinil, pyrimethanil, ethirimol, mepanipyrim, fluopyram, dimoxystrobin, SYP-3773, SYP-3810 and the like;
b.11) quinoline bactericide, selected from but not limited to dithianon, propoxymoline, phenoxyquinoline, quinoliflumein (quinoflulin), and the like;
b.12) dithiocarbamate bactericides or antiviral agents selected from but not limited to one of metiram, thiram, ziram, amobam, zineb, maneb, mancozeb, propineb and the like;
b.13) other fungicides or antivirals or plant growth regulators, selected from, but not limited to, diphenfos, fosetyl-aluminium, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydrorosinate, fenpiclonil, fludioxonil, isovinyl ketoxime lactam, cnidium lactone, Dufulin, phenactone, mehtanine, polyhexamethylene biguanide hydrochloride, bromothalonil, indazolesulfamide, copper oxychloride, copper nonylon, oxine-copper, moroxydine hydrochloride, copper succinate, xinafoate acetate, amino-oligosaccharin, lentinan, benziothiazolinone, ethylicin, probenazole, diclocyanamide, physcion, chrysophanol, fluxazole-activated ester, S-abscisin, amino-oligosaccharin, zinc sulfate, berberine and pharmaceutically acceptable salts (e.g. berberine hydrochloride, berberine sulphate, berberine sulphate, berberine hydrochloride, berberine sulphate, berberine hydrochloride, berberine sulphate, berberine, Eugenol, sulfur, copper sulfate pentahydrate, bismerthiazol, isolongifolenoximelactam, garlicin, guaiacol, quinolactaside, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, ziconazol zinc hydrate, ametoctramide, Pyribencarb, fluthianil (OK-5203), meptyldinocopine, Pyriofenone, fenpyrzamine, Valifenalate, Tolprocarb, isofemamide, Isopyrazam, Penflufen, benzovindlufulpy (SYN545192), Tebufloquin, Oxathiapiprolin, spiroxamine, spirocyprodinil, fosetyl-aluminum, iprobenfos, matrine, kurarinone, and the like; or the plant growth regulator is selected from one of but not limited to diethyl aminoethyl hexanoate, forchlorfenuron, compound sodium nitrophenolate, brassin, gibberellin, 6-benzylaminopurine, triacontanol, naphthylacetic acid or its medicinal salt, paclobutrazol, ethephon, etc.
The composition of the new metsulobicopper compound contains an active ingredient A and any one or more active ingredients B selected from but not limited to azoxystrobin, kresoxim-methyl, pyraclostrobin, enestroburin, trifloxystrobin, pyraclostrobin, fluoxastrobin, kresoxim-methyl, alkene oxime amine or metominostrobin, cyhalostrobin, Picarbitrazox, triflourinamide, pyraclostrobin, coumoxystrobin, clopicoline, UBF307, KZ165, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, myclobutanil, cyproconazole, penconazole, propiconazole, tetraconazole, triadimenol, bitertanol, triadimenol, metconazole, ipconazole, prothioconazole, imibenconazole, cyproconazole, metalaxyl, flutolanil, mandipropamid, boscalid, fluoxafen, cyhalofenamid, cyhalonil, triflumizole, triflumi, Imazalil, fenamidone, oxpoconazole, oryzanol, procymidone, iprodione, vinclozolin, captan, dimeticone, propamocarb hydrochloride, benomyl, carbendazim, thiophanate-methyl, valcarb, benthiavalicarb, jinggangmycin, streptomycin sulfate, kasugamycin, shenqimycin, oxadixyl, hymexazol, famoxadone, pyrisoxazole, tridemorph, dimethomorph, flumorph, cyprodinil, pyrimethanil, ethirimol, mepanipyrim, fluopyram, dithianon, propoxymine, phenoxyquinoline, metiram, thiram, amobam, zineb, maneb, propineb, fenamiphos, fosetyl-Al, chlorothalonil, isoprothiolane, or copper hydroxide, copper rosinate, copper dehydroabietate, fenpiclonic, flufen, fenamidone, fenamate, fenamidone, fenapanil, Dianiline, validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshenmycin, nong-antibiotic 120, aureonycin, chanchmycin, dufulofulfosu, phenazon, prothioconazole, phenylthioimidazole, chlorofluoromethoate (mefentrifluoconazole, mefentrifuconazole), iprifluconazole (ipfenthifluzole), fluthiacetophenone, probenazole, physcion, chrysophanol, fluthiazopyrazole, probenazole, diclosamide, physcion, chrysophanol, fluzole-activated ester, dichlorooxazole and mesylozole, S-abscisic acid, amino-oligosaccharide, zinc sulfate, dehydroberberine, isocyanine hydrochloride, hydrogen sulfate, berberine sulfate, danum, isolongifolactam, allicin, guaiacol, quinacride, quinolamide, ketoxime acetate, chlornuron, cyanuric acid, thiochloride, thiocyanogen, chlorfenapyr, chlorfena, Carvacrol, ziconazol hydrate, thifluzamide, tiadinil, ethaboxam, silthiopham, furametpyr, cyflufenamid, fluopicolide, zoxamide, fenhexamid, cyprodinil, flusulfamide, sulfenamide, oryzamide, Bixafen, Fluxapyroxad, Sedaxane, ametoctradin, Pyribencarb, fluanil, Meptyldinocap, Pyriofenone, Fenpyrazamine, valifenamine, Tolprocarb, isofluzam, Penflufen, benzoIzod (SYN545192), tebuflofen, Oxathromolin, furazol, fenbuconazole, fluquinconazole, spiroxamine, pyrimethanil, pyraclostrobin, pyrifos, metoclopramide, the weight ratio of the active component A to the active component B is preferably 1: 80-80: 1, and the more preferred weight ratio is 1: 60-60: 1.
The novel copper bisulphite compound is used for preparing a pharmaceutical composition containing the novel copper bisulphite compound, and the novel compound or the composition and a pharmaceutically acceptable carrier are prepared into a pharmaceutically acceptable preparation which is selected from but not limited to dry suspending agent, wettable powder, granules, dispersible granules, tablets, effervescent tablets, microcapsules, water dispersible granules, suspending agent, suspoemulsion, emulsion in water, microemulsion, missible oil, controlled release or sustained release preparation, microcapsule preparation, oil suspending agent, dispersible liquid (DC), seed treatment dry powder, seed treatment dispersible powder, granules, dispersible granules, microcapsule suspending agent, seed treatment microcapsule suspending agent or suspended seed coating agent and the like.
In the composition preparation, the pharmaceutically acceptable carrier is selected from one or more of wetting agent, adhesive, dispersing agent, thickening agent, antifreezing agent, preservative, disintegrating agent, stabilizing agent, film forming agent, defoaming agent, coloring agent, lubricant or glidant, filler and/or water.
The new compound or the pharmaceutical composition thereof is applied to the preparation of the drugs for preventing and treating diseases on crops and promoting the growth and development of the crops.
The diseases are selected from but not limited to: one or more of canker, stripe disease, rust disease, glume blight, net blotch, powdery mildew, downy mildew, epidemic disease, leaf spot, take-all disease, snow mold, smut, leaf blight, brown spot or rice blast. Chinese cabbage: soft rot bacterial diseases, black spot, anthracnose, rust disease, powdery mildew, zinc deficiency and aged leaves; peanut: peanut bacterial wilt, root rot disease and peanut leaf spot; rice: stiff seedlings, yellow seedling rot, bacterial streak, bacterial leaf blight, sheath blight, rice blast and zinc deficiency fire burning seedlings; cucumber: bacterial angular leaf spot, canker, downy mildew, target disease, yellow spot disease, zinc deficiency and yellowing of leaves; the virus can be inactivated; tomato: bacterial canker, late blight, brown spot, anthracnose, lobular disease, inactivating virus; at the initial stage of the disease, the solution is diluted by 100 times and sprayed by 800 times. The dilution factor is increased (decreased) seriously. Continuously preventing and treating for 2-3 times at an interval of 5-12 days. Note the secondary dilution spray.
The bactericidal composition has a very remarkable synergistic effect. According to the fact that the bactericidal effect of the bisultap copper new compound component A and the component B is greater than the sum of the bactericidal effects of the bisultap copper new compound component A and the component B, the synergistic effect of the bactericidal composition is obvious.
When the component B is an acrylic ester bactericide or antiviral drug of the formula B.1), the mass ratio of I to B is selected from but not limited to 5: 50-80: 1, and the preferred mass ratio is 20: 30-40: 5.
When the component B is the triazole bactericide of the formula B.2), the mass ratio of A to B is selected from but not limited to 5: 50-80: 1, and the preferred mass ratio is 20: 20-40: 5.
When the component B is the formula B.3) amide bactericide, the mass ratio of A to B is selected from but not limited to 5: 40-80: 1, and the preferred mass ratio is 20: 20-40: 5.
When the component B is the imidazole bactericide of the formula B.4), the mass ratio of A to B is selected from but not limited to 5: 60-80: 1, and the preferred mass ratio is 20: 30-40: 10.
When the component B is a dicarboximide bactericide of a formula B.5), the mass ratio of A to B is selected from but not limited to 5: 60-80: 1, and the preferred mass ratio is 20: 50-40: 10.
When the component B is a carbamate bactericide of a formula B.6), the mass ratio of A to B is selected from but not limited to 5: 80-80: 5, and the preferred mass ratio is 20: 60-40: 10.
When the component B is B.7) antibiotic bactericide or antiviral drug, the mass ratio of A to B is selected from but not limited to 5: 80-80: 1, and the preferred mass ratio is 20: 70-40: 2.
When the component B is B.8) oxazole bactericide, the mass ratio of A to B is selected from but not limited to 5: 60-80: 5, and the preferred mass ratio is 20: 50-40: 10.
When the component B is a morpholine bactericide or an antiviral drug of a formula B.9), the mass ratio of A to B is selected from but not limited to 5: 80-80: 5, and the preferred mass ratio is 20: 50-40: 10.
When the component B is a pyrimidine bactericide of a formula B.10), the mass ratio of A to B is selected from but not limited to 5: 60-80: 10, and the preferred mass ratio is 20: 50-40: 10.
When the component B is a quinazol (azol) one bactericide of formula B.11, the mass ratio of A to B is selected from but not limited to 5: 60-80: 10, and the preferred mass ratio is 20: 50-40: 10.
When the component B is a dithiocarbamate bactericide or antiviral drug of a formula B.12), the mass ratio of A to B is selected from but not limited to 5: 80-80: 10, and the preferred mass ratio is 20: 50-40: 10.
When the component B is shown as a formula B.13) other bactericides or antiviral drugs or plant growth regulators, the mass ratio of A to B is selected from but not limited to 5: 80-80: 1, and the preferred mass ratio is 20: 50-50: 10.
The novel compounds or the bactericidal compositions thereof have good bactericidal activity or antiviral activity and are effective against pathogenic bacteria and fungi, for example, selected from but not limited to the following: xanthomonas (Xanthomonas), Pseudomonas (Pseudomonas), Erwinia (Erwinia) among pathogenic bacteria; ascomycetes in pathogenic fungi (Ascomycetes): venturia (Venturia), Erysiphe (Erysiphe), Sclerotinia (Sclerotinia); basidiomycetes (Basidiomycetes) in pathogenic fungi: smut (Ustilago), Gibberella (Gibberella); oomycetes (Oomycota) in pathogenic fungi: phytophthora (Phytophthora), Plasmopara (Plasmopara); fungi imperfecti (Deuteromyces) in pathogenic fungi: rhizoctonia (Rhizoctonia), Botrytis (Botrytis), Pyricularia (Pyricularia), Cercospora (Cercospora), Helminthosporium (Bipolaris), Colletotrichum (Colletotrichum), and the like.
The novel compound or the bactericidal composition thereof is selected from but not limited to be used for preventing and treating bacterial wilt, bacterial angular leaf spot, soft rot, ulcer disease, anthracnose, downy mildew, epidemic disease, rice blast, false smut, banded sclerotial blight, bakanae disease, powdery mildew, rust disease, leaf blight, gray mold, leaf spot, alternaria leaf spot, anthracnose, smut, fusarium wilt, black spot, scab, ring spot, brown spot, root rot, sclerotinia rot, fusarium wilt or scab.
The novel compound or the bactericidal composition thereof has good compatibility with plants, reduces the stress tolerance of the plants, and particularly reduces the seedling, young tip, flower and young fruit parts which are particularly sensitive to the plants.
