CN102516268A - Oxazole thiadiazole organic copper compound, its preparation method, preparation and application in controlling agricultural plant diseases - Google Patents
Oxazole thiadiazole organic copper compound, its preparation method, preparation and application in controlling agricultural plant diseases Download PDFInfo
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Abstract
The invention discloses an oxazole thiadiazole organic copper compound, its preparation method, preparation and application in controlling agricultural plant diseases. The preparation method comprises the following steps: adding 3-hydroxy-5-methyl isoxazole (hymexazol) and 2-amino-5-mercapto-1,3,4-thiadiazole and cupric salts in an organic solvent, reacting for 0.5-2 h, after the reaction successively carrying out separation, washing and drying to obtain the novel oxazole thiadiazole organic copper compound, that is, Cu-3-hydroxy-5-methyl isoxazole-2-amino-5-mercapto-1,3,4-thiadiazole. The obtained compound has stable properties and wide fungicide spectrum, can be made into wettable powder, dry suspending agents and aqueous suspending agents and the like, has outstanding control effects on main diseases of various crops, especially can control the diseases caused by Fusarium, aphanomyces invadans, Pythium aphanidermatum, and Corticium, and has special efficacy on various soil borne diseases and seedling damping off.
Description
Technical field
The invention belongs to the pesticide chemical technical field, particularly Yi Zhong oxazole thiadiazole organocopper compound and preparation method thereof, preparation and the purposes in control agricultural plants disease.
Background technology
3-hydroxy-5-methyl-isoxazole (disliking mould spirit) molecular formula is C
4H
5NO
2, molecular weight is 99, is dissolved in most of organic solvents, and is all stable in acid, alkaline solution; Non-corrosiveness is a kind of systemic fungicide and plant-growth regulator, and it has interior absorption and conductivity; Can directly be absorbed, get in the plant materials, move very rapid by plant root. in root system, move and only just moved to stem in 3 hours; Move to the plant whole body in 24 hours, it is two kinds of glucosides at the intravital meta-bolites of plant, plant is had the effect that promotes growth and well developed root system.In addition; The 3-hydroxy-5-methyl-isoxazole has efficiently, the characteristics of low toxicity and environmental protection; Be used for powerful soil sterilization and seed disinfection,, remarkable prevention effect all arranged like sickle-like bacteria, the rotten bacterium of seedling, pythium spp, rhizoctonia, root shell bacterium, snow germ etc. to various fungal diseases of plants.Adaptable across paddy rice, wheat, cotton, beet, tobacco, vegetables, nursery stock, fruit tree, cereal, oily section, melon, lawn, flowers and other crops by above-mentioned pathogenetic bacteria and fungus-caused crop pest.
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.
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.Not seeing as yet at present has novel oxazole thiadiazole compound copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1; 3; The relevant report of 4-thiadiazoles and preparation method thereof; Do not find that more the 4-thiadiazoles is used for the relevant report of agricultural plants disease control with this novel oxazole thiadiazole compound copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3.
Summary of the invention
The object of the present invention is to provide a kind of novel oxazole thiadiazole organocopper compound; Provide simultaneously that a kind of preparation method is simple, cost is low, the preparation method of the novel oxazole thiadiazole organocopper compound of environmental protection; Preparation De oxazole thiadiazole organocopper compound stable in properties; Fungicidal spectrum is wide, can be used for preventing and treating the agricultural plants disease.
To achieve these goals, the present invention has adopted following technical scheme:
An oxazole thiadiazole organocopper compound, concrete name is called copper-3-hydroxy-5-methyl-isoxazole-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 Shang Shu oxazole thiadiazole organocopper compound may further comprise the steps:
With the 3-hydroxy-5-methyl-isoxazole of 6.5-7.0g purity 99% and the 2-amino-5-sulfydryl-1,3 of 5.3-5.8g purity 98%, it is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that the 4-thiadiazoles adds the 160-260ml massfraction; Heating for dissolving gets solution A, is in the cupric salt adding 25ml water of 95-99% with 2.5-3.0g purity; 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 55-70 ℃; Staticly settle after stirring end, precipitation separation will precipitate and use washing with alcohol; Use water washing then, dry after the washing yellowish green toner end shape oxazole thiadiazole organocopper compound.
