CN111423472A - Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof - Google Patents

Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof Download PDF

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CN111423472A
CN111423472A CN201811588695.4A CN201811588695A CN111423472A CN 111423472 A CN111423472 A CN 111423472A CN 201811588695 A CN201811588695 A CN 201811588695A CN 111423472 A CN111423472 A CN 111423472A
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manganese
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刘力
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    • C—CHEMISTRY; METALLURGY
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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
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    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/72—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
    • 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
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/82—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 three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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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
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
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    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity

Abstract

Compared with a single preparation, the broad-spectrum sterilization low-toxicity low-residue growth-promoting Saisen manganese-zinc compound or compound not only can sterilize crops but also can supplement manganese and zinc when being applied to the crops; compared with the prior art, the preparation has the advantages of accurate preparation content, reduction of complicated preparation processes, convenience in application, easiness in preparation, lower energy consumption, greenness, environmental friendliness, better storage stability or prevention and control effect and the like; the compound is suitable for preparing a composition containing the compound and pesticides for preventing and treating various bacterial and fungal diseases on crops and/or promoting the health or growth and development of the crops, or is applied to medicaments in the fields of protecting industrial materials from being damaged by bacteria and the like.

Description

Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof
Technical Field
The invention relates to the technical field of pesticides, and particularly provides a novel compound or compound of Thiessen manganese zinc with broad-spectrum sterilization, low toxicity, low residue and capability of promoting crop growth, a composition of the compound or the compound, and a preparation method and application of the compound or the composition.
Background
The chemical name of the phyllanthus emblica is N, N' -methylene-bis (2-amino-5-mercapto-1, 3, 4-thiadiazole), and the molecular formula is C5H6N6S4The molecular weight of 278.34 is a systemic therapeutic bactericide which is independently created in China, has the characteristics of high efficiency, low toxicity, low residue, long lasting period and strong systemic property, has better control effect on bacterial leaf blight, bacterial leaf streak and citrus canker of rice, and can be popularized and used in China for nearly 40 years. The technique for producing the original drug of the bismerthiazol is listed in the technical catalog of export restriction of prohibited export in China, and belongs to the chemical pesticide production technique of independent intellectual property rights in China (document 1, the eosin reappearance in the bismerthiazol market [ J)]Today's pesticides, 2012 (07): 41-42.;]。
the bisultap has multiple functions of systemic absorption, conduction, prevention, protection, treatment and the like, the effect of the treatment effect is greater than the protection effect, the bisultap is a high-efficiency and safe systemic bactericide, and the bisultap has good prevention and treatment effects on bacterial diseases such as rice bacterial leaf blight, rice bacterial leaf streak, Chinese cabbage soft rot, tomato bacterial wilt, potato bacterial wilt, tomato canker, citrus canker, and bacterial perforation of stone fruit trees (peaches, apricots, plums and the like). The bactericidal composition is used for preventing and treating plant bacterial diseases, has long lasting period, stable pesticide effect and 10-14 days of residual effect, and does not have phytotoxicity to crops. For preventing and treating bacterial leaf blight of rice, 15-22.5 g of 25% wettable powder (proper dosage when the disease condition is serious) is added into water for spraying by 6-7.5 kg per hundred square meters. Applying the pesticide to the seedling bed for 1-2 times at the leaf stage of 4-5 leaves at intervals of 7-10 days, and treating bacterial leaf streak [ document 2, Dongkun. 11.; literature 3, Sunmitong, Yeqingshuang pesticide and application technology thereof [ J ] Chinese agronomy report, 1985 (01): 21.; document 4, dungeon, royal wather, zonufin, linrong, bismerthiazol safety risk management countermeasure and recommendation [ J ]. pesticide science and management, 2015, 36 (06): 8-12.; ].
After the leaf-feather-stem-leaf-tuber crops are irradiated for 2-16 hours, the activity of the leaf-feather-stem-leaf-tuber crops on the rice bacterial blight is obviously enhanced. The disease inhibiting effect of the composition on the 10 th day is more than 80 percent when the composition is applied 1 day before and at the time of inoculation, the disease inhibiting effect of the composition on the 15 th day is about 60 percent when the composition is applied 1 day after inoculation, which shows that the photoproduct not only has good protection effect, but also the treatment effect after the suction of the blades is obviously enhanced compared with that of a parent body. The residual period of the photo product applied to the leaf surface is prolonged by 5 to 7 days compared with that of the parent body; the root has good systemic effect, and the disease inhibiting effect reaches about 90 percent after 10 days of root application. The photoproduct solution still has stable activity after 1 year dark storage [ literature 5, Yueyongde, Huari mao, Tangfeng, Yeqingshuang for photoactivation study of rice bacterial leaf blight [ J ]. proceedings of agriculture university of Anhui, 1995 (04): 356-360.].
The action mechanism of phyllanthus: in the structure, the thiazole group has no inhibition on bacteria in vitro, but is a high-efficiency therapeutic agent in vivo, and the medicament causes the bacteria to be seriously damaged in a pored duct of a plant, so that the cell wall of the bacteria is thinned and then collapsed, and the bacteria are killed. Recent studies have reported that the fungicide bisultap induces direct and/or indirect resistance of Rice against various pests, and therefore bisultap can be Used as a broad-spectrum chemoinducer [ document 4, Zhou Pengyong, MoXiaochang, et al, the common Used bacterial bismuthyl proteins Rice pest control herbal medicaments [ J ]. International patent of molecular sciences, 2018, 19(5) ].
Zhejiang agricultural university reports the determination method and result of toxicity of the new bactericide of the leaf-Binyang to the water fleas. 3 daphnia herd pairs K2Cr2O7The standard control agent test 24h L C50 respectively shows 1.41, 0.58 and 8.93 mg/L. the concentration of the bismerthiazol under ISO requirement of No. 1 flea group 24, 48 and 72h L C50 respectively show 197.8, 110.2 and 78.2 mg/L. the concentration of the bismerthiazol under 6.4 × 10-6 has no influence on the reproduction of the daphnia2Cr2O7The order is consistent. The research result shows that the phyllanthus is low-toxic or approximately non-toxic to the daphnia (literature 5, Hannong, Chen He Xin, fan Defang, Huangxin, Wu Mian Hangzhou. preliminary toxicity research of phyllanthus to the daphnia [ J]Agricultural environmental science journal, 1992 (06): 264-267+288.]。
The toxicity and influence of the bisultap yessoensis on silkworms of different varieties and ages are comprehensively researched by a pesticide environmental toxicology research institute of Zhejiang agricultural university, which adopts various indoor toxicity tests and field silkworm cocoon yield and quality investigation, and the results show that: the high-concentration phyllobis virens has no obvious acute toxicity and other adverse effects on the adult silkworms of different varieties and instars, and factors such as dosage forms, dosage amounts, infection time and the like have different degrees of influence on the hunger resistance of the ant silkworms, particularly the infection time has the largest influence, but the infection of the adult silkworms by the high-concentration phyllobis virens has no influence on indexes such as yield, quality and the like of cocoons [ document 6, Hannong, Chengxin, Huangxin, and the like, and the bactericide phyllobis virens has no influence on toxicity research [ J ] environmental pollution and prevention and treatment of the silkworms, 1995 (02): 14-16+ 46; ].
The acute and subacute toxicity of the gavage and feed-contaminated Bingqing to the quails is also researched by Zhejiang agricultural university, the test result shows that the acute oral administration L D-50 of the Bingqing to the females and the males is 3578 and 2960 mg/L g respectively, which belongs to low-toxicity pesticide, the effects of the Bingqing on emaciation and cholinesterase on the brain and whole blood are probably the main action forms of the Bingqing, the Bingqing has reversible inhibition effect on the egg laying rate and has no effect on organ coefficients.
Saisentong copper, chemical name is N, N' -methylene-bis (2-amino-5-mercapto-1, 3, 4-thiadiazole) copper, molecular formula is C5H4N6S4Cu with molecular weight of 339.9 is thiazole organic copper broad-spectrum bactericide (document 6, pesticide for preventing and treating crop bacterial diseases CN: 1109500), 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 production [ reference 7, Zhang Chun Biao, Lidi Xing, Wang Xiang, He Yonglin, novel bactericide-Saisentong [ J ] copper []World pesticide, 2007 (02): 53-54; document 8, Zhang Chun Bing, Lidi Yu, Wang physique, He Yonglin, creating high-efficiency safe bactericide-Saisentong, 2006-11-22, twenty-second China plant protection information exchange and farm chemical trade Association]。
Many data indicate that chloroplasts contain high amounts of manganese, which is a necessary trace element for maintaining chloroplast structure. In chloroplasts, manganese binds to proteins to form enzyme proteins, which are indispensable participants in photosynthesis. In the absence of manganese, the membrane structure is destroyed, so that chloroplast is disintegrated, and the chlorophyll content is reduced. For example, when sugar beet is lack of manganese, the number, volume and chlorophyll content of chloroplast in palisade tissue and sponge tissue cells are obviously reduced.
Manganese can promote seed germination and early growth of seedlings, has a stimulating effect on the effect of auxin on promoting coleoptile elongation, can accelerate the hydrolysis process of starch and protein in seeds, and promotes monosaccharide and amino acid to be timely used by seedlings. Sufficient manganese supply can also improve the fruit setting rate and has good effect on early fruit setting of young fruit trees. In addition, manganese has a good effect on the formation of vitamin C and the strengthening of mechanical tissues of the stem, etc.
Manganese also has an effect on root growth. In the absence of manganese, the lateral roots of the plants almost completely stop growing, and the number of small cells without vacuoles in the roots increases. This also indicates that manganese deficiency has a greater effect on cell elongation than on division.
Currently, biszinc and bismanganese (thiasen zinc and thiasen manganese), although synthesized, have not been prepared (patent document 6, agricultural chemicals for controlling bacterial diseases of crops, CN: 1109500].
As far as the present, there is no published Saisen manganese zinc compound reported in the literature at home and abroad, and the preparation method and the application thereof, and the manganese zinc bactericide is supplemented when the bactericide is required in the agriculture and forestry production.
Polymorphs of chemical drugs play an important role in drug research and are suitable for better pharmaceutical needs. 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 for quantitative analysis or characterization of compound structures, and has been used by Barta et al to identify unknown compounds as early as the second international conference on thermal analysis in 1968.
Disclosure of Invention
The invention relates to a new thiasen manganese zinc compound or compound, which can sterilize and supplement trace elements of manganese and zinc, namely the new thiasen manganese zinc compound or compound and hydrate thereof, N, N' -methylene-bis (2-amino-5-mercapto-1, 3, 4-thiadiazole) manganese zinc and hydrate thereof, and C5H4N6S4(Mn)v(Zn)KThe water content is 0.0-15%; or the molecular formula is C5H4N6S4(Mn)v(Zn)K·wH2O, water content 0.0-15%, wH2O is used for ensuring that the water content can be between 0.0 and 15 percent under normal conditions, the molar ratio of manganese to zinc in the Thisen manganese-zinc molecules is between 0.001 and 0.999: 0.999 and 0.001, the molar ratio of manganese to zinc in the Thisen manganese-zinc molecules is between 0.0001 and 0.9999, the sum of the molar ratio of manganese to zinc in the Thisen manganese-zinc molecules is equal to 1, namely V + K is 1, and the composition, the preparation method and the application thereof. The invention has the function of sterilizing the Thiessen manganese zinc or the novel Thiessen manganese zinc compound or compound and the water thereofAny pharmaceutical or agrochemical acceptable preparation which is added with water or made into water or solvent, or made into bactericide, etc. is within the protection scope of the present invention.
The thiasen manganese zinc compounds or complexes of the present invention include, but are not limited to, the following:
[C5H4N6S4(Mn)0.95(Zn)0.05the water content is 0.00-15%]，[C5H4N6S4(Mn)0.5(Zn)0.5The water content is 0.0-15%]，[C5H4N6S4(Mn)0.9(Zn)0.1The water content can be 0.0-15%]，
[C5H4N6S4(Mn)0.8(Zn)0.2The water content is 0.0-15%]，[C5H4N6S4(Mn)0.7(Zn)0.3The water content is 0.0-15%]，[C5H4N6S4(Mn)0.65(Zn)0.35The water content is 0.0-15%]，[C5H4N6S4(Mn)0.6(Zn)0.4The water content is 0.0-15%]，[C5H4N6S4(Mn)0.4(Zn)0.6The water content is 0.0-15%]，
[C5H4N6S4(Mn)0.35(Zn)0.65The water content is 0.0-15%]，[C5H4N6S4(Mn)0.3(Zn)0.7The water content is 0.0-15%]，[C5H4N6S4(Mn)0.2(Zn)0.8The water content is 0.0-15%]，[C5H4N6S4(Mn)0.1(Zn)0.9The water content is 0.0-15%]，[C5H4N6S4(Mn)0.05(Zn)0.95The water content is 0.0-15%]；
Or [ C5H4N6S4(Mn)0.95(Zn)0.05·wH2O, water content of 0.0-15%]，
[C5H4N6S4(Mn)0.5(Zn)0.5·wH2O, water content of 0.0-12%]，[C5H4N6S4(Mn)0.9(Zn)0.1·wH2O, water content of 0.0-12%]，[C5H4N6S4(Mn)0.8(Zn)0.2·wH2O, water content of 0.0-12%]，
[C5H4N6S4(Mn)0.7(Zn)0.3·wH2O, water content of 0.0-12%]，
[C5H4N6S4(Mn)0.65(Zn)0.35·wH2O, water content of 0.0-15%]，[C5H4N6S4(Mn)0.6(Zn)0.4·wH2O, water content of 0.0-15%]，[C5H4N6S4(Mn)0.4(Zn)0.6·wH2O, water content of 0.0-15%]，
[C5H4N6S4(Mn)0.35(Zn)0.65·wH2O, water content of 0.0-15%]，[C5H4N6S4(Mn)0.3(Zn)0.7·wH2O, water content of 0.0-15%]，[C5H4N6S4(Mn)0.2(Zn)0.8·wH2O, water content of 0.0-15%]，
[C5H4N6S4(Mn)0.1(Zn)0.9·wH2O, water content of 0.0-15%]，
[C5H4N6S4(Mn)0.05(Zn)0.95·wH2O, water content of 0.0-15%]；
Hydrate of Thisen manganese Zinc Compound or Complex [ C5H4N6S4(Mn)0.9(Zn)0.1]、
[C5H4N6S4(Mn)0.5(Zn)0.5、[C5H4N6S4(Mn)0.7(Zn)0.3]、[C5H4N6S4(Mn)0.65(Zn)0.35]、
[C5H4N6S4(Mn)0.6(Zn)0.4]、[C5H4N6S4(Mn)0.4(Zn)0.6]、[C5H4N6S4(Mn)0.3(Zn)0.7]、
[C5H4N6S4(Mn)0.2(Zn)0.8]、[C5H4N6S4(Mn)0.8(Zn)0.2]、[C5H4N6S4(Mn)0.1(Zn)0.9]、
[C5H4N6S4(Mn)0.05(Zn)0.95]The water content of the hydrate can be about 1.5-15.0%; wherein, Thisen manganese zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]The water content of the 1 hydrate can be between 4.5 and 6.5 percent;
although the Saisentong copper or the bismerthiazol is used at present, the manganese deficiency and the zinc deficiency of some crops needing to be sterilized by the Saisentong copper or the bismerthiazol cannot be effectively supplemented, the current no Saisentong zinc and the Saisentong manganese single preparation is on the market or related compounding, and if the compounding is used, the problem of inconvenience in preparation or the problem of accurate preparation dosage exists, or the growth and sterilization of the crops are influenced, the excessive dosage or the phytotoxicity of the crops is caused, or the adverse effects in multiple aspects are caused. The Thiessen manganese-zinc compound or the Thiessen manganese-zinc compound is prepared by reacting in a solution state, so that a uniform and stable-content product is favorably formed, the physical mixing of two solid substances can not be comparable to that of the product, if the Thiessen manganese-zinc compound is physically mixed, the leaf blue double zinc and the leaf blue double manganese need to be prepared respectively, the preparation is more complicated than the preparation of a single Thiessen manganese-zinc compound, and the mixing of the leaf blue double zinc and the leaf blue double manganese cannot be completely and uniformly mixed, so that effective quality control is realized. In addition, the study also finds that the Saisen manganese zinc hydrate with better stability has better accessibility, can form better selection on pharmacy or pesticides, and is ignored for a long time.