Within the scope of the present invention, the plants or crops referred to in this disclosure are preferably or selected from, but not limited to, the following species: cereal wheat, barley, rice, corn, sorghum, sweet potato, etc.; fruit trees such as apple, pear, peach, hickory, walnut, orange, grape, lychee, banana, longan, mango and loquat; vegetables such as cucumber, watermelon, snake gourd, towel gourd, melon, spinach, celery, tomato, pepper, eggplant, ginger, shallot, garlic, leek, cabbage, Chinese cabbage, strawberry, asparagus lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam, taro, lotus root, water chestnut, water bamboo and the like; sugar plants such as sugar beet, sugar cane, etc.; oil crops such as soybean, peanut, rape, sesame, sunflower and the like; or such as tobacco, tea, cotton, etc. This list is not meant to be limiting in any way.
The novel compounds of the present invention or compositions thereof are also useful as pharmaceuticals in the field of protecting industrial materials from pathogens, including or selected from, but not limited to, wood, paper, leather, buildings, etc., and the compositions of the present invention can prevent undesirable effects such as rot, discoloration, or mold.
The novel compounds of the present invention or compositions thereof are effective against the following plant diseases selected from, but not limited to:
cucumber bacterial angular leaf spot, tobacco wildfire, solanaceous bacterial wilt and the like caused by Pseudomonas (Pseudomonas) strains;
cucumber bacterial leaf blight, cabbage black rot, citrus canker and the like caused by Xanthomonas (Xanthomonas) strains;
chinese cabbage soft rot and pear fire blight caused by Erwinia (Erwinia) strains;
blight of potato and tomato caused by phytophthora (Pyhtophthora) strains;
grape downy mildew caused by Plasmopara species, and the like;
powdery mildew caused by Erysiphe (Erysiphe) strains such as tobacco, sesame, sunflower and melon and the like;
gibberellic disease and bakanae disease of rice of various graminaceous plants such as barley, wheat and corn caused by gibberellic (Gibberella) strains;
apple scab caused by Venturia (Venturia) strains, and the like;
various plant Sclerotinia caused by Sclerotinia (sclerotiotinia) strains, and the like;
wheat powdery mildew caused by Ustil-ago strain;
gray mold of various plants caused by Botrytis (Botrytis) strains, and the like;
rice blast caused by Pyricularia (Pyricularia) strains, etc.;
cercospora (Cercospora) strains cause brown spot of sugar beet, brown spot of peanut, etc.;
diseases such as corn small spot disease and rice flax leaf spot caused by Helminthosporium (Bipolaris) strain;
cotton blight and rice sheath blight caused by rhizoctonia (Rhi-zoctonia) strains;
anthracnose of various fruit trees and vegetables such as apple, pear, cotton, grape, white gourd, cucumber, pepper, eggplant and the like caused by anthrax (Colletotrichum) strains; grape downy mildew caused by downy mildew, etc.; tomato or peanut bacterial wilt and the like caused by Lao's bacillus strains; tomato canker caused by clavibacterium species, and the like.
Of particular interest is furthermore the very marked improvement in the ability of the plants or seeds to withstand stress, for example restoration of growth, greenish leaf, promotion of root growth, etc., when the plants or seeds are exposed to adverse growth conditions or are damaged, the fact that the plants have good tolerance to the active compound composition at the concentrations required for controlling plant diseases, allowing the flowers and fruits and seeds of the aerial parts of the plants to be treated. The term "adverse conditions" includes improper humidity, hail, drought, low temperature, heavy rain, etc.
The fungicidal compositions of the present invention are used in a method which comprises applying to the plants to be treated or their locus of growth, or seeds, or materials, in admixture, a total effective active fungicidal amount of the active compounds of formula a and formula B. The application may be before or after the fungal infestation of the material, plant or seed.
The formula A is the novel bisultap compound, and the formula B is a bactericidal active compound selected from any one or more of the B.1) -B.13).
The term "growing locus" as used herein includes a field where plants are grown or where seeds of cultivated plants are sown or where seeds are buried in soil. The term "seed" includes plant propagation material such as cuttings, seedlings, seeds, germinated or soaked seeds.
The novel compound or the composition thereof of the present invention can be prepared into solid or liquid preparations acceptable for agriculture or agricultural chemicals. The novel compounds or compositions can be prepared in a known manner by mixing the active ingredients A and B with pharmaceutically or agriculturally acceptable adjuvants or adjuvants. The preparation is selected from but not limited to dry suspending agent, wettable powder, granule, dispersible granule, tablet, effervescent tablet, microcapsule, water dispersible granule, suspending agent, suspoemulsion, aqueous emulsion, controlled release or slow release preparation, sustained release or controlled release tablet or capsule or pellet, microcapsule preparation, oil suspending agent, dispersible liquid (DC), seed treatment dry powder, seed treatment dispersible powder, granule, dispersible granule, microcapsule suspending agent, seed treatment microcapsule suspending agent or suspension seed coating agent and the like.
The novel compounds or compositions thereof of the present invention are prepared from pharmaceutically or agriculturally acceptable adjuvants or auxiliary components selected from, but not limited to, wetting agents, binders, dispersants, thickeners, antifreezes, preservatives, disintegrants, stabilizers, synergists, film formers, antifoaming agents, colorants, lubricants or glidants, emulsifiers, pH adjusters, fillers, and/or water, and other known substances useful for stabilizing or activating the active ingredients in the formulations, and are various ingredients commonly used in preparation or agriculturally and pharmaceutically acceptable, and the specific ingredients and amounts thereof are determined by experiments as needed.
The wetting agent is selected from one or more of EO/PO block polyether, fatty alcohol-polyoxyethylene ether, fatty alcohol ethoxy compound, tallow ethoxy ammonium salt, alkyl naphthalene sulfonate, alkyl naphthalene sodium sulfonate, alkyl naphthalene calcium sulfonate, fatty alcohol-polyoxyethylene ether sulfate, acyl glutamate and the like which are acceptable in pharmacy.
The dispersing agent is selected from one or more of sodium naphthalene sulfonate condensate, sodium phenol sulfonate condensate, sodium methyl naphthalene sulfonate formaldehyde condensate, sodium lignin sulfonate, sodium methylene dinaphthalene sulfonate, sodium acrylic acid homopolymer, polycarboxylate dispersing agent, dioctyl sodium sulfosuccinate, EO/PO block polyether, maleic acid-acrylic acid copolymer sodium salt, Darun D06, Darun DCM-82 and the like which are acceptable in pharmacy;
wherein the polycarboxylate dispersant is selected from, but not limited to: products of foreign companies: 1) geropon T/36 and Geropon T/72 (polycarboxylates) from Solvay (Solvay) (Protoya); 2) tersperse2700 (polyacrylic acid graft copolymer), Tersperse2735 (polyacrylic acid graft copolymer, liquid) and Tersperse2100 from Huntsman corporation; 3) Yus-WG5 (polycarboxylate), CH7000 (white liquid), Yus-WG5 and Yus-WP1, respectively, from Takemoto (bamboo fat and oil Co., Ltd., Japan). 4) Atlox 4913 (copolymer of methacrylic acid/methyl methacrylate and polyoxyethylene) and Atlox Metaperse 550S (modified acrylic acid-styrene copolymer) from Croda (Heda). 5) Sokalan PA15/20 (acrylic acid homopolymer sodium salt), Sokalan CP 5 (acrylic acid-maleic acid copolymer sodium salt), Sokalan HP 25 (modified polycarboxylate), and Sokalan PA80S (polyacrylic acid) from BASF (BASF) corporation. 6) Dispersogen PSL 100 (polyacrylate graft copolymer) from Clariant (Craine). 7) Agrilan700 (modified polyacrylate copolymer) from akzo nobel (akksonobel). 8) Emulson AG TP1 (polycarboxylate, white emulsion) from Lamberti (Ningbo di), Emulson AG TRN 14105 (polycarboxylate comb structure). 9) Tanatex chemical company D1001 (polycarboxylate). 10) DURAMAXM D-205 (liquid), D-305 (liquid), D-518 (polycarboxylate) from Dow corporation. Products of domestic companies: 1) beijing Guangyuan company: GY-D (D03-D08) series products (polycarboxylates of styrene sulfonate polymers). 2) Mokk chemical technology company, beijing han: d1001, D1002, D1003 (polycarboxylate). 3) LG-3 (polycarboxylate), Beijing university of Physician. 4) Shanghai is a large polymer materials ltd: SD-816, SD-817, SD-818, SD-819 (polycarboxylate). 5) Jiangsu Optic chemical science and technology: SP-2728, SP-2750, SP-2836 (polycarboxylate). 6) Beijing Grignard (Green-times) auxiliaries: one or more of greensperse BD55, BD58, BE13 (liquid) (polycarboxylate) and the like which are pharmaceutically acceptable.
The emulsifier is selected from one or more of sodium dodecyl benzene sulfonate, calcium dodecyl benzene sulfonate, fatty alcohol potassium phosphate ester, alkylphenol polyoxyethylene phosphate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene, polyoxyethylene sorbitan fatty acid ester, propylene glycol polyoxyethylene polyoxypropylene ether block copolymer, span or span series (such as span-40, span-60, span-80 and the like), tween series (such as tween-40, tween-60, tween-80 and the like), agricultural milk 700#, agricultural milk 2201#, TX-10, agricultural milk 1601 (common name: phenethylphenol polyoxyethylene polyoxypropylene ether), agricultural milk 600#, agricultural milk 400# and the like which are acceptable in pharmacy;
the thickener is selected from, but not limited to, pectin, acacia, tragacanth, xanthan gum, sodium alginate, magnesium aluminum silicate, sodium carboxymethylcellulose, calcium carboxymethylcellulose, sodium starch phosphate, sodium starch octenylsuccinate, polyvinyl alcohol, cross-linked carboxymethylcellulose, cross-linked polyvinylpyrrolidone, low-substituted hydroxypropylcellulose, polyethylene glycol 800-, PEG-8 dioleate, PEG-200 glyceryl stearate, PEG-n (n ═ 28, 200) glyceryl tallowate, PEG-7 hydrogenated castor oil, PEG-40 jojoba oil, PEG-2 laurate, PEG-120 methyl glucose dioleate, PEG-150 pentaerythrityl tetrastearate, PEG-55 propylene glycol oleate, PEG-160 sorbitan triisostearate, PEG-n (n ═ 8, 75, 100) stearate, PEG-150/decyl/SMDI copolymer (polyethylene glycol-150/decyl/methacrylate copolymer), PEG-150/stearyl/SMDI copolymer, PEG-90. Isostearate, PEG-8PPG-3 dilaurate, cetyl myristate, cetyl palmitate, ethylene glycol C18-36, pentaerythrityl stearate, pentaerythrityl behenate, propylene glycol stearate, behenyl ester, cetyl ester, glyceryl tribehenate, glyceryl trihydroxystearate, etc.
The solvent is selected from one or more of toluene, xylene, trimethylbenzene, cyclohexanone, N-methyl pyrrolidone, solvent oil (trade marks of S-150, S-180 and S-200), biodiesel, methyl esterified vegetable oil, methyl oleate, fatty acid methyl ester, soybean oil, turpentine-based vegetable oil, methanol, ethanol, isopropanol, N-butanol, sec-butyl acetate, ethylene glycol monoethyl ether, water and the like; the water is deionized water, distilled water, pure water, etc.
The antifreezing agent is one or more of pharmaceutically acceptable materials such as ethylene glycol, propylene glycol, glycerol, polyethylene glycol 100-2000, isopropanol, urea, inorganic salts such as sodium chloride and the like.
The film forming agent is selected from one or more of pharmaceutically acceptable polymers with adhesive and film forming properties, such as polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, polyethylene glycol methacrylate, carboxymethyl cellulose, gum arabic, xanthan gum, starch, polyethylene glycol 2000-20000 and the like.
The disintegrating agent is selected from one or more of urea, sucrose, glucose, sodium chloride, ammonium sulfate, sodium sulfate, soluble starch, modified starch, microcrystalline cellulose, cross-linked carboxymethyl cellulose, sodium carboxymethyl starch, cross-linked polyvinylpyrrolidone, low-substituted hydroxypropyl cellulose, surfactant (sodium dodecyl sulfate, etc.) and the like which are acceptable in pharmacy.
The preservative is selected from one or more of formaldehyde, phenyl salicylate, butyl p-hydroxybenzoate, methyl paraben, ethyl paraben, propyl paraben, potassium sorbate, benzoic acid, sodium benzoate and the like which are acceptable in pharmacy.
The stabilizer is selected from one or more of glycerol, epoxidized soybean oil, epichlorohydrin, triphenyl phosphite, glycidyl ether or pentaerythritol, xylitol, 2, 6-di-tert-butyl-4-methylphenol, polyethylene glycol 400-20000, disodium EDTA 2 hydrate, calcium sodium EDTA 4 hydrate, sorbitol, sodium carboxymethyl cellulose, ionic surfactant or nonionic surfactant, hydroxyethyl or propyl cellulose, polyvinyl alcohol, span series, Tween series, alginate series and the like which are acceptable in pharmacy.
