CN102516189B - Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease - Google Patents
Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease Download PDFInfo
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Abstract
The invention discloses an oxazole organic copper compound, and a preparation method and a preparation thereof and purpose thereof in control of agricultural plant diseases. The method comprises steps of: carrying out aqueous phase process on hydroxylamine hydrochloride and ethyl acetoacetate too generate 3-hydroxy-5-methyl isoxazole; adding the compound and cupric salt into an organic solvent for reaction; successively carrying out separation, washing and drying after the reaction. The preparation method of the invention is simple, practical, low-cost and pollution-free; and the prepared novel oxazole compound copper-3-hydroxy-5-methyl isoxazole has stable property and wide sterilization spectrum, can be used in controlling agricultural plant diseases, especially in controlling diseases canused by Fusarium sp, Aphanomyces invadans, pythium and corticium, and has special effects on various soil borne diseases and seedling blight.
Description
Technical field
The invention belongs to pesticide chemical technical field, particularly Yi Zhong oxazole class 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, all stable in acid, alkaline solution, non-corrosiveness, is a kind of systemic fungicide and plant-growth regulator.The interior absorption and the conductivity that have, can directly be absorbed by plant root, enters in plant materials, mobile very rapid.In root system, move and only within 3 hours, just move to stem, in 24 hours, move to plant whole body, its meta-bolites in plant materials is two kinds of glucosides, has the effect of Promoting plant growth, well developed root system.In addition, 3-hydroxy-5-methyl-isoxazole has efficiently, the feature of low toxicity and environmental protection, for powerful soil sterilization and seed disinfection, to various fungal diseases of plants, as sickle-like bacteria, the rotten bacterium of seedling, pythium spp, rhizoctonia, root shell bacterium, snow germ etc. all have significant prevention effect.Be widely used in 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.
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 feature such as be difficult for developing immunity to drugs of area; it is a class wide-spectrum bactericide; in the agriculture bacterium of control and fungal disease, there is purposes widely; the existing provide protection of copper fungicide; there are again certain treatment and eradicant action; in addition; also there is good tackiness; can form one deck medicine film in crop surface; thereby reach resistance of rainwater washing against, the feature that the lasting period is long.Copper fungicide mainly comprises Inorganic Copper preparation and organic copper preparation at present.Wherein common Inorganic Copper preparation has copper hydroxide, Basic Chrome Sulphate (Bordeaux mixture), copper oxychloride.The protective fungicide that is characterized in having advantage, cost is low, but shortcoming is: the first, easily produce poisoning, at florescence and young fruit period, forbid or limit use; The second, miscibility is poor, and Inorganic Copper preparation great majority are alkaline agricultural chemicals, can not with most of mixed pesticides, use inconvenience; The 3rd, easily cause the increment of mite class and blister mite, increase cost accounting; The 4th, the effect for the treatment of is not strong, is not easy to use on paddy rice.
In copper agent, still take at present Inorganic Copper preparation as main.But the growth momentum of organic copper preparation is very powerful, quite there is the trend of " the latecomers surpass the old-timers ".In recent years, China many agricultural chemicals producer drive on boldly to organic copper preparation one after another on a large scale, and friend peasant also enjoys all benefits of preventing and treating that organic copper preparation brings, so organic copper preparation becomes " unexpected rival " who is a dark horse in disinfectant use in agriculture.The machine copper agent of common are 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 is all the product innovation with Chinese independent intellectual property right, Dou Shi China is the national emphasis product innovation of imitated other countries expired patent invention recently, be outstanding person and the market rising star in organic copper preparation, market potential is very considerable.
Organic copper preparation comes into one's own, and is by no means accidental.It than Inorganic Copper preparation 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 most sterilant, miticide, sterilant and plant-growth regulator and can not cause chemical reaction, alleviated the work burden that peasant causes because repeatedly spraying medicine, saved working time, medication is saved worry more; D, the organic copper preparation scope of application and more extensive on the usage period are also 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 organic copper preparation, cupric ion and compound synergy, dual mechanism sterilization, sterilization more thoroughly, more efficient.
