CN102516265A - Thiadiazole quinoline organic copper compound, preparation method thereof, preparation thereof, and application thereof in controlling agricultural plant diseases - Google Patents
Thiadiazole quinoline organic copper compound, preparation method thereof, preparation thereof, and application thereof in controlling agricultural plant diseases Download PDFInfo
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- CN102516265A CN102516265A CN2011104016378A CN201110401637A CN102516265A CN 102516265 A CN102516265 A CN 102516265A CN 2011104016378 A CN2011104016378 A CN 2011104016378A CN 201110401637 A CN201110401637 A CN 201110401637A CN 102516265 A CN102516265 A CN 102516265A
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Abstract
The invention discloses a thiadiazole quinoline organic copper compound, a preparation method thereof, a preparation thereof, and an application thereof in controlling agricultural plant diseases. According to the invention, 2-amino-5-sulfhydryl-1,3,4-thiadiazole, 8-oxyquinoline and cupric salt are added to an organic solvent; the mixture is subject to a reaction for 1-3h; when the reaction is finished, a product is separated, washed, and dried, such that the thiadiazole quinoline organic copper compound is obtained. The preparation method provided by the invention is simple and feasible; the cost is low; and no environment pollution is caused. The prepared novel thiadiazole quinoline compound which is copper-2-amino-5-sulfhydryl-1,3,4-thiadiazole-8-oxyquinoline is advantaged in stable property and wide sterilizing spectrum. The compound can be widely applied for controlling agricultural plant diseases such as tomato late blinght, cucumber downy mildew, lychee downy mildew, apple ring spot, paddy bacterial blight and bacterial leaf streak, and citrus canker.
Description
Technical field
The invention belongs to the pesticide chemical technical field, particularly a kind of thiadiazoles quinoline organocopper compound and preparation method thereof, preparation and the purposes in control agricultural plants disease.
Background technology
2-amino-5-sulfydryl-1,3,4-thiadiazoles molecular formula is 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.
The oxine molecular formula is C
9H
7NO, molecular weight is 145.16, is white or faint yellow crystallization or crystalline powder; Water insoluble and ether is dissolved in ethanol, acetone, chloroform, benzene or diluted acid, is amphoteric substance; Can be dissolved in strong acid, highly basic; In alkali, be ionized into negative ion, ability binding hydrogen ions in acid, solvability is minimum when PH=7.Being prone to reactions such as generation is nitrated, sulfonation, oxidation, is the useful intermediates of organic synthesis (like medicine).Also can be used as rna synthesis inhibitor, beard and hair trichobacteria, myrothecium verrucaria and trichoderma viride are had the sterilization restraining effect, its mantoquita complex compound is good sterilant.
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, the dual mechanism sterilization, sterilization is more thorough, and is 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.Not seeing as yet at present has thiadiazoles quinolines copper-2-amino-5-sulfydryl-1; 3; The relevant report of 4-thiadiazoles-oxine and preparation method thereof; Do not find that more 4-thiadiazoles-oxine is used for the relevant report of agricultural plants disease control with thiadiazoles quinolines copper-2-amino-5-sulfydryl-1,3.
Summary of the invention
The object of the present invention is to provide a kind of new thiobizole quinoline organocopper compound; Provide simultaneously that a kind of preparation method is simple, cost is low, the preparation method of the new thiobizole quinoline organocopper compound of environmental protection; The thiadiazoles quinoline organocopper compound stable in properties of preparation; Fungicidal spectrum is wide, can be widely used in the control of agricultural plants disease.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of thiadiazoles quinoline organocopper compound, concrete name is called copper-2-amino-5-sulfydryl-1,3, and 4-thiadiazoles-oxine, this compound have suc as formula the chemical structural formula shown in 1:
The preparation method of above-mentioned thiadiazoles quinoline organocopper compound may further comprise the steps:
With the 2-amino-5-sulfydryl-1,3 of 5.0-5.9g purity 99%, it is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that the oxine of 4-thiadiazoles and 6.4-7.3g purity 98% adds the 140-260ml massfraction; Heating for dissolving gets solution A, in the cupric salt adding 25ml water with 2.5-3.0g purity 95-99%; Get 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 1h in 64-75 ℃; Staticly settle after stirring end, precipitation separation will precipitate and use washing with alcohol; Use water washing then, dry after the washing the Powdered thiadiazoles quinoline of beige organocopper compound.