The addition of said methanol aqueous solution or aqueous ethanolic solution is can dissolve 3-hydroxy-5-methyl-isoxazole and 2-amino-5-sulfydryl-1,3, and the 4-thiadiazoles is 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 25-30min.
The preparation of Shang Shu oxazole thiadiazole organocopper compound, said preparation comprises 20-90% De oxazole thiadiazole organocopper compound 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% De oxazole thiadiazole organocopper compounds, 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.
Shang Shu oxazole thiadiazole organocopper compound the control agricultural plants bacillary with fungal disease in purposes.
Said agricultural plants comprises farm crop, fruit tree or vegetables; Said farm crop are paddy rice, wheat, corn, beans, cotton, tobacco, watermelon, beet or Chinese cabbage; Said fruit tree is apple tree, pear tree or peach; Said vegetables are tomato, paprike, eggplant, cucumber or green onion, garlic class; Said bacterial disease is rice leaf spot bacteria, ralstonia solanacearum, bacterial stripe bacterium or ulcer bacteria; Said fungal disease is the rotten germ of gibberellic hypha, seedling, rotten mildew fungus, silk nuclear germ, root shell germ, avenges little germ, sheath blight fungus, wilt or sclerotium germ.
The invention has the advantages that: first; Main raw material 3-hydroxy-5-methyl-isoxazole of the present invention and 2-amino-5-sulfydryl-1,3, the 4-thiadiazoles is with low cost; Raw material is easy to get; Be prepared novel oxazole thiadiazole organocopper compound copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3, the 4-thiadiazoles 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 novel oxazole thiadiazole organocopper compound copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of the present invention's preparation; 3,4-thiadiazoles stable in properties, chance strong acid, highly basic do not decompose; Can use with Multiple Pesticides, solve the drawback of inorganic in the past copper and organic copper fungicide compounding property difference; The 4th; The prepared De oxazole of the present invention thiadiazole organocopper compound 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 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 Suo Shu oxazole thiadiazole organocopper compound of the present invention to be prepared from; Fungicidal spectrum is wide, and is not only efficient to bacterium, and fungi even the germ that is difficult to prevent and treat are all had efficiently; Especially can prevent and treat the disease that sickle mycete, silk capsule mould, pythium spp and corticium cause, various soil-borne diseases and rice shoot damping-off are had special efficacy.
Description of drawings
Fig. 1 prepares the mass spectrum of De oxazole thiadiazole organocopper compound for the present invention.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the oxazole thiadiazole organocopper compound of the present invention's preparation.
The oxazole thiadiazole 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, with reference to appearance dislike a mould spirit, derosal is commercial product.
Embodiment 1
With 6.6g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.4g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles and 160ml massfraction are in 75% the disposable input 250ml reaction flask of aqueous ethanolic solution; Heating for dissolving under 72 ℃ temperature, solution A, be that 99% cupric sulfate pentahydrate and 25ml zero(ppm) water join in the 250ml reaction flask with 2.5g purity; Heating, and under 44 ℃ temperature, stir it is fully dissolved treats that copper sulfate is in water fully after the dissolving; Under the effect of stirring, dropwise (every 0.02～0.05ml) drips in the aqueous solution of copper sulfate, within 28min, dropwises solution A; Temperature control is at 70 ℃ then, and stirring reaction 1h staticly settles 3.5h after the reaction; Fully after the layering, remove upper solution, lower floor's yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively; In thermostatic drying chamber, dry down then, get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3 in 105 ℃; The 4-thiadiazoles, structure is shown below
Like Fig. 1, shown in 2, detect m/z in the mass spectrum and be 293 characteristic peak and NMR hydrogen spectrogram intermediate value and be 2.36,5.81 and 6.99 characteristic peak.