In the market, the producer that produces organic copper preparation is more and more, and the controlling object of registration is also more and more extensive, and bacterial disease, fungal disease and Disease all, among control, have been realized the hope of peasant " Yi Yao Zhiduo County is sick ".In addition, organic copper preparation also can be used for going out except moss, lichens, kills snail, oncomelania and carries out seed treatment, preserving fruit and vegetable utilizing storage and supplement the effects such as crop trace element.The technical superiority of organic copper preparation is that organic copper preparation great majority are neutral, have better affinity and being mixed property, safety easy to use, convenient operation; " copper content " of organic copper preparation is lower, less to the pollution of environment, less on the impact of mite class, less on the florescence of farm crop and young fruit period impact, uses safety and relieved more.
Although copper fungicide exists many superiority, excessive cupric ion very easily causes poisoning to crop.There are some researches show, cupric ion gets final product kill pathogenic organisms when 10mg/L, when its concentration reaches 30mg/L, can cause poisoning to sensitive plant.Have not yet to see the relevant report of You oxazole compounds copper-3-hydroxy-5-methyl-isoxazole and preparation method thereof, more do not find the relevant report for agricultural plants disease control Jiang oxazole compounds copper-3-hydroxy-5-methyl-isoxazole.
Summary of the invention
The object of the present invention is to provide a kind of novel oxazole class organocopper compound, provide that a kind of preparation method is simple, cost is low, the preparation method of the novel oxazole class organocopper compound of environmental protection simultaneously, preparation oxazole class organocopper compound stable in properties, fungicidal spectrum is wide, can be widely used in control agricultural plants disease.
For achieving the above object, the present invention has adopted following technical scheme:
An oxazole class organocopper compound, concrete name is called copper-3-hydroxy-5-methyl-isoxazole, and this compound has chemical structural formula as shown in Equation 1:
The preparation method of Shang Shu oxazole class organocopper compound, comprises the following steps:
It is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that 2.4-5.4g 3-hydroxy-5-methyl-isoxazole is added to 140-280ml massfraction, heating for dissolving, obtain solution A, the cupric salt that is 95-99% by 1.2-3.0g purity adds in 25ml water, obtain the mixture of cupric salt and water, solution A is added drop-wise in the mixture of cupric salt and water, after dropwising, in 55-65 ℃, stir 1h, stirring staticly settles after finishing, precipitation separation, to precipitate by washing with alcohol, and then wash with water, washing post-drying obtains green flour powder oxazole class organocopper compound.
The addition of described methanol aqueous solution or aqueous ethanolic solution is as the criterion can dissolve 3-hydroxy-5-methyl-isoxazole; When cupric salt is water-soluble, the addition of water is as the criterion can dissolve cupric salt, and when cupric salt is water insoluble, the addition of water is being as the criterion by moistening cupric salt.
The preparation method of described 3-hydroxy-5-methyl-isoxazole, comprises the following steps:
The oxammonium hydrochloride that is 98% by 9.6g purity is dissolved in 100ml pure water, stirring is cooled to and after 0-5 ℃, adds the aqueous sodium hydroxide solution of 50ml massfraction 30% to neutralize to obtain mixed solution, mixed solution is dripped within 15-20min in 100ml methyl aceto acetate, after dropwising, in 0-5 ℃, stir 1.5h, the vitriol oil that adds 30ml massfraction 98% after stirring, then at 25 ℃, stir 2h, stir final vacuum and concentrate to obtain light yellow crystal, by benzene reflux 2h for light yellow crystal, after refluxing, steam and desolventize, then use normal hexane recrystallization, obtain 3-hydroxy-5-methyl-isoxazole (disliking mould spirit).
Described cupric salt includes but not limited to copper sulfate, cupric chloride, copper hydroxide, cupric nitrate or neutralized verdigris.
Described solution A dropwises in 20-30min.
The preparation of Shang Shu oxazole class organocopper compound, said preparation comprises 20-90% oxazole class organocopper compound by massfraction, and surplus is auxiliary material, and the formulation of said preparation comprises wettable powder, water dispersible granules or suspension concentrate.