The defoaming agent is selected from one or more of silicone defoaming agents (including but not limited to AFE-316, Tanafoam SLX, Tanaform S, Tanaform AF and the like), polyether defoaming agents, polyether modified silicone defoaming agents (including but not limited to DF-825, DF-281, DT-650, DM-115M, DM-193, DM198, DM-M1040, DM-1090, DM-DA1952, LM-110, JH-935 and the like), N-type defoaming agents, sucrose fatty acid ester defoaming agents, fatty alcohol defoaming agents, composite defoaming agents and the like which are acceptable in pharmacy.
The pharmaceutically acceptable pH regulator may be a pharmaceutically acceptable inorganic acid or organic acid, an inorganic base or an organic base, or may be a generalized lewis acid or base, and may contain one or more selected from, but not limited to, hydrochloric acid, phosphoric acid, propionic acid, acetic acid and acetate, lactic acid and its pharmaceutically acceptable salts, citric acid pharmaceutically acceptable salts, sodium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, phosphate, tartaric acid and its pharmaceutically acceptable salts, borax, boric acid, polyhydroxy carboxylic acid and its pharmaceutically acceptable salts, such as one or more of glucuronic acid, gluconic acid, lactobionic acid, malic acid, threonic acid, glucoheptonic acid, ammonia, triethanolamine, triethylamine, diethylenetriamine, and the like.
The colorant is selected from one or more of iron oxide, titanium oxide, azo dye and the like which are acceptable in pharmacy.
The filler is selected from one or more of sodium sulfate, ammonium sulfate, urea, sucrose, glucose, diatomite, talcum powder, bentonite, attapulgite, kaolin, light calcium carbonate, white carbon black, starch, modified starch, microcrystalline cellulose, cyclodextrin, sorbitol, mannitol, calcium phosphate and the like which are acceptable in pharmacy;
the pharmaceutically acceptable wetting agent and the binding agent are selected from one or more of starch, gelatinized starch, methyl cellulose, sodium carboxymethyl cellulose, ethyl cellulose, low-substituted hydroxypropyl cellulose, polyvinylpyrrolidone, PVP K-30, tragacanth, alginic acid and salts thereof and the like;
the pharmaceutically acceptable lubricant and glidant are selected from one or more of stearic acid, magnesium stearate, polyethylene glycol 4000-20000, talcum powder, superfine silica powder, lauryl magnesium sulfate and the like which are pharmaceutically acceptable;
for wettable powders, the adjuvants which may be used are selected from, but not limited to: dispersing agent, wetting agent and filler are one or more of the same pharmaceutically acceptable materials as described in the invention.
For the water dispersible granule, the water dispersible granule is selected from but not limited to one or more of dispersing agents, wetting agents, disintegrating agents, binding agents, stabilizing agents, fillers and the like which are selected from but not limited to those described before in the invention.
For the suspending agent, the auxiliaries which can be used are selected from, but not limited to: dispersing agents, emulsifiers, wetting agents, thickeners, preservatives, defoamers, stabilizers, antifreeze agents and the like are one or more of those previously described herein.
For suspended seed coatings, adjuvants that may be used are selected from, but not limited to: binders such as one or more selected from the group consisting of polysaccharide high molecular compounds (soluble starch, polypropylene graft copolymer, xanthan gum, microbial mucilage), cellulose derivatives (hydroxypropyl methylcellulose, sodium carboxymethylcellulose, ethyl cellulose), marine algae such as sodium alginate, agar, rosin, paraffin, gelatin, pectin, polyvinyl alcohol, polyethylene glycol, polyvinyl acetate, polyacrylamide, polyvinyl pyrrolidone and water-soluble synthetic products of polyol polymers, inorganic binders (magnesium aluminum silicate, clay, water glass, gypsum); dispersing agents, emulsifiers, wetting agents, thickeners, preservatives, defoamers, stabilizers, antifreeze agents and the like are as described previously herein.
The preparations or medicaments of the active compound combinations described in the present invention can be prepared by customary methods.
The preparation for preventing and treating plant diseases of the composition generally comprises 1-90 mass percent of active compounds, preferably 20-60 mass percent.
The fungicidal composition of the present invention may be used in the form of its own concentrate or in the form of a generally conventional formulation, using a method of pouring, spraying, misting, dressing, broadcasting or brushing depending on the nature of the target disease, and the total effective active fungicidal amount applied varies depending on weather conditions, crop conditions or application methods.
The fungicidal active compound combinations according to the invention have very outstanding advantages:
1. the bactericidal composition has obvious synergistic effect, and can give full play to the characteristics that the new leaf-bronze compound has high efficiency on bacterial diseases, is universally effective on fungal diseases and has good protective performance;
2. the bactericidal composition consists of active ingredients with different action mechanisms, can effectively slow down the generation of disease resistance, and reduces the resistance risk caused by the single use of a new leaf-bronze compound or any other known active compound;
3. the bactericidal composition improves the antibacterial or bacteriostatic effect, enlarges the disease prevention spectrum, can simultaneously play a good role in preventing or treating bacterial diseases and partial fungal diseases of crops, reduces the times of medication and relieves the environmental pressure, thereby playing the role of prevention and comprehensive control;
4. the sterilization composition reduces the using amount of the medicament by compounding, lightens the pressure of the pesticide on the environment and simultaneously reduces the cost;
5. the bactericidal composition can obviously improve the tolerance of crops, so that the safety of the pesticide to the crops is higher;
6. the bactericidal composition can supplement trace elements, thereby promoting the growth of plants and improving the stress resistance and disease resistance.
Drawings
FIG. 1 is a thermogram spectrum of biscopper folinate 1 hydrate (example 1)
FIG. 2 is a thermogram spectrum of biscopper folinate 1.25 hydrate (example 3)
FIG. 3 is a thermogram spectrum of biscopper folinate 1.5 hydrate (example 4)
Detailed Description
Other than in the examples, and where otherwise indicated, all numbers expressing quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about", and thus, unless otherwise indicated, the numerical parameters set forth in this specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present disclosure, and at the very least, and are not intended to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations. The numerical values set forth in the specific examples are reported as precisely as possible, and any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing.
It is noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents and, therefore, for example, unless the context clearly dictates otherwise. If reference is made to a composition containing "a compound" including mixtures of two or more compounds, it is further noted that the term "or" generally includes "and/or" unless the context clearly dictates otherwise.
As used herein, the term "obtained" or "obtaining" refers to isolating a compound of value at a level of content or purity, including but not limited to, greater than 90%, 95%, 96%, 97%, 98%, and 99%. The content or purity level may be determined by a high performance liquid chromatography method specified in the 2010 version of chinese pharmacopoeia standards for copper folin. The infrared spectrum data of the sample is measured by a Fourier transform infrared spectrometer, and the used instruments comprise a Nexus intelligent Fourier transform infrared spectrometer (Thermo Nicolet) and the like.
The present "solvate" is meant herein to also include crystalline forms of molecules, atoms and/or ions of solvent molecules that penetrate into the crystal structure, which may be in a regular and/or disordered arrangement, and which are solvates of the present invention.
Polymorphism herein refers to crystals having the same chemical composition but differing in the spatial arrangement of the molecules, atoms and/or ions that form the crystal.
Pharmaceutical or agrochemical compositions: as used herein, "pharmaceutical or pesticidal composition" refers to a composition of a medicament or a composition of a pesticide, which may contain at least one pharmaceutically acceptable carrier.
As used herein, "pharmaceutically acceptable excipient or carrier" refers to a pharmaceutically acceptable carrier or vehicle suitable for administration of the compounds provided herein, including any such carriers known to those skilled in the art to be suitable for a particular mode of administration.
In the present invention, the "which" in the pharmaceutically acceptable salt or solvate thereof or the clathrate thereof represents one of them or either of them unless otherwise specified.
In the present invention, unless otherwise specified, "suitable amount" means a preferred or optimum amount or the minimum required amount or mass or weight or volume or the like required for carrying out the present invention.
In the present invention, unless otherwise specified, "such a combination or a combination thereof" means a multi-component mixture of the respective elements described, for example, two, three, four and up to the maximum possible multi-component mixture.
In the present invention, all "parts" and percentages (%) may refer to parts by weight or percent by weight volume, unless otherwise indicated.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention, and not to limit the scope of the claims.
And (3) moisture determination: the moisture was measured using V310S-KHF lithium battery material and a Karl moisture tester (Sichuan cereal science and technology Co., Ltd.) dedicated to electrode membranes. The method comprises the following steps: connecting an air source to a heating furnace, bottling the dried sample into a heating tank, setting the temperature to be about 170 ℃, and increasing the temperature: 30 ℃/min, adjusting the flow of dry nitrogen to 50ml/min, purging the sample bottle and the pipeline to possibly have water, and waiting for re-balancing. Taking a dried sample bottle and filling about 0.04-0.1g of sample; delay of titration: 180S; and (3) deduction of drift: automatic; blank deduction: deducting; the rest were operated as specified in the instrument instructions.
Infrared spectrum: potassium bromide pellets were pressed and the IR spectral data of the samples were measured using instruments including the US Thermo electric company NICOLET 5700FTIR Spectrometer, Nexus intelligent Fourier transform Infrared Spectrometer (Thermo Nicolet) and the like. Name of infrared spectrometer instrument company: the united states thermoelectric company NICOLET 5700FTIR Spectrometer, uses the functions: the mid-infrared light is 4000-400cm-1, and the resolution is 4 cm-1. The maximum can reach 0.09cm < -1 >. Thermal analysis method
And (3) testing conditions are as follows: setsys 16, Setaram, sample size 310mg, rate of temperature rise: 10K/min, N2 flow rate: 50ml/min, temperature: generally, the temperature is about room temperature to 400 ℃.
Surprisingly, characteristically, the hydrates of the present invention have a corresponding endothermic peak at the weight loss plateau of the thermogram (TG-DTA or TG-DSC) showing the crystalline hydrates of the biscopper phyllinate, such as its 1 hydrate or 1.25 hydrate or 1.5 hydrate, etc.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1 preparation of biscopper folinate 1 hydrate (Saisentong α type compound)
Adding 8.352g of refined bisultap into a 250ml flask at room temperature, adding 50ml of water, stirring, adding 40ml of aqueous solution of 2.42g of sodium hydroxide, stirring for dissolving, then adding 30ml of aqueous solution of 7.491g of copper sulfate pentahydrate, quickly separating out solid, stirring for 30 minutes at about 40 ℃, standing for half an hour at room temperature, performing suction filtration, rinsing the solid with a small amount of water and isopropanol until no sulfate is contained in the filtrate, performing suction filtration, spreading the obtained solid, and performing forced air drying at about 60 ℃ for about 5 hours to obtain 8.6g of yellow-green solid; HPLC: the HPLC main peak retention time is consistent with that of the Saisentong copper; moisture content by the Karl Fischer method was 4.99%, thermal analysis: a plateau weight loss of about 4.76% (see fig. 1), with a corresponding endothermic peak (DTA) at the weight loss plateau before about 166 ℃, which is within the error range of the result for a sample containing 1 crystal water (theoretical 5.03%); infrared Spectrum (v)KBr maxcm-1): 3275.2, 3169.4, 1605.6, 1514.3, 1398.0, 1366.7, 1342.9, 1241.7, 1036.9, 756.3, 681.3, 619.0; theoretical value of elemental analysis: 16.78% of C, 1.69% of H, 23.38% of N, 35.83% of S and 17.75% of Cu; measured value: 16.65% of C, 1.75% of H, 23.31% of N, 35.74% of S and 17.83% of Cu.
Example 2 preparation of bisbronze 1 hydrate
Adding 8.352g of phyllanthus emblica in a 500ml flask, adding 40ml of water, stirring, dropwise adding 2.56g (dissolved in 20ml of water) of potassium hydroxide aqueous solution, stirring to dissolve, then adding 30ml of 5.99g of copper acetate monohydrate aqueous solution, quickly separating out solid, stirring for 20 minutes at about 40 ℃, adding 10ml of ethanol, stirring for 5 minutes, standing for half an hour at room temperature, performing suction filtration, rinsing the solid with a small amount of water until no acetate exists in the filtrate, performing suction filtration, spreading the obtained solid, performing forced air drying at about 45 ℃ for 1 hour, and drying at about 60 ℃ for about 5 hours to obtain 10.5g of yellow-green solid; HPLC: the retention time of the HPLC main peak is consistent with that of the HPLC main peak of the copper cyclonite; moisture content by the Karl Fischer method was 4.92%, thermal analysis: the plateau weight loss was about 5.16% with a corresponding endothermic peak (DTA) at the weight loss plateau before about 168 ℃, which is within the error range of the result for the sample containing 1 crystal water (theoretical 5.03%).