The addition of said methanol aqueous solution or aqueous ethanolic solution is can dissolve 2-amino-5-sulfydryl-1,3, and 4-thiadiazoles and oxine are as the criterion; When cupric salt was water-soluble, the addition of water was as the criterion can dissolve cupric salt, and when cupric salt was water insoluble, the addition of water was being as the criterion by moistening 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 thiadiazoles quinoline organocopper compound, said preparation comprises the thiadiazoles quinoline 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 that by massfraction 20～90% thiadiazoles quinoline organocopper compound, 1～10% wetting agent, 1～10% dispersion agent, surplus are 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 thiadiazoles quinoline 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 are paddy rice, wheat, corn, soybean, cotton, peanut, watermelon, rape or sesame; Said fruit tree is apple tree, litchi, citrus trees or peach; Said vegetables are tomato or cucumber; Said bacterial disease is rice leaf spot bacteria, bacterial stripe bacterium or ulcer bacteria; Said fungal disease is rust, phytophthora root rot bacterium, Pseudoperonospora cubensis, wheel line bacterium disease, leaf spot fungi, stem point rot bacterium, sheath blight fungus, wilt or sclerotium germ.
The invention has the advantages that: the first, main raw material 2-amino of the present invention-5-sulfydryl-1,3,4-thiadiazoles and oxine are with low cost, and raw material is easy to get, for prepared new thiobizole quinoline organocopper compound provides good cost advantage; The second, characteristics such as preparation method of the present invention has the reaction conditions gentleness, and technology is easy are easy to suitability for industrialized production, and do not produce the three wastes, environmentally safe; The 3rd, the thiadiazoles quinoline organocopper compound stable in properties of the present invention preparation is met strong acid, highly basic does not decompose, and can use with Multiple Pesticides, has solved in the past inorganic copper and the drawback of organic copper fungicide compounding property difference; The 4th; The thiadiazoles quinoline organocopper compound of the present invention's preparation forms coordination compound with organic molecule and cupric ion; The release of cupric ion can reach the concentration of kill pathogenic organisms; Simultaneously can not cause poisoning again, therefore possess the potentiality of the novel organic copper sterilant that is developed to efficient, nontoxic, lasting and environmental protection crop; The 5th; The sterilant that adopts thiadiazoles quinoline organocopper compound according to the invention to be prepared from; Fungicidal spectrum is wide, and bacterium and the microbial disease of fungoid disease are all had control effect, can be widely used in the control of tomato late blight, cucumber downy mildew, downy mildew of lichee, ring rot of apple, bacterial blight of rice and agricultural plants diseases such as bacterial stripe, citrus ulcer; In addition, the mould inhibitor that also can be used as rope, line, leather, vinyl plastics.
Description of drawings
Fig. 1 is the mass spectrum of the thiadiazoles quinoline organocopper compound of the present invention's preparation.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the thiadiazoles quinoline organocopper compound of the present invention's preparation.
The thiadiazoles quinoline organocopper compound that Fig. 3 prepares for the present invention is used for bacterial stripe bacterium bacteriostatic test and surveys periodic fungistatic effect figure.
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 with reference to an appearance derosal.
Embodiment 1
With 5.6g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 6.4g purity are that 98% oxine and 260ml massfraction are in 75% the disposable input 500ml reaction flask of aqueous ethanolic solution, heating for dissolving under 75 ℃ temperature; Solution A, be that 99% cupric sulfate pentahydrate and 25ml zero(ppm) water join in the 500ml reaction flask with 2.5g purity, heating, and stirring is fully dissolved it under 42 ℃ temperature; 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, within 27min, dropwises solution A; Temperature control is at 70 ℃ then, and stirring reaction 1h staticly settles 4.5h after the reaction; Fully after the layering, remove upper solution, lower floor's beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively; In thermostatic drying chamber, dry down then, get the beige powder and be copper-2-amino-5-sulfydryl-1,3 in 105 ℃; 4-thiadiazoles-oxine, structure is shown below
Like Fig. 1, shown in 2, detecting m/z in the mass spectrum and be 339 characteristic peak and NMR hydrogen spectrogram intermediate value is 6.99,7.03,7.61,7.64,7.70,8.39 and 8.89 characteristic peak.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline organocopper compound wettable powder.