Moreover, the invention also finds the advantages of the new thiasen manganese zinc compound in the production and manufacturing process or the environment-friendly disposal process, the temperature required for preparing the leafy double zinc and the leafy double manganese in the prior art in the document 1(CN1152869) is as high as 70-80 ℃, and the drying temperature of the embodiment is 100 ℃, so that more energy is consumed, the construction of energy-saving production is not facilitated, the total impurities are increased, and the storage stability of the raw materials is not facilitated; this reflects the better availability of the Thiessen manganese zinc hydrate with different degrees of better stability during the production process, and also demonstrates the greater ease of production of the material of the invention.
The new Thisen manganese zinc compound prepared by the invention changes the bad characteristic of strong electrostatic adsorption of the crude Thisen manganese zinc compound, the electrostatic adsorption strength of the new Thisen manganese zinc compound with different structures is obviously reduced compared with the crude Thisen manganese zinc compound, and the embodiment 1-2A is compared with the embodiment
1. Comparative study of flowability of solid
The new phyllobium compound, the anhydrous substance sample and 0.500 g of a commercially available sample of the phyllobium are respectively and accurately weighed and placed in the middle of commercially available weighing paper, the weighed paper is horizontally and uniformly spread to be about 1-2mm thick, so that the spreading areas of the samples on the weighing paper are basically equal, the weighing paper is folded into a ditch shape, then the solid powder of the weighing paper naturally flows down and is poured onto another piece of weighing paper vertical to the horizontal plane, the weight difference before and after calculation is carried out, the experiment is repeated for three times, the average value is obtained, and the results are shown as follows.
TABLE 1 comparative study of solid flowability
Figure BDA0001918187580000041
The results show that the transfer loss of the Yeqing Shuangcommercially available sample and the Yeqing Shuangnu type compound is more than 100% of that of each example, the difference shows significance, the raw materials of the method of example 1-2A, the method of example 1-4A, the method of the raw materials of example 1-6A, the method of example 1-7A and the method of example 1-9A have better fluidity than the Yeqing Shuangcommercially available sample and the Yeqing Shuangnu type compound, the good fluidity of the original drug can reduce the process loss and the environmental pollution, and the preparation is more convenient.
The obtained Thisen manganese zinc containing crystal water has lower hygroscopicity than the Thisen manganese zinc without crystal water, better stability and sliding property, is more beneficial to improving the operability of pesticide preparations, is convenient to store and transport, reduces the manufacturing cost and cost, and is also beneficial to preparation manufacture.
Surprisingly, the thieson manganese zinc hydrate of the invention has a characteristic endothermic peak under a weight loss platform (under a weight loss curve before about 157 ℃) of a thermogram (TG-DSC or TG-DTA) which shows the thieson manganese zinc hydrate with a novel structure, such as the thieson manganese zinc 1 hydrate, the thieson manganese zinc 2 hydrate and the like.
The preparation of the Thiessen manganese zinc compound includes but is not limited to the following methods:
adding the phyllobium pratense or solvent compound (including phyllobium pratense v type compound) thereof into a reaction vessel, adding water and/or 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-C6Stirring for dissolving one or more of low molecular weight nitrile, adding one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate and potassium hydroxide or their water solution, stirring, adding manganese salt or its solvent compound or its mixed solution and zinc salt or its solvent compound or its mixed solution, wherein the manganese salt or its solvent compound is selected from manganese sulfate, manganese sulfate monohydrate, manganese chloride 4 hydrate, manganese acetate 4 hydrate, manganese sulfate monohydrate, manganese chloride, manganese sulfate monohydrate, manganese sulfate, manganese chloride 4 hydrate, manganese,Manganese nitrate, manganese nitrate 4 hydrate or one or more of water solution thereof, water-soluble zinc salt is selected from zinc sulfate, zinc sulfate heptahydrate, zinc chloride, zinc acetate, zinc nitrate or one or more of water solution thereof, stirring, precipitating solid sufficiently, 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-C6Washing one or more of the low molecular weight halohydrocarbon once to several times, filtering, washing the obtained solid with one or more of water, C1-C6 low molecular weight alcohol, C2-C8 lower ether, C3-C8 low molecular weight ketone and C1-C6 lower halohydrocarbon, filtering, and drying to obtain Saisen manganese zinc or Saisen manganese zinc hydrate;
wherein, the bisfolin or the solvent compound thereof used in the reaction: the equivalent ratio of one of alkali (selected from but not limited to sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium isooctanoate and the like) is about 1: 1-1.2; the weight volume ratio of the phytin bis (weight g) and water, or C1-C6 low molecular alcohol, or C2-C8 lower ether (selected from but not limited to diethyl ether, tetrahydrofuran, isopropyl ether and the like), or C2-C6 lower nitrile (selected from but not limited to acetonitrile, propionitrile and the like) 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 (ml); the total equivalent ratio of the bisultap to the manganese salt and the zinc salt is about 1: 0.98-1.1.
The synthesis solvent of the Thiessen manganese zinc or the Thiessen manganese zinc crystal hydrate 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 and the like.
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 compound described as "lower or low molecular" occurs once in the text, and the number of carbon atoms of any other unlabeled compound of the same type described as "lower or low molecular" is consistent with the numbers 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., 90-110 deg.C), 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.
In the present invention, the moisture content of the new thiasen manganese zinc compounds, the anhydrous thiasen manganese zinc, and the like is measured by the karl fischer method with reference to the first method a of chinese pharmacopoeia appendix VIII M, 2010 version, and the moisture content of the related compounds and the like is measured by a specific karl fischer moisture measuring instrument.
On the one hand, the invention provides different thiasen manganese-zinc compounds and preparation methods thereof, so that the control of the manganese-zinc ratio in the thiasen manganese-zinc compound manganese-zinc is far better than that of the physical mixture of the thiasen manganese and the thiasen zinc in the same ratio, the preparation process is simplified, two drying processes are saved, and a large amount of working hours and cost are saved.
The present invention also provides a pharmaceutical composition comprising any one or more of the novel thiasen manganese zinc compounds prepared by the process of the present invention, and one or more pharmaceutically acceptable excipients. The invention further provides a process for preparing the formulation comprising combining any one or more of the novel thiasen manganese zinc compound formulations prepared by the process of the invention or with at least one or pharmaceutically acceptable excipients.
The invention further provides the application of the new thiasen manganese zinc compound in preparing pesticide compositions for sterilization and the like.
Compared with single Thisen manganese or Thisen zinc, the novel Thisen manganese zinc compound provided by the invention not only forms a stable compound at one time, but also can provide manganese and zinc microelements, provides conditions for promoting the growth of crops, provides a multi-target sterilization means, and provides a means for protecting the growth of crops.
Compared with the single Thisen manganese or the Thisen zinc and then the mixture, the novel Thisen manganese zinc compound or the novel Thisen manganese zinc compound reduces the complexity of fractional production, is beneficial to reducing energy consumption and reduces the production and operation cost of products.
The preparation cost of the new thiasen manganese zinc compound is reduced by a plurality of times compared with that of a single thiasen manganese or thiasen zinc compound.
The new Saisen manganese zinc compound is easier to prepare than the Saisen manganese or Saisen zinc anhydrous substance, the preparation temperature of the product of the invention is greatly lower than that of the Saisen manganese or Saisen zinc anhydrous substance of examples 2 and 3 in a comparative document (the comparative document, pesticide for preventing and treating bacterial diseases of crops, CN: 1109500), and the invention is beneficial to saving time and energy consumption.
This reflects that the new thiasen manganese zinc compound or compound with better stability has better availability in the production process and lower energy consumption advantage, 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 new thiasen manganese zinc compounds or complexes of the present invention are easier to prepare than the formulations of thiasen manganese or thiasen zinc anhydrate.
The new compound has no efflorescence phenomenon but has good sliding property, and the pharmaco tends to select a drug form with better stability from the bulk drugs, namely the compound with better stability tends to be selected as the bulk drug from the past.
2. Comparative experiment for quality controllability of preparation
The accuracy of the content of the original pesticide of the pesticide preparation has an important effect on a control tool for preventing crop diseases, the content of each bag of the preparation cannot have absolute equality due to errors of the loading amount and the like in the preparation process of the preparation, therefore, a quality range is set in the quality control of the preparation (for example, the marking amount of the main pesticide is often set to be 90-110%) to control the content index and the like of the preparation, if the original pesticide absorbs moisture to cause inaccurate weighing, the content of the finished product of the preparation must be controlled to be 90-110% of the legal marking amount of the anhydrous main pesticide, and the reject ratio of the finished product can be greatly improved. Under the conditions of RH62 + -5% and 25 + -2 ℃, the raw materials of the new thiasen manganese-zinc compounds with determined contents and the anhydrous raw materials of the phylline dimanganese and the phylline dimanganese which have determined contents and meet the molecular structure proportion of examples 1-1A, 1-3A and 1-5A [ the raw material mixture of the phylline dimanganese and the phylline dimanganese (molar ratio is 1: 1), the raw material mixture of the phylline dimanganese and the phylline dimanganese (molar ratio is 8: 2) and the raw material mixture of the phylline dimanganese and the phylline dimanganese (molar ratio is 2: 8) ] with different sources are respectively dispersed and spread to form a thickness of about 5 mm and are exposed in the air for 24 hours, then samples are respectively weighed according to the predetermined contents, and the preparation with the main drug indication amount of 90-110% (the content specification is 20g of the thiasen manganese-zinc per bag is prepared according to the method of the embodiment 8 in the present, the marked amount of manganese is calculated by the theoretical content of manganese), when the raw material medicament is accurately weighed by 100 percent of the marked amount of the main medicament anhydride, namely 2000 g of Saisen manganese zinc with the same weight is added according to the absolute anhydride calculation for preparing 100 bags of unit preparations, the rest auxiliary materials and the mixture ratio are the same. The content of manganese and zinc in each bag of Thisen manganese-zinc preparation is measured by randomly taking 40 bags with qualified weight difference in the finished product of the final preparation (the content of manganese and zinc in the sample is measured by the method of reference in the following literature: Aliskiu. Abu, Aliskizi. Aili, Wang Asahi. flame atomic absorption spectrometry is used for measuring copper, iron, manganese and zinc [ J ] in fennel, the spectral laboratory, 2012, 29 (04): 2357. 2359.; Zhang, Hu national, flame atomic absorption spectrometry is used for measuring zinc, copper, manganese [ J ] in water shield, the proceedings of Wuhan chemical institute of technology, 1997 (03): 15-17.; the sample is pretreated by dissolving with aqua regia composed of nitric acid and hydrochloric acid), the content of manganese in each bag of Thisen manganese-zinc preparation exceeds the marked amount (the content is 20 g/bag, (the content of Thisen manganese or zinc is unqualified, and the content of manganese or zinc is marked by the theoretical content of 90-110 percent), the experimental results are shown in table 2 below.
TABLE 2 comparative experimental results on the controllability of the preparation
Figure BDA0001918187580000071
The two experimental results show that the sample prepared by the bulk drug of the embodiment method has no unqualified condition, the yield of the Thiessen manganese zinc new compound or the compound is far higher than that of the Thiessen manganese zinc anhydrous raw material when the solid preparation is prepared, and the sterilization capability of the Thiessen manganese zinc new compound or the compound is reduced when the content of the main drug of the preparation is reduced, so that the Thiessen manganese zinc new compound is unfavorable for preventing and treating the germs of crops.