The component of described wettable powder comprises that by massfraction 20～90% oxazole class organocopper compounds, 1～10% wetting agent, 1～10% dispersion agent, surplus are filler.
Described wetting agent is one or more the composition in Sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, octyl phenol polyoxyethylene ether, Nonyl pheno base ether or octylphenol polyethylene oxyethylene group ether sulfate; Described dispersion agent is one or more the composition 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 sulfonate or carboxymethyl cellulose; Described filler is one or more the composition in diatomite, white carbon black, wilkinite, light calcium carbonate or attapulgite.
The purposes of Shang Shu oxazole class organocopper compound in the bacillary and fungal disease of control agricultural plants.
Described agricultural plants comprises farm crop, fruit tree or vegetables; Described farm crop are paddy rice, wheat, corn, beans, cotton, tobacco, watermelon, beet or Chinese cabbage; Described fruit tree is apple tree, pear tree, citrus or peach; Described vegetables are tomato, paprike, eggplant, cucumber or green onion, garlic class; Described bacterial disease is ralstonia solanacearum, rice leaf spot bacteria or ulcer bacteria; Described fungal disease is gibberellic hypha, seedling maize ear rot bacterium, rotten mildew fungus, silk core germ, root shell germ, avenges micro-germ, sheath blight fungus, wilt or sclerotium germ.
The invention has the advantages that: the first, main raw material of the present invention is with low cost, and raw material is easy to get, and has good cost advantage, the second, preparation method of the present invention has reaction conditions gentleness, and the features such as simple process are easy to suitability for industrialized production, and do not produce the three wastes, environmentally safe, the 3rd, the oxazole class organocopper compound stable in properties that the present invention is prepared, chance strong acid, highly basic do not decompose, can be mixed with Multiple Pesticides, solved Inorganic Copper and the poor drawback of organic copper fungicide compounding in the past, the 4th, the prepared oxazole of the present invention class organocopper compound is the coordination compound that organic molecule and cupric ion form, the release of cupric ion can reach the concentration of kill pathogenic organisms, can not cause poisoning to crop again simultaneously, therefore be applicable to exploitation efficient, nontoxic, the novel organic copper sterilant of lasting and environmental protection, the 5th, the sterilant that adopts Suo Shu oxazole class organocopper compound of the present invention to be prepared from, fungicidal spectrum is wide, not only efficient to bacterium, the germ that fungi is even difficult to control has efficiently, especially can prevent and treat sickle mycete, silk capsule mould, the disease that pythium spp and corticium cause, various soil-borne diseases and rice shoot damping-off are had to special efficacy.
Accompanying drawing explanation
Fig. 1 is the mass spectrum that the present invention prepares oxazole class organocopper compound.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the oxazole class organocopper compound prepared of the present invention.
Fig. 3 is the fungistatic effect figure of the present invention when preparing oxazole class organocopper compound and measuring for bacterial wilt of tomato bacterium bacteriostatic test.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this, below in all embodiment, reference sample is disliked mould spirit, derosal is commercial product.
The oxammonium hydrochloride that is 98% by 9.6g purity (industrial goods) is dissolved in 100ml pure water, stirring is cooled to and after 5 ℃, adds the aqueous sodium hydroxide solution of 50ml massfraction 30% to neutralize to obtain mixed solution, by mixed solution dropwise (every 0.02～0.04ml) drip in 100ml methyl aceto acetate, within 15min, dropwise, then temperature control is at 5 ℃, stirring reaction 1.5h, the vitriol oil that adds after completion of the reaction 30ml massfraction 98%, stirring reaction 2h at 25 ℃, reaction final vacuum concentrates to obtain light yellow crystal, by benzene reflux 2h for light yellow crystal, steaming desolventizes, finally use normal hexane recrystallization, obtain compound 3-hydroxy-5-methyl-isoxazole, get in the disposable input 500ml reaction flask of aqueous ethanolic solution that 3-hydroxy-5-methyl-isoxazole that 4.6g makes and 140ml massfraction are 75%, heating for dissolving at the temperature of 72 ℃, obtain solution A, the cupric sulfate pentahydrate that is 99% by 2.4g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 42 ℃, after treating that copper sulfate dissolves completely in water, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the aqueous solution of copper sulfate, within 26min, dropwise, then temperature control is at 62 ℃, stirring reaction 1h, after reaction, staticly settle 4.6h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 102 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole, structure is shown below,
As Fig. 1, shown in 2, detect m/z in mass spectrum and be 259 characteristic peak and NMR hydrogen spectrogram intermediate value and be 2.36 and 5.81 characteristic peak.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 50.0%, Sodium dodecylbenzene sulfonate 3.0%, sulfonated lignin 5.0%, diatomite 42.0% prepared by the present embodiment, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 50% oxazole class organocopper compound wettable powder.
