CN102516267A - Thiodiazole copper compound, and its preparation method, preparation and application in control of agricultural plant diseases - Google Patents
Thiodiazole copper compound, and its preparation method, preparation and application in control of agricultural plant diseases Download PDFInfo
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- CN102516267A CN102516267A CN2011104018960A CN201110401896A CN102516267A CN 102516267 A CN102516267 A CN 102516267A CN 2011104018960 A CN2011104018960 A CN 2011104018960A CN 201110401896 A CN201110401896 A CN 201110401896A CN 102516267 A CN102516267 A CN 102516267A
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- Prior art keywords
- copper
- preparation
- thiazole
- compound
- organic copper
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- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 239000005749 Copper compound Substances 0.000 title claims abstract 13
- -1 Thiodiazole copper compound Chemical class 0.000 title claims description 20
- 201000010099 disease Diseases 0.000 title abstract description 9
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- 239000004563 wettable powder Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 19
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract 14
- 150000001880 copper compounds Chemical class 0.000 claims abstract 12
- 150000001879 copper Chemical class 0.000 claims abstract 5
- 239000007900 aqueous suspension Substances 0.000 claims abstract 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 29
- 241000894006 Bacteria Species 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000004562 water dispersible granule Substances 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
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- 239000000843 powder Substances 0.000 claims description 10
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 9
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
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- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 claims 1
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- 239000010949 copper Substances 0.000 abstract description 51
- 229910052802 copper Inorganic materials 0.000 abstract description 51
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明属于有机铜农用杀菌剂领域，公开了一种噻唑类有机铜化合物及其制备方法、制剂及在防治农业植物病害中的用途，将2-巯基苯并噻唑和2-氨基-5-巯基-1，3，4-噻二唑以及二价铜盐加入到有机溶剂中进行反应，反应结束后依次进行分离、洗涤、干燥即得一种新型噻唑类有机铜化合物，其生产路线具有原料廉价易得，工艺简单等特点，该化合物性质稳定，杀菌谱广，可加工成可湿性粉剂、干悬浮剂以及水悬浮剂等制剂，对多种农作物主要病害防效显著，对环境安全。The invention belongs to the field of organic copper agricultural fungicides, and discloses a thiazole organic copper compound and its preparation method, preparation and application in preventing and controlling agricultural plant diseases. -1,3,4-thiadiazole and divalent copper salt are added to the organic solvent for reaction, and after the reaction is completed, they are separated, washed and dried in sequence to obtain a new type of thiazole organic copper compound, and its production route has cheap raw materials. Easy to obtain, simple process, etc., the compound is stable in nature and has a wide bactericidal spectrum. It can be processed into wettable powder, dry suspension concentrate, water suspension concentrate and other preparations. It has significant control effects on various major crop diseases and is environmentally safe.
Description
Technical field
The invention belongs to the pesticide chemical technical field, particularly a kind of thiazoles organocopper compound and preparation method thereof, preparation and the purposes in control agricultural plants disease.
Background technology
The 2-mercaptobenzothiazole molecular formula is C
7H
5NS
2, molecular weight is 167.24, pale yellow powder is dissolved in basic solns such as propyl alcohol, ethanol, chloroform, ammoniacal liquor, sodium hydroxide and yellow soda ash, is slightly soluble in benzene, water insoluble and gasoline.Main as vulcanizer (captax), also, be commonly called as mercaptobenzothiaz01e or M agent, but its activity is lower as agricultural bactericide, fail to be used widely.2-mercaptobenzothiazole also is used as the inhibiter of metallic copper in the industry, be the inhibition mechanism of inquiring into 2-mercaptobenzothiazole, and 2-mercaptobenzothiazole and copper effect are by broad research.Literature research finds that 2-mercaptobenzothiazole comes from 2-mercaptobenzothiazole and monovalence copper formation title complex (Qian Wenying etc. to the provide protection of metallic copper; Spectrochemistry research alpha-mercapto benzothiazole is to the inhibition principle of copper; Chinese Journal of Inorganic Chemistry, 1999,15 (06): 756-760; I.P.Khullar, and U.Agarewala, Can.J.Chem.1975,53,1165).