The invention not only prepares a stable new Thisen manganese zinc compound, but also provides a composition of the new compound, the bactericidal active compound composition contains a new Thisen manganese zinc compound or a compound A and any one of other known bactericidal active or antiviral drug compounds B, and the novel Thisen manganese zinc compound or the compound A is applied to preventing and treating 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 Saisen manganese zinc compound is used for preparing a pharmaceutical composition or a pesticide composition which comprises an effective dose of the Saisen manganese zinc compound, an effective dose of a bactericidal drug or an antibacterial drug or an antiviral drug, or a plant growth regulator or an effective dose of a pesticide acceptable in pesticides, and other pharmaceutically acceptable auxiliary materials to prepare a pharmaceutically acceptable pesticide preparation; namely, preparing a new pharmaceutical composition or a pesticide composition from an effective dose of a new Saisen manganese Zinc compound as an active ingredient A and an effective dose of an 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 compounds selected from B.1) -B.13) and pharmaceutically acceptable salts or solvate compounds thereof (the active ingredient B is selected from pesticide compounds in the following references, 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 Fungicide, chemical industry Press, 2017, Beijing; c: zheng Gui Ling, Sun Jia Long, the modern pesticide application technology series: volume of insecticides, chemical industry publishers, 2017, Beijing; d: sunjilong, modern pesticide synthesis technology, published by chemical industry publishers, 2011, Beijing; e: a modern pesticide handbook, Liu Chang Liang, Yang Ji Chun, chemical industry Press, 2018, Beijing; document F: the Liu Chang Ling master code, world pesticides: volume of bactericides, press of chemical industry, beijing, press time: 2006; document G: liu Chang Shu (national pesticide universities): volume of insecticides, chemical industry publishers, beijing, 2012; ) (ii) a
B.1) a strobilurin fungicide or an antiviral agent selected from one or more of azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, enestroburin, fluoxastrobin, picoxystrobin, kresoxim-methyl, enestroburin or metominostrobin, phenamaclurex, Picarbitrazox, orysastrobin, pyraclostrobin, coumoxystrobin, cloxacarb, pyraclostrobin, UBF307, KZ165, probenazole, diclosamide and the like;
b.2) triazole fungicide, which is selected from one or more of difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, hexaconazole, myclobutanil, penconazole, propiconazole, tetraconazole, triadimenol, bitertanol, triadimefon, metconazole, ipconazole, prothioconazole, imazazole, triticonazole, cyproconazole, meperfluorfen (mefenrifluconazole), iprifluorazole, triflumizole, fenbuconazole, fluquinconazole, furconazole, penconazole, etaconazole, triflumizole, diniconazole, triadimefon and the like;
b.3) an amide fungicide selected from one or more of metalaxyl, metalaxyl-M, flutolanil, mandipropamid, boscalid, fluopyram, carboxin, Bixafen, penflufen, epoxiconazole, Fluxapyroxad, penthiopyrad, thifluzamide, fluopicolide and isopyrazam, fluofen, fluoxafen, cycloflusulfamide, methiavalicarb, benalaxyl-p-ethyl, thifluzamide, tiadinil, ethaboxam, silthiopham, fluvalicarb-isopropyl, fenpyrad-isopropyl, zoxamide, fenhexamid, cyprodinil, flusulfamide, metosulam, oryzamide, Bixafen, Fluxapyroxad, Sedaxane and the like;
b.4) one of the imidazole bactericides is selected from one or more of cyazofamid, triflumizole, imazalil, fenamate, prothioconazole, phenylthioimidazole, thiabendazole, imazalil, fuberidazole, prochloraz manganese complex, prochloraz copper complex and the like;
b.5) dicarboximide bactericides selected from one or more of procymidone, iprodione, vinclozolin, captan, dimethachlon, tolclofos-methyl and the like;
b.6) carbamate bactericides selected from one or more of propamocarb hydrochloride, diethofencarb, benomyl, carbendazim, thiophanate-methyl, iprovalicarb, benthiavalicarb-isopropyl, valicarb-Valifenalate and the like;
b.7) antibiotic bactericide or antiviral agent selected from one or more of validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshengmycin, pesticide 120, aureonucleomycin, changchin, tetramycin, etc.;
b.8) oxazole bactericide selected from one or more of oxadixyl, hymexazol, famoxadone, pyrisoxazole, fluorothiazolepyrietone, benfurazolesulfone, dichloroazole and methanesulfonylazole;
b.9) morpholine bactericide or antiviral drug, which is selected from one or more of tridemorph, dimethomorph, flumorph, moroxydine hydrochloride and the like;
b.10) a pyrimidine bactericide which is selected from one or more of cyprodinil, pyrimethanil, ethirimol, mepanipyrim, fluopyram, dimoxystrobin, SYP-3773, SYP-3810 and the like;
b.11) quinoline bactericide, which is selected from one or more of dithianon, propoxymoline, phenoxyquinoline, quinoliflumein (quinoflulin) and the like;
b.12) dithiocarbamate bactericides or antiviral agents selected from one or more 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, dipheny phosphine, fosetyl-aluminium, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydrorosinate, fenpiclonil, fludioxonil, isolong vinyl ketoxime lactam, cnidium lactone, Dufulin, phenoconone, methiiramine, polyhexamethylene biguanide hydrochloride, bromothalonil, indazolesulfamide, copper nonyloconate, oxine-copper, moroxydine hydrochloride, copper succinate, xinafoate acetate, amino-oligosaccharin, lentinan, benziothiazolin, ethylicin, allibenzothiazole, diclorocyanid, emodin methyl ether, chrysophanol, fluzole activated ester, S-abscisin, amino-oligosaccharin, zinc pyridinates, berberine and pharmaceutically acceptable salts (such as berberine hydrochloride, berberine, etc.), eugenol, berberine, Sulfur, copper sulfate pentahydrate, copper oxychloride, copper hydroxide, basic copper sulfate, bismerthiazol, isolongifolenoxime lactam, allicin, guaiacol, quinolactaside, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, zinc thiazole hydrate, ametoctradin, Pyribencarb, Pyriofenone, fluthianil (OK-5203), Meptyldinocap, fenpyrzamine, Tolprocarb, isoflunamid, Isopyrazam, Penflufen, benzovindifiunfluor (545192), Tebufloquin, Oxathiapiprolin, spiroxamine, spirocyprodinil, fosetyl aluminum, iprobenfos, matrine, kurarinone, thiabendazole copper or its hydrate, thiencoppen or its hydrate, benzophenone, fluorodipivoxil, methyl jasmonate, and the like; or the plant growth regulator is selected from one or more of diethyl aminoethyl hexanoate, forchlorfenuron, compound sodium nitrophenolate, brassin, gibberellin, 6-benzylaminopurine, triacontanol, naphthylacetic acid or medicinal salt thereof, paclobutrazol, ethephon, methyl naphthylacetate, fluroxypyr, trinexapac-ethyl, uniconazole, indolebutyric acid, pyridinol, trinexapac-ethyl, chlormequat-ethyl, brassin lactone, producin, glyphosate and the like;
the pesticide is selected from but not limited to chlorfluazuron, tefluazuron, chlorfluazuron, flufenoxuron, hexaflumuron, flucycloxuron, chlorfluazuron, chlorbenzuron, diflubenzuron, diafenthiuron, hydrazine, buprofezin, fenoxycarb, fenoxanil, pyrazofos, methyl parathion, chlorzophos, pyridaphethione, quinalphos, fosthiazate, diazinon, phoxim, fenitrothion, pirimiphos, fenprophos, fenacet, profenofos, chlorpyrifos-methyl, prothioconazole, profenofos, methidathion, carbosulfan, valacyclovir, fenobucarb, isoprocarb, carfentrazone, pirimicarb, metolcarb, carbaryl, methiocarb, methomyl, metolcarb, metominostrobin, cyhalothrin, bifenthrin, fenpropathrin, cypermethrin, fenpropathrin, pyraflufen, pyraclofen, Any one or more of beta-cypermethrin, deltamethrin, tetrabromthrin, ethofenprox, or pentathrin, abamectin, emamectin benzoate, ivermectin, or pharmaceutically acceptable salts thereof (active ingredient B is selected from but not limited to insecticide or acaricide in document A, C, D, E, G, document A: Liuchang, Ministry of Chaibaoshan, creation and synthesis of new pesticide, chemical industry Press, 2013, Beijing, document C: Zhenggui Ling, Sunjilong, modern pesticide application technology book: insecticide roll, chemical industry Press, 2017, Beijing, D: Sunjilong, modern pesticide synthesis technology, chemical industry Press publication, 2011, Beijing, E: modern pesticide, Liuchang, Yangyuchun, chemical industry Press, 2018, Beijing, Changhou, Changhuang, world pesticide roll, chemical industry publishers, beijing, 2012; ).
The composition of the novel thiflusenmanganese zinc compound contains an active ingredient A and any one active ingredient B selected from but not limited to azoxystrobin, kresoxim-methyl, pyraclostrobin, enestroburin, trifloxystrobin, pyraclostrobin, fluoxastrobin, kresoxim-methyl, alkene oxime amine or metominostrobin, cyhalostrobin, Picarbitrazox, trifloxystrobin, pyraclostrobin, coumoxystrobin, clopicolinate, UBF307, KZ165, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, cyproconazole, penconazole, propiconazole, tetraconazole, triadimenol, bitertanol, triadimenol, metconazole, ipconazole, prothioconazole, imazamide, triticonazole, cyproconazole, metalaxyl, flutolanilide, mandipropamid, picolide, fluopyram, fluoxafen, cyhalofenamid, cyazofamid, triflumizole, fenamidone, oxpoconazole, oryzalin, procymidone, iprodione, vinclozolin, captan, dimethomorph, propamocarb hydrochloride, benomyl, carbendazim, thiophanate-methyl, valvacarb, benthiavalicarb, validamycin, streptomycin sulfate, kasugamycin, promethamycin, hymexazol, famoxadone, pyrisoxazole, tridemorph, dimethomorph, flumorph, cyprodinil, pyrimethanil, ethaboxam, flufenamid, dithianon, propoxymine, phenoxyquinoline, metiram, thiram, ziram, amobam, zineb, maneb, mancozeb, propineb, diphenphos, fosetyl-Al, chlorothalonil, isoprothiolane, or copper hydroxide, copper rosinate, copper dehydroabietate, fenpiclonite, fludioxonil, prochloraz complex, prochloraz, proc, Osthole, dianisidine, validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshenmycin, nong antibiotic 120, aureonycin, chanchmycin, kasugamycin, Dufulin, phenazon, prothioconazole, phenylbenzimidazole, fluroxypyr (mefentrifluoconazole, mefentrifluconazole), iprifluconazole (ipfentrifiunazole), fluthiazopyrazole, allylbenzothiazole, physcion, chrysophanol, fluthiazopyrazole, allylcyamide, coumarin, physcion, chrysophanol, fluxarates, dichlorooxazole and mestranilizole, S-abscisin, amino-oligosaccharin, zinc sulfate, berberine hydrochloride, berberine sulfate, berberine, danese, isofolenolide, longifolacin, guaiacol, guaiazulene, guaiazulone, guaiazulene, and other pharmaceutically acceptable salts thereof, Quinolacctacide, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, zinc metconazole hydrate, thifluzamide, tiadinil, ethaboxam, silthiopham, furametpyr, cyflufenamid, fluopicolide, zoxamide, fenhexamid, cyprodinil, sulfmate, sulfflusulfamide, fluxafluxapyroxad, Sedaxane, ametoctradin, Pyribencarb, fluthianil, Meptyldinocap, Pyriofenone, fepyrazamine, valifenamate, Tolprocarb, Isoflutam, Isopyrazam, penfluufun, Benzovindiflupyr (Benzovindiflupyr), tebufenquin, Oxifluorfen, trifloxystrobin, fluquinconazole, fenpropaquizamide, flufenacetrin, flufen, flufenacetrin, flufenacetrimonium, flufenim, famoxadone, Iprovalicarb, furilazole, azaconazole, epoxiconazole, triflumizole, tebuconazole, flufenoxuron, triflumuron, flucycloxuron, chlorfluazuron, chlorbenzuron, chlorfluazuron, diflubenzuron, diafenthiuron, pyrazofos, buprofezin, fenobucarb, fenobuconazole, pyrazofos, parathion-methyl, chlorpyrifos, pyridaphenthion, quinalphos, triazophos, fosthiazate, diazinon, phoxim, fenitrothion, pirimiphos-methyl, fenthion, fenitrole, profenofos-profenofos, chlorpyrifos-methyl, prothiofos, methidathion, dimethoate, malathion, methidathion, carbosulfan, fenobucarb, isoprocarb, or a pharmaceutically acceptable salt or solvent compound thereof, chlorfenapyr, The pesticide composition comprises triazamate, pirimicarb, metolcarb, mixed metolcarb, carbaryl, methiocarb, methomyl, or thiodicarb, cyhalothrin, cyfluthrin, bifenthrin, fenpropathrin, fenvalerate, cypermethrin, beta-cypermethrin, deltamethrin, tetrabromthrin, ethofenprox, or pentothrin, abamectin, emamectin benzoate, ivermectin or pharmaceutically acceptable salts thereof, and the weight ratio of the active component A to the active component B is preferably 1: 80-80: 1, and more preferably 1: 60-60: 1.
The Saisen manganese zinc new compound is used for preparing a pharmaceutical composition containing the Saisen manganese zinc new compound, and the new 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 agents, wettable powder, granules, dispersing granules, tablets, effervescent tablets, microcapsules, water dispersible granules, suspending agents, suspoemulsions, aqueous emulsions, microemulsions, emulsifiable solutions, controlled-release or sustained-release preparations (sustained-release or controlled-release tablets or capsules, sustained-release or controlled-release pellets, or sustained-release or controlled-release granules), microcapsule preparations, oil suspending agents, dispersible agents (DC), seed treatment dry powder, seed treatment dispersible powder, granules, dispersing granules, microcapsule suspending agents, seed treatment microcapsule suspending agents or suspended seed coatings 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 Saisen manganese zinc compound or the application of the pharmaceutical composition thereof is the application in preparing 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.
The thiasen manganese zinc new compound has a unique action mechanism, and in the thiasen manganese zinc sterilization mechanism, the thiasen manganese zinc new compound has a unique prevention effect of a thiazole group on bacteria (the thiazole group is a high-efficiency therapeutic agent in a plant body), has excellent prevention and treatment effects of zinc ions and manganese ions on fungi and bacteria, has good internal absorption performance, and has double effects of good treatment and protection. The duration of the drug effect is determined, and the duration of the 30% suspension of the new Thiessen manganese-zinc compound can reach 10-14 days under the common dosage.
The bactericidal composition has a very remarkable synergistic effect. According to the fact that the sterilizing effect of the new thiasen manganese zinc compound, namely the component A and the component B, of the sterilizing composition is greater than the sum of the sterilizing effect of the new thiasen manganese zinc compound, namely the component A and the component B, the synergistic effect of the sterilizing 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 (oxazolyl) one bactericide of the 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, Pseudomonas, Erwinia among pathogenic bacteria; ascomycetes in pathogenic fungi: venturia, Erysiphe, Sclerotinia; basidiomycetes in pathogenic fungi: ustilago, gibberella; oomycetes in pathogenic fungi: phytophthora, Plasmopara; fungi imperfecti in pathogenic fungi: rhizoctonia, Botrytis, Pyricularia, Cercospora, Helminthosporium, anthrax, etc.