The 50% oxazole class organocopper compound wettable powder being mixed with is carried out to bacteriostatic test mensuration, with the wettable powder (auxiliary material and content thereof are all with 50% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 50% evil or derosal, make reference sample, the bacterial wilt of tomato bacterium that strains tested provides for Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo.Germ is activation according to a conventional method before test, used medium is ordinary broth nutrient agar, substratum consists of: peptone 10g, 5 grams of extractum carniss, 25 grams of agar powders, 5 grams, sodium-chlor, 1 gram of dipotassium hydrogen phosphate, distilled water 1000ml, prepare according to ordinary method.Connect bacterium test and carry out on Bechtop, the culture dish connecing after bacterium is put into constant incubator immediately, and temperature is 37 ℃, observations, record after 24h.Fungistatic effect is as Fig. 3, and wherein, figure upper left, upper right and downside are followed successively by derosal (667ppm), dislikes mould spirit (667ppm) and the fungistatic effect of 50% oxazole class organocopper compound wettable powder (667ppm) to bacterial wilt of tomato bacterium.Can Kan Chu oxazole class organocopper compound wettable powder restraining and sterilizing bacteria successful under 667ppm from Fig. 3 be better than contrasting pesticide carbendazim and dislike mould spirit, inhibition zone is roughly 4 times of derosal control group, dislike mould spirit 3 times.
Embodiment 2
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 1.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 20.0%, octyl phenol polyoxyethylene ether 1.0%, sodium dibutyl naphthalene sulfonate formaldehyde condensation products 4.5%, white carbon black 74.5% prepared by the present embodiment, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 20% oxazole class organocopper compound wettable powder.
Strains tested is rice leaf spot bacteria, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 20% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 20% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 20% evil or derosal, do reference sample.Result shows: 20% oxazole class organocopper compound wettable powder is the in the situation that of dilution 500 times (ultimate density is 400ppm), to the bacteriostasis rate of test organisms, be 88%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 500 times (ultimate density is 400ppm), the bacteriostasis rate of test organisms is respectively to 30% and there is no fungistatic effect.
Embodiment 3
Get in the disposable input 500ml reaction flask of methanol aqueous solution that the mould spirit of evil that the commercial purity of 4.8g is 98% and 240ml massfraction are 95%, heating for dissolving at the temperature of 80 ℃, obtains solution A, the cupric sulfate pentahydrate that is 99% by 2.4g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 40 ℃, after treating that copper sulfate dissolves completely in water, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the aqueous solution of copper sulfate, within 25min, dropwise, then temperature control is at 65 ℃, stirring reaction 1h, after reaction, staticly settle 4h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 110 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 90.0% prepared by the present embodiment, Nonyl pheno base ether 3.5%, novalgin formaldehyde condensation products 1.0%, wilkinite 5.5%, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 90% oxazole class organocopper compound wettable powder.
Strains tested is rhizoctonia cerealis, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 90% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 90% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 90% evil or derosal, make reference sample.Result shows: 90% oxazole class organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density is 900ppm), to the bacteriostasis rate of test organisms, be 98%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 1000 times (ultimate density is 900ppm), the inhibiting rate of test organisms is respectively to 39% and 53%.
Embodiment 4
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 3.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 70.0% prepared by the present embodiment, octylphenol polyethylene oxyethylene group ether sulfate 10.0%, sodium dibutyl naphthalene sulfonate formaldehyde condensation products 5.5%, attapulgite 14.5%, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 70% oxazole class organocopper compound wettable powder.