2-amino-5-sulfydryl-1,3, the molecular formula of 4-thiadiazoles are C
2H
3N
3S
2, molecular weight is 133.20, white crystalline powder is dissolved in organic solvents such as hot water and pyridine, N, is dissolved in methyl alcohol, acetone slightly.Be mainly used in sterilant bismerthiazol pesticide intermediate and medicine intermediate.
Copper fungicide is as a kind of tradition, important sterilant, have the Application and Development time the earliest, duration of service is the longest, use the maximum and characteristics such as be difficult for developing immunity to drugs of area, is one type of wide-spectrum bactericide; In agriculture bacterium of control and fungal disease, purposes is widely arranged; The existing provide protection of copper fungicide has certain treatment and eradicant action again, in addition; Also has good tackiness; Can form one deck medicine film in crop surface, thereby reach resistance of rainwater washing against, the characteristics that the lasting period is long.Copper fungicide mainly comprises inorganic copper agent and organic copper preparation at present.Wherein common inorganic copper agent has verditer, Basic Chrome Sulphate (Bordeaux mixture), copper oxychloride.Be characterized in having the protective fungicide of advantage, cost is low, but shortcoming is: the first, be easy to generate poisoning, and forbid or limit use at florescence and young fruit period; The second, miscibility is poor, and inorganic copper agent great majority are alkaline agricultural chemicals, can not with most of mixed pesticides, use inconvenience; The 3rd, be prone to cause the increment of mite class and blister mite, the covert control cost that increases; The 4th, the effect of treatment is not strong, on paddy rice, is not easy to use.
In copper agent, be main still at present with inorganic copper agent.But the growth momentum of organic copper preparation is very powerful, and the trend of " the latecomers surpass the old-timers " is quite arranged.In recent years, China many agricultural chemicals producer drive on boldly to the organic copper preparation one after another on a large scale, and friend peasant also enjoys all benefits of preventing and treating that the organic copper preparation brings, so the organic copper preparation becomes " unexpected rival " who is a dark horse in the disinfectant use in agriculture.Common organic copper preparation comprises Thiodiazole-copper (dragon gram bacterium), copper rosinate, amber adipic acid copper (DT), copper humate, lipid acid copper, nitroacid copper, oxinecopper, copper naphthenate, copploid liquid, amino acid copper, venus crystals, amine sulfonic acid copper.These three organic copper preparations of Thiodiazole-copper, oxinecopper and 30% nonylphenolsulfonate copper microemulsion wherein; It all is product innovation with Chinese independent intellectual property right; It all is the national emphasis product innovation of the imitated recently other countries of China expired patent invention; Be outstanding person and the market rising star in the organic copper preparation, market potential is very considerable.
The organic copper preparation comes into one's own, and is by no means accidental.It than inorganic copper agent have more qualitatively, the technical and advantage used: A, organic copper preparation be more safe and reliable, good with Environmental compatibility, crop is difficult for producing poisoning, peasant's medication is felt more relieved; B, organic copper preparation are difficult for causing the propagation of red spider and blister mite because not injuring natural enemy " crinosity bacterium ", alleviated peasant's economical load and medication hidden danger; C, organic copper preparation affinity are fairly good; Can be mixed mutually with the overwhelming majority's sterilant, miticide, sterilant and plant-growth regulator and can not cause chemical reaction; Alleviated the peasant because of repeatedly spraying the labor load that medicine causes, saved working time, medication is saved worry more; D, the organic copper preparation scope of application and more extensive on the usage period also are difficult for producing poisoning under florescence and young fruit period regular service condition; The copper content of E, organic copper preparation, residual quantity are relatively low, low in the pollution of the environment; F, in the organic copper preparation, cupric ion and compound synergy, dual mechanism sterilization, sterilization more thoroughly, more efficient.
In the market, the producer that produces the organic copper preparation is more and more, the controlling object of registration also more and more widely, bacterial disease, fungal disease and viral disease all among control, have realized the hope of peasant " a medicine Zhiduo County is sick ".In addition, the organic copper preparation also can be used for going out except that moss, lichens, kills snail, oncomelania and carry out seed treatment, preserving fruit and vegetable utilizing to store and replenish effects such as crop trace element.The technical superiority of organic copper preparation is the organic copper preparation, and " it is neutral that great majority are, and has better affinity and being mixed property, and safety easy to use is convenient to operation; " copper content " of organic copper preparation is lower, and be littler to the pollution of environment, littler to the influence of mite class, littler to florescence and the young fruit period influence of farm crop, uses safety and relieved more.