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 strains; cucumber bacterial leaf blight, cabbage black rot, citrus canker and the like caused by xanthomonas strains; chinese cabbage soft rot and pear fire blight caused by Erwinia strains; epidemic diseases of potato and tomato caused by phytophthora; grape downy mildew caused by monascus strains and the like; powdery mildew caused by Erysiphe strains such as tobacco, sesame, sunflower and melon; gibberellic disease and bakanae disease of rice of various graminaceous plants such as barley, wheat and corn caused by gibberellic strains; scab of apple caused by scab bacteria; various plant sclerotinia diseases caused by sclerotinia species, etc.; wheat smut caused by smut bacteria; gray mold of various plants caused by Botrytis strains, etc.; rice blast caused by Pyricularia species; cercospora species cause sugar beet brown spot, peanut brown spot, etc.; corn small spot, rice flax leaf spot and other diseases caused by Helminthosporium strain; rhizoctonia strains causing cotton blight and rice sheath blight, etc.; anthracnose of various fruit trees and vegetables such as apples, pears, cotton, grapes, white gourds, cucumbers, hot peppers, eggplants and the like caused by anthrax bacteria; 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.
The novel compound or the bactericidal composition thereof is selected from one or more of bacterial wilt, bacterial angular leaf spot, soft rot, canker, 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, black ear disease, fusarium wilt, black spot, scab, ring spot, brown spot, root rot, basal rot, wildfire, ginger temperature, sand skin disease, sclerotinia rot, fusarium wilt or scab take-all, zinc-deficient yellowing leaves, lobular disease, inactivated virus, bakanae disease, bacterial perforation or other diseases of zinc deficiency or manganese deficiency.
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; 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 crops such as tobacco, tea, cocoa, cotton, or zinc and or manganese deficient; 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.
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 Thiessen manganese zinc new compound, and the formula B is any one or more of the active compounds of the bactericidal or antiviral drugs or the plant growth regulators selected from the B.1) to the 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, 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 suspended seed coating agent, etc.
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, Geropon T/36 and Geropon T/72 (polycarboxylates) from Solvay (Sorovi) Inc. (Prodi), 2) Terspese 2700 (polyacrylic acid graft copolymer), Terspese 2735 (polyacrylic acid graft copolymer, liquid) and Terspese 2100 from Huntsman, 3) Yos-WG 5 (polycarboxylates) from Takemoto (bamboo oil & fat Co., Ltd.), CH7000 (white liquid), Yos-WG 5, Yos-WP 1.4) Atlox 13 (copolymer of methyl methacrylate/methyl acrylate and polyethylene) from Croda (Po) Inc., Atlox-styrene copolymer of Atlox 550S (modified acrylic acid-styrene copolymer of methyl methacrylate and polyethylene), and Aklan PA 2/20 (acrylic acid homopolymer) of BASF (Baslon) and SP 5 (polyacrylic acid graft polycarboxylate), the modified polycarboxylate copolymer of polyacrylic acid polyacrylate Na PA 2/20 (acrylic acid homopolymer) from Astroson No. 11, No. SP 5) BASF (Bayssopen polycarboxylate) (Nonson Nonspro-Ph) (Nonsp 27, No. 11, No. 7, No. 11, No. 8, No. 2-Gersten Polycarboxil 2000 from Takeson & gt 27, No. 11, No. 23, No. 8, No. 11, No. 8, No. 5, No. 8, No. 5, No. 8, No. 5, No. 8, No. 5, No. 8, No. 5, No. 8, No. 5, No. 8, No. 5.
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 S L X, Tanaform S, tanaformAF 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, L M-110, JH-935 and the like), N-type defoaming agents, sucrose fatty acid esters, fatty alcohol defoaming agents, complex type defoaming agents and the like which are pharmaceutically acceptable.
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 fully exert the characteristics of high efficiency of the new Thiessen manganese zinc compound on bacterial diseases, universal effectiveness on fungal diseases and good protective performance of the new Thiessen manganese zinc compound;
2. the bactericidal composition consists of active ingredients with different action mechanisms, can effectively slow down the resistance generation of diseases, and reduces the resistance risk caused by the single use of a Thisen manganese zinc new compound or any other known active compound;
3. the bactericidal composition can improve the antibacterial or bacteriostatic effect, expand the disease prevention spectrum, simultaneously play a good role in preventing or treating bacterial diseases and partial fungal diseases of crops, reduce the frequency of medication and relieve 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, promote the growth of plants and improve the stress resistance and disease resistance.
Drawings
FIG. 1 shows Thisen manganese zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]Thermogram spectrum of hydrate (example 1-2A)
FIG. 2 shows Thisen manganese zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]Infrared spectrum of hydrate (example 1-2A)
FIG. 3 shows Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]Thermogram spectrum of hydrate (example 1-2A)
FIG. 4 shows Thisen manganese zinc [ C ]5H4N6S4(Mn)0.8(Zn)0.2]Thermogram spectrum of hydrate (examples 1-4A)
FIG. 5 shows Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.8(Zn)0.2]Infrared spectrum of hydrate (example 1-4A)
FIG. 6 shows Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.2(Zn)0.8]Thermogram spectrum of hydrate (examples 1-6A)
FIG. 7 shows Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.2(Zn)0.8]Infrared spectrum of hydrate (examples 1-6A)
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 separating a valuable content or purity level of a compound, including but not limited to greater than 90%, 95%, 96%, 97%, 98%, and 99% content or purity levels, which may be determined by high performance liquid chromatography, L C-MS, flame atomic absorption spectroscopy, 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.
The "ranges" disclosed herein are in the form of lower and upper limits. There may be one or more lower limits, and one or more upper limits, respectively. The given range is defined by the selection of a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular range. All ranges that can be defined in this manner are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 50-100 and 80-120 are listed for particular parameters, with the understanding that ranges of 50-100 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and or 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and/or 2-5.
In the present invention, unless otherwise specified, "suitable amount" means a preferred or optimal amount or mass or weight or volume or the like required to complete 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.
In the present invention, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 10" indicates that all real numbers between "0 to 10" have been listed herein, and "0 to 10" is only a shorthand representation of the combination of these numbers.
In the present invention, unless otherwise indicated, the integer numerical range "a-b" represents a shorthand representation of any combination of integers between a and b, where a and b are both integers. For example, the integer numerical range "1-N" means 1, 2.
The term "a" or "an" as used herein means "at least one" if not otherwise specified.
All percentages (including weight percentages) stated herein are based on the total weight of the composition, unless otherwise specified. In the present invention, the sum of the percentages of the components in all compositions is 100%, unless otherwise specified.
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 163 ℃, and increasing the temperature rise speed: 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. The dried sample bottles were filled with approximately 0.05-0.2g of sample, the remainder being handled as specified in the instrument instructions.
The infrared spectrum is potassium bromide tablet, the infrared spectrum data of the sample is measured, and the used instruments comprise a United states thermoelectricity company NICO L ET 5700 FTIR Spectrometer, a Nexus intelligent Fourier transform infrared Spectrometer (ThermoNicolet) and the like, the name of the Infrared Spectrometer instrument company is United states thermoelectricity company NICO L ET 5700 FTIR Spectrometer, the using function is that the middle infrared is 4000-.
Thermal analysis method test conditions: setsys 16, Setaram corporation, sample size about 3-10mg, 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 below the weight loss plateau of the thermogram (TG-DTA or TG-DSC) showing the crystalline hydrate of thiesenesenza, e.g., the 1 hydrate thereof.
Powder X-ray diffraction method Using D8Advance X-ray diffractometer from Bruker, Germany, Voltage: about 30-60kv, current: about 30-100mA, scanning speed: 10 deg/min, copper target, wavelength
Figure BDA0001918187580000182
: 1.54, diffraction angle 2 theta, scanning range 3-60 degrees, and measuring the powder X-ray diffraction pattern of the sample, wherein all peak positions are within +/-0.2 degrees 2 theta; the drawings and data in this specification are mutually attested. Some compounds appear amorphous and some polymorphic under the copper target. Example 1-2A thiesen manganese zinc crystalline hydrates of the present invention may have corresponding characteristic values at locations including the following 2 θ ± 0.2 values:
Figure BDA0001918187580000181
Figure BDA0001918187580000191
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1-1A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]Preparation of novel compounds
Adding 8.349g of phyllidium lactone (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 2.45g of sodium hydroxide solution dissolved in a proper amount of water, stirring for dissolving, then adding 2.535g of manganese sulfate monohydrate (0.015mol) and 4.314g of zinc sulfate heptahydrate (0.015mol) solution dissolved in a proper amount of water, precipitating in ten minutes, stirring for half an hour at about 40 ℃, taking out, standing for cooling, performing suction filtration, washing the solid with a small amount of water until sulfate ions do not exist, performing suction filtration, spreading the obtained solid, performing forced air drying at about 50 ℃ for about 4 hours to obtain 8.2g of brown gray solid; the melting point is more than 290 ℃; theoretical value of elemental analysis: c17.84%, H1.20%, N24.97%, S38.11%; measured value: 17.72% of C, 1.13% of H, 24.82% of N and 38.23% of S; content analysis (atomic absorption spectroscopy): mn8.21% (theoretical value 8.16%), Zn9.63% (theoretical value 9.71%)
Example 1-2A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.5(Zn)0.5]Preparation of hydrates
Adding 8.349g of phyllidium lactone (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 2.45g of sodium hydroxide solution dissolved in a proper amount of water, stirring for dissolving, then adding 2.535g of manganese sulfate monohydrate (0.015mol) and 4.314g of zinc sulfate heptahydrate (0.015mol) solution dissolved in a proper amount of water, stirring for half an hour at about 35 ℃, taking out, standing for cooling, performing suction filtration, washing the solid with a small amount of water until sulfate ions do not exist, performing suction filtration, spreading the obtained solid, and performing forced air drying for about 4 hours at about 50 ℃ to obtain 8.2g of brown gray solid; the melting point is more than 280 ℃; the moisture content was 5.42% by the Karl method (within the error range of 5.08% from the theoretical value of 1 hydrate); thermal analysis: the platform weight loss is about 5.63% (see figure 1), and a corresponding endothermic peak (DTA) is provided under the weight loss platform; infrared spectrum (v)KBr maxcm-1) (see FIG. 2): 3373.8, 3277.4, 3175.9, 1612.3, 1508.9, 1434.3, 1390.4, 1346.4, 1124.1, 1079.6, 1050.1, 998.7, 757.3, 706.8, 627.9, 504.5; x powder diffraction: a plurality of distinct characteristic peaks (powder X-ray diffraction, see figure 3) measured at diffraction angle 20 over a range of 3-60 ° are about: 8.21,9.86, 10.55, 13.34,13.82, 15.49, 15.97, 17.75, 19.15, 19.78, 20.74, 22.28, 22.56, 22.95, 23.71, 24.33, 24.92, 25.36, 26.18, 27.97, 29.82, 30.80, 31.29, 33.13, 35.78, 36.30; elemental analysis: theoretical value: c17.33%, H1.75%, N24.25%, S37.01%; measured value: 17.22% of C, 1.82% of H, 24.13% of N and 37.12% of S; content analysis (atomic absorption spectroscopy): mn7.89% (theoretical 7.93%), Zn9.38% (theoretical 9.43%)
Examples 1-3A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.8(Zn)0.2]Preparation of the Compounds
Adding 8.349g of phyllidium lactone (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding a 5% sodium hydroxide solution, stirring to ensure that the solid is just dissolved, then adding 4.056g of manganese sulfate monohydrate (0.024mol) and 1.726g of zinc sulfate heptahydrate (0.006mol) dissolved in a proper amount of water, stirring for half an hour at about 40 ℃, taking out, standing, cooling, carrying out suction filtration, washing the solid with a small amount of water until sulfate ions do not exist, carrying out suction filtration, spreading the obtained solid, and drying by air blowing at about 50 ℃ for about 4 hours to obtain 8.2g of brown gray solid; the melting point is more than 280 ℃; theoretical value of elemental analysis: 18.01% of C, 1.21% of H, 25.21% of N and 38.47% of S; measured value: 18.12% of C, 1.29% of H, 25.13% of N and 38.55% of S; content analysis (atomic absorption spectroscopy): mn13.15% (theoretical 13.18%), Zn3.87% (theoretical 3.92%).
Examples 1-4A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.8(Zn)0.2]Preparation of hydrates
Adding 8.349g of phyllidium lactone (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 8% sodium hydroxide solution, stirring to enable the solid to be just dissolved, then adding 4.056g of manganese sulfate monohydrate (0.024mol) and 1.726g of zinc sulfate heptahydrate (0.006mol) dissolved in a proper amount of water, stirring for half an hour at about 35 ℃, taking out, standing, cooling, carrying out suction filtration, washing the solid with a small amount of water until sulfate ions do not exist, carrying out suction filtration, spreading the obtained solid, and drying for about 4 hours at about 50 ℃ by blowing to obtain 8.2g of brown gray solid; the melting point is more than 280 ℃; the water content is 5.68 percent by Karl method; thermal analysis: weight loss of the platform of about 5.72%, (See fig. 4), with a corresponding endothermic peak (DTA) under the weightless plateau; infrared spectrum (v)KBr maxcm-1) (see FIG. 5): 3294, 1609, 1522, 1367.4, 1246.6, 1128, 1044, 756.9, 691.9, 617.8; content analysis (atomic absorption spectroscopy): 12.46 percent of Mn12 and 3.65 percent of Zns.
Examples 1-5A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.2(Zn)0.8]Preparation of
Adding 8.349g of phyllidium bicolor (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 8% sodium hydroxide solution, stirring to enable the solid to be just dissolved, then adding 1.014g of manganese sulfate monohydrate (0.006mol) and 6.902g of zinc sulfate heptahydrate (0.024mol) dissolved in a proper amount of water, stirring for half an hour at about 30 ℃, taking out, standing, cooling, carrying out suction filtration, washing the solid with a small amount of water until the filtrate has no sulfate ions, carrying out suction filtration, spreading the obtained solid, and drying for about 4 hours at about 50 ℃ by blowing to obtain 8.2g of brown gray solid; the melting point is more than 280 ℃; infrared spectrum (v)KBr maxcm-1): (ii) a Theoretical value of elemental analysis: c17.68%, H1.19%, N24.74%, S37.76%; measured value: c17.53%, H1.29%, N24.61%, S37.83%. Content analysis (atomic absorption spectroscopy): mn3.15% (theoretical value 3.23%), Zn15.37% (theoretical value 15.40%)
Examples 1-6A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.2(Zn)0.8]Preparation of hydrates
Adding 8.349g of phyllidium bicolor (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 8% sodium hydroxide solution, stirring to just dissolve the solid, adding 1.014g of manganese sulfate monohydrate and 6.902g of zinc sulfate heptahydrate (0.024mol) dissolved in proper amount of water, stirring for half an hour at about 38 ℃, taking out, standing, cooling, performing suction filtration, washing the solid with a small amount of water until the filtrate has no sulfate ions, performing suction filtration, spreading the obtained solid, and performing forced air drying at about 60 ℃ for about 4 hours to obtain 8.2g of brown gray solid; the melting point is more than 260 ℃; the water content is 6.67 percent by Karl Fischer's method; thermal analysis: the platform weight loss is about 6.62% (see figure 6), and the corresponding endothermic peak (DTA) is provided under the weight loss platform; infrared spectrum (v)KBr maxem-1) (see FIG. 7): 3295.6, 3177.6, 1609.3, 1523.6, 1400.0, 1367.2, 1245.8, 1131.1, 1049.2, 763.4, 689.5, 632.7, 509.4; content analysis (atomic absorption spectroscopy): mn3.06%, Zn14.32%.