Strains tested is lawn rotten mildew fungus, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 70% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 70% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 70% evil or derosal, make reference sample.Result shows: 70% oxazole class organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density is 700ppm), to the bacteriostasis rate of test organisms, be 95%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 1000 times (ultimate density is 700ppm), the bacteriostasis rate of test organisms is respectively to 35% and 45%.
The oxammonium hydrochloride that is 98% by 9.6g purity (industrial goods) is dissolved in 100ml pure water, stirring is cooled to and after 3 ℃, adds the aqueous sodium hydroxide solution of 50ml massfraction 30% to neutralize to obtain mixed solution, mixed solution dropwise (every 0.02～0.04ml) drip in 100ml methyl aceto acetate, within 18min, dropwise, then temperature control is at 3 ℃, stirring reaction 1.5h, the vitriol oil that adds after completion of the reaction 30ml massfraction 98%, at 25 ℃, stirring reaction 2h final vacuum concentrates to obtain light yellow crystal, by benzene reflux 2h for light yellow crystal, steaming desolventizes, finally use normal hexane recrystallization, obtain compound 3-hydroxy-5-methyl-isoxazole, get in the disposable input 500ml reaction flask of methanol aqueous solution that 3-hydroxy-5-methyl-isoxazole that 4.6g makes and 200ml massfraction are 75%, heating for dissolving at the temperature of 75 ℃, obtain solution A, the cupric chloride that is 95% by 2.2g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 45 ℃, after copper to be chlorinated dissolves completely in water, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the aqueous solution of cupric chloride, within 20min, dropwise, then temperature control is at 63 ℃, stirring reaction 1h, after reaction, staticly settle 5h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 105 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole.
Get each material of following weight percent; Copper-3-hydroxy-5-methyl-isoxazole 80% prepared by the present embodiment, sodium dibutyl naphthalene sulfonate 4%, succinate sodium sulfonate (a kind of alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfonate) 10%, light calcium carbonate 6%, cross 320 mesh sieves after by said ratio, each material fully being mixed, ground and obtain 80% oxazole class organocopper compound wettable powder.
Strains tested is Germ To Soybean Frogeye Leaf Spot, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 80% oxazole class organocopper compound wettable powder being mixed with is carried out to bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 80% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 80% evil or derosal, make reference sample.Result shows: 80% oxazole class organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density 800ppm), to the inhibiting rate of test organisms, be 97%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 1000 times (ultimate density is 800ppm), the bacteriostasis rate of test organisms is respectively to 33% and 40%.
Embodiment 6
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 5.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 60%, Sodium dodecylbenzene sulfonate and sodium dibutyl naphthalene sulfonate prepared by the present embodiment are (by weight, Sodium dodecylbenzene sulfonate: sodium dibutyl naphthalene sulfonate=1: composition 6% 3), carboxymethyl cellulose 3%, diatomite and attapulgite are (by weight, diatomite: attapulgite=1: composition 31% 1), after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 60% oxazole class organocopper compound wettable powder.
Strains tested is cotton-wilt fusarium, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 60% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 60% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 60% evil or derosal, do reference sample.Result shows: 60% oxazole class organocopper compound wettable powder is the in the situation that of dilution 200 times (ultimate density is 3000ppm), to the bacteriostasis rate of test organisms, be 98.5%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 200 times (ultimate density is 3000ppm), the bacteriostasis rate of test organisms is respectively to 58% and there is no fungistatic effect.
Embodiment 7
Get in the disposable input 500ml reaction flask of aqueous ethanolic solution that the mould spirit of evil that the commercial purity of 5.0g is 98% and 180ml massfraction are 95%, heating for dissolving at the temperature of 60 ℃, obtains solution A, the copper hydroxide that is 98% by 2.8g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir at the temperature of 35 ℃, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the mixture of copper hydroxide and water, within 30min, dropwise, then temperature control is at 60 ℃, stirring reaction 1h, after reaction, staticly settle 4.5h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 100 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 30% prepared by the present embodiment, octyl phenol polyoxyethylene ether, Nonyl pheno base ether and octylphenol polyethylene oxyethylene group ether sulfate are (by weight, octyl phenol polyoxyethylene ether: Nonyl pheno base ether: composition 10% octylphenol polyethylene oxyethylene group ether sulfate=1: 1: 1), sulfonated lignin and carboxymethyl cellulose are (by weight, lignin-sulphonate: carboxymethyl cellulose=2: composition 7% 1), white carbon black, wilkinite and light calcium carbonate are (by weight, white carbon black: wilkinite: light calcium carbonate=2.5: 1: 1.8) composition 53%, by said ratio, each material is fully mixed, after grinding, cross 320 mesh sieves and obtain 30% oxazole class organocopper compound wettable powder.