Although there are many meliority in copper fungicide, excessive cupric ion very easily causes poisoning to crop.There are some researches show that cupric ion gets final product kill pathogenic organisms when 10mg/L, when its concentration reaches 30mg/L, then can cause poisoning to sensitive plant.Do not see at present the relevant report that novel thiazole class organocopper compound and preparation method thereof is arranged as yet, more do not find this novel thiazole class organocopper compound is used for the relevant report of agricultural plants disease control.
Summary of the invention
The object of the present invention is to provide a kind of novel thiazole class organocopper compound; Provide simultaneously that a kind of preparation method is simple, cost is low, the preparation method of the novel thiazole class organocopper compound of environmental protection; The thiazoles organocopper compound stable in properties of preparation; Fungicidal spectrum is wide, can be widely used in control agricultural plants disease.
To achieve these goals, the present invention has adopted following technical scheme:
A kind of thiazoles organocopper compound, concrete name is called copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, and 4-thiadiazoles, this compound have suc as formula the chemical structural formula shown in 1:
The preparation method of above-mentioned thiazoles organocopper compound may further comprise the steps:
With 4.5-7.0g purity is that 99% 2-mercaptobenzothiazole and 3.3-5.8g purity are 2-amino-5-sulfydryl-1,3 of 98%, and the 4-thiadiazoles adds in the aqueous ethanolic solution or methanol aqueous solution of 180-260mL massfraction 75-95%; Heating for dissolving gets solution A, with 2.5-5.0g purity be the cupric salt of 95-99% add in the 25-40ml water the mixture of cupric salt and water, solution A is added drop-wise in the mixture of cupric salt and water; Dropwise the back and stir 0.5-2h in 55-70 ℃; Staticly settle after stirring end, precipitation separation will precipitate and use washing with alcohol; Use water washing then, the oven dry of washing back promptly gets the Powdered thiazoles organocopper compound of tawny.
The addition of said methanol aqueous solution or aqueous ethanolic solution is can dissolve 2-mercaptobenzothiazole and 2-amino-5-sulfydryl-1; 3; The 4-thiadiazoles is as the criterion, and when cupric salt was water-soluble, the addition of water was as the criterion can dissolve cupric salt; When cupric salt was water insoluble, the addition of water was being as the criterion by wetting cupric salt.
Said cupric salt includes but not limited to copper sulfate, cupric chloride, verditer, cupric nitrate or neutralized verdigris.
Said solution A dropwises in 22-30min.
The preparation of above-mentioned thiazoles organocopper compound, said preparation comprises the thiazoles organocopper compound of 20-90% by massfraction, and surplus is an auxiliary material, and the formulation of said preparation comprises wettable powder, water dispersible granules or suspension concentrate.
The component of said wettable powder comprises the thiazoles organocopper compound of 20-90%, the wetting agent of 1-10%, the dispersion agent of 1-10% by massfraction, and surplus is a filler.
Said wetting agent is one or more the compsn in X 2073, sodium dibutyl naphthalene sulfonate, octylphenol polyethylene ethenoxy group ether, Nonyl pheno base ether or the octylphenol polyethylene ethenoxy group ether sulfate; Said dispersion agent is one or more the compsn in sulfonated lignin, sodium dibutyl naphthalene sulfonate formaldehyde condensation products, naphthalenesulfonic acid-formaldehyde condensate, novalgin formaldehyde condensation products, alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphonate or the CMC 99.5; Said filler is one or more the compsn in zeyssatite, WHITE CARBON BLACK, wilkinite, light calcium carbonate or the attapulgite.
Above-mentioned thiazoles organocopper compound the control agricultural plants bacillary with fungal disease in purposes.
Said agricultural plants comprises farm crop, fruit tree or vegetables, and said farm crop comprise paddy rice, wheat, corn, soybean, cotton, peanut, watermelon, rape or sesame; Said vegetables comprise tomato or cucumber; Said fruit tree comprises apple tree, pear tree or peach; Said bacterial disease comprises rice leaf spot bacteria or ulcer bacteria; Said fungal disease is rust, sheath blight fungus, leaf spot fungi, wilt, sclerotium germ or stem point rot bacterium.