Example 3 preparation of biscopper folinate 1.25 hydrate (Saisentong copper β type compound)
Adding 8.352g of refined phyllanthus emblica in a 500ml flask, adding 40ml of water, stirring, dropwise adding 2.45g (dissolved in 20ml of water) of sodium hydroxide aqueous solution for dissolving, stirring for 30 minutes, then adding 30ml of aqueous solution of 7.491g of blue vitriol, quickly separating out solid, stirring for 20 minutes at about 40 ℃, standing for half an hour at room temperature, carrying out suction filtration, rinsing the solid with a small amount of water until no sulfate exists in filtrate, carrying out suction filtration, spreading the obtained solid, drying for 1 hour at about 45 ℃ by blowing, and drying for about 4 hours at about 50 ℃ to obtain 10.5g of yellow-green solid; HPLC: the HPLC main peak retention time is consistent with that of the Saisentong copper; moisture by the Karl Fischer method was 6.17%, thermal analysis: the plateau weight loss was about 6.29% (see fig. 2), with a corresponding endothermic peak (DTA) at the weight loss plateau before about 168 ℃, which is within the error range of the result for the sample containing 1.25 crystal waters (theoretical 6.21%). Infrared Spectrum (v)KBr maxcm-1): 3275.0, 3169.1, 1605.2, 1514.2, 1398.3, 1366.6, 1342.3, 1241.2, 1036.9, 756.0, 681.7, 619.5; theoretical value of elemental analysis: 16.57% of C, 1.81% of H, 23.19% of N, 35.39% of S and 17.53% of Cu; measured value: 16.51% of C, 1.87% of H, 23.07% of N, 35.48% of S and 17.46% of CuI.
Example 4 preparation of biscopper folinate 1.5 hydrate (omega type compound)
Adding 8.352g of refined bisultap in a 250ml flask at room temperature, adding 50ml of water, stirring, adding 20ml of aqueous solution of 2.5g of sodium hydroxide, stirring for dissolving, and adding pentahydrate30ml of aqueous solution of 7.491g of copper sulfate is stirred for half an hour at about 40 ℃, 10ml of ethanol is added, the mixture is placed for half an hour at room temperature, the filtration is carried out, a small amount of water is used for washing the solid until no sulfate exists in the filtrate, the filtration is carried out, the obtained solid is spread to be thin and dried overnight at room temperature by utilizing about two-stage natural wind power, and the air blast drying is carried out for about 5 hours at about 45 ℃ to obtain 8.6g of yellow-green solid; HPLC: the retention time of the main peak of the HPLC retention time is consistent with that of the HPL of the phyllocopterides copper; moisture by the Karl method was 7.12%, thermal analysis: the weight loss of the platform is about 6.96 percent (see figure 3), and the corresponding endothermic peak (DTA) is arranged under the weight loss platform before 172 ℃, which is in an error range with the result that the sample contains 1.5 crystal water (theoretical value is 7.37 percent); infrared Spectrum (v)KBr maxcm-1): 3274.5, 3168.8, 1604.3, 1512.7, 1397.6, 1366.2, 1342.1, 1241.5, 1036.2, 756.1, 681.3, 619.2; theoretical value of elemental analysis: 16.37% of C, 1.92% of H, 22.90% of N, 34.95% of S and 17.32% of Cu; measured value: 16.45% of C, 1.83% of H, 22.97% of N, 35.04% of S and 17.25% of Cu.
Example 4-1A preparation of Broccoli 1.5 hydrate (Thisen copper omega type Compound)
Adding 8.352g of refined lividide into a 250ml flask at room temperature, adding 50ml of water, stirring, adding 20ml of aqueous solution of 2.5g of sodium hydroxide, stirring, adding 30ml of aqueous solution of 4.09g of copper sulfate, stirring for half an hour at about 40 ℃, adding 10ml of methanol, standing for half an hour at room temperature, performing suction filtration, rinsing the solid with a small amount of water, performing suction filtration, spreading the obtained solid, drying overnight at room temperature by using about three-stage natural wind power, and performing forced air drying at about 45 ℃ for about 5 hours to obtain 8.6g of yellow-green solid; moisture by the Karl method was 7.42%, thermal analysis: a plateau weight loss of about 7.52% with a corresponding endothermic peak (DTA) at the weight loss plateau before about 165 ℃, which is within the error range of the result for the sample containing 1.5 crystal waters (theoretical 7.37%); theoretical value of elemental analysis: 16.37% of C, 1.92% of H, 22.90% of N, 34.95% of S and 17.32% of Cu; measured value: 16.28 percent of C, 1.99 percent of H, 22.82 percent of N, 35.02 percent of S and 17.22 percent of Cu.
Example 5: preparation of Water dispersible granules
60% of the new phyllobicopper compound, 3% of sodium dodecyl benzene sulfonate, 4% of polycarboxylate dispersant (SD-819), 5% of ammonium chloride, 5% of talcum powder and 20% of sodium sulfate are respectively sieved by a 200-mesh sieve, then the components are fully mixed, the mixture is crushed by air flow, 5% of aqueous solution of PVP K-30 is added until the total amount is 100%, the mixture is uniformly mixed, boiled and granulated, dried, sieved by a 20-mesh sieve, subpackaged and inspected to obtain the water dispersible granule.
Example 6: preparation of Thiessen copper suspension
20% of a new phyllobicopper compound (calculated by the weight of anhydrous substances), 4.0% of tallow ethoxylated amine salt, 1.0% of sodium salt of a naphthalenesulfonic acid condensation product, 1.0% of sodium salt of an acrylic acid homopolymer, 0.2% of xanthan gum, 2.5% of sodium starch phosphate, 5.0% of propylene glycol, 0.5% of potassium sorbate, 0.5% of a polyether defoamer and distilled water which are supplemented to 100% are put into a sand mill for sanding for 120 minutes and filtered to obtain the suspending agent.
Example 7: preparation of Thiessen copper suspension
30 percent of the new phyllocos biscopper compound (by weight of anhydrous substances), 2.0 percent of phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt (601PT), 2 percent of nonylphenol polyoxyethylene ether (NP-10), 3 percent of urea, 0.15 percent of xanthan gum, 1 percent of magnesium aluminum silicate, 0.1 percent of polyether modified organic silicon defoamer (DM198), 4003 percent of polyethylene glycol, 0.5 percent of potassium sorbate and pure water are added to 100 percent and put into a sand mill for sand milling for 120 minutes and filtered by a 60-mesh sieve to obtain the 20 percent suspending agent. The obtained suspending agent has the following technical indexes: the appearance is a flowable liquid, the particle size D90 (1-5 mu m) is more than 90%, the suspension rate is more than 95%, the dispersibility in water is excellent, and the cold and heat stability and the dilution stability are both qualified. The Thiessen copper suspending agent can be sprayed on plants or crops by diluting 300-fold and 500-fold liquid with water.
Example 8: preparation of 20% bisultap copper new compound water dispersible granule
Weighing 20 g of the new biscupronickel compound (based on the weight of the anhydrous substance), 3 g of the dispersant (2700) for pesticide, 5g of the sodium salt of the alkyl naphthalene sulfonic acid polycondensate, 2g of the wetting agent (1004) for pesticide, 4 g of ammonium sulfate, 10 g of soluble starch and kaolin to make up to 100 g. The materials are uniformly mixed, crushed to more than 325 meshes in a jet mill, added with a proper amount of 75 percent ethanol water solution, mixed, put into an extrusion granulator for granulation, dried at 60 ℃ and sieved to prepare the water dispersible granules.
EXAMPLE 9 preparation of Thiessen copper Dry suspension
The formula is as follows: 40% of a biscopper bisultap new compound, 4% of urea, 2% of sodium dodecyl sulfate, 5% of sodium lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 10% of sorbitol, 2% of methyl cellulose, 0.1% of polyether modified organic silicon defoamer (DF-825), 0.1% of polyethylene glycol-8001%, 0.3% of calcium sodium EDTA (calcium EDTA) hydrate, and the balance of kaolin being 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and water accounting for 110 percent of the weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 95% of the particle size is between 0.2 and 5 microns, then pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be between 3.0 and 6.5Mpa, the inlet temperature of drying gas is 110-140 ℃, the outlet temperature is 55 to 70 ℃, and the granulated material is screened to obtain the 80 to 150-mesh dry suspending agent.
Example 10: preparation of thiasen copper azoxystrobin compound suspending agent
30% of a biscuprum metschluke new compound (by weight of anhydrous substances), 20% of azoxystrobin, 2% of fatty alcohol-polyoxyethylene ether, 3% of alkyl naphthalene sodium sulfonate, 1% of methylene dinaphthalene sodium sulfonate, 3% of maleic acid-acrylic acid homopolymer sodium salt, 0.05% of xanthan gum, 0.6% of magnesium aluminum silicate, 2.3% of starch sodium octenyl succinate, 2% of glycerol, 0.4% of phenyl salicylate, 0.1% of an organic silicon defoamer (tanoform AF) and 100% of pure water are supplemented, the mixture is put into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 20 minutes and then is conveyed into a sand mill, and the compound suspending agent is obtained after 3 times of circular sanding.
Example 11: preparation of thiasen copper trifloxystrobin compound dry suspending agent
The formula is as follows: 30% of a biscupronickel new compound (by weight of the anhydride) and 20% of trifloxystrobin, 4% of urea, 2% of sodium dodecyl sulfate, 5% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 10% of sorbitol, 2% of methyl cellulose, 0.1% of polyether modified silicone defoamer (DF-825), polyethylene glycol-8001% and kaolin to make up 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials according to the formula amount and pure water accounting for 110 percent of the weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sanding machine until 95% of the particle size is between 0.2 and 5 microns, then pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be 3.0 to 6.5Mpa, the inlet temperature of the drying gas is 110-.
Example 12: preparation of compound suspending agent
45% of active compound [ 40% of biscuprum metschluke new compound (based on the weight of anhydrous substances) and 5% of difenoconazole ], 2.0% of alkyl naphthalene sulfonate, 1.2% of acyl glutamate, 1.3% of fatty alcohol-polyoxyethylene ether sulfate, 2.0% of phenol sulfonic acid condensate sodium salt, 3.0% of sodium methyl naphthalene sulfonate formaldehyde condensate, 1.0% of starch sodium octenyl succinate, 0.3% of methyl cellulose, 2.0% of glycerol, 0.2% of butyl p-hydroxybenzoate, 0.1% of organosilicon defoamer (Tanaform AF) and 100% of pure water are fed into a high-shear homogenizing emulsifying machine for high-speed shearing for 25 minutes, then pumped into a sand mill for 90 minutes, and the compound suspending agent is obtained after filtration.
Example 13: preparation of thiasen copper fluorothiazole pyrithylone compound dry suspending agent
The formula is as follows: 30% of a biscopper compound (by weight of anhydrous substance) and 10% of fluorothiazolepyrithylone, 4% of urea, 2% of sodium dodecyl sulfate, 5% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), PVP K-304%, 0.2% of xanthan gum, 10% of sorbitol, 2% of methyl cellulose, 0.1% of polyether modified organosilicon defoamer (DF-825), 0.1% of polyethylene glycol-8001% and kaolin for the balance of 100%; the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials according to the formula amount and pure water accounting for 110 percent of the weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sanding machine until 95% of the particle size is between 0.2 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80-150-mesh dry suspending agent.
Example 14: preparation of thiasen copper pyraclostrobin compound dry suspending agent
The formula is as follows: 30% of biscupronickel new compound (by weight of anhydrous substance) and 20% of pyraclostrobin, 4% of urea, 2% of sodium dodecyl sulfate, 5% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 0.1% of polyether modified silicone defoamer (DM-1090), polyethylene glycol-8001% and kaolin for the balance of 100%; the preparation process comprises the following steps: mixing the raw materials and the auxiliary materials according to the formula amount and pure water accounting for 120 percent of the weight of the raw materials and the auxiliary materials, and stirring to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 95% of the particle size is between 0.2 and 5 microns, pumping the suspension slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80 to 150-mesh compound pesticide dry suspending agent.
Example 15: preparation of compound pesticide suspending agent
32% of active compound [ 30% of a new phyllobium bronze compound (based on the weight of anhydrous substances) and 2% of diniconazole ], 2.0% of tallow ethoxy ammonium salt, 0.1% of xanthan gum, 1% of acyl glutamate, 2.0% of phenol sulfonic acid condensate sodium salt, 2.0% of methyl naphthalene sodium formaldehyde condensate, 2.0% of octenyl succinic acid starch sodium, 2.0% of glycerol, 0.2% of butyl p-hydroxybenzoate, 0.2% of organosilicon antifoaming agent (tanoform S) and 100% of deionized water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 25 minutes, pumped into a sand mill to be ground for 90 minutes, and filtered by a 60-mesh sieve to obtain the 32% of active compound.