The 50% thiadiazoles quinoline organocopper compound wettable powder that is mixed with is carried out bacteriostatic test to be measured; Do with reference to appearance with the wettable powder that contains 50% derosal (auxiliary material and content thereof are all with 50% thiadiazoles quinoline organocopper compound wettable powder of present embodiment), strains tested is the bacterial stripe bacterium 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 to the bacterial stripe bacterium; The wettable powder (667ppm) that 4 contained medicines of virgin paper sheet that are positioned at the petridish periphery among the figure are derosal, being positioned at 1 contained medicine of virgin paper sheet of petridish intermediary is thiadiazoles quinoline organocopper compound wettable powder (667ppm).From Fig. 3, can find out and adopt sterilant restraining and sterilizing bacteria effect under 667ppm of thiadiazoles quinoline organocopper compound preparation obviously to be superior to contrasting pesticide carbendazim, inhibition zone roughly is 5 times of derosal control group.
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 1.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline 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% thiadiazoles quinoline 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 that contains 20% derosal (auxiliary material and content are all with 20% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 20% thiadiazoles quinoline organocopper compound wettable powder is under the situation of dilution 500 times (ultimate density is 400ppm); Bacteriostasis rate to test organisms is 97%; 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 5.5g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 6.6g purity are that 98% oxine and 240ml massfraction are in 95% the disposable input 500ml reaction flask of methanol aqueous solution, heating for dissolving under 95 ℃ temperature; Solution A, be that 99% cupric sulfate pentahydrate and 25ml zero(ppm) water join in the 500ml reaction flask with 2.5g purity, heat; And under 40 ℃ temperature, stir it is fully dissolved, treat that copper sulfate is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.04ml) drips in the aqueous solution of copper sulfate, within 25min, dropwises, and temperature control is at 68 ℃ then solution A; Stirring reaction 1h staticly settles 4h after the reaction, fully after the layering; Remove upper solution, lower floor's beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 110 ℃ then; Get the beige powder and be copper-2-amino-5-sulfydryl-1,3,4-thiadiazoles-oxine.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline 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% thiadiazoles quinoline 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 that contains 90% derosal (auxiliary material and content thereof are all with 90% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 90% thiadiazoles quinoline organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density is 900ppm); Bacteriostasis rate to test organisms is 95%; And the wettable powder of derosal is 45% to the inhibiting rate of test organisms under the situation of dilution 1000 times (ultimate density is 900ppm).
Embodiment 4
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 3.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline 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% thiadiazoles quinoline 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 that contains 70% derosal (auxiliary material and content thereof are all with 70% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 70% thiadiazoles quinoline organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density is 700ppm); Bacteriostasis rate to test organisms is 94%; And the wettable powder of derosal is 48% to the bacteriostasis rate of test organisms under the situation of dilution 1000 times (ultimate density is 700ppm).
Embodiment 5
With 5.7g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 6.7g purity are that 98% oxine and 200ml massfraction are in 75% the disposable input 500ml reaction flask of methanol aqueous solution, heating for dissolving under 80 ℃ temperature; Solution A, be that 95% cupric chloride and 25ml zero(ppm) water join in the 500ml reaction flask with 2.6g purity, heat; And under 50 ℃ temperature, stir it is fully dissolved, treat that cupric chloride is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.04ml) drips in the aqueous solution of cupric chloride, within 22min, dropwises, and temperature control is at 66 ℃ then solution A; Stirring reaction 1h staticly settles 5h after the reaction, fully after the layering; Remove upper solution, lower floor's beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 102 ℃ then; Get the beige powder and be copper-2-amino-5-sulfydryl-1,3,4-thiadiazoles-oxine.