The invention has the advantages that: 1, main raw material 2-mercaptobenzothiazole of the present invention and 2-amino-5-sulfydryl-1; 3; The 4-thiadiazoles is with low cost, and raw material is easy to get, and for prepared novel thiazole class organocopper compound is used to prevent and treat the agricultural plants disease good cost advantage is provided; 2, the method for the present invention's preparation is simple, is easy to suitability for industrialized production, and produces the three wastes hardly, compliance with environmental protection requirements; 3, the novel thiazole class organocopper compound stable in properties of preparation, chance strong acid, highly basic do not decompose, and can use with Multiple Pesticides, have solved the drawback of inorganic in the past copper and organic copper fungicide compounding property difference; Fungicidal spectrum is wide; Not only efficient to bacterium; Fungi even the germ that is difficult to prevent and treat are all had efficiently, 4, the prepared thiazoles organocopper compound of the present invention forms coordination compound with organic molecule and cupric ion, make the release of cupric ion can reach the concentration of kill pathogenic organisms; Simultaneously can not cause poisoning again, therefore be applicable to the novel organic copper sterilant of developing efficient, nontoxic, lasting and environmental protection crop.
Description of drawings
The mass spectrum of the thiazoles organocopper compound of Fig. 1 the present invention preparation.
The hydrogen nuclear magnetic resonance spectrogram of the thiazoles organocopper compound of Fig. 2 the present invention preparation.
The thiazoles organocopper compound of Fig. 3 the present invention preparation is used for Kiwifruit ulcer bacteria bacteriostatic test and surveys periodic fungistatic effect figure; A is the fungistatic effect of derosal to the Kiwifruit ulcer bacteria, and b is the fungistatic effect of 50% thiazoles organocopper compound wettable powder to the Kiwifruit ulcer bacteria.
Embodiment
Below in conjunction with embodiment the present invention is described further, but protection scope of the present invention is not limited thereto, below among all embodiment, be commercial product derosal with reference to appearance.
Embodiment 1
With 6.6g purity is that 99% 2-mercaptobenzothiazole, 5.4g purity are 2-amino-5-sulfydryl-1 of 98%; 3; 4-thiadiazoles and 260ml massfraction are in 75% the disposable input 500ml reaction flask of aqueous ethanolic solution, heating for dissolving under 74 ℃ temperature, solution A; With 2.5g purity is that 99% cupric sulfate pentahydrate and 25ml zero(ppm) water join in the 500ml reaction flask, heating, and under 42 ℃ temperature, stir it is fully dissolved; Treat that copper sulfate dissolves fully in water after, under the effect of stirring, dropwise (every 0.02～0.04ml) drips in the aqueous solution of copper sulfate solution A; Within 28min, dropwise, temperature control is at 70 ℃ then, stirring reaction 1h; Staticly settle 4.5h after the reaction, fully after the layering, remove upper solution; Lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 105 ℃ then, gets the tawny powder and is copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1; 3, the 4-thiadiazoles, structure is following:
Like Fig. 1, shown in 2, detect m/z in the mass spectrum and be 361 characteristic peak and NMR hydrogen spectrogram intermediate value and be 6.99,7.53,8.01 and 8.18 characteristic peak.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 50.0%, X 2073 3.0%, sulfonated lignin 5.0%, zeyssatite 42.0% are crossed 320 mesh sieves by said ratio with each material thorough mixing, grinding back and are got 50% thiazoles organocopper compound wettable powder.