Example 16: preparation of thiasen copper epoxiconazole compound dry suspending agent
The formula is as follows: 30% of biscopper bisbronze new compound (by weight of the anhydride) and 5% of epoxiconazole, 4% of urea, 2% of sodium lauryl sulfate, 2% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), PVP K-304%, xanthan gum 0.2%, starch sodium octenylsuccinate 0.5%, sorbitol 10%, methyl cellulose 2%, starch sodium octenylsuccinate 1.0%, polyethylene glycol-8001%, DM-10900.1%, kaolin to make up 100%; the preparation process comprises the following steps: mixing the raw materials and the auxiliary materials in the formula amount and pure water with the same weight as the raw materials and the auxiliary materials, and stirring to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until the particle size of D90 is 0.2-5 microns, pumping the suspension slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be 2.0-7.0Mpa, the inlet temperature of drying gas is 110-140 ℃, the outlet temperature is 55-70 ℃, and the granulated material is screened to obtain the 80-150-mesh dry suspending agent.
Example 17: preparation of compound suspending agent
Adding 10% of a biscuprum metschluke new compound (by weight of an anhydride), 40% of flusilazole, 2.0% of fatty alcohol-polyoxyethylene ether, 0.1% of xanthan gum, 1.0% of tallow ethoxy amine salt, 3.0% of macromolecular polycarboxylate (Geropon T/36), 1% of phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt (601PT), 1.0% of dioctyl sulfosuccinic acid sodium salt, 3.0% of urea, 3.78% of DM 1930.1 and 100% of deionized water into a high-shear homogenizing emulsifying machine for high-speed shearing for 20min, and homogenizing by using the high-pressure homogenizing machine to obtain the compound suspending agent.
Example 18: preparation of compound suspending agent
30% of a biscuprum bisilicon new compound, 20% of flutriafol, 2.0% of fatty alcohol ethyl oxide, 0.3% of methyl cellulose, 1.0% of EO/PO block polyether, 1.0% of alkyl naphthalene sulfonate, 2% of polycarboxylate (SPED-300), 1.5% of acrylic acid homopolymer sodium salt, 2.0% of isopropanol, 0.05% of polyether defoamer, 0.05% of organic silicon defoamer (tanoform AF) and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes, then conveyed into a sand mill and subjected to circular sanding for 3 times to obtain the compound suspending agent.
Example 19: preparation of thiasen copper tebuconazole compound suspending agent
30 percent of bisultap copper new compound (by weight of anhydrous substances) and 10 percent of tebuconazole, 0.3 percent of hydroxypropyl cellulose, 3.0 percent of fatty alcohol-polyoxyethylene ether, 2.0 percent of sodium methyl naphthalene sulfonate formaldehyde condensate, 2 percent of polycarboxylate (SPED-300), 2.0 percent of epichlorohydrin, 2.0 percent of glycerol, 0.2 percent of xanthan gum, DM-10900.1 percent and pure water are fully mixed, then the mixture is put into a high-shear homogenizing and emulsifying machine for high-speed shearing, coarse grinding and homogenizing, and then the mixture is pumped into a sand mill for sand grinding until the particle size of D90 is 0.2-5 microns, and the mixture is filtered by a 60-mesh sieve to obtain the suspending agent.
Example 20: preparation of compound suspending agent
35% of active compound [ 30% of a new biscuprum metschluke compound (based on the weight of anhydrous substances) and 5% of hexaconazole composition ], 2% of polycarboxylate (SPED-300), 2.0% of acyl glutamate, 1% of fatty alcohol polyoxyethylene ether sulfate, 1.0% of phenol sulfonic acid condensate sodium salt, 2.0% of a sodium methyl naphthalene sulfonate formaldehyde condensate, 2.0% of octenyl succinic starch sodium, 0.1% of xanthan gum, 5.0% of epoxidized soybean oil, 2.0% of glycerol, 0.15% of an organosilicon antifoaming agent (Tanaform AF) and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 25 minutes, then the mixture is pumped into a sand mill for 90 minutes, and the mixture is filtered by a 60-mesh sand mill to obtain the compound suspending agent.
Example 21: preparation of thiasenil copper myclobutanil compound dry suspending agent
The formula is as follows: 30% of biscuprum metschluide new compound (by weight of anhydrous substance) and 12% of myclobutanil, 4% of urea, 2% of sodium dodecyl sulfate, 2% of polycarboxylate (SPED-300), 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenyl succinate, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, polyethylene glycol-8001%, 0.1% of polyether modified silicone defoamer (DF-825), and kaolin to make up 100%; the preparation process is the same as in example 16.
Example 22: preparation of compound composition suspending agent
30% of thiason copper new compound (prepared by the method of example 1 and calculated by weight of anhydrous substance) and 10% of penconazole, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 0.1% of xanthan gum, 4.0% of polymeric polycarboxylate, 0.5% of magnesium aluminum silicate, 2.0% of isopropanol, 0.1% of organic silicon defoamer (tanoform AF) and 100% of pure water are supplemented, and the mixture is put into a high-shear homogenizing emulsifying machine to be sheared at high speed for 30 minutes, then is conveyed into a sand mill, and is circularly sanded for 3 times to obtain the compound suspending agent.
Example 23: preparation of compound suspending agent
35% of a biscuprum bisilicon new compound (by weight of anhydrous substances) and 5% of kasugamycin, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 2.0% of sodium methylene dinaphthalene sulfonate, 3.0% of high-molecular polycarboxylate (Geropon T/36), 0.3% of xanthan gum, 2.0% of urea, 0.1% of organic silicon defoamer (tanoform AF), 0.9% of EDTA calcium sodium 4 hydrate and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes, and then the mixture is conveyed into a sand mill to be sanded for 3 times in a circulating manner to obtain the compound suspending agent.
Example 24: preparation of compound suspending agent
30% of a biscuprum bisilicon new compound, 5% of a triadimenol composition, 1.3% of alkyl naphthalene sulfonate, 2.0% of acyl glutamate, 1% of fatty alcohol polyoxyethylene ether sulfate, 1.0% of phenol sulfonic acid condensate sodium salt, 2.0% of a methyl naphthalene sodium formaldehyde condensate, 2.0% of sodium starch octenyl succinate, 2.0% of glycerol, 0.1% of tanoform AF, 0.5% of sodium calcium EDTA and 100% of pure water are supplemented, the mixture is put into a high-shear homogenizing emulsifying machine for high-speed shearing for 25 minutes, then pumped into a sand mill for sand milling for 90 minutes, and filtered by a 60-mesh sieve to obtain the compound suspending agent.
Example 25: preparation of compound suspending agent
30% of a biscuprum metschluke new compound, 10% of bitertanol, 2% of polycarboxylate (SPED-300), 2% of acyl glutamate, 1.0% of fatty alcohol polyoxyethylene ether, 1.0% of sodium phenolsulfonic acid condensate, 2% of a sodium methyl naphthalene sulfonate formaldehyde condensate, 1% of sodium starch octenyl succinate, 0.3% of ethyl cellulose, 2.0% of urea, 0.5% of DM 1980.1%, 0.5% of sodium calcium EDTA and 100% of pure water are supplemented, the mixture is put into a high-shear homogenizing emulsifying machine for high-speed shearing for 25 minutes, and then pumped into a sand mill for sand milling for 90 minutes, and filtered by a 60-mesh sieve, so that the compound suspending agent is obtained.
Example 26: preparation of compound suspending agent
Adding 20% of a biscuprum metschluke new compound (by weight of anhydrous substances) and 20% of thiediazole copper, 2% of polycarboxylate (SPED-300), 2.0% of acyl glutamate, 1.0% of fatty alcohol polyoxyethylene ether sulfate, 1.0% of phenolsulfonic acid condensate sodium salt, 2.0% of methyl naphthalene sulfonate formaldehyde condensate, 1.0% of sodium carboxymethylcellulose, 2.0% of glycerol, DM1980.1 and pure water to 100%, adding the mixture into a high-shear homogenizing emulsifying machine, shearing at a high speed for 25 minutes, pumping the mixture into a sand mill, sanding for 90 minutes, and filtering by a 60-mesh sieve to obtain the compound suspending agent.
Example 27: preparation of compound suspending agent
Adding 25% of a new phyllobis copper compound, 25% of metalaxyl, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 2.0% of naphthalene sulfonic acid condensate sodium salt, 4.0% of high-molecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 2.0% of urea, 0.1% of polyether modified organic silicon defoamer (DM-198) and pure water to 100%, adding the mixture into a high-shear homogenizing emulsifying machine, shearing the mixture at a high speed for 30 minutes, conveying the mixture into a sand mill, and circularly sanding the mixture for 3 times to obtain the compound suspending agent.
Example 28: preparation of compound suspending agent
20.0 percent of a new phyllo-bronze compound, 20.0 percent of flutolanil, 4.0 percent of fatty alcohol ethyl oxide, 1.0 percent of EO/PO block polyether, 1.0 percent of acrylic homopolymer sodium salt, 4.0 percent of high-molecular polycarboxylate (Geropon T/36), 0.5 percent of polyvinyl alcohol, 5.0 percent of epoxidized soybean oil, 2.0 percent of urea, 0.1 percent of polyether modified organic silicon defoamer (DM198) and 100 percent of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes and then conveyed into a sand mill to be circularly sanded for 3 times to obtain the compound suspending agent.
Example 29: preparation of compound dry suspending agent
The formula is as follows: 30% of biscopper bismerhyl compound (by weight of the anhydride) and 21.2% of fluxapyroxad, 4% of urea, 2% of sodium lauryl sulfate, 2% of polycarboxylate (SPED-300), 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenyl succinate, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 1% of polyethylene glycol-8001%, DM-1980.1%, 0.5% of calcium sodium EDTA 4 hydrate, and the balance of diatomaceous earth to 100%;
the preparation process comprises the following steps: mixing the raw materials and the auxiliary materials in the formula amount and pure water with the same weight as the raw materials and the auxiliary materials, and stirring to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until the particle size of 90% is between 0.1 and 5 microns, then pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be 3.0 to 6.5Mpa, the inlet temperature of drying gas is 110-140 ℃, the outlet temperature is 55 to 70 ℃, and the granulated material is screened to obtain the 80 to 150-mesh dry suspending agent.
Example 30: preparation of compound suspending agent
20% of a new phyllocos leaf biscopperin compound, 40% of thiabendazole, 3.0% of an aliphatic alcohol ethoxy compound, 1.0% of alkyl naphthalene sulfonate, 4.0% of fatty alcohol polyoxyethylene ether sulfate, 3.0% of a phenolsulfonic acid condensate sodium salt, 1.5% of methylene dinaphthalene sodium sulfonate, 0.5% of a methyl naphthalene sodium formaldehyde condensate, 0.8001% of polyethylene glycol, 0.15% of a polyether modified organic silicon defoamer (DM198), 0.5% of EDTA calcium sodium, and 100% of distilled water are added, the mixture is put into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30min, and the mixture is homogenized by a high-pressure homogenizing machine to obtain.
Example 31: preparation of thiasen copper metalaxyl compound dry suspending agent
The formula is as follows: 30% biscupronickel new compound (by weight of the anhydride) and 15% metalaxyl, urea 4%, sodium lauryl sulfate 2%, lignosulfonate 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, xanthan gum 0.2%, sodium starch octenylsuccinate 0.5%, sorbitol 10%, methylcellulose 2%, sodium starch octenylsuccinate 1.0%, polyethylene glycol-8001%, polyether modified silicone defoamer (DM-198) 0.1%, calcium sodium EDTA 0.5%, kaolin to 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 130% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sanding machine until the particle size of 90% is between 0.1 and 5 microns, then pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be 2.0 to 7.0Mpa, the inlet temperature of drying gas is 110-140 ℃, the outlet temperature is 55 to 70 ℃, and the granulated material is screened to obtain the 80-150-mesh dry suspending agent.
Example 32: preparation of compound suspending agent
The preparation method comprises the steps of supplementing 100% of 60% of a new phyllobicopper compound, 5% of tetramycin, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 2.0% of a naphthalene sulfonic acid condensate sodium salt, 4.0% of a high-molecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 2.0% of urea, 1930.15% of DM and pure water, putting the mixture into a high-shear homogenizing and emulsifying machine for high-speed shearing for 30 minutes, conveying the mixture into a sand mill, and performing circular sanding for 3 times to obtain the compound suspending agent.