Take off each material of stating weight percentage; Copper-2-amino-5-the sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 80%, sodium dibutyl naphthalene sulfonate 4%, succinate sodium sulfonate (a kind of 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% thiadiazoles quinoline organocopper compound wettable powder.
Strains tested is an xanthomonas oryzae pv. oryzicola; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 80% thiadiazoles quinoline 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 that contains 80% derosal (auxiliary material and content thereof are all with 80% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 80% thiadiazoles quinoline 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 35% to the bacteriostasis rate of test organisms under the situation of dilution 1000 times (ultimate density is 800ppm).
Embodiment 6
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 5.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline 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% thiadiazoles quinoline 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 that contains 60% derosal (auxiliary material and content thereof are all with 60% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 60% thiadiazoles quinoline organocopper compound wettable powder is under the situation of dilution 200 times (ultimate density is 3000ppm); Bacteriostasis rate to test organisms is 95%; 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).
With 5.0g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 6.8g purity are that 98% oxine and 140ml massfraction are in 95% the disposable input 500ml reaction flask of aqueous ethanolic solution; Heating for dissolving under 85 ℃ temperature, solution A, be that 98% verditer and 25ml zero(ppm) water join in the 500ml reaction flask with 2.8g purity; Heating, and under 45 ℃ 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 beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 100 ℃ then; Get the beige powder and be copper-2-amino-5-sulfydryl-1,3,4-thiadiazoles-oxine.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline organocopper compound wettable powder.
Strains tested is a citrus ulcer bacteria; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 30% thiadiazoles quinoline 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 that contains 30% derosal (auxiliary material and content thereof are all with 30% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 30% thiadiazoles quinoline 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 40% to the bacteriostasis rate of test organisms under the situation of dilution 400 times (ultimate density is 750ppm).
Embodiment 8
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 7.
Take off each material of stating weight percentage: the copper-2-amino-5-sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles-oxine 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% thiadiazoles quinoline organocopper compound wettable powder.
Strains tested is a Sclerotinia sclerotiorum; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 40% thiadiazoles quinoline 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 that contains 40% derosal (auxiliary material with and content all with 40% thiadiazoles quinoline organocopper compound wettable powder of present embodiment).The result shows: 40% thiadiazoles quinoline 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 32% to the bacteriostasis rate of test organisms under the situation of dilution 400 times (ultimate density is 1000ppm).
Embodiment 9
With 5.8g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 6.5g purity are that 98% oxine and 220ml massfraction are in 85% the disposable input 500ml reaction flask of methanol aqueous solution, heating for dissolving under 70 ℃ temperature; Solution A, be that 95% cupric nitrate and 25ml zero(ppm) water join in the 500ml reaction flask with 2.5g purity, heat; And under 48 ℃ temperature, stir it is fully dissolved, treat that cupric nitrate is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.04ml) drips in the aqueous solution of cupric nitrate, within 30min, dropwises, and temperature control is at 75 ℃ then solution A; Stirring reaction 1h staticly settles 4.8h after the reaction, fully after the layering; Remove upper solution, lower floor's beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 108 ℃ then; Get the beige powder and be copper-2-amino-5-sulfydryl-1,3,4-thiadiazoles-oxine.
With weight percentage is the copper-2-amino-5-sulfydryl-1 of 50% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles-oxine and water dispersible granules is used for the conventional bacteriostatic test mensuration of stalk of sesame point rot bacterium after processing thiadiazoles quinoline 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 that contains 50% derosal (auxiliary material and content thereof are all with the thiadiazoles quinoline organocopper compound water dispersible granules of present embodiment).The result shows: 3g thiadiazoles quinoline organocopper compound water dispersible granules is put in the 1000mL water, be 93% to the bacteriostasis rate of test organisms, and the water dispersible granules of 3g derosal is put in the 1000mL water, is 55% to the bacteriostasis rate of test organisms.
Embodiment 10
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 9.