The 50% thiazoles organocopper compound wettable powder that is mixed with is carried out bacteriostatic test to be measured; Wettable powder (auxiliary material and content thereof are all with 50% thiazoles organocopper compound wettable powder in the present embodiment) to contain 50% derosal is done with reference to appearance, and strains tested is the Kiwifruit ulcer bacteria that Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo provides.Germ is pressed the ordinary method activation before test; Used substratum is the ordinary broth nutrient agar; Substratum consists of: peptone 10g, Carnis Bovis seu Bubali cream 5 grams, agar powder 25 grams, sodium-chlor 5 grams, potassium hydrogenphosphate 1 gram, zero(ppm) water 1000ml, prepare according to ordinary method.Connect bacterium test and on Bechtop, carry out, the petridish that connects behind the bacterium is put into constant incubator immediately, and temperature is 37 ℃, behind the 24h, and observations, record.Fungistatic effect such as Fig. 3; Wherein, The wettable powder of derosal (667ppm) to the fungistatic effect of Kiwifruit ulcer bacteria shown in Fig. 3 a, 50% thiazoles organocopper compound wettable powder (667ppm) to the fungistatic effect of Kiwifruit ulcer bacteria shown in Fig. 3 b.Can find out that from Fig. 3 the restraining and sterilizing bacteria effect of thiazoles organocopper compound wettable powder under 667ppm obviously is superior to contrasting pesticide carbendazim, inhibition zone roughly is 3 times of derosal control group.
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 1.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 20.0%, octylphenol polyethylene ethenoxy group ether 1.0%, sodium dibutyl naphthalene sulfonate formaldehyde condensation products 4.5%, WHITE CARBON BLACK 74.5% are crossed 320 mesh sieves by said ratio with each material thorough mixing, grinding back and are promptly got 20% thiazoles organocopper compound wettable powder.
Strains tested is a rice leaf spot bacteria; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 20% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 20% thiazoles organocopper compound wettable powder in the present embodiment) that contains 20% derosal.The result shows: 20% thiazoles organocopper compound wettable powder is under the situation of dilution 500 times (ultimate density is 400ppm); Bacteriostasis rate to test organisms is 89%; And the wettable powder of derosal does not have fungistatic effect to test organisms basically under the situation of dilution 500 times (ultimate density is 400ppm).
Embodiment 3
With 4.5g purity is that 99% 2-mercaptobenzothiazole, 5.6g purity are 2-amino-5-sulfydryl-1 of 98%; 3; 4-thiadiazoles and 180ml massfraction are in 95% the disposable input 500ml reaction flask of methanol aqueous solution, heating for dissolving under 85 ℃ temperature, solution A; With 2.5g purity is that 99% cupric sulfate pentahydrate and 25ml zero(ppm) water join in the 500ml reaction flask, heating, and under 30 ℃ temperature, stir it is fully dissolved; Treat that copper sulfate dissolves fully in water after, under the effect of stirring, dropwise (every 0.02～0.04ml) drips in the aqueous solution of copper sulfate solution A; Within 25min, dropwise, temperature control is at 65 ℃ then, stirring reaction 1h; Staticly settle 4h after the reaction, fully after the layering, remove upper solution; Lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 110 ℃ then, gets the tawny powder and is copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1; 3, the 4-thiadiazoles.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 90.0%, Nonyl pheno base ether 3.5%, novalgin formaldehyde condensation products 1.0%, wilkinite 5.5% are crossed 320 mesh sieves by said ratio with each material thorough mixing, grinding back and are promptly got 90% thiazoles organocopper compound wettable powder.
Strains tested is the ring rot of apple bacterium; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 90% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 90% thiazoles organocopper compound wettable powder in the present embodiment) that contains 90% derosal.The result shows: 90% thiazoles organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density is 900ppm); Bacteriostasis rate to test organisms is 97%; And the wettable powder of derosal is 44% to the inhibiting rate of test organisms under the situation of dilution 1000 times (ultimate density is 900ppm).
Embodiment 4
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 3.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 70.0%, octylphenol polyethylene ethenoxy group ether sulfate 10.0%, sodium dibutyl naphthalene sulfonate formaldehyde condensation products 5.5%, attapulgite 14.5% are crossed 320 mesh sieves by said ratio with each material thorough mixing, grinding back and are promptly got 70% thiazoles organocopper compound wettable powder.
Strains tested is the downy mildew of lichee bacterium; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 70% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 70% thiazoles organocopper compound wettable powder in the present embodiment) that contains 70% derosal.The result shows: 70% thiazoles organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density is 700ppm); Bacteriostasis rate to test organisms is 96%; And the wettable powder of derosal is 46% to the bacteriostasis rate of test organisms under the situation of dilution 1000 times (ultimate density is 700ppm).