Examples 1-7A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.3(Zn)0.7]Preparation of crystalline hydrates
Adding 8.349g (calculated by bisultap) of a bisultap v-type compound (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding a proper amount of a 10% sodium hydroxide aqueous solution, stirring to be just dissolved, then adding 1.782g of manganese chloride 4 hydrate (0.009mol) and 6.04g of zinc sulfate heptahydrate (0.021mol) dissolved in a proper amount of water, stirring for half an hour at room temperature, taking out, standing, cooling, performing suction filtration, washing the solid with a small amount of water until the filtrate has no sulfate ions, performing suction filtration, spreading the obtained solid, performing forced air drying at about 60 ℃ for about 4 hours, and standing at room temperature for 1 day to obtain 8.1g of a brown solid; the melting point is more than 250 ℃; the water content is 9.25% by Karl Fischer's method; thermal analysis: the platform weight loss is about 9.31%, and a corresponding endothermic peak (DTA) is arranged under the weight loss platform; content analysis (atomic absorption spectroscopy): mn4.38 percent and Zn12.23 percent.
Examples 1-8A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.1(Zn)0.9]Preparation of the Compounds
Adding 8.349g (calculated by phyllidium) of phyllobium nu type compound (0.03mol) into a 250ml flask at room temperature, adding 30ml of water, stirring, adding 8% sodium hydroxide solution, stirring to ensure that the solid is just dissolved, then adding 0.594g of manganese chloride 4 hydrate (0.003mol) and 7.765g of zinc sulfate heptahydrate (0.027mol) dissolved in a proper amount of water, stirring for half an hour at room temperature, taking out, standing, cooling, carrying out suction filtration, washing the solid with a small amount of water until the filtrate has no sulfate ions, carrying out suction filtration, spreading the obtained solid, and drying for about 4 hours by air blowing at about 100 ℃ to obtain 7.9g of brown gray solid; the melting point is more than 260 ℃; theoretical value of elemental analysis: 17.62% of C, 1.18% of H, 24.66% of N and 37.64% of S; measured value: 17.50% of C, 1.26% of H, 22.53% of N and 37.71% of S; content analysis (atomic absorption spectroscopy): mn1.56% (theoretical 1.61%), Zn17.21% (theoretical 17.27%).
Examples 1-9A Thisen manganese Zinc [ C ]5H4N6S4(Mn)0.9(Zn)0.1]Preparation of hydrates
Adding 8.349g of phyllidium bicolor (0.03mol) into a 250ml flask at room temperature, adding 35ml of water, stirring, adding 6% sodium hydroxide solution, stirring to ensure that the solid is just dissolved, then adding 5.344g of manganese chloride 4 hydrate (0.027mol) and 0.863g of zinc sulfate heptahydrate (0.003mol) dissolved in proper amount of water, stirring for half an hour at room temperature, taking out, standing, cooling, performing suction filtration, washing the solid with a small amount of water and ethanol until the filtrate has no sulfate ions, performing suction filtration, spreading the obtained solid, and performing forced air drying at about 55 ℃ for about 4 hours to obtain 7.8g of brown gray solid; the melting point is more than 250 ℃; infrared spectrum (v)KBr maxcm-1)：3294.3，3176.2，1608.2，1523.1，1400.7，1368.5，1245.4，1131.6，1048.5，763.2，689.3，632.6，509.2。
Examples 1-10A: thisen manganese zinc compound [ C ]5H4N6S4(Mn)0.7(Zn)0.3]Or a hydrate thereof, with reference to example 1-1A or reference example 1-2A; examples 1-11A: [ C ]5H4N6S4(Mn)0.65(Zn)0.35]Or hydrates thereof, are prepared according to examples 1-3A or examples 1-3A; example 2: [ C ]5H4N6S4(Mn)0.6(Zn)0.4]Or hydrates thereof, with reference to examples 1-5A or examples 1-5A; example 3: [ C ]5H4N6S4(Mn)0.4(Zn)0.6]Or a hydrate thereof, according to the corresponding method as in reference example 1-1A or reference example 1-2A; thisen manganese zinc compound [ C ]5H4N6S4(Mn)0.7(Zn)0.3]、[C5H4N6S4(Mn)0.65(Zn)0.35]、[C5H4N6S4(Mn)0.6(Zn)0.4]、[C5H4N6S4(Mn)0.4(Zn)0.6]、[C5H4N6S4(Mn)0.3(Zn)0.7]、[C5H4N6S4(Mn)0.2(Zn)0.8]、[C5H4N6S4(Mn)0.8(Zn)0.2]The hydrate has a water content of about 1.5-15.0%.
Example 4: preparation of wettable powder
40% Thisen manganese zinc hydrate (prepared by the method of example 1-2A), 1.0% sodium salt of a naphthalenesulfonic acid condensate, 4.0% of a polymeric polycarboxylate, 2.0% of talc, 5.0% of light calcium carbonate, and kaolin were thoroughly mixed to a total of 100%, and then the mixture was subjected to ultrafine pulverization to a certain particle size to obtain a wettable powder. The wettable powder contains 40 percent of Thisen manganese zinc hydrate.
Example 5: preparation of Water dispersible granules
60% of a Thisen manganese zinc new compound (calculated by weight of anhydrous substances), 3% of sodium dodecyl benzene sulfonate, 4% of polycarboxylate dispersant (SD-819), 5% of ammonium chloride, 5% of sodium carboxymethyl starch, 2% of methyl cellulose, 0.15% of xanthan gum, 4% of sodium sulfate, 4% of polyvinylpyrrolidone (PVP K-30), 0.1% of polyether modified organic silicon defoamer (DM-1090) and the balance of silica gel micropowder to 100%; a proper amount of pure water;
the preparation process comprises the steps of crushing raw medicines and auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-1090) according to the formula amount into 300-mesh-sieve-sieved powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-1090 by using a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for wet granulation, sieving by a 40-mesh sieve to prepare granules, drying at 50-60 ℃ for about 3 hours, sieving the solid granules by a 40-mesh sieve for finishing granules, and subpackaging the granules in bags by a subpackaging machine to obtain the water dispersible granules.
Example 6: preparation of Thiessen manganese zinc suspending agent
The preparation method comprises the steps of adding 20% of a Thisen manganese zinc new compound (prepared by the method of example 1-4A) (based on the weight of anhydrous substances), 4.0% of tallow ethoxy amine salt, 1.0% of sodium salt of naphthalene sulfonic acid condensate, 1.0% of sodium salt of 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 polyether defoamer and distilled water to 100%, sanding for 120 minutes in a sand mill, and filtering to obtain the suspending agent.
Example 7: preparation of Thiessen manganese zinc suspending agent
30% of a new thiseno manganese zinc compound (prepared by the method of example 1-6A) (based on the weight of anhydrous substances), 2.0% of phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt (601PT), 2% of nonylphenol polyoxyethylene ether (NP-10), 3% of urea, 0.15% of xanthan gum, 1% of magnesium aluminum silicate, 0.1% of a polyether modified organic silicon defoamer (DM198), 4003% of polyethylene glycol, 0.5% of potassium sorbate and pure water are added to 100%, and the mixture is put into a sand mill for sand milling for 120 minutes and filtered by a 60-mesh sieve to obtain the 20% 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 manganese zinc suspending agent can be sprayed on plants or crops by diluting 300-fold and 500-fold liquid with water.
Example 8: preparation of New Thisen manganese Zinc Compound Water dispersible granule (20% Thisen manganese Zinc)
20g of the Thiessen manganese zinc new compound (calculated by the weight of anhydrous substance), 3g of the dispersant for pesticide (2700), 5g of the sodium salt of the condensation polymer of alkyl naphthalene sulfonic acid, 2g of the wetting agent for pesticide (1004), 4g of ammonium sulfate, 10 g of soluble starch and calcium carbonate are weighed 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 Thisen manganese Zinc Dry suspension
The formula is as follows: 40% of Thisen manganese zinc new compound (by weight of anhydrous substance), 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), 0.3% of polyethylene glycol-8001% of calcium sodium EDTA 4 hydrate, and the balance of 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 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 10: preparation of thiasen manganese zinc azoxystrobin compound suspending agent
30% of Thisen manganese zinc new compound (by weight of anhydrous substance) and 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 organosilicon defoamer (tanoform AF) and 100% of pure water are added into a high-shear homogenizing emulsifying machine to be sheared at high speed for 20 minutes, then conveyed into a sand mill and sanded circularly for 3 times to obtain the compound suspending agent.
Example 11: preparation of thiasen manganese zinc trifloxystrobin compound dry suspending agent
The formula is as follows: 30% Thisen manganese Zinc New Compound (prepared by method 1-7A) and 20% Trifloxystrobin, urea 4%, sodium dodecyl sulfate 2%, lignosulfonate 5%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, Xanthan gum 0.2%, sorbitol 10%, methylcellulose 2%, polyether modified Silicone antifoam agent (DF-825) 0.1%, polyethylene glycol-20001%, 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 Thiessen manganese zinc new compound (based on the weight of anhydrous substance) 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 methyl naphthalene sulfonate formaldehyde condensate, 1.0% of octenyl succinic acid starch sodium, 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 added 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 manganese zinc fluorine thiazole pyrithylone compound dry suspending agent
The formula is as follows: 30% of thiasen manganese zinc new compound (by weight of anhydrous substance) and 10% of fluorothiazole pyrithylone, 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 organic silicon defoamer (DF-825), 10001% of polyethylene glycol and kaolin for making 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, 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 manganese zinc pyraclostrobin compound water dispersible granules
The formula is as follows: 30% of a Thisen manganese zinc new compound (by weight of anhydrous substance) and 20% of pyraclostrobin, 4% of urea, 5% of sodium carboxymethyl starch, 5% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 0.1% of xanthan gum, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 2% of sodium dodecyl sulfate, 4% of polyvinylpyrrolidone (PVP K-30), 0.1% of polyether modified organic silicon defoamer (DM-1090) and the balance of kaolin being 100%; a proper amount of pure water;
the preparation process comprises the steps of crushing raw medicines and auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-1090) according to the formula amount into 300-mesh-sieve-sieved powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-1090 by using a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for wet granulation, sieving by a 40-mesh sieve to prepare granules, drying at 50-60 ℃ for about 3 hours, sieving the solid granules by a 40-mesh sieve for finishing granules, and subpackaging the granules in bags by a subpackaging machine to obtain the water dispersible granules.
Example 15: preparation of compound pesticide suspending agent
32% of active compound [ 30% of Thisen manganese zinc new compound (by weight of anhydrous substance) 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 sulfonate 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 supplemented, the mixture is put into a high-shear homogenizing emulsifying machine to be subjected to high-speed shearing for 25 minutes, then the mixture is pumped into a sand mill to be subjected to sand milling for 90 minutes, and the mixture is filtered by a 60-mesh sieve, so that the.
Example 16: preparation of thiasen manganese zinc epoxiconazole water dispersible granule
The formula is as follows: 30% Thiessen manganese Zinc New Compound (by weight of anhydrate) and 5% epoxiconazole, Urea 4%, sodium carboxymethyl starch 5%, lignosulfonate 2%, polycarboxylate dispersant (SD-819) 4%, Xanthan gum 0.2%, sodium octenyl succinate starch 0.6%, methyl cellulose 2%, PVP K-304%, sodium lauryl sulfate 2%, DM-10900.1%, Kaolin to make up 100%; a proper amount of pure water;
the preparation process comprises the steps of crushing raw medicines and auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-1090) according to the formula amount into 300-mesh-sieve-sieved powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-1090 by using a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for bonding for wet granulation, sieving by a 40-mesh sieve for preparing granules, drying at 50-60 ℃ for about 3 hours, sieving the solid granules by a 40-mesh sieve for finishing granules, and subpackaging the granules in bags by a subpackaging machine to obtain the water dispersible granules.
Example 17: preparation of compound suspending agent
Adding 10% of Thisen manganese zinc new compound (by weight of anhydrous substances) and 40% of flusilazole, fatty alcohol polyoxyethylene ether 2.0%, xanthan gum 0.1%, tallow ethoxy amine salt 1.0%, polymeric polycarboxylate (Geropon T/36) 3.0%, phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt (601PT) 1%, dioctyl sulfosuccinic acid sodium salt 1.0%, urea 3.0%, DM 1930.1% and deionized water to 100%, adding into a high-shear homogenizing emulsifying machine, shearing at high speed for 20min, and homogenizing by using a high-pressure homogenizing machine to obtain the compound suspending agent.
Example 18: preparation of compound suspending agent
30% of Thisen manganese zinc 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 supplemented, put into a high-shear homogenizing and emulsifying machine for high-speed shearing 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 Thisen manganese zinc tebuconazole compound suspending agent
30 percent of Thiessen manganese zinc 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 Thisen manganese zinc new compound (prepared by the method of example 1-9A) (based on the weight of anhydrous substance) and 5% of hexaconazole composition ], polycarboxylate (SPED-300) 2%, acylglutamate 2.0%, fatty alcohol polyoxyethylene ether sulfate 1%, phenol sulfonic acid condensate sodium salt 1.0%, sodium methyl naphthalene sulfonate formaldehyde condensate 2.0%, sodium starch octenyl succinate 2.0%, xanthan gum 0.1%, epoxidized soybean oil 5.0%, glycerol 2.0%, organosilicon defoamer (Tanaform AF) 0.15%, pure water to 100%, putting into a high-shear homogenizing emulsifying machine for high-speed shearing for 25 minutes, pumping into a sand mill for 90 minutes, and filtering through a 60-mesh sieve to obtain the compound suspending agent.