Example 33: preparation of Chunleisen copper reclaimed compound suspending agent
35% of a bisultap new compound (by weight of anhydrous substances), 2% of kasugamycin, 3% of zhongshengmycin, 2.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 1.0% of sodium lignosulfonate, 3.0% of high-molecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 5% of epoxidized soybean oil, 2.0% of urea, 1980.1% of DM, 0.5% of EDTA calcium sodium and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at high speed for 30 minutes, then the mixture is conveyed into a sand mill, and the compound suspending agent is obtained by circulating sand milling for 3 times.
Example 34: preparation of suspending agent of composition
Adding 45% of active compound [ 10.0% of new phyllocos biscopper compound (based on the weight of anhydrous substance) and 35.0% of propamocarb hydrochloride ], 3.0% of fatty alcohol-polyoxyethylene ether, 1.0% of EO/PO block polyether, 4.0% of macromolecular polycarboxylate (Geropon T/36), 0.5% of starch phosphate sodium, 1.0% of pentaerythritol, 2.0% of urea, 0.1% of polyether modified organic silicon defoamer (DM198) and 100% of pure water to 100%, adding the mixture into a high-shear homogenizing emulsifying machine, shearing at high speed for 30 minutes, conveying the mixture into a sand mill, and performing circulating sand milling for 3 times to obtain the compound suspending agent.
Example 35: preparation of suspending agent of composition
50% of a new phylloconazole compound, 10% of validamycin, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 1.0% of low-substituted hydroxypropyl cellulose, 2.0% of a methyl naphthalene sodium formaldehyde condensate, 4.0% of high-molecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 2.0% of urea, 0.1% of polyether modified organic silicon defoamer (DM-198), 0.5% of EDTA calcium sodium 4 hydrate and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes, then conveyed into a sand mill, and circularly sanded for 3 times to obtain the compound suspending agent.
Example 36: preparation of Chunleisen copper reclaimed composition dry suspending agent
The formula is as follows: 35% of biscopper bismerthiazol new compound (by weight of anhydride), 2% of kasugamycin, 3% of zhongshengmycin, 4% of urea, 2% of sodium dodecyl sulfate, 2% of Darun DCM-822%, 4% of polycarboxylate dispersant (SD-819), 2% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenyl succinate, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 0.1% of polyether modified silicone defoamer (DM198), polyethylene glycol-8001% and kaolin for 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 130% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sanding machine until the particle size of 90% is 0.1-5 microns, then pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, wherein the spray pressure is controlled to be 2.0-7.0Mpa, the inlet temperature of drying gas is 110-.
Example 37: preparation of suspending agent of composition
20 percent of a biscuprum bisulphite new compound, 20 percent of oryzanol, 2.3 percent of alkyl naphthalene sulfonate, 2.0 percent of acyl glutamate, 1.0 percent of fatty alcohol polyoxyethylene ether sulfate, 1.0 percent of phenol sulfonic acid condensate sodium salt, 2.0 percent of methyl naphthalene sodium formaldehyde condensate, 2.0 percent of octenyl succinic starch sodium, 1 percent of pentaerythritol, 2.0 percent of glycerol, 0.1 percent of DM-115M and pure water are supplemented to 100 percent, and the mixture is put into a high-shear homogenizing emulsifying machine for high-speed shearing for 25 minutes, pumped into a sand mill for sand milling for 90 minutes and filtered by a 60-mesh sieve to obtain the compound suspending agent.
Example 38: preparation of suspending agent of composition
Adding 25.0% of a new phyllo-bronze compound, 25.0% of hymexazol, 4.0% of alkyl naphthalene sulfonate, 1.0% of EO/PO block polyether, 1.0% of methylene dinaphthalene sodium sulfonate, 3.5% of high-molecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 5.0% of epoxidized soybean oil, 2.0% of urea, 0.1% of ethylparaben, 0.1% of EDTA calcium sodium 4 hydrate, 0.1% of DM-115M and 100% of pure water into a high-shear homogenizing emulsifying machine, shearing at a high speed for 30 minutes, conveying into a sand mill, and circularly sanding for 3 times to obtain the compound suspending agent.
Example 39: dry suspension preparation of compositions
The formula is as follows: 20% biscopper new compound (by weight of the anhydride) and 15% dimethomorph, urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, xanthan gum 0.2%, starch sodium octenyl succinate 0.5%, sorbitol 10%, methyl cellulose 2%, starch sodium octenyl succinate 1.0%, DM 1980.1%, polyethylene glycol-8001%, diatomaceous earth to 100%; the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 130% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sanding machine until 90% of the particle size is between 0.1 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 2.0 to 7.0Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80-150-mesh dry suspending agent.
Example 40: preparation of dry suspending agent of compound composition
The formula is as follows: 30% biscuprum new compound (by weight of the anhydride) and 30% chlorothalonil, urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, xanthan gum 0.2%, starch sodium octenyl succinate 0.5%, sorbitol 10%, methyl cellulose 2%, starch sodium octenyl succinate 1.0%, DM 1980.1%, polyethylene glycol-8001%, diatomaceous earth to 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 130% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 90% of the particle size is between 0.1 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80 to 150-mesh dry suspending agent.
EXAMPLE 41 Dry suspension preparation of Thiessen copper syringyl ester composition
The formula is as follows: 30% of biscopper bisbronze new compound (by weight of the anhydride) and 10% of coumoxystrobin, 4% of urea, 2% of sodium lauryl sulfate, 2% of polycarboxylate (SPED-300), 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenylsuccinate, 10% of sorbitol, 2% of methylcellulose, 1.0% of starch sodium octenylsuccinate, DM 1980.1%, polyethylene glycol-8001%, 0.8% of calcium sodium EDTA 4 hydrate, and the balance of diatomaceous earth being 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 130% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 90% of the particle size is between 0.1 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80 to 150-mesh dry suspending agent.
Example 42 preparation of Thiessen copper and orysastrobin compounded dry suspending agent
The formula is as follows: 30% of biscuprum new compound (by weight of anhydrous substance) and 10% of orysastrobin, 4% of urea, 2% of sodium dodecyl sulfate, 2% of polycarboxylate (SPED-300), 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenyl succinate, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, DM-DA 19520.1%, polyethylene glycol-8001%, 0.5% of calcium sodium EDTA 4 hydrate, and the balance of diatomite being 100%; the preparation process is the same as example 41.
Example 43: preparation of thidiazuron copper and prothioconazole dry suspending agent
The formula is as follows: 30% biscuprum new compound (by weight of the anhydride) and 17.4% prothioconazole, urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, xanthan gum 0.2%, starch sodium octenyl succinate 0.5%, sorbitol 10%, methyl cellulose 2%, starch sodium octenyl succinate 1.0%, DM-1980.1%, polyethylene glycol-8001%, calcium sodium EDTA 4 hydrate 0.5%, diatomaceous earth to 100%; the preparation process is the same as example 41.
Example 44: preparation of novel copper thiessen compound and pyraclostrobin dry suspending agent
The formula is as follows: 30% of biscupronickel new compound (by weight of the anhydride) and 20% of tolfenpyrad, 4% of urea, 2% of sodium lauryl sulfate, 2% of polycarboxylate (SPED-300), 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 0.2% of xanthan gum, 0.5% of starch sodium octenylsuccinate, 10% of sorbitol, 2% of methyl cellulose, 1.0% of starch sodium octenylsuccinate, DM-DA19520.1, polyethylene glycol-8001%, 0.5% of calcium sodium EDTA 4 hydrate, and kaolin to make up 100%; the preparation process is the same as example 41.
Example 45: preparation of thiasen copper fluoxastrobin compounded dry suspending agent
The formula is as follows: 30% biscopper bisbronze new compound (by weight of the anhydride) and 20% fluoxastrobin, urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, xanthan gum 0.2%, starch sodium octenylsuccinate 0.5%, sorbitol 8%, methyl cellulose 2%, starch sodium octenylsuccinate 1.0%, DM 1980.1%, polyethylene glycol-8001%, calcium sodium EDTA 4 hydrate 0.5%, kaolin to 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 120% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 90% of the particle size is between 0.1 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80 to 150-mesh dry suspending agent.
Example 46: thiosendan and fludioxonil wettable powder
Weighing 20 g of a biscuprum new compound (based on the weight of anhydrous substances), 25 g of fludioxonil, 3 g of sodium alkyl naphthalene sulfonate polycondensate, 2g of sodium dodecyl sulfate, 3 g of white carbon black and kaolin to make up to 100 g. The materials are uniformly mixed and crushed to be more than 325 meshes in a jet mill to prepare the wettable powder.
Example 47: preparation of phyllobicopper new compound and isolonging vinyl ketoxime lactam wettable powder
20 g of the new phyllobicopper compound (prepared by the method of example 3), 20 g of the iso-long vinyl ketoxime lactam, 3 g of SD-819 (polycarboxylate), 2g of sodium dodecyl sulfate, 3 g of white carbon black and kaolin are weighed to complement to 100 g. The materials are uniformly mixed and crushed to be more than 325 meshes in a jet mill to prepare the wettable powder.
Example 48-76 preparation of Compound wettable powder
TABLE 4 preparation of wettable powders of the respective built-up pesticides (preparation according to example 47)
Figure RE-GDA0001845365540000271
Figure RE-GDA0001845365540000281
Note: the new compound of Saisentong (A), component No. one of the compound examples in Table 4, was prepared by the method of example 1 and the double No. was prepared by the method of example 2.
Example 77: preparation of 40% bisultap new compound and cyproconazole wettable powder
Weighing 20 g of the bisultap new compound (prepared by the method of example 3 and calculated by the weight of anhydrous substances), 20 g of cyproconazole, 063 g of Darun D, 3 g of Darun DCM-822 g of white carbon black and kaolin to make up to 100 g. The materials are uniformly mixed and crushed to be more than 325 meshes in a jet mill to prepare the wettable powder.
Examples 78-142 preparation of Compound wettable powders
TABLE 5 preparation of the compounded wettable powders (preparation according to the procedure of example 77)
Figure RE-GDA0001845365540000282
Figure RE-GDA0001845365540000291
Note: the new compound (a) of the component thiesenon copper in the single compound in table 5 was prepared by the method of example 1, and the double compound was prepared by the method of example 2; the weights of the Saisentong new compound (A), the main drug in examples 78 to 142 in Table 4 were calculated as anhydrous or crystalline hydrate and the Saisentong new compound.
Example 143: preparation of pesticide composition dispersible granules
Adding 10% of thiason copper new compound (prepared by the method of example 1), 3% of tebuconazole, 6.2% of metalaxyl, 15.4% of prothioconazole, 4% of EO/PO block polyether, 3% of naphthalene sulfonate, 5% of soluble starch, 1% of xanthan gum and 100% of diatomite, fully mixing, putting into a high-shear homogenizing and emulsifying machine for high-speed shearing, coarse grinding and homogenizing, pumping into a sand mill for sand grinding until the particle size of D90 is 0.2-5 microns, and granulating and molding by a conventional process to obtain the water dispersible granule.
Example 144: preparation of seed coating agent with four active ingredients
The suspension type seed coating agent is prepared by adding 5% of a thiason copper new compound (prepared by the method of example 3), 2.75% of metalaxyl, 6.88% of prothioconazole, 1.0% of fludioxonil, 1.0% of alkyl naphthalene sulfonate, 3.0% of fatty alcohol polyoxyethylene ether, 1.0% of acrylic acid homopolymer sodium salt, 1.0% of carboxymethyl cellulose, 3.0% of glycerol, 0.2% of xanthan gum, DM 1980.1%, 0.2% of azo dye, 0.2% of polyethylene glycol-8001%, 0.3% of EDTA calcium sodium 4 hydrate and 100% of pure water to 100%, fully mixing, putting into a high-shear homogenizing emulsifying machine for high-speed shearing, coarse grinding and homogenizing, pumping into a sand mill for sand grinding until the particle size of D90 is 0.2-5 micrometers, and filtering through a 60-mesh sand mill to obtain the suspension type.
Example 145: preparation of suspended seed coating agent
Adding 3% of thiason copper new compound, 3.59% of penflufen, 5.74% of metalaxyl, 7.18% of prothioconazole, 2.0% of alkyl naphthalene sulfonate, 3.0% of fatty alcohol polyoxyethylene ether, 2.0% of methyl naphthalene sulfonate formaldehyde condensate, 2.0% of gum arabic, 3.0% of glycerol, 0.2% of xanthan gum, 0.2% of ferric oxide, 3.0% of DM 1980.1% and 100% of pure water, fully mixing, putting into a high-shear homogenizing emulsifying machine for high-speed shearing coarse grinding and homogenizing, pumping into a sand mill for sand grinding until the particle size of D90 is 0.2-5 microns, and filtering by a 60-mesh sieve to obtain the suspension seed coating.