Take off each material of stating weight percentage: the copper-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole organocopper compound wettable powder.
The 50% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out bacteriostatic test to be measured; With contain 50% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 50% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance, 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, wherein, figure left side upper rightly is followed successively by derosal (667ppm) with the bottom right, dislike mould spirit (667ppm) He the wettable powder (667ppm) of oxazole thiadiazole organocopper compound to bacterial stripe bacterium fungistatic effect.But the restraining and sterilizing bacteria effect of Kan Chu oxazole thiadiazole organocopper compound wettable powder obviously is superior to contrasting pesticide carbendazim and dislikes mould spirit from Fig. 3, and inhibition zone roughly is 4 times of derosal control group, dislike mould spirit 3 times.
Embodiment 2
Copper-3-hydroxy-5-methyl-isoxazole-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-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 20% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 20% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 20% oxazole thiadiazole organocopper compound wettable powder is under the situation of dilution 500 times (ultimate density is 400ppm); Bacteriostasis rate to test organisms is 94%; And the wettable powder of disliking mould spirit or derosal is under the situation of dilution 500 times (ultimate density is 400ppm), and the bacteriostasis rate of test organisms is respectively 30% and do not have fungistatic effect basically.
Embodiment 3
With 6.5g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.6g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles and 240ml massfraction are in 95% the disposable input 500ml reaction flask of methanol aqueous solution, heating for dissolving under 85 ℃ 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 35 ℃ temperature, stir it is fully dissolved, treat that copper sulfate is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.05ml) drips in the aqueous solution of copper sulfate, within 25min, dropwises, and temperature control is at 65 ℃ then solution A; Stirring reaction 1h staticly settles 4h after the reaction, fully after the layering; Remove upper solution, lower floor's yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 110 ℃ then; Get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
Take off each material of stating weight percentage: the copper-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 90% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 90% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 90% oxazole thiadiazole organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density is 900ppm); Bacteriostasis rate to test organisms is 96%; And the wettable powder of disliking mould spirit or derosal is under the situation of dilution 1000 times (ultimate density is 900ppm), and the inhibiting rate of test organisms is respectively 44% and 35%.
Embodiment 4
Copper-3-hydroxy-5-methyl-isoxazole-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-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 70% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 70% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 70% oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 1000 times (ultimate density is 700ppm), is 46% to the bacteriostasis rate of test organisms.
Embodiment 5
With 6.7g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.7g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles and 260ml 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 45 ℃ temperature, stir it is fully dissolved, treat that cupric chloride is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.05ml) drips in the aqueous solution of cupric chloride, within 26min, dropwises, and temperature control is at 64 ℃ then solution A; Stirring reaction 1h staticly settles 3h after the reaction, fully after the layering; Remove upper solution, lower floor's yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 102 ℃ then; Get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
Take off each material of stating weight percentage; Copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-the sulfydryl-1 of present embodiment preparation; 3; 4-thiadiazoles 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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out bacteriostatic test according to ordinary method measures, with contain 80% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 80% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 80% oxazole thiadiazole organocopper compound wettable powder is under the situation of dilution 1000 times (ultimate density 800ppm); Inhibiting rate to test organisms is 97%; And the wettable powder of disliking mould spirit or derosal is under the situation of dilution 1000 times (ultimate density is 800ppm), is 33% and 28% to the bacteriostasis rate of test organisms.
Embodiment 6
Copper-3-hydroxy-5-methyl-isoxazole-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-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 60% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 60% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 60% oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 200 times (ultimate density is 3000ppm), and the bacteriostasis rate of test organisms is respectively 48% and do not have fungistatic effect basically.