It with 6.7g purity 99% 2-mercaptobenzothiazole; 5.7g purity is 2-amino-5-sulfydryl-1,3 of 98%, 4-thiadiazoles and 220ml massfraction are in 75% the disposable input 500ml reaction flask of methanol aqueous solution; Heating for dissolving under 80 ℃ temperature gets solution A; With 2.6g purity is that 95% cupric chloride and 25ml zero(ppm) water join in the 500ml reaction flask, heating, and under 45 ℃ temperature, stir it is fully dissolved; Treat that cupric chloride dissolves fully in water after, under the effect of stirring, dropwise (every 0.02～0.04ml) drips in the aqueous solution of cupric chloride solution A; Within 22min, dropwise, temperature control is at 62 ℃ then, stirring reaction 1h; Staticly settle 5h after the reaction, fully after the layering, remove upper solution; Lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 102 ℃ then, gets the tawny powder and is copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1; 3, the 4-thiadiazoles.
Take off each material of stating weight percentage; Copper-2-mercaptobenzothiazole-2-amino-5-the sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 80%, sodium dibutyl naphthalene sulfonate 4%, alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphonate 10%, light calcium carbonate 6% are crossed 320 mesh sieves by said ratio with each material thorough mixing, grinding back and are promptly got 80% thiazoles organocopper compound wettable powder.
Strains tested is the grey speck of soybean bacterium; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 80% thiazoles organocopper compound wettable powder that is mixed with is carried out bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 80% thiazoles organocopper compound wettable powder in the present embodiment) that contains 80% derosal.The result shows: 80% thiazoles organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density 800ppm); Inhibiting rate to test organisms is 98%; And the wettable powder of derosal is 33% to the bacteriostasis rate of test organisms under the situation of dilution 1000 times (ultimate density is 800ppm).
Embodiment 6
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 5.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 60%, X 2073 and sodium dibutyl naphthalene sulfonate are (by weight; X 2073: compsn 6% sodium dibutyl naphthalene sulfonate=1: 3), CMC 99.5 3%, zeyssatite and attapulgite are (by weight; Zeyssatite: compsn 31% attapulgite=1: 1), by said ratio 320 mesh sieves are crossed in each material thorough mixing, grinding back and promptly get 60% thiazoles organocopper compound wettable powder.
Strains tested is a cotton-wilt fusarium; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 60% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 60% thiazoles organocopper compound wettable powder in the present embodiment) that contains 60% derosal.The result shows: 60% thiazoles organocopper compound wettable powder is under the situation of dilution 200 times (ultimate density is 3000ppm); Bacteriostasis rate to test organisms is 98%; And the wettable powder of derosal does not have fungistatic effect to test organisms basically under the situation of dilution 200 times (ultimate density is 3000ppm).
Embodiment 7
It with 7.0g purity 99% 2-mercaptobenzothiazole; 5.8g purity is 2-amino-5-sulfydryl-1,3 of 98%, 4-thiadiazoles and 200ml massfraction are in 95% the disposable input 500ml reaction flask of aqueous ethanolic solution; Heating for dissolving under 60 ℃ temperature obtains solution A; With 2.8g purity is that 98% verditer and 25ml zero(ppm) water join in the 500ml reaction flask, heating, and under 35 ℃ temperature, stir, under the effect of stirring; Dropwise (every 0.02～0.04ml) drips in the mixture of verditer and water, within 30min, dropwises, and temperature control is at 65 ℃ then solution A; Stirring reaction 1h staticly settles 4.2h after the reaction, fully after the layering; Remove upper solution, lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 100 ℃ then; Get the tawny powder and be copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 30%, octylphenol polyethylene ethenoxy group ether, Nonyl pheno base ether and octylphenol polyethylene ethenoxy group ether sulfate are (by weight; Octylphenol polyethylene ethenoxy group ether: Nonyl pheno base ether: octylphenol polyethylene ethenoxy group ether sulfate=1: 1: 1) compsn 10%, sulfonated lignin and CMC 99.5 are (by weight; Lignin-sulphonate: CMC 99.5=2: 1) compsn 7%, WHITE CARBON BLACK, wilkinite and light calcium carbonate are (by weight; WHITE CARBON BLACK: wilkinite: compsn 53% light calcium carbonate=2.5: 1: 1.8), by said ratio 320 mesh sieves are crossed in each material thorough mixing, grinding back and promptly get 30% thiazoles organocopper compound wettable powder.