Example 146: preparation of four active ingredient suspension seed coating agent
1% of thiason copper new compound, 1.47% of prothioconazole, 0.29% of tebuconazole, 8.59% of imidacloprid, 2.0% of sodium naphthalene sulfonate, 3.0% of macromolecular polycarboxylate (Geropon T/36), 2.0% of sodium methyl naphthalene sulfonate formaldehyde condensate, 2.0% of polyvinyl acetate, 3.0% of glycol, 0.2% of sodium carboxymethyl cellulose, 0.1% of EDTA calcium sodium 4 hydrate, 0.2% of DM1980.1, 0.2% of titanium oxide and 100% of pure water are added, fully mixed, put into a high-shear homogenizing emulsifying machine for high-speed shearing, coarse grinding and homogenizing, then pumped into a sand mill for sand grinding until the D90 particle size is 0.2-5 microns, and filtered by a 60-mesh sand grinder to obtain the suspension type seed coating agent.
Example 147: preparation of seed treatment dry powder
6% of Saisentong new compound (prepared by the method of example 1), 4% of carbendazim, 3% of naphthalene sulfonic acid condensation product sodium salt, 2.0% of talcum powder, 5.0% of light calcium carbonate and diatomite are added to 100%, and the mixture is fully mixed and then is subjected to superfine grinding to obtain a dry powder.
Example 148 preparation of 299 Compound Dry suspension
TABLE 6 preparation of the formulated dry suspension formulations in the tables (adjuvant formulation as in example 45, prepared according to the method of example 45)
Figure RE-GDA0001845365540000301
Figure RE-GDA0001845365540000311
Note: table 6 shows only the ratios of the main drug or active ingredient or crude drug of example 148-299 in percentage (all calculated as anhydrous substance or weight ratio), A is Thiessen copper new compound (example No. is prepared by the method of example 1, and No. is prepared by the method of example 2), the other ingredients or adjuvants are respectively used according to the ratio of example 45, and the preparation of each example is carried out according to the preparation process of example 45.
Example 300: preparation of dry suspending agent compounded by thiason copper triacontanol brassin
The formula is as follows: 20% Thiessen copper New Compound (by weight of anhydrate) and 1% triacontanol, 0.7% brassin, 4% urea, 2% sodium lauryl sulfate, 2% polycarboxylate (SPED-300), 4% polycarboxylate dispersant (SD-819), 4% polyvinylpyrrolidone (PVP K-30), 0.2% xanthan gum, 0.5% sodium starch octenyl succinate, 8% sorbitol, 2% methyl cellulose, 1.0% sodium starch octenyl succinate, DM 1980.1%, polyethylene glycol-8001%, 0.5% calcium sodium EDTA hydrate 4, kaolin to 100%;
the preparation process comprises the following steps: mixing and stirring the raw materials and the auxiliary materials in the formula amount and pure water accounting for 120% of the total weight of the raw materials and the auxiliary materials to obtain slurry. And (3) sanding the uniformly mixed slurry by a sand mill until 90% of the particle size is between 0.1 and 5 microns, pumping the suspended emulsion slurry into a pressure type spray dryer for drying and granulation, controlling the spray pressure to be 3.0 to 6.5Mpa, controlling the inlet temperature of drying gas to be 110-140 ℃ and the outlet temperature to be 55 to 70 ℃, and screening the granulated material to obtain the 80 to 150-mesh dry suspending agent.
Example 301: preparation of dry suspending agent compounded by thiasen copper benzyl amino purine compound sodium nitrophenolate
The formula is as follows: 30% Thiessen copper new compound (by weight of anhydrate) and 0.2% 6-benzylaminopurine, 0.3% sodium nitrophenolate complex, 4% urea, 2% sodium lauryl sulfate, 2% polycarboxylate (SPED-300), 4% polycarboxylate dispersant (SD-819), 4% polyvinylpyrrolidone (PVP K-30), 0.2% xanthan gum, 0.5% sodium starch octenyl succinate, 8% sorbitol, 2% methylcellulose, 1.0% sodium starch octenyl succinate, DM 1980.1%, polyethylene glycol-8001%, 0.5% calcium sodium EDTA 4 hydrate, kaolin to make up 100%; the procedure is as in example 300.
Example 302
According to the embodiment of the invention, the Synergy Ratio (SR) of the A and B medicaments compounded according to a certain proportion can be determined by measuring the indoor toxicity, and the combined action is evaluated; SR < 0.5 is antagonistic action, SR < 1.5 is additive action, and SR > 1.5 is synergistic action.
The test method comprises the following steps: after the effective inhibition concentration range of each medicament is determined through pre-test, the medicaments are respectively treated with a plurality of doses according to the content of effective components, and pure water is set for comparison. The experiment is carried out by referring to 'pesticide bioassay technology' (edited by Chengninchun university, published by Beijing university of agriculture publishers, 1998) and 'pesticide indoor bioassay test criterion bactericide', and the toxicity of the medicament to different crop germs is determined by adopting a hypha growth rate method. After the germs are cultured in a potato agar medium (PDA) for 72h at 26 +/-1 ℃ in an incubator in a clean area, the colony diameter is measured by a cross method on a sterile operating platform, and the net growth amount and the hypha growth inhibition rate of each treatment are calculated.
The net growth (mm) is a measure of colony diameter-5
Hypha growth inhibition ratio (%) (control net growth amount treatment group net growth amount)/control net growth amount]X 100 converting the inhibition rate of hypha growth into a probability value (y), converting the concentration of the medicinal solution (. mu.g/mL) into a logarithmic value (x), andthe least square method determines a regression equation of virulence (y ═ a + bx), and from this, the EC of each drug is calculated50The value is obtained. Meanwhile, the combined Synergistic Ratio (SR) of the two medicaments in different proportions is calculated according to the Wadley method, the antagonism is achieved when the SR is less than 0.5, the addition effect is achieved when the SR is more than or equal to 0.5 and less than or equal to 1.5, and the synergism is achieved when the SR is more than 1.5. The calculation formula is as follows:
theoretical (combination) EC50 ═ (a + B)/[ (measured EC50 value for a/a) + (measured EC50 value for B/B) ]
In the formula, a is the proportion of the active ingredient A in the composition, and B is the proportion of the active ingredient B in the composition.
Synergy Ratio (SR) — theoretical EC50 value/observed EC50 value
The toxicity of the thiesencopper new compound (example 1 method) and flumorph in the in vitro test on potato late blight bacteria was measured, and the test object is potato late blight bacteria, and the results are shown in table 7.
TABLE 7 virulence determination of the combination of the Thiessen copper new compound (A) and flumorph (B) for in vitro experiments on potato late blight pathogen
Figure RE-GDA0001845365540000331
The test result shows that: the novel Saisentong compound can effectively sterilize, has an additive effect or a synergistic effect with the flumorph (B) in a mixing ratio of 40: 1-1: 40, can save labor and time cost by applying at the same time, has the synergistic effect between 10: 1-1: 10, and effectively delays the generation of resistance by compounding the novel Saisentong compound with the flumorph (B).
Example 303 the in vitro bactericidal effect of the composition of the thienconcopper new compound (example 2 method) and difenoconazole on alternaria leaf spot was studied with reference to the method in example 302, and the test subject was alternaria leaf spot, and the results are shown in table 8.
8. Toxicity determination of thiason copper new compound (A) and difenoconazole (B) compounded on in-vitro experiment of rice brown spot pathogen
Test agent Proportioning Observation EC50(mg/L) Theoretical EC50(mg/L) Synergistic Ratio (SR)
A 1∶0 12.03
B 0∶1 31.42
A∶B 40∶1 11.37 12.21 1.07
A∶B 20∶1 9.21 12.39 1.35
A∶B 10∶1 8.05 12.74 1.58
A∶B 1∶1 6.58 17.39 2.64
A∶B 1∶10 9.94 27.35 2.75
A∶B 1∶20 18.45 29.11 1.58
A∶B 1∶40 26.72 30.16 1.13
The test result shows that: the novel thiasentong compound can effectively sterilize, has additive action or synergistic action with the difenoconazole (B) in the mixing ratio of 40: 1-1: 40, can save labor and time cost by applying the compound at the same time, has obvious synergistic action when the ratio is 10: 1-1: 20, and effectively delays the generation of resistance by compounding.
Example 304 the in vitro bactericidal effect of the new thiessen copper compound (example 3 method) compounded with pyraclostrobin on cucumber powdery mildew was studied with reference to the method in example 302, and the test object was cucumber powdery mildew, and the results are shown in table 9.
TABLE 9 toxicity test of Thiessen copper new compound (A) and pyraclostrobin (B) in vitro experiment of cucumber powdery mildew
Figure RE-GDA0001845365540000332
Figure RE-GDA0001845365540000341
The test results in table 9 show that: the thiasentong copper new compound can effectively sterilize, has addition or synergy with the pyraclostrobin (B) in the mixing ratio of 40: 1-1: 40, can reduce the labor hour and cost when being applied, has remarkable synergy when the mixing ratio is 4: 1-1: 4, and can effectively delay the generation of resistance to powdery mildew of cucumber.
Example 305 the in vitro bactericidal effect of the new thiessen copper compound (example 1 method) and the fluoroether carboxamide (B) formulated component on cotton fusarium wilt pathogen was studied with reference to the method of example 302, the test object was cotton fusarium wilt pathogen, and the experimental results are shown in table 10.
TABLE 10 toxicity test results of the combination of Thiessen copper new compound (A) and fluoroether carboxamide (B) against Fusarium oxysporum F.sp.sp.gossypii
Figure RE-GDA0001845365540000342
The test result shows that: the thiasentong copper new compound can effectively sterilize, has additive action or synergistic action with the mixture ratio of the thiasentong copper new compound to the fluoride ether bacteria amide (B) of 40: 1-1: 40, can save labor and time expenses by applying at the same time, has obvious synergistic action when the mixture ratio is 5: 1-1: 5, and effectively delays the generation of resistance by compounding.
Example 306 the in vitro bactericidal effect of the new thiessen copper compound (example 2 method) and enestroburin compounded component on the colletotrichum citrulli was studied with reference to the method of example 302, the test object was colletotrichum citrulli, and the test results are shown in table 11.
TABLE 11 blending of Thiessen copper New Compound (A) with enestroburin (B) against virulence of Colletotrichum citrulli
Test agent Proportioning Observation EC50(mg/L) Theoretical EC50(mg/L) Synergistic Ratio (SR)
A 1∶0 39.58
B 0∶1 1.76
A∶B 40∶1 23.32 26.33 1.13
A∶B 20∶1 14.47 19.97 1.38
A∶B 10∶1 8.83 13.77 1.56
A∶B 1∶1 1.32 3.49 2.65
A∶B 1∶5 1.35 2.18 1.61
A∶B 1∶10 1.56 2.00 1.28
A∶B 1∶20 1.64 1.92 1.17
The test result shows that: the thiasentong copper new compound can effectively sterilize, has additive action or synergistic action with enestroburin (B) in the mixing ratio of 40: 1-1: 20, can save labor and time cost by applying the compound at the same time, has obvious synergistic effect when the ratio is 10: 1-1: 5, and effectively delays the generation of resistance by compounding.
Industrial applicability and the like and descriptions thereof and the like:
the present invention has been described in detail with reference to the specific embodiments and examples, but it should be understood that the scope of the present invention is not limited thereto, and it will be apparent to those skilled in the art that various modifications, improvements, substitutions and combinations can be made to the technical solution of the present invention and the embodiments thereof without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

1. The novel compound of the phyllobizine is characterized in that: the new compound of the bisultap copper is a bisultap copper crystal hydrate with the molecular formula of C5H4N6S4Cu·nH2O, wherein n is 1, 1.25, 1.5.
2. The bisultap novel compound according to claim 1, which is a thienson copper 1 hydrate crystal compound that is a thienson copper α type crystal compound or a bisultap α type crystal compound.
3. The bisultap novel compound according to claim 1, which is a thiason copper 1.25 hydrate crystal compound or a thiason copper β crystal compound or a bisultap β crystal compound.
4. The bisultap compound according to claim 1, wherein: the new phyllocopterus compound is a Thisentong 1.5 hydrate, namely a Thisentong omega-type crystal compound or a phyllocopterus omega-type crystal compound.