Example 21: preparation of thiasen manganese zinc myclobutanil compound water dispersible granule
The formula is as follows: 30% Thisen manganese Zinc New Compound (by dry weight) and 12% myclobutanil, Urea 4%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, sodium carboxymethyl starch 5%, polyvinylpyrrolidone (PVP K-30) 4%, sodium lauryl sulfate 2%, xanthan gum 0.2%, sodium starch octenyl succinate 0.5%, methyl cellulose 2%, polyether modified silicone defoamer (DF-825) 0.1%, kaolin to 100%; a proper amount of water; the preparation process is the same as in example 16.
Example 22: preparation of compound composition suspending agent
30% of thiasen manganese zinc new compound (prepared by the method of example 1 and calculated by the weight of anhydrous substances) 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 high molecular 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, the mixture is put into a high-shear homogenizing emulsifying machine to be sheared at a high speed for 30 minutes, then the mixture is conveyed into a sand mill, and the compound suspending agent is obtained after 3 times of circular sand grinding.
Example 23: preparation of compound suspending agent
Adding 35% of Thiessen manganese zinc 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 (tanform AF), 0.9% of EDTA calcium sodium 4 hydrate and 100% of pure water into a high-shear homogenizing emulsifying machine for high-speed shearing for 30 minutes, then conveying the mixture into a sand mill, and circularly sanding for 3 times to obtain the compound suspending agent.
Example 24: preparation of compound suspending agent
30% of Thisen manganese zinc new compound and 5% of 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 methyl naphthalene sodium formaldehyde condensate, 2.0% of octenyl succinic starch sodium, 2.0% of glycerol, 0.1% of tanoform AF, 0.5% of EDTA calcium sodium 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 Thisen manganese zinc new compound, 10% of bitertanol, 2% of polycarboxylate (SPED-300), 2% of acyl glutamate, 1.0% of fatty alcohol polyoxyethylene ether, 1.0% of phenolsulfonic acid condensate sodium salt, 2% of 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 EDTA calcium sodium 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 Thiessen manganese zinc new compound (by weight of anhydrous substances) and 20% of Thiodiazole copper, 2% of polycarboxylate (SPED-300), 2.0% of acyl glutamate, 1.0% of fatty alcohol polyoxyethylene ether sulfate, 1.0% of phenol sulfonic acid condensate sodium salt, 2.0% of methyl naphthalene sodium formaldehyde condensate, 1.0% of sodium carboxymethyl cellulose, 2.0% of glycerol, DM1980.1 and pure water to 100%, adding the mixture into a high-shear homogenizing emulsifying machine, shearing at 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 Thiessen manganese zinc new 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
Adding 20.0% of Thisen manganese zinc new compound, 20.0% of flutolanil, 4.0% of fatty alcohol ethyl oxide, 1.0% of EO/PO block polyether, 1.0% of acrylic homopolymer sodium salt, 4.0% 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 polyether modified organic silicon defoamer (DM198) and 100% of pure water to 100%, adding the mixture into a high-shear homogenizing emulsifying machine, carrying out high-speed shearing for 30 minutes, conveying the mixture into a sand mill, and carrying out circulating sanding for 3 times to obtain the compound suspending agent.
Example 29: preparation of compound water dispersible granule
The formula is as follows: 30% Thiosen manganese Zinc New Compound (prepared by method 1-4A) and 21.2% Fluxapyroxad, sodium sulfate 4%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, sodium carboxymethyl starch 5%, polyvinylpyrrolidone (PVP K-30) 4%, sodium lauryl sulfate 2%, Xanthan gum 0.1%, starch sodium octenyl succinate 0.5%, Ethyl cellulose 2%, DM-1980.1%, calcium sodium EDTA 4 hydrate 0.5%, diatomaceous earth to 100%; a proper amount of pure water;
the preparation process comprises the steps of crushing the raw materials and the auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-198) according to the formula ratio into 300-mesh powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-198 with a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for bonding for wet granulation, sieving with a 40-mesh sieve for preparing granules, drying at 50-60 ℃ for about 3 hours, sieving with a 40-mesh sieve for finishing granules, and subpackaging in bags by a subpackaging machine to obtain the water dispersible granules.
Example 30: preparation of compound suspending agent
20 percent of thiasen manganese zinc new compound, 40 percent of thiabendazole, 3.0 percent of fatty alcohol ethoxy compound, 1.0 percent of alkyl naphthalene sulfonate, 4.0 percent of fatty alcohol polyoxyethylene ether sulfate, 3.0 percent of phenol sulfonic acid condensate sodium salt, 1.5 percent of methylene dinaphthalene sodium sulfonate, 0.5 percent of methyl naphthalene sodium formaldehyde condensate, polyethylene glycol-8001 percent, 0.15 percent of polyether modified organic silicon defoamer (DM198), 0.5 percent of EDTA calcium sodium, and distilled water which is supplemented to 100 percent are put into a high-shear homogenizing emulsifying machine to be sheared at high speed for 30min, and then the compound suspending agent is obtained after homogenizing by the high-pressure homogenizing machine.
Example 31: preparation of thiasen manganese zinc metalaxyl compound water dispersible granules
The formula is as follows: 30% of a Thisen manganese zinc new compound (by weight of the anhydride) and 15% of metalaxyl, 4% of urea, 4% of low-substituted hydroxypropyl cellulose, 2% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 2% of sodium lauryl sulfate, 0.2% of xanthan gum, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 0.1% of polyether modified silicone defoamer (DM-198), 0.5% of calcium sodium EDTA, the balance being 100%;
the preparation process comprises the steps of crushing the raw materials and the auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-198) according to the formula ratio into 300-mesh powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-198 with a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for bonding for wet granulation, sieving with a 40-mesh sieve for preparing granules, drying at 50-60 ℃ for about 3 hours, sieving with a 40-mesh sieve for finishing granules, and subpackaging in bags by a subpackaging machine to obtain the water dispersible granules.
Example 32: preparation of compound suspending agent
The preparation method comprises the steps of supplementing 100% of a new Thiessen manganese zinc compound with 5% of tetramycin, 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, 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 manganese-zinc reclaimed compound suspending agent
The compound suspending agent is prepared by putting 35% of a new Thisen manganese zinc compound (prepared by the method of example 1-2A) (based on the 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 macromolecular polycarboxylate (Geropon T/36), 0.5% of polyvinyl alcohol, 5% of epoxidized soybean oil, 2.0% of urea, DM 1980.1%, 0.5% of EDTA calcium sodium and 100% of pure water into a high-shear homogenizing emulsifying machine, shearing at a high speed for 30 minutes, then conveying into a sand mill, and circularly sanding for 3 times.
Example 34: preparation of suspending agent of composition
Adding 45% of active compound [ 10.0% of Thiessen manganese zinc new 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 Thisen manganese zinc new 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 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 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 manganese zinc neutral composition dry suspending agent
The formula is as follows: 35% of Thiessen manganese zinc new compound (by weight of anhydrous substance), 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, 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 Thisen manganese zinc new compound, 20 percent of thermal ester of paddy, 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 then the mixture is put 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, thus obtaining the compound suspending agent.
Example 38: preparation of suspending agent of composition
The preparation method comprises the steps of adding 25% of Thiessen manganese zinc new compound (prepared by the method of example 1-6A) and 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 circulating for 3 times to obtain the compound sand grinding suspending agent.
Example 39: dry suspension preparation of compositions
The formula is as follows: 20% Thisen manganese Zinc New Compound (prepared by method 1-2A) 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%, sorbitol 10%, methylcellulose 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% Thisen manganese Zinc New Compound (by weight of anhydrate) 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%, sorbitol 10%, methylcellulose 2%, sodium starch 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 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 41 preparation of Dry suspension of Thiessen Mn Zinc syringyl ester composition
The formula is as follows: 30% Thisen manganese Zinc New Compound (by weight of anhydrate) and 10% coumoxystrobin, urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, Xanthan gum 0.2%, sorbitol 10%, methylcellulose 2%, sodium starch octenyl succinate 1.0%, DM 1980.1%, polyethylene glycol-8001%, calcium sodium EDTA 4 hydrate 0.8%, 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 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 42 preparation of Thiessen manganese zinc and orysastrobin compounded dry suspending agent
The formula is as follows: 30% of Thisen manganese zinc 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, 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 thisenese manganese zinc and prothioconazole dry suspending agent
The formula is as follows: 30% Thisen manganese Zinc New Compound (by weight of anhydrate) 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%, sorbitol 10%, methyl cellulose 2%, sodium starch 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 thisen manganese zinc compound and pyraclostrobin dry suspending agent
The formula is as follows: 30% Thisen manganese Zinc New Compound (by weight of anhydrate) and 20% Zosteramide, Urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, Xanthan gum 0.2%, sorbitol 10%, methylcellulose 2%, sodium starch octenyl succinate 1.0%, DM-DA 19520.1%, polyethylene glycol-8001%, calcium sodium EDTA 4 hydrate 0.5%, Kaolin to 100%; the preparation process is the same as example 41.
Example 45: preparation of thisen manganese zinc fluoxastrobin compounded dry suspending agent
The formula is as follows: 30% Thisen manganese Zinc New Compound (by weight of anhydrate) and 20% Fluoroazoxystrobin, Urea 4%, sodium lauryl sulfate 2%, polycarboxylate (SPED-300) 2%, polycarboxylate dispersant (SD-819) 4%, polyvinylpyrrolidone (PVP K-30) 4%, Xanthan gum 0.2%, sorbitol 8%, methylcellulose 2%, sodium starch octenyl succinate 1.0%, DM 1980.1%, polyethylene glycol-8001%, calcium sodium EDTA 4 hydrate 0.5%, Kaolin to make up 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 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 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 46: thinsen manganese zinc and fludioxonil wettable powder
Weighing 20g of Thiessen manganese zinc new compound (based on the weight of anhydrous substances), 25 g of fludioxonil, 3g of alkyl naphthalene sulfonic acid polycondensate sodium salt, 2g of sodium dodecyl sulfate, 3g 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 thiasen manganese zinc new compound and isolong vinyl ketoxime lactam wettable powder
20g of the Thiessen manganese zinc new compound (prepared by the method of example 3), 20g of iso-long vinyl ketoxime lactam, 3g of SD-819 (polycarboxylate), 063 g of Darun D, 2g of sodium dodecyl sulfate, 3g 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 2 preparation of wettable powders of the respective built-up pesticides (preparation according to example 47)
Figure BDA0001918187580000291
Note: the new Saisen manganese Zinc compound (A) as the component of the compound example is recycled according to the numbering sequence of the technical products prepared by the methods of examples 1-2A, examples 1-4A, examples 1-6A, examples 1-7A and examples 1-9A
Example 77: preparation of water dispersible granule of 40% Thiessen manganese zinc compound and cyproconazole
Weighing 20g of a new Thisen manganese zinc compound (prepared by the method of example 3 and calculated by the weight of anhydrous substances), 20g of cyproconazole, 4% of urea, 4% of low-substituted hydroxypropyl cellulose, 2% of lignosulfonate, 4% of polycarboxylate dispersant (SD-819), 4% of polyvinylpyrrolidone (PVP K-30), 2% of sodium dodecyl sulfate, 0.2% of xanthan gum, 2% of methyl cellulose, 1.0% of starch sodium octenyl succinate, 0.1% of polyether modified organic silicon defoamer (DM-198), 0.5% of calcium sodium EDTA and 100% of kaolin;
the preparation process comprises the steps of crushing the raw materials and the auxiliary materials (except the auxiliary materials comprising sodium dodecyl sulfate, PVP K-30 and DM-198) according to the formula ratio into 300-mesh powder, dissolving and mixing the auxiliary materials comprising the sodium dodecyl sulfate, the PVP K-30 and the DM-198 with a proper amount of pure water, placing the powder into a GH L series efficient wet mixing granulator, adding the aqueous solution for bonding for wet granulation, sieving with a 40-mesh sieve for preparing granules, drying at 50-60 ℃ for about 3 hours, sieving with a 40-mesh sieve for finishing granules, and subpackaging in bags by a subpackaging machine to obtain the water dispersible granules.
Examples 78-284 preparation of Water-dispersible granules
TABLE 3 preparation of the respective built Water dispersible granules (preparation by reference to the procedure of example 77)
Figure BDA0001918187580000301
Figure BDA0001918187580000311
Note: the compound component of the new Thisen manganese zinc compound (A) (in the table, the mantissa No. 1-10 of the embodiment are respectively used for preparing raw material medicaments by the methods of the embodiment 1-1A to the embodiment 1-10A); in the tables, the weight of the Thisen manganese Zinc novel Compound (A), which is the main drug in examples 78 to 284, was calculated as an anhydride or as a crystalline hydrate and the Thisen manganese Zinc novel Compound.
Example 285: preparation of pesticide composition dispersible granules
Adding 10% of thiasen manganese zinc 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 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 286: preparation of seed coating agent with four active ingredients
The suspension type seed coating agent is prepared by adding 100% of 5% of thiasen manganese zinc new compound (prepared by an example 3 method), 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, 0.8001% of polyethylene glycol-8001%, 0.3% of EDTA calcium sodium 4 hydrate 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 through a 60-mesh sand grinder.
Example 287: preparation of suspended seed coating agent
Adding 3% of thiasen manganese zinc 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 sodium 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, carrying out high-speed shearing coarse grinding and homogenizing, pumping into a sand mill for sanding 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 288: preparation of four active ingredient suspension seed coating agent
1% of thiasen manganese zinc 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, and 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 289: preparation of seed treatment dry powder
6% of Thiessen manganese zinc 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 dry powder is obtained by superfine grinding to a certain particle size.
Example 290 preparation of 445 Complex Dry suspending agent
TABLE 4 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 BDA0001918187580000321
Figure BDA0001918187580000331
Figure BDA0001918187580000341
Note: the table shows only the ratio of the main drug or active component or raw drug of example 290-445 in percentage (all calculated as the weight or weight ratio of the anhydride or the Thisen manganese zinc new compound), A is the Thisen manganese zinc new compound (in the table, the A component is recycled according to the number sequence of the raw drug prepared by the methods of examples 1-2A, 1-4A, 1-6A, 1-7A and 1-9A), the rest components or auxiliary materials are respectively taken according to the ratio of example 45, and the preparation of each example is respectively carried out according to the preparation process of example 45.
Example 446: preparation of dry suspending agent compounded by Thisen manganese zinc triacontanol brassin
The formula is as follows: 20% Thisen manganese Zinc New Compound (by weight of Anhydrous matter) 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, 1% starch sodium octenyl succinate, 8% sorbitol, 2% methyl cellulose, DM 1980.1%, polyethylene glycol-8001%, 0.5% calcium sodium EDTA hydrate, 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 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 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 447: preparation of dry suspending agent compounded by thiasen manganese zinc benzyl amino purine compound sodium nitrophenolate
The formula is as follows: 30% Thisen manganese zinc new compound (by weight of the anhydride) 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% methyl cellulose, 1.0% sodium starch octenyl succinate, DM 1980.1%, polyethylene glycol-8001%, 0.5% calcium sodium EDTA hydrate 4, kaolin to make up 100%; the procedure is as in example 446.