With weight percentage is the copper-2-amino-5-sulfydryl-1 of 60% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles-oxine and water dispersible granules is used for the conventional bacteriostatic test mensuration of grey speck of soybean bacterium after processing thiadiazoles quinoline organocopper compound water dispersible granules according to ordinary method; The grey speck of soybean bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the water dispersible granules that contains 60% derosal (auxiliary material and content thereof are all with the thiadiazoles quinoline organocopper compound water dispersible granules of present embodiment).The result shows: 3g thiadiazoles quinoline organocopper compound water dispersible granules is put in the water of 1000mL, be 95% to the bacteriostasis rate of test organisms, and the dispersible granule of 3g derosal water is put in the 1000mL water, is 33% to the bacteriostasis rate of test organisms.
Embodiment 11
With 5.9g purity is 2-amino-5-sulfydryl-1,3 of 99%, and 4-thiadiazoles, 7.3g purity are that 98% oxine and 180ml massfraction are in 85% the disposable input 500ml reaction flask of aqueous ethanolic solution, heating for dissolving under 88 ℃ temperature; Solution A, be that 99% a water acetic acid copper and 25ml zero(ppm) water join in the 500ml reaction flask with 3.0g purity, heat; And under 50 ℃ temperature, stir it is fully dissolved, treat that neutralized verdigris is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.04ml) drips in the aqueous solution of neutralized verdigris, within 25min, dropwises, and temperature control is at 64 ℃ then solution A; Stirring reaction 1h staticly settles 4.6h after the reaction, fully after the layering; Remove upper solution, lower floor's beige throw out is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 106 ℃ then; Get the beige powder and be copper-2-amino-5-sulfydryl-1,3,4-thiadiazoles-oxine.
With weight percentage is the copper-2-amino-5-sulfydryl-1 of 20% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles-oxine and suspension concentrate is used for the conventional bacteriostatic test mensuration of peach ulcer bacteria after processing thiadiazoles quinoline organocopper compound suspension concentrate by ordinary method; The peach ulcer bacteria is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, does with reference to appearance with the suspension concentrate that contains 20% derosal (auxiliary material and content thereof are all with the thiadiazoles quinoline organocopper compound suspension concentrate of present embodiment).The result shows: thiadiazoles quinoline organocopper compound suspension concentrate is under the situation of dilution 200 times (ultimate density is 1000ppm); Bacteriostasis rate to test organisms is 96%; 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-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 11.
With weight percentage is the copper-2-amino-5-sulfydryl-1 of 30% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles-oxine and suspension concentrate is used for the conventional bacteriostatic test mensuration of tomato late blight bacterium after processing thiadiazoles quinoline 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 that contains 30% derosal (auxiliary material and content thereof are all with the thiadiazoles quinoline organocopper compound suspension concentrate of present embodiment).The result shows: thiadiazoles quinoline 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 54% to the bacteriostasis rate of test organisms under the situation of dilution 200 times (ultimate density is 1500ppm).
Embodiment 13
Copper-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles-oxine is with embodiment 11.
With weight percentage is the copper-2-amino-5-sulfydryl-1 of 40% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles-oxine and suspension concentrate is used for the conventional bacteriostatic test mensuration of cucumber fusarium axysporum after processing thiadiazoles quinoline 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 that contains 40% derosal (auxiliary material and content thereof are all with the thiadiazoles quinoline organocopper compound suspension concentrate of present embodiment).The result shows: thiadiazoles quinoline 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 thiadiazoles quinoline organocopper compound (copper-2-amino-5-sulfydryl-1 of the present invention's preparation; 3; 4-thiadiazoles-oxine) fungistatic effect obviously is superior to derosal; Its 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)
1. thiadiazoles quinoline organocopper compound, it is characterized in that: this compound has suc as formula the chemical structural formula shown in 1:
2. one kind prepares the method for thiadiazoles quinoline organocopper compound according to claim 1, it is characterized in that: may further comprise the steps:
With the 2-amino-5-sulfydryl-1,3 of 5.0-5.9g purity 99%, it is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that the oxine of 4-thiadiazoles and 6.4-7.3g purity 98% adds the 140-260ml massfraction; Heating for dissolving gets solution A, in the cupric salt adding 25ml water with 2.5-3.0g purity 95-99%; Get 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 1h in 64-75 ℃; Staticly settle after stirring end, precipitation separation will precipitate and use washing with alcohol; Use water washing then, dry after the washing the Powdered thiadiazoles quinoline of beige organocopper compound.