Embodiment 7
With 7.0g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.8g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles and 180ml massfraction are in 95% the disposable input 500ml reaction flask of aqueous ethanolic solution; Heating for dissolving under 65 ℃ 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 35 ℃ temperature, stir, under the effect of stirring; Dropwise (every 0.02～0.05ml) drips in the mixture of verditer and water, within 30min, dropwises, and temperature control is at 68 ℃ then solution A; Stirring reaction 1h staticly settles 4.2h after the reaction, fully after the layering; Remove upper solution, lower floor's yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 100 ℃ then; Get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
Take off each material of stating weight percentage: the copper-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole 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% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 30% dislike mould spirit or derosal wettable powder (auxiliary material and content thereof are all with 30% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 30% oxazole thiadiazole organocopper compound wettable powder is under the situation of dilution 400 times (ultimate density is 750ppm); Bacteriostasis rate to test organisms is 96%; And the wettable powder of disliking mould spirit or derosal is under the situation of dilution 400 times (ultimate density is 750ppm), and the bacteriostasis rate of test organisms is respectively 42% and 38%.
Embodiment 8
Copper-3-hydroxy-5-methyl-isoxazole-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-3-hydroxy-5-methyl-isoxazole-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% oxazole thiadiazole organocopper compound wettable powder.
Strains tested is a Sclerotinia sclerotiorum; Provide by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo; The 40% oxazole thiadiazole organocopper compound wettable powder that is mixed with is carried out conventional bacteriostatic test according to ordinary method measures, with contain 40% dislike mould spirit or derosal wettable powder (auxiliary material with and content all with 40% oxazole thiadiazole organocopper compound wettable powder of present embodiment) do with reference to appearance.The result shows: 40% oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 400 times (ultimate density is 1000ppm), and the bacteriostasis rate of test organisms is respectively 36% and 33%.
Embodiment 9
With 6.8g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.5g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles 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 38 ℃ temperature, stir it is fully dissolved, treat that cupric nitrate is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.05ml) drips in the aqueous solution of cupric nitrate, within 28min, dropwises, and temperature control is at 55 ℃ then solution A; Stirring reaction 1h staticly settles 4.8h after the reaction, fully after the layering; Remove upper solution, lower floor's yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 108 ℃ then; Get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
With weight percentage is the copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of 50% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and water dispersible granules is Chenged by ordinary method Zhi and is used for the conventional bacteriostatic test of stalk of sesame point rot bacterium behind the oxazole thiadiazole organocopper compound water dispersible granules and measures; Stalk of sesame point rot bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, dislikes water dispersible granules (auxiliary material and content thereof are all with present embodiment De oxazole thiadiazole organocopper compound water dispersible granules) the do reference appearance of mould spirit or derosal to contain 50%.The result shows: 3g oxazole thiadiazole organocopper compound water dispersible granules is put in the 1000mL water; Bacteriostasis rate to test organisms is 98%; Put in the 1000mL water and 3g dislikes the water dispersible granules of mould spirit or derosal, the bacteriostasis rate of test organisms is respectively 45% and 40%.
Embodiment 10
Copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 9.
With weight percentage is the copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of 60% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and water dispersible granules is Chenged according to ordinary method Zhi and is used for the conventional bacteriostatic test of pear tree alternaria behind the oxazole thiadiazole organocopper compound water dispersible granules and measures; The pear tree alternaria is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, dislikes water dispersible granules (auxiliary material and content thereof are all with present embodiment De oxazole thiadiazole organocopper compound water dispersible granules) the do reference appearance of mould spirit or derosal to contain 60%.The result shows: 3g oxazole thiadiazole organocopper compound water dispersible granules is put in the water of 1000mL; Bacteriostasis rate to test organisms is 97%; Put in the water of 1000mL and 3g dislikes the water dispersible granules of mould spirit or derosal, the bacteriostasis rate of test organisms is respectively 33% and 25%.