Example 448
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 (%) (control net growth-treatment net growth)/control net growth]× 100 converting the inhibition rate of hyphal growth into a probability value (y), converting the concentration of the drug solution (. mu.g/m L) into a logarithm value (x), calculating a regression equation of virulence (y: a + bx) by the least squares method, and calculating the EC of each drug50The 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 thiasen manganese zinc new compound (the method of example 1-2A) and thiram mixed in proportion on soybean root rot pathogen in an in vitro experiment is measured, the test object is the soybean root rot pathogen, and the results are shown in the following table.
TABLE 5 virulence determination of the Thiessen manganese Zinc New Compound (A) compounded with thiram (B) in vitro experiments on Soybean root rot
Figure BDA0001918187580000351
The test result shows that: the thiasen manganese zinc new compound can effectively sterilize, has an additive effect or a synergistic effect with the thiram (B) in a mixing ratio of 20: 1-1: 20, can save labor and time cost by applying at the same time, has a synergistic effect in a ratio of 10: 1-1: 10, and effectively delays the generation of resistance by compounding.
Example 449 the in vitro bactericidal effect of the phytoalexin (according to literature methods), the thiasen manganese zinc new compound (example 1-4A method) and the thiabendazole complex on bacterial blight disease of rice was studied with reference to the method of example 448, and the test subjects were bacterial blight disease of rice, and the results are shown in the following table.
TABLE 6 determination of toxicity of Thiessen Mn-Zn new compound (A) and Thielamine A in vitro experiment on bacterial blight of rice
Test agent Proportioning Observation EC50 (mg/L) Theoretical EC50 (mg/L) Synergistic Ratio (SR)
A 1∶0 39.37
B 0∶1 45.04
A∶B 40∶1 30.23 39.49 1.31
A∶B 20∶1 26.11 39.61 1.52
A∶B 10∶1 21.24 39.83 1.88
A∶B 1∶1 21.33 42.01 1.97
A∶B 1∶10 27.58 44.46 1.61
A∶B 1∶20 29.69 44.73 1.51
A∶B 1∶40 35.82 44.88 1.25
The test result shows that: the thiasen manganese zinc new compound can effectively sterilize, has additive action or synergistic action with the thia-methyl induced amine (B) in the mixing ratio of 40: 1-1: 40, can greatly save labor and time cost by applying, has obvious synergistic action when the mixing ratio is 20: 1-1: 20, and effectively delays the generation of resistance by compounding.
Example 450 the in vitro bactericidal effect of the thiasen manganese zinc complex (example 1-4A method) compounded with kasugamycin on leptospora brassicae was studied with reference to the method of example 448, the test subject was leptospora brassicae, and the results are shown in the following table.
TABLE 7 virulence test results for the composite pair of cabbage soft rot pathogens blended with Thiessen manganese-zinc complex (A) and kasugamycin (B)
Figure BDA0001918187580000352
Figure BDA0001918187580000361
The experimental results show that: the thiasen manganese-zinc compound can effectively sterilize, has an additive effect or a synergistic effect with the kasugamycin (B) in a mixing ratio of 20: 1-1: 20, can reduce labor hour and cost when applied, has a remarkable synergistic effect when the ratio is 10: 1-1: 10, and can effectively delay the generation of drug resistance to cabbage soft rot germs.
EXAMPLE 451 Ex vivo bactericidal effect of Thisen manganese Zinc Complex (method of examples 1-6A) and benomyl (B) formulated components on Sclerotinia citrea was studied with reference to the method of example 448, and the test subjects were Sclerotinia citrea, and the experimental results are shown in the following table.
TABLE 8 toxicity test results of Thiessen manganese-zinc complex (A) and benomyl (B) compounded on Sclerotinia scabra
Figure BDA0001918187580000362
The experimental results show that: the thiasen manganese zinc new compound can effectively sterilize, has additive action or synergistic action with benomyl (B) in the mixing ratio of 40: 1-1: 40, can save labor and time cost by applying, has obvious synergistic effect when the ratio is 10: 1-1: 20, and effectively delays the generation of resistance by compounding.
Example 452 the in vitro bactericidal effect of the new thiasen manganese zinc compounds (examples 1-7A method) and metalaxyl-M compounded components on cucumber angular leaf spot pathogen was studied with reference to the method of example 448, the test object was cucumber angular leaf spot pathogen, and the experimental results are shown in the following table.
TABLE 9 virulence to cucumber angular leaf spot pathogen when mixing Thiessen manganese zinc new compound (A) with metalaxyl-M (B)
Test agent Proportioning Observation EC50 (mg/L) Theoretical EC50 (mg/L) Synergistic Ratio (SR)
A 1∶0 15.54
B 0∶1 16.22
A∶B 40∶1 13.36 15.56 1.16
A∶B 20∶1 10.32 15.57 1.51
A∶B 10∶1 9.25 15.60 1.69
A∶B 1∶1 8.79 15.87 1.81
A∶B 1∶5 8.99 16.10 1.79
A∶B 1∶10 9.85 16.16 1.64
A∶B 1∶20 10.66 16.19 1.52
A∶B 1∶40 14.34 16.20 1.13
The experimental results show that: the thiasen manganese zinc new compound can effectively sterilize, has additive action or synergistic action with metalaxyl-M (B) in the mixing ratio of 40: 1-1: 40, can save labor and time cost by applying at the same time, has obvious synergistic effect when the mixing ratio is 20: 1-1: 20, and effectively delays the generation of resistance by compounding.
Example 453 refers to the method of example 448 to study the in vitro bactericidal effect of the thisen manganese-zinc complex (method of examples 1-6A) and validamycin on rhizoctonia cerealis, the test object is rhizoctonia cerealis, and the experimental results are shown in the following table.
TABLE 10 toxicity of Thiessen Mn-Zn complex (A) and validamycin (B) against Rhizoctonia cerealis
Test agent Proportioning Observation EC50 (mg/L) Theoretical EC50 (mg/L) Synergistic Ratio (SR)
A 1∶0 163.07
B 0∶1 10.43
A∶B 40∶1 118.65 120.2 1.01
A∶B 20∶1 89.03 96.10 1.08
A∶B 10∶1 46.32 69.97 1.51
A∶B 1∶1 11.45 19.61 1.71
A∶B 1∶5 7.61 12.36 1.62
A∶B 1∶10 7.35 11.40 1.55
A∶B 1∶20 8.47 10.92 1.29
The experimental results show that: the thiasen manganese-zinc compound can effectively sterilize, has an additive effect or a synergistic effect with the validamycin (B) in a mixing ratio of 40: 1-1: 40, can reduce labor hour and cost in application, has an obvious synergistic effect when the mixing ratio is 10: 1-1: 10, and effectively delays the generation of resistance after compounding.
Example 454 the in vitro bactericidal effect of the combination of bismerthiazol, the new thisen manganese zinc compound (examples 1-6A) and copper oxychloride on the tomato canker was studied with reference to the method of example 448, and the test subject was the tomato canker pathogen, and the results are shown in the following table.
TABLE 11 determination of toxicity of Thiessen manganese zinc new compound (A) and copper oxychloride (B) compounded on in vitro experiment of tomato canker pathogen
Test agent Proportioning Observation EC50 (mg/L) Theoretical EC50 (mg/L) Synergistic Ratio (SR)
Bismerthiazol 35.92
A 1∶0 22.63
B 0∶1 35.57
A∶B 40∶1 19.54 22.83 1.17
A∶B 20∶1 15.28 23.03 1.51
A∶B 10∶1 14.77 23.40 1.58
A∶B 1∶1 14.25 27.66 1.94
A∶B 1∶10 20.63 33.81 1.64
A∶B 1∶20 25.63 34.63 1.35
A∶B 1∶40 27.38 35.08 1.28
The above experimental results show that: the novel thiasen manganese zinc compound can effectively sterilize, has stronger sterilization capability than bismerthiazol, has addition effect or synergistic effect with the copper oxychloride (B) in a mixing ratio of 40: 1-1: 40, can reduce the working hour and cost when applied, has remarkable synergistic effect when the ratio is 20: 1-1: 10, and effectively delays the generation of resistance after 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 Thisen manganese zinc compound is characterized in that: the molecular formula of the Thisen manganese zinc compound is as follows:
C5H4N6S4(Mn)V(Zn)Kwater content of 0.00-15%, or C5H4N6S4(Mn)V(Zn)K·wH2O, the water content is 0.00-15%, the molar ratio of manganese to zinc in the Thisen manganese-zinc compound molecule is 0.0001-0.9999: 0.9999-0.0001, the sum of the molar ratio of manganese to zinc in the Thisen manganese-zinc compound molecule is equal to 1, namely V + K is equal to 1.
2. The thiasen manganese zinc compound of claim 1, wherein: the molecular formula of the Thisen manganese zinc compound comprises [ C5H4N6S4(Mn)0.95(Zn)0.05The water content is 0.00-15%]，[C5H4N6S4(Mn)0.5(Zn)0.5The water content is 0.0-15%],[C5H4N6S4(Mn)0.9(Zn)0.1The water content is 0.0-15%],[C5H4N6S4(Mn)0.8(Zn)0.2The water content is 0.0-15%],[C5H4N6S4(Mn)0.7(Zn)0.3The water content is 0.0-15%],[C5H4N6S4(Mn)0.65(Zn)0.35The water content is 0.0-15%]，[C5H4N6S4(Mn)0.6(Zn)0.4The water content is 0.0-15%],[C5H4N6S4(Mn)0.4(Zn)0.6The water content is 0.0-15%],[C5H4N6S4(Mn)0.35(Zn)0.65The water content is 0.0-15%]，[C5H4N6S4(Mn)0.3(Zn)0.7The water content is 0.0-15%],[C5H4N6S4(Mn)0.2(Zn)0.8The water content is 0.0-15%],[C5H4N6S4(Mn)0.1(Zn)0.9The water content is 0.0-15%]，[C5H4N6S4(Mn)0.05(Zn)0.95The water content is 0.0-15%]；
Or [ C5H4N6S4(Mn)0.95(Zn)0.05·wH2O, water content of 0.00-15%]，[C5H4N6S4(Mn)0.5(Zn)0.5·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.9(Zn)0.1·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.8(Zn)0.2·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.7(Zn)0.3·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.65(Zn)0.35·wH2O, water content of 0.00-15%]，[C5H4N6S4(Mn)0.6(Zn)0.4·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.4(Zn)0.6·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.35(Zn)0.65·wH2O, water content of 0.00-15%]，[C5H4N6S4(Mn)0.3(Zn)0.7·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.2(Zn)0.8·wH2O, water content of 0.00-15%],[C5H4N6S4(Mn)0.1(Zn)0.9·wH2O, water content of 0.00-15%]，[C5H4N6S4(Mn)0.05(Zn)0.95·wH2O, water content of 0.00-15%]。
3. The thiasen manganese zinc compound of any of claims 1-2, wherein: the Thisen manganese zinc compound is Thisen manganese zinc 1 hydrate, C5H4N6S4(Mn)0.5(Zn)0.5·H2O。
4. The thiasen manganese zinc compound of claim 3, wherein: measured by powder X-ray diffraction method, the diffraction angle 2 theta, in the measurement range of 3-60 degrees, has corresponding characteristic values at the following 2 theta values: 8.21,9.86, 10.55, 13.34, 13.82, 15.49, 15.97, 17.75, 19.15, 19.78, 20.74, 22.28, 22.56, 22.95, 23.71, 24.33, 24.92, 25.36, 26.18, 27.97, 29.82, 30.80, 31.29, 33.13, 35.78, 36.30.