3. according to the said a kind of method for preparing thiadiazoles quinoline organocopper compound of claim 2, it is characterized in that: said cupric salt includes but not limited to copper sulfate, cupric chloride, verditer, cupric nitrate or neutralized verdigris.
4. according to the said a kind of method for preparing thiadiazoles quinoline organocopper compound of claim 2, it is characterized in that: said solution A dropwises in 22-30min.
5. preparation of thiadiazoles quinoline organocopper compound according to claim 1; It is characterized in that: said preparation comprises the thiadiazoles quinoline organocopper compound of 20-90% by massfraction; Surplus is an auxiliary material, and the formulation of said preparation comprises wettable powder, water dispersible granules or suspension concentrate.
6. according to the preparation of the said a kind of thiadiazoles quinoline organocopper compound of claim 5, it is characterized in that: the component of said wettable powder comprises that by massfraction 20～90% thiadiazoles quinoline organocopper compound, 1～10% wetting agent, 1～10% dispersion agent, surplus are filler.
7. according to the preparation of the said a kind of thiadiazoles quinoline organocopper compound of claim 6, it is characterized in that: 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.
One kind according to claim 1 thiadiazoles quinoline organocopper compound the control agricultural plants bacillary with fungal disease in purposes.
9. said according to Claim 8 a kind of thiadiazoles quinoline organocopper compound the control agricultural plants bacillary with fungal disease in purposes; It is characterized in that: said agricultural plants comprises farm crop, fruit tree or vegetables, and said farm crop are paddy rice, wheat, corn, soybean, cotton, peanut, watermelon, rape or sesame; Said fruit tree is apple tree, litchi, citrus trees or peach; Said vegetables are tomato or cucumber; Said bacterial disease is rice leaf spot bacteria, bacterial stripe bacterium or ulcer bacteria; Said fungal disease is rust, phytophthora root rot bacterium, Pseudoperonospora cubensis, wheel line bacterium disease, leaf spot fungi, stem point rot bacterium, sheath blight fungus, wilt or sclerotium germ.
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| CN109430275A (en) * | 2018-10-25 | 2019-03-08 | 中国农业科学院植物保护研究所 | Agricultural bactericide and application with bactericidal activity |
| CN111423472A (en) * | 2018-12-24 | 2020-07-17 | 刘力 | Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof |
| CN111454284A (en) * | 2020-06-01 | 2020-07-28 | 河南福瑞得生物科技有限公司 | Organic copper compound, preparation method and application thereof |
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| CN102174031A (en) * | 2011-03-24 | 2011-09-07 | 南开大学 | 1,2,3-thiadiazole-1,3,4-thiadiazole compounds and preparation method and application thereof |
| CN102225918A (en) * | 2010-06-12 | 2011-10-26 | 利尔化学股份有限公司 | 1,2,3-thiadiazole formyl urea compounds as well as preparation method and application thereof |
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| CN102225918A (en) * | 2010-06-12 | 2011-10-26 | 利尔化学股份有限公司 | 1,2,3-thiadiazole formyl urea compounds as well as preparation method and application thereof |
| CN101885724A (en) * | 2010-07-09 | 2010-11-17 | 南京工业大学 | Heterocyclic ketone-containing N-substituted phenyl pyrazole compound, preparation method thereof and application thereof in prevention and control of plant diseases and insect pests |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109430275A (en) * | 2018-10-25 | 2019-03-08 | 中国农业科学院植物保护研究所 | Agricultural bactericide and application with bactericidal activity |
| CN111423472A (en) * | 2018-12-24 | 2020-07-17 | 刘力 | Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof |
| CN111454284A (en) * | 2020-06-01 | 2020-07-28 | 河南福瑞得生物科技有限公司 | Organic copper compound, preparation method and application thereof |
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