Embodiment 11
With 6.9g purity is that 99% 3-hydroxy-5-methyl-isoxazole, 5.3g purity are 2-amino-5-sulfydryl-1,3 of 98%, and 4-thiadiazoles and 200ml massfraction are in 85% the disposable input 500ml reaction flask of aqueous ethanolic solution, heating for dissolving under 68 ℃ 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 40 ℃ temperature, stir it is fully dissolved, treat that neutralized verdigris is in water fully after the dissolving, under the effect of stirring; Dropwise (every 0.02～0.05ml) 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 yellow-green precipitate thing is used absolute ethyl alcohol (or ethanol) and water washing successively, in thermostatic drying chamber, dries down in 106 ℃ then; Get the yellow-green colour powder and be copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
With weight percentage is the copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of 20% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is Chenged by ordinary method Zhi and is used for the conventional bacteriostatic test of fusarium graminearum behind the oxazole thiadiazole organocopper compound suspension concentrate and measures; Fusarium graminearum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, dislikes suspension concentrate (auxiliary material and content thereof are all with present embodiment De oxazole thiadiazole organocopper compound suspension concentrate) the do reference appearance of mould spirit or derosal to contain 20%.The result shows that: oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 200 times (ultimate density is 1000ppm), and the test organisms bacteriostasis rate is respectively 32% and do not have fungistatic effect basically.
Embodiment 12
Copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 11.
With weight percentage is the copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of 30% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is Chenged by ordinary method Zhi and is used for the conventional bacteriostatic test of tomato late blight bacterium behind the oxazole thiadiazole organocopper compound suspension concentrate and measures; The tomato late blight bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, dislikes suspension concentrate (auxiliary material and content thereof are all with present embodiment De oxazole thiadiazole organocopper compound suspension concentrate) the do reference appearance of mould spirit or derosal to contain 30%.The result shows that: oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 200 times (ultimate density is 1500ppm), and the bacteriostasis rate of test organisms is respectively 44% and 42%.
Embodiment 13
Copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1,3, the preparation method of 4-thiadiazoles is with embodiment 11.
With weight percentage is the copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1 of 40% present embodiment preparation; 3; The conventional auxiliary material of 4-thiadiazoles and suspension concentrate is Chenged by ordinary method Zhi and is used for the conventional bacteriostatic test of cucumber fusarium axysporum behind the oxazole thiadiazole organocopper compound suspension concentrate and measures; Cucumber fusarium axysporum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, dislikes suspension concentrate (auxiliary material and content thereof are all with present embodiment De oxazole thiadiazole organocopper compound suspension concentrate) the do reference appearance of mould spirit or derosal to contain 40%.The result shows that: oxazole thiadiazole 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 disliking mould spirit or derosal is under the situation of dilution 200 times (ultimate density is 2000ppm), and the bacteriostasis rate of test organisms is respectively 24% and do not have fungistatic effect basically.
The present invention prepares De oxazole thiadiazole organocopper compound (copper-3-hydroxy-5-methyl-isoxazole-2-amino-5-sulfydryl-1; 3; The 4-thiadiazoles) fungistatic effect obviously is superior to disliking mould spirit and derosal; Fungistatic effect be dislike mould spirit 3-4 doubly, be derosal 3-5 doubly, be all very significantly to the bacillary or restraining and sterilizing bacteria effect of fungoid germ.
Claims (9)
1. Yi Zhong oxazole thiadiazole organocopper compound, it is characterized in that: this compound has suc as formula the chemical structural formula shown in 1:
2. one kind prepares a method of stating oxazole thiadiazole organocopper compound like claim 1, it is characterized in that: may further comprise the steps:
With the 3-hydroxy-5-methyl-isoxazole of 6.5-7.0g purity 99% and the 2-amino-5-sulfydryl-1,3 of 5.3-5.8g purity 98%, it is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that the 4-thiadiazoles adds the 160-260ml massfraction; Heating for dissolving gets solution A, is in the cupric salt adding 25ml water of 95-99% with 2.5-3.0g purity; 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 55-70 ℃; Staticly settle after stirring end, precipitation separation will precipitate and use washing with alcohol; Use water washing then, dry after the washing yellowish green toner end shape oxazole thiadiazole organocopper compound.