5. The method for producing the bisultap compound according to any one of claims 1 to 4, wherein: the preparation method comprises the following steps:
adding the bisultap into a reaction vessel, adding water and/or an organic solvent C1-C6Low molecular alcohol of (2), C2-C8Low molecular ether of (2), C2-C6Dissolving one or more of the low molecular nitriles in water or organic solvent solution of alkali selected from but not limited to sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide and sodium isooctanoate, stirring, adding copper salt selected from but not limited to copper sulfate, copper sulfate pentahydrate, copper chloride dihydrate, copper acetate monohydrate, copper nitrate or aqueous solution thereof, stirring, fully precipitating solid, filtering, adding water and C1-C6Low molecular alcohol of (2), C2-C8Low molecular ether of (2), C3-C8Low molecular ketone of (2), C2-C6Low molecular nitrile of (2), C1-C6Low molecular halogenated hydrocarbon of C2-C8Washing one or more of the low molecular weight esters once to several times, filtering, and drying the obtained solid to obtain a novel phyllobis copper compound, namely a phyllobis copper crystalline hydrate;
wherein, the bismerthiazol used in the reaction: one of the bases has an equivalent ratio of about 1: 1 to 1.1; the weight volume ratio of the phytin and water, or C1-C6 low molecular alcohol, or C2-C8 lower ether, or C2-C6 lower nitrile organic solvent is as follows: 1 (g): 3.5 to 60(ml), preferably in the ratio: 1 (g): 5 to 40 (ml); the equivalence ratio of the bisultap to one or more of the copper salts is about 1: 0.98-1.05;
wherein, the organic solvent C1-C6The low molecular alcohol of (1) is selected from but not limited to methanol, ethanol, isopropanol and butanol; c2-C6The low molecular nitrile of (a) is selected from, but not limited to, acetonitrile; c2-C8The low molecular ether or low molecular ether of (2) is selected from but not limited to diethyl ether, isopropyl ether, tetrahydrofuran, methyl tetrahydrofuran; c1-C6The lower halogenated hydrocarbon is selected from but not limited to dichloromethane and chloroform; c2-C8The low molecular ester is selected from but not limited to butyl acetate, ethyl acetate and ethyl formate; c3-C8The low molecular ketone is selected from but not limited to acetone, butanone and isohexanone.
6. The bisultap compound according to any one of claims 1 to 5, wherein: the compound is used for preparing a new pharmaceutical composition from an effective dose of an active ingredient A, namely a new compound of the phyllocopterus leaf and an effective dose of an active ingredient B, and preparing a pharmaceutically acceptable pesticide preparation from the new pharmaceutical composition and pharmaceutically acceptable auxiliary materials; wherein the weight ratio of active ingredient A to active ingredient B is preferably 1: 180-100: 1, and the active ingredient B is selected from but not limited to any one or more compounds selected from B.1) -B.13) and pharmaceutically acceptable salts thereof; wherein the weight ratio of the active component A to the active component B is preferably 100: 1-1: 100; wherein, the weight ratio of the active component A to the active component B can also be preferably 80: 1-1: 80;
wherein, B.1) the strobilurin fungicide or antiviral agent is selected from one of but not limited to azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, enestroburin, fluoxastrobin, picoxystrobin, kresoxim-methyl, alkene oxime amine or metominostrobin, phenamacril, Picarbuzox, orysastrobin, pyraclostrobin, coumoxystrobin, triclopyricarb, benzothiostrobin, UBF307, KZ165, probenazole and diclosamide;
b.2) triazole fungicide selected from but not limited to one of difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, hexaconazole, myclobutanil, penconazole, propiconazole, tetraconazole, triadimenol, triadimefon, metconazole, ipconazole, prothioconazole, imazazole, triticonazole, cyproconazole, mefentriflumizole mefentriflunazole, ipriflamotriazole, ipfentriflunazole, bromuconazole, fenbuconazole and fluquinconazole;
b.3) an amide fungicide selected from one of but not limited to metalaxyl, metalaxyl-M, flutolanil, mandipropamid, boscalid, fluopyram, carboxin, Bixafen, penflufen, epoxiconazole, Fluxapyroxad, penthiopyrad, thifluzamide, fluopicolide and isopyrazam, fluofen, fluoxafen, cycloflusulfamide, methiavalicarb, benalaxyl-m, thifluzamide, tiadinil, ethaboxam, silthiopham, cyflufenamid, fluopyram, zoxamide, fenhexamid, cyprodinil, flusulfamide, metosulam, oryzamide, Bixafen, Fluxapyroxad, Sedaxane;
b.4) one of imidazole bactericides which is selected from one of but not limited to cyazofamid, triflumizole, imazalil, fenamidone, oxpoconazole, albendazole and phenylthioimidazole;
b.5) the dicarboximide bactericide is selected from one of but not limited to procymidone, iprodione, vinclozolin, captan, dimethachlon and tolclofos-methyl;
b.6) carbamate bactericide which is selected from one of but not limited to propamocarb hydrochloride, diethofencarb, benomyl, carbendazim, thiophanate-methyl, iprovalicarb and benthiavalicarb;
b.7) antibiotic bactericide or antiviral agent selected from, but not limited to, validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshengmycin, pesticide 120, aureonucleomycin, Changchuan mould, and tetramycin;
b.8) an oxazole based fungicide selected from but not limited to one of oxadixyl, hymexazol, famoxadone, pyrisoxazole, oxadixyl fluorothiazole, benfurazolesulfone, dichloroazole and methanesulfonylazole;
b.9) morpholine bactericide or antiviral drug, which is selected from but not limited to one of tridemorph, dimethomorph, flumorph and moroxydine hydrochloride;
b.10) a pyrimidine bactericide which is selected from but not limited to one of cyprodinil, pyrimethanil, ethirimol, mepanipyrim, fluopyram, dimoxystrobin, SYP-3773 and SYP-3810;
b.11) quinoline bactericide, which is selected from but not limited to one of dithianon, propoxymoline, phenoxyquinoline and quinoliflumein;
b.12) dithiocarbamate bactericide or antiviral agent selected from but not limited to one of metiram, thiram, ziram, amobam, zineb, maneb, mancozeb and propineb;
b.13) other fungicides or antivirals or plant growth regulators, selected from, but not limited to, diphenoxylate, fosetyl-aluminium, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydroabietate, fenpiclonil, fludioxonil, isovinyl ketoxime lactam, osthole, Dufulin, phenaconone, mehtanin, polyhexamethylene biguanide hydrochloride, bromothalonil, amisulbrom, copper oxychloride, nonylocet, oxine-copper, moroxydine hydrochloride, copper succinate, xinafoate acetate, amino-oligosaccharin, lentinan, benziothiazolinone, ethylicin, probenazole, diclocyanamide, physcion, chrysophanol, fluconazole-activated ester, S-abscisin, amino-oligosaccharin, zinc sulfate, pharmaceutically acceptable salts, eugenol, sulfur, copper sulfate pentahydrate, bisulphate, bismerthiazol, Isolongifolenoxim lactam, allicin, guaiacol, quinolactaside, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, ziconazol zinc hydrate, ametoctradin, Pyribencarb, fluganil, Meptyldinocap, Pyriofenone, Fenpyrazamine, Valifenalate, Tolprocarb, isoflutam, Isopyrazam, Penflufen, benzovindifluppy, Tebufloquin, Oxathiapiprolin, spiroxamine, fosetyl-aluminum, iprobenfos, matrine, kurarinone, and the like; or the plant growth regulator is selected from one of but not limited to diethyl aminoethyl hexanoate, forchlorfenuron, compound sodium nitrophenolate, brassin, gibberellin, 6-benzylaminopurine, triacontanol, naphthylacetic acid or its medicinal salt, paclobutrazol, ethephon, etc.
7. The composition of the bisultap compound as claimed in claim 6, wherein: the bactericide contains an active ingredient A and any one or more active ingredients B selected from but not limited to azoxystrobin, kresoxim-methyl, pyraclostrobin, enestroburin, trifloxystrobin, pyraclostrobin, fluoxastrobin, kresoxim-methyl, enestroburin or metominostrobin, cyazoxystrobin, Picarbitraconazole, orysastrobin, pyraclostrobin, coumoxystrobin, clotrimoxystrobin, UBF307, KZ165, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, cyproconazole, penconazole, propiconazole, tetraconazole, triadimenol, bitertanol, triadimenol, metconazole, ipconazole, prothioconazole, imazalil, triticonazole, cyproconazole, metalaxyl, flutolanilide, mandipropamid, picolinamide, fluopyramide, fluoxafen-fluoride, cyazofamid, triflumizole, imazamidone, imazachlor, triflumilast, triflumizole, triflumilast, pyriproxyfen, procymidone, iprodione, vinclozolin, captan, dimethomorph, propamocarb hydrochloride, benomyl, carbendazim, thiophanate-methyl, valvacarb, benthiavalicarb, validamycin, streptomycin sulfate, kasugamycin, shenqinmycin, oxadixyl, hymexazol, famoxadone, pyrisoxazole, tridemorph, dimethomorph, flumorph, cyprodinil, pyrimethanil, ethirimol, mepanipyrim, flufenamid, dithianon, propoxymine, phenoxyquinoline, metiram, thiram, ziram, zineb, maneb, mancozeb, propineb, diphenfos, fosetyl-Al, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydroabietate, fenpiclonil, fludioxonil, prochloraz complex, validamine complex, validamycin sulfate, streptomycin, Kasugamycin, tetramycin, shengmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshenmycin, antinomycin 120, aureonucleomycin, changchin, Dufulin, phenazon, prothioconazole, phenylthioimidazole, fluroxypyr, iprodione, fluthiacetophenone, probenazole, allylbenzothiazole, physcion, chrysophanol, fluthiazopyrazole, allylbenzothiazole, diclosamide, physcion, chrysophanol, fluzole-activated ester, dichlorooxazole and methanesulfonylazole, S-elicitor, amino-oligosaccharin, zinc sulfate, berberine hydrochloride, berberine sulfate, folpet, isolongifolenoximinamide, allicin, guaiacol, quinolactide, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, zinc seconazole, zinc seosulfate hydrate, thiflufenazamide, tiadinil, thifenhexamide, thiofenacetrimide, thifenpyr, The composition is characterized by comprising ethaboxam, silthiopham, furametpyr, cyflufenamid, fluopyram, zoxamide, fenhexamid, cyclopropanamide, flusulfamide, sulfenamide, metryanodine, Pyriofenone, Fenpyrazamine, oryzamide, Bixafen, Fluxapyroxad, Sedaxane, ametoctradin, Pyribencarb, fluthianil, Meptyldinocap, Pyriofenone, ferpazamine, Valifenalate, Tolprocarb, isofamid, Isopyrazam, Penflufen, benzovindifluppy, tebuflozin, oxazopiprolin, furametpyr, fenbuconazole, fluquinconazole, spiroxamine, fosetyl-ethyl-aluminium, tolmetil, isocumyl, tolnaftate, propazofamide, propazofamid, propamocarb, matrine, or a plant growth regulator, and the like, and preferably 1-80 or more preferably 1-80 weight or 1-80 weight of a pharmaceutically acceptable salt of a compound.
8. The bisultap compound according to any one of claims 1 to 7, wherein: the bisultap compound or the composition thereof and a pharmaceutically acceptable carrier are prepared into a pharmaceutically acceptable preparation, and the pharmaceutically acceptable preparation is selected from but not limited to dry suspending agents, wettable powder, granules, dispersible granules, tablets, effervescent tablets, microcapsules, water dispersible granules, suspending agents, suspoemulsions, aqueous emulsions, controlled-release or sustained-release preparations, sustained-release or controlled-release tablets or capsules or pellets, microcapsule preparations, oil suspending agents, dispersible liquids (DC), seed treatment dry powder, seed treatment dispersible powder, granules, dispersible granules, microcapsule suspending agents, seed treatment microcapsule suspending agents or suspension seed coating agents and the like.
9. The composition according to claims 6, 8, characterized in that: the pharmaceutically acceptable carrier is selected from, but not limited to, wetting agents, binders, dispersants, thickeners, antifreezes, preservatives, disintegrants, stabilizers, film formers, antifoaming agents, colorants, lubricants or glidants, emulsifiers, fillers, and/or water.
10. Use of the bisultap compound or the pharmaceutical composition thereof according to any one of claims 1 to 9, wherein: the application of the compound in preparing medicines for preventing and treating diseases on crops and/or promoting the health or growth and development of the crops or medicines in the field of protecting industrial materials from being invaded by germs;
the diseases are selected from but not limited to: one or more of canker, streak disease, rust disease, glume blight, net blotch, powdery mildew, downy mildew, epidemic disease, leaf spot, take-all disease, snow mold, smut, leaf blight, brown spot or rice blast;
the crops are preferably or selected from but not limited to the following categories: cereal wheat, barley, rice, corn, sorghum, sweet potato; fruit trees such as apple, pear, peach, hickory, orange, grape, lychee, banana, longan, mango and loquat; vegetables such as cucumber, watermelon, snake gourd, towel gourd, melon, spinach, celery, tomato, pepper, eggplant, ginger, shallot, garlic, leek, cabbage, Chinese cabbage, strawberry, asparagus lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam, taro, lotus root, water chestnut and water bamboo; sugar plants such as beet and sugarcane; oil crops such as soybean, peanut, rape, sesame and sunflower; or such as tobacco, tea.
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