5. The process for producing a thiasen manganese zinc compound according to any one of claims 1 to 4, characterized in that: the preparation method comprises the following steps:
adding phyllobium pratense or its solvent compound into a reaction container, adding water, stirring, adding one or several of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate and potassium hydroxide or their aqueous solution, stirring to dissolve, adding manganese salt or its solvent compound or its solution and one or several of zinc salt or its solvent compound or its solution, the manganese salt or its solvent compound is selected from manganese sulfate, manganese sulfate monohydrate, manganese chloride 4 hydrate, manganese acetate 4 hydrate, manganese nitrate 4 hydrate or its aqueous solution, the water-soluble zinc salt is selected from one or several of zinc sulfate, zinc heptahydrate, zinc chloride, zinc acetate, zinc nitrate or their aqueous solution, stirring, fully precipitating solid, filtering, adding water and organic solvent C, stirring1-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 ester(s) once to several times, filtering, and drying the obtained solid to obtain a Thisen manganese zinc compound;
wherein the equivalent ratio of the labyrinthine or a solvent compound thereof to the base used in the reaction is about 1: 1 to 1.2; the weight volume ratio of the phyllobium pratense or the solvent compound thereof to one or more of water, C1-C6 low molecular alcohol, C2-C8 lower ether or C2-C6 low molecular nitrile organic solvent is generally as follows: 1 (g): 3.5 to 60(ml), preferably in the ratio: 1 (g): 5 to 40 (ml); the total equivalent ratio of the bisultap to the manganese and zinc salts is preferably about 1: 0.98-1.05;
wherein, the organic solvent C1-C6Is selected from the group consisting ofBut are not limited to, methanol, ethanol, isopropanol, 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 thiasen manganese zinc compound of any one of claims 1-5, wherein: the pesticide composition or the pesticide composition which consists of the Thisen manganese zinc compound with effective dose and the bactericidal drug with effective dose or the antibacterial drug or the antiviral drug andor the plant growth regulator or the pesticide acceptable with effective dose and other pharmaceutically acceptable auxiliary materials is prepared into a pharmaceutically acceptable pesticide preparation; namely, preparing a new pharmaceutical composition or a pesticide composition from an effective dose of an active ingredient A, namely a Thiessen manganese zinc compound, and an effective dose of an active ingredient B; wherein the weight ratio of the active component A to the active component B can be 180: 1-1: 100, and the weight can be calculated by anhydrous substance or water-containing substance; wherein, the weight ratio of the active component A to the active component B is preferably 100: 1-1: 100, and the weight can be calculated by anhydrous substance or water-containing substance; wherein, the weight ratio of the active component A to the active component B is preferably 80: 1-1: 80, and the weight can be calculated by anhydrous substance or water-containing substance; the active ingredient B is selected from any one or more of B.1) -B.13) or a pesticide and a pharmaceutically acceptable salt or a solvent compound thereof; active ingredient B is selected from pesticidal compounds not limited to the following references, reference a: liu Chang Ling, Chaobaoshan master edition, new pesticide creation and synthesis, chemical industry Press, 2013, Beijing; document B: sunjilong, Qijunshan, a modern pesticide application technology book, Fungicide roll, chemical industry Press, 2017, Beijing; document C: zhengguiling, Sun Jialong, modern pesticide application technology book, pesticide volume, chemical industry Press, 2017, Beijing; document D, Sun Jialong, modern pesticide synthesis technology, published by chemical industry publishers, 2011, Beijing; document E, a modern pesticide handbook, Liuchang, Yangjichun, chemical industry Press, 2018, Beijing;
b.1) a strobilurin fungicide or an antiviral agent selected from one or more of azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, enestroburin, fluoxastrobin, picoxystrobin, kresoxim-methyl, enestroburin or metominostrobin, phenamaclurex, Picarbitrazox, orysastrobin, pyraclostrobin, coumoxystrobin, cloxacarb, pyraclostrobin, UBF307, KZ165, probenazole and diclosamide;
b.2) triazole fungicide, which is selected from one or more of difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, tebuconazole, hexaconazole, myclobutanil, penconazole, propiconazole, tetraconazole, triadimenol, bitertanol, triadimefon, metconazole, ipconazole, prothioconazole, imazazole, triticonazole, cyproconazole, mefentriflunazole, ipfentriflunazole, bromuconazole, fenbuconazole, fluquinconazole, furconazole, penconazole, epoxiconazole, triflumizole, diniconazole and triadimefon;
b.3) an amide fungicide selected from one or more of metalaxyl, metalaxyl-M, flutolanil, mandipropamid, boscalid, fluopyram, carboxin, Bixafen, penflufen, epoxiconazole, Fluxapyroxad, penthiopyrad, thifluzamide, fluopicolide and isopyrazam, fluofen, fluoxafen, cycloflusulfamide, methiavalicarb, benalaxyl-p-ethyl, thifluzamide, tiadinil, ethaboxam, silthiopham, fluvalicarb-isopropyl, fenpyrad-isopropyl, zoxamide, fenhexamid, cyprodinil, flusulfamide, metosulam, oryzamide, Bixafen, Fluxapyroxad and Sedaxane;
b.4) one of the imidazole bactericides is selected from one or more of cyazofamid, triflumizole, imazalil, fenamate, prothioconazole, phenylthioimidazole, thiabendazole, imazalil, fuberidazole, prochloraz manganese complex and prochloraz copper complex;
b.5) the dicarboximide bactericide is selected from one or more of procymidone, iprodione, vinclozolin, captan, dimethachlon and tolclofos-methyl;
b.6) carbamate bactericide which is selected from one or more of propamocarb hydrochloride, diethofencarb, benomyl, carbendazim, thiophanate-methyl, iprovalicarb, benthiavalicarb-isopropyl and valienamine Valifenalate;
b.7) antibiotic bactericide or antiviral agent selected from one or more of validamycin, streptomycin sulfate, kasugamycin, tetramycin, shenqinmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshengmycin, pesticide 120, aureonucleomycin, changchin, and tetramycin;
b.8) oxazole bactericide selected from one or more of oxadixyl, hymexazol, famoxadone, pyrisoxazole, fluorothiazolepyrietone, benfurazolesulfone, dichloroazole and methanesulfonylazole;
b.9) morpholine bactericide or antiviral drug, which is selected from one or more of tridemorph, dimethomorph, flumorph and moroxydine hydrochloride;
b.10) a pyrimidine bactericide which is selected from one or more of cyprodinil, pyrimethanil, ethirimol, mepanipyrim, fluopyram, dimoxystrobin, SYP-3773 and SYP-3810;
b.11) quinoline bactericide which is selected from one or more of dithianon, propoxymoline, phenoxyquinoline and quinoflulin;
b.12) dithiocarbamate bactericides or antiviral agents selected from one or more 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, dipheny phosphine, fosetyl-aluminium, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydrorosinate, fenpiclonil, fludioxonil, isolong vinyl ketoxime lactam, cnidium lactone, Dufulin, phenoconone, methiiramine, polyhexamethylene biguanide hydrochloride, bromothalonil, indazolesulfamide, copper nonyloconate, oxine-copper, moroxydine hydrochloride, copper succinate, xinafoate acetate, amino-oligosaccharin, lentinan, benziothiazolin, ethylicin, allibenzothiazole, diclorocyanid, emodin methyl ether, chrysophanol, fluzole activated ester, S-abscisic acid, amino-oligosaccharin, zinc pyridinates, berberine and pharmaceutically acceptable salts such as berberine hydrochloride, berberine, sulfate, eugenol, berberine hydrochloride, Sulfur, copper sulfate pentahydrate, copper oxychloride, copper hydroxide, basic copper sulfate, bismerthiazol, isolongifolenoxime lactam, allicin, guaiacol, quinolactaside, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, zinc thiazole hydrate, ametoctradin, Pyribencarb, Pyriofenone, fluthianil, Meptyldinocap, Fenpyrazamine, Tolprocarb, isoferamide, Isopyrazam, Penflufen, benzovindifpyrin, tebuflozin, Oxathiapiprolin, spiroxamine, fosetyl aluminum, iprobenfos, matrine, kurarinone, thiabendazole copper or a hydrate thereof, metrafenone, diflumetofen, methyl jasmonate; or the plant growth regulator is selected from one or more of diethyl aminoethyl hexanoate, forchlorfenuron, compound sodium nitrophenolate, brassin, gibberellin, 6-benzylaminopurine, triacontanol, naphthylacetic acid or medicinal salt thereof, paclobutrazol, ethephon, methyl naphthylacetate, fluroxypyr, trinexapac-ethyl, uniconazole, indolebutyric acid, pyridinol, trinexazine, chlormequat-n, brassin lactone, prodigol and glyphosate;
the pesticide is selected from but not limited to chlorfluazuron, tefluazuron, chlorfluazuron, flufenoxuron, hexaflumuron, flucycloxuron, chlorfluazuron, chlorbenzuron, diflubenzuron, diafenthiuron, hydrazine, buprofezin, fenoxycarb, fenoxanil, pyrazofos, methyl parathion, chlorzophos, pyridaphethione, quinalphos, fosthiazate, diazinon, phoxim, fenitrothion, pirimiphos, fenprophos, fenacet, profenofos, chlorpyrifos-methyl, prothioconazole, profenofos, methidathion, carbosulfan, valacyclovir, fenobucarb, isoprocarb, carfentrazone, pirimicarb, metolcarb, carbaryl, methiocarb, methomyl, metolcarb, metominostrobin, cyhalothrin, bifenthrin, fenpropathrin, cypermethrin, fenpropathrin, pyraflufen, pyraclofen, One or more of beta-cypermethrin, deltamethrin, tralomethrin, ethofenprox, or pentothrin, abamectin, emamectin benzoate, ivermectin or pharmaceutically acceptable salts thereof, and the like, wherein the active ingredient B is selected from but not limited to insecticides or acaricides and the like in document A, C, D, E, G, and document A: liu Chang Ling, Chaibaoshan Master eds, "creation and Synthesis of New pesticides," chemical industry Press, 2013, Beijing; document C: zhengguiling, Sun Jialong, the book of modern pesticide application technology, volume of pesticides, chemical industry Press, 2017, Beijing; d, Sunjilong, modern pesticide synthesis technology, published by chemical industry publishers, 2011, Beijing; e, a modern pesticide handbook, Liu Chang Liang, Yang Ji Chun, chemical industry Press, 2018, Beijing; document G Liu Chang Shu "world pesticide Pan: insecticide roll", chemical industry Press, Beijing, 2012.
7. The composition of thiasen manganese zinc compounds of claim 6, wherein: the bactericide contains an active ingredient A and any one active ingredient B selected from but not limited to azoxystrobin, kresoxim-methyl, pyraclostrobin, enestroburin, trifloxystrobin, pyraclostrobin, fluoxastrobin, kresoxim-methyl, enestroburin, alkene oxime amine or metominostrobin, cyhalostrobin, Picarbuzox, orysastrobin, pyraclostrobin, coumoxystrobin, clotrimtrobin, UBF307, KZ165, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, flusilazole, flutriafol, triadimenol, triadimefon, metconazole, ipconazole, prothioconazole, imibenconazole, triticonazole, cyproconazole, metalaxyl, flutolanil, fenpyrad, picolide, fluopicolide, flutriamid, flutriafol, cyazofamid, triflumizole, imazamidone, imazalil, oryzalil, oryzalin, triflumilast, fenpyroxastrobilus, Iprodione, vinclozolin, captan, dimetachlone, propamocarb hydrochloride, benomyl, carbendazim, thiophanate-methyl, iprovalicarb, benthiavalicarb, validamycin, streptomycin sulfate, kasugamycin, shenqimycin, oxadixyl, hymexazol, famoxadone, pyrisoxazole, tridemorph, dimethomorph, flumorph, cyprodinil, pyrimethanil, ethirimol, mepanipyrim, flufenamid, dithianon, proquinazine, phenoxyquinoline, metiram, thiram, ziram, amobam, zineb, maneb, mancozeb, fenamiphos, fosetyl-aluminum, chlorothalonil, isoprothiolane, fludioxonil or copper hydroxide, copper rosinate, copper dehydroabietate, fenpiclonil, fludioxonil, prochloraz, a manganese complex, prochloraz, validamine complex, validamycin sulfate, streptomycin, Kasugamycin, tetramycin, shengmycin, polyoxin, ningnanmycin, streptomycin sulfate, zhongshenmycin, nong' S antibiotic 120, aureonucleomycin, changchin, kasugamycin, Dufulin, phenazon, prothioconazole, phenylimidazole, Chlorofluoroethanoconazole, iprifluorene trifluoroconazole, Fluthiazolopyrone, allylbenzothiazole, physcion methyl ether, chrysophanol, Fluthiazolopyrone, allylbenzothiazole, diclocyanamide, physcion methyl ether, chrysophanol, Fluconazole-activated ester, dichlorooxazole and methanesulfonylazole, S-abscisic acid, amino-oligosaccharin, zinc sulfate, berberine hydrochloride, berberine sulfate, folpet, isolongifolenoxime lactam, allicin, guaiacol, Quinolactacide, dehydroacetic acid, chlorobromoisocyanuric acid, carvacrol, zium, zinc secoisolazole hydrate, thiflufenamide, thiflufenacetrin, chlorfenapyr, chlorfena, Tiadinil, ethaboxam, silthiopham, furametpyr, cyflufenamid, fluopicolide, zoxamide, fenhexamid, cyprodinil, flusulfamide, sulfenamide, fenpyrazamide, oryzamide, Bixafen, Fluxapyroxad, Sedaxane, ametoctradin, Pyribencarb, fluanil, meptylodinil, Pyriofenone, Fenpyrazamine, valinamine, Valifenalate, Tolprocarb, isoflutamide, Isopyrazam, Penflufen, bezafidifloron, tebufenpyrad, tebuflomezine, oxapicrolin, furazolidone, fenbuconazole, fluquinconazole, spiroxamine, fosetyl-ethyl-aluminium, tolclofos-methyl, iprovalicarb, mefenoxaprop-ethyl, dimethoxam, isoprothiolan, tebuconazole, dimethoxamine, teflufenoxafen, dimethofenoxapride, mefenoxafen, metoclopramide, flufenacetrimonium, thifenpyroxate, tebuconazole, thifenzopyr, tebuconazole, thiflufenacetrimonazine, tebuconazole, thifenpyraclostrobin, tebuconazole, thiflufen, tebuconazole, thifenpropiconazole, tebuconazole, thifenpropiconazole, thifenpyroxafen, thifenpropiconazole, or a hydrate, or a, Chlorfluazuron, teflubenzuron, chlorfluazuron, flufenoxuron, flucycloxuron, chlorfluazuron, chlorbenzuron, diflubenzuron, diafenthiuron, bromate, buprofezin, fenoxycarb, or tebufenozide, pyrazofos, parathion-methyl, chlorzophos, pyridaphenthion, quinalphos, triazophos, diazinon, phoxim, fenitrothion, pirimiphos, fenthion, fenpropathrin, cyanophos, profenofos, chlorpyrifos-methyl, prothiofos-methyl, profenofos, dimethoate, malathion, methidathion, carbosulfan, prothiocarb, fenbucarb, fenobucarb, isoprocarb, triazamate, metolcarb, carbaryl, methomyl, methiocarb-methyl, methomyl, metolcarb, or thiodicarb, cyfluthrin, bifenthrin, fenpropathrin, cyhalothrin, cyhalothri, One or more of deltamethrin, tetrabromthrin, ethofenprox, or pentothrin, abamectin, emamectin, ivermectin or pharmaceutically acceptable salts thereof, wherein the weight ratio of the active component A to the active component B is preferably 1: 80-80: 1, and more preferably 1: 60-60: 1.
8. The thiasen manganese zinc compound of any one of claims 1-7, wherein: the new compound or the composition thereof and a pharmaceutically acceptable carrier are prepared into a pharmaceutically acceptable preparation which is selected from but not limited to wettable powder, water dispersible granules, suspending agents, dry suspending agents, suspoemulsions, aqueous emulsions, granules, dry seed treatment powder, dispersible seed treatment powder, microcapsule suspending agents, seed treatment suspending agents, powder, granules, tablets, effervescent tablets, controlled-release or sustained-release preparations, microcapsule preparations, oil suspending agents, dispersible liquid, dry seed treatment powder, dispersible seed treatment microcapsule suspending agents or suspension seed coating agents.
9. The broad-spectrum bactericidal nuisance free growth promoting manganese compound and combination composition thereof of claim 6, wherein: 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 thiasen manganese zinc compounds or compositions thereof according to any one of claims 1-7, characterized in that: 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 crop plants are preferably or selected from, but not limited to, the following species: 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 crops such as tobacco, tea, cotton, or zinc and or manganese deficient; the diseases are selected from but not limited to: bacterial wilt, bacterial angular leaf spot, soft rot, canker, 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, basal rot, wildfire, ginger leaf blight, sand skin disease, sclerotinia, fusarium wilt or scab take all round, zinc deficiency yellowing leaf, lobular disease, inactivated virus, bakanae disease, bacterial perforation disease or other zinc or manganese deficiency scab.
CN201811588695.4A 2018-12-24 2018-12-24 Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof Pending CN111423472A (en)

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