3. according to the method for the said a kind of Zhi Bei oxazole thiadiazole 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 method for the said a kind of Zhi Bei oxazole thiadiazole organocopper compound of claim 2, it is characterized in that: said solution A dropwises in 25-30min.
5. preparation of stating oxazole thiadiazole organocopper compound like claim 1; It is characterized in that: said preparation comprises 20-90% De oxazole thiadiazole organocopper compound 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 Yi Zhong of claim 5 oxazole thiadiazole organocopper compound, it is characterized in that: the component of said wettable powder comprises that by massfraction 20～90% De oxazole thiadiazole organocopper compounds, 1～10% wetting agent, 1～10% dispersion agent, surplus are filler.
7. according to the preparation of the said Yi Zhong of claim 6 oxazole thiadiazole organocopper compound, 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 as claim 1 state oxazole thiadiazole organocopper compound the control agricultural plants bacillary with fungal disease in purposes.
9. said according to Claim 8 Yi Zhong oxazole thiadiazole 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; Said farm crop are paddy rice, wheat, corn, beans, cotton, tobacco, watermelon, beet or Chinese cabbage; Said fruit tree is apple tree, pear tree or peach; Said vegetables are tomato, paprike, eggplant, cucumber or green onion, garlic class; Said bacterial disease is rice leaf spot bacteria, ralstonia solanacearum, bacterial stripe bacterium or ulcer bacteria; Said fungal disease is the rotten germ of gibberellic hypha, seedling, rotten mildew fungus, silk nuclear germ, root shell germ, avenges little germ, sheath blight fungus, wilt or sclerotium germ.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107232210A (en) * | 2017-05-04 | 2017-10-10 | 浙江大学 | Application of the thiadiazole compound on paddy bacterial rice shoot damping-off control medicament is prepared |
| CN109369568A (en) * | 2018-11-20 | 2019-02-22 | 浙江龙湾化工有限公司 | A kind of thiadiazoles fungicide and its preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885724A (en) * | 2010-07-09 | 2010-11-17 | 南京工业大学 | N-substituted phenylpyrazole compound containing heterocyclic ketone, preparation thereof and application thereof in preventing and treating plant diseases and insect pests |
| CN101891710A (en) * | 2010-07-27 | 2010-11-24 | 南开大学 | 4-halogenated methyl-1,2,3-thiadiazole compounds and preparation method and application thereof |
| CN101921244A (en) * | 2010-09-02 | 2010-12-22 | 南开大学 | Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof |
| 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 |
-
2011
- 2011-12-06 CN CN201110401897.5A patent/CN102516268B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | N-substituted phenylpyrazole compound containing heterocyclic ketone, preparation thereof and application thereof in preventing and treating plant diseases and insect pests |
| CN101891710A (en) * | 2010-07-27 | 2010-11-24 | 南开大学 | 4-halogenated methyl-1,2,3-thiadiazole compounds and preparation method and application thereof |
| CN101921244A (en) * | 2010-09-02 | 2010-12-22 | 南开大学 | Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107232210A (en) * | 2017-05-04 | 2017-10-10 | 浙江大学 | Application of the thiadiazole compound on paddy bacterial rice shoot damping-off control medicament is prepared |
| CN109369568A (en) * | 2018-11-20 | 2019-02-22 | 浙江龙湾化工有限公司 | A kind of thiadiazoles fungicide and its preparation method and application |
| CN109369568B (en) * | 2018-11-20 | 2023-04-11 | 浙江龙湾化工有限公司 | Thiadiazole bactericide and preparation method and application thereof |
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