Strains tested is a peanut Cercospora bacteria; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 30% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 30% thiazoles organocopper compound wettable powder in the present embodiment) that contains 30% derosal.The result shows: 30% thiazoles organocopper compound wettable powder is under the situation of dilution 400 times (ultimate density is 750ppm); Bacteriostasis rate to test organisms is 97%; And the wettable powder of derosal is 38% to the bacteriostasis rate of test organisms under the situation of dilution 400 times (ultimate density is 750ppm).
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 7.
Take off each material of stating weight percentage: the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 40%, X 2073 and Nonyl pheno base ether are (by weight; X 2073: compsn 8% Nonyl pheno base ether=1: 3), sodium dibutyl naphthalene sulfonate formaldehyde condensation products, sodium naphthalene sulfonate yuban, novalgin formaldehyde condensation products and succinate sodium sulfonate (a kind of alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphonate) are (by weight; Sodium dibutyl naphthalene sulfonate formaldehyde condensation products: sodium naphthalene sulfonate yuban: novalgin formaldehyde condensation products: alkylphenol-polyethenoxy base ether formaldehyde condensation products sulphonate=2: 1: 3: 4) compsn 10%, WHITE CARBON BLACK and attapulgite are (by weight; WHITE CARBON BLACK: compsn 42% attapulgite=3: 1), by said ratio 320 mesh sieves are crossed in each material thorough mixing, grinding back and promptly get 40% thiazoles organocopper compound wettable powder.
Strains tested is a Sclerotinia sclerotiorum; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 40% thiazoles organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measure, do with reference to appearance with the wettable powder (auxiliary material and content thereof are all with 40% thiazoles organocopper compound wettable powder in the present embodiment) that contains 40% derosal.The result shows: 40% thiazoles organocopper compound wettable powder is under the situation of dilution 400 times (ultimate density is 1000ppm); Bacteriostasis rate to test organisms is 95%; And the wettable powder of derosal is 36% to the bacteriostasis rate of test organisms under the situation of dilution 400 times (ultimate density is 1000ppm).
Embodiment 9
It with the pure mass concentration of 6.8g 99% 2-mercaptobenzothiazole; 5.5g purity is 2-amino-5-sulfydryl-1,3 of 98%, 4-thiadiazoles and 240ml massfraction are in 85% the disposable input 500ml reaction flask of methanol aqueous solution; Heating for dissolving under 70 ℃ temperature obtains solution A; With 2.5g purity is that 95% cupric nitrate and 25ml zero(ppm) water join in the 500ml reaction flask, heating, and under 38 ℃ temperature, stir it is fully dissolved; Treat that cupric nitrate dissolves fully in water after, under the effect of stirring, dropwise (every 0.02～0.04ml) drips in the aqueous solution of cupric nitrate solution A; Within 28min, dropwise, temperature control is at 55 ℃ then, stirring reaction 2h; Staticly settle 4.8h after the reaction, fully after the layering, remove upper solution; Lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 108 ℃ then, gets the tawny powder and is copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1; 3, the 4-thiadiazoles.
With weight percentage is the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of 50% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and water dispersible granules is used for the conventional bacteriostatic test mensuration of stalk of sesame point rot bacterium after processing thiazoles organocopper compound water dispersible granules by ordinary method; Stalk of sesame point rot bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the water dispersible granules (auxiliary material and content thereof are all with the thiazoles organocopper compound water dispersible granules in the present embodiment) that contains 50% derosal.The result shows: 3g thiazoles organocopper compound water dispersible granules is put in the 1000mL water, be 98% to the bacteriostasis rate of test organisms, and the water dispersible granules of 3g derosal is put in the 1000mL water, is 45% to the bacteriostasis rate of test organisms.
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 9.
With weight percentage is the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of 60% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and water dispersible granules is used for the conventional bacteriostatic test mensuration of pear tree alternaria after processing thiazoles organocopper compound water dispersible granules according to ordinary method; The pear tree alternaria is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the water dispersible granules (auxiliary material and content thereof are all with the thiazoles organocopper compound water dispersible granules in the present embodiment) that contains 60% derosal.The result shows: 3g thiazoles organocopper compound water dispersible granules is put in the 1000mL water, be 97% to the bacteriostasis rate of test organisms, and the water dispersible granules of 3g derosal is put in the 1000mL water, is 33% to the bacteriostasis rate of test organisms.
Embodiment 11
It with 6.9g purity 99% 2-mercaptobenzothiazole; 3.3g purity is 2-amino-5-sulfydryl-1,3 of 98%, 4-thiadiazoles and 240ml massfraction are in 85% the disposable input 500ml reaction flask of aqueous ethanolic solution; Heating for dissolving under 68 ℃ temperature obtains solution A; With 5.0g purity is that 99% water acetic acid copper and 40ml zero(ppm) water join in the 500ml reaction flask, heating, and under 40 ℃ temperature, stir it is fully dissolved; Treat that neutralized verdigris dissolves fully in water after, under the effect of stirring, dropwise (every 0.02～0.04ml) drips in the aqueous solution of neutralized verdigris solution A; Within 25min, dropwise, temperature control is at 64 ℃ then, stirring reaction 0.5h; Staticly settle 4.6h after the reaction, fully after the layering, remove upper solution; Lower floor's tawny throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 106 ℃ then, gets the tawny powder and is copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1; 3, the 4-thiadiazoles.
With weight percentage is the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of 20% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is used for the conventional bacteriostatic test mensuration of fusarium graminearum after processing thiazoles organocopper compound suspension concentrate by ordinary method; Fusarium graminearum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the suspension concentrate (auxiliary material and content thereof are all with the thiazoles organocopper compound suspension concentrate in the present embodiment) that contains 20% derosal.The result shows: thiazoles organocopper compound suspension concentrate is under the situation of dilution 200 times (ultimate density is 1000ppm); Bacteriostasis rate to test organisms is 98%; And the suspension concentrate of derosal does not have fungistatic effect to test organisms basically under the situation of dilution 200 times (ultimate density is 1000ppm).
Embodiment 12
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 11.
With weight percentage is the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of 30% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is used for the conventional bacteriostatic test mensuration of tomato late blight bacterium after processing thiazoles organocopper compound suspension concentrate by ordinary method; The tomato late blight bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the suspension concentrate (auxiliary material and content thereof are all with the thiazoles organocopper compound suspension concentrate in the present embodiment) that contains 30% derosal.The result shows: thiazoles organocopper compound suspension concentrate is under the situation of dilution 200 times (ultimate density is 1500ppm); Bacteriostasis rate to test organisms is 97%; And the suspension concentrate of derosal is 52% to the bacteriostasis rate of test organisms under the situation of dilution 200 times (ultimate density is 1500ppm).
Embodiment 13
Copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 11.
With weight percentage is the copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of 40% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is used for the conventional bacteriostatic test mensuration of cucumber fusarium axysporum after processing thiazoles organocopper compound suspension concentrate by ordinary method; Cucumber fusarium axysporum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the suspension concentrate (auxiliary material and content thereof are all with the thiazoles organocopper compound suspension concentrate in the present embodiment) that contains 40% derosal.The result shows: thiazoles organocopper compound suspension concentrate is under the situation of dilution 200 times (ultimate density is 2000ppm); Bacteriostasis rate to test organisms is 95%; And the suspension concentrate of derosal does not have fungistatic effect to test organisms basically under the situation of dilution 200 times (ultimate density is 2000ppm).
The novel thiazole class organocopper compound (copper-2-mercaptobenzothiazole-2-amino-5-sulfydryl-1 of the present invention's preparation; 3; The 4-thiadiazoles) fungistatic effect obviously is superior to derosal; Fungistatic effect be derosal 2-5 doubly, be all very significantly to the bacillary or restraining and sterilizing bacteria effect of fungoid germ.
Claims (9)
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| CN107353131B (en) * | 2017-08-25 | 2020-12-04 | 新疆农业科学院土壤肥料与农业节水研究所(新疆维吾尔自治区新型肥料研究中心) | Foliar medicinal fertilizer for preventing and treating walnut leaf edge scorch and preparation and application thereof |
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