Strains tested is eggplant cotton disease bacterium, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 30% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder (auxiliary material and content thereof are all with 30% oxazole class organocopper compound wettable powder in the present embodiment) that contains the mould spirit of 30% evil or derosal, make reference sample.Result shows: 30% oxazole class organocopper compound wettable powder is the in the situation that of dilution 400 times (ultimate density is 750ppm), to the bacteriostasis rate of test organisms, be 95%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 400 times (ultimate density is 750ppm), the bacteriostasis rate of test organisms is respectively to 25% and 55%.
Embodiment 8
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 7.
Get each material of following weight percent: copper-3-hydroxy-5-methyl-isoxazole 40% prepared by the present embodiment, Sodium dodecylbenzene sulfonate and Nonyl pheno base ether are (by weight, Sodium dodecylbenzene sulfonate: Nonyl pheno base ether=1: composition 8% 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 sulfonate) are (by weight, sodium dibutyl naphthalene sulfonate formaldehyde condensation products: sodium naphthalene sulfonate yuban: novalgin formaldehyde condensation products: composition 10% alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfonate=2: 1: 3: 4), white carbon black and attapulgite are (by weight, white carbon black: attapulgite=3: composition 42% 1), by said ratio, each material is fully mixed, after grinding, cross 320 mesh sieves and obtain 40% oxazole class organocopper compound wettable powder.
Strains tested is root rot of beets bacterium, by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, provided, the 40% oxazole class organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, with the wettable powder that contains the mould spirit of 40% evil or derosal (auxiliary material with and content all with 40% oxazole class organocopper compound wettable powder in the present embodiment), make reference sample.Result shows: 40% oxazole class organocopper compound wettable powder is the in the situation that of dilution 400 times (ultimate density is 1000ppm), to the bacteriostasis rate of test organisms, be 92%, and the wettable powder of disliking mould spirit or derosal is the in the situation that of dilution 400 times (ultimate density is 1000ppm), the bacteriostasis rate of test organisms is respectively to 32% and 50%.
Embodiment 9
The oxammonium hydrochloride that is 98% by 9.6g purity (industrial goods) is dissolved in 100ml pure water, stirring is cooled to and after 0 ℃, adds the aqueous sodium hydroxide solution of 50ml massfraction 30% to neutralize to obtain mixed solution, mixed solution dropwise (every 0.02～0.04ml) drip in 100ml methyl aceto acetate, within 20min, dropwise, then temperature control is at 0 ℃, stirring reaction 1.5h, the vitriol oil that adds after completion of the reaction 30ml massfraction 98%, stirring reaction 2h at 25 ℃, reaction final vacuum concentrates to obtain light yellow crystal, by benzene reflux 2h for light yellow crystal, steaming desolventizes, finally use normal hexane recrystallization, obtain compound 3-hydroxy-5-methyl-isoxazole, get in the disposable input 500ml reaction flask of methanol aqueous solution that 3-hydroxy-5-methyl-isoxazole that 2.4g makes and 220ml massfraction are 85%, heating for dissolving at the temperature of 70 ℃, obtain solution A, the cupric nitrate that is 95% by 1.2g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 38 ℃, after treating that cupric nitrate dissolves completely in water, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the aqueous solution of cupric nitrate, within 28min, dropwise, then temperature control is at 55 ℃, stirring reaction 1h, after reaction, staticly settle 4.8h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 108 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole.
Copper-3-hydroxy-5-methyl-isoxazole prepared by the present embodiment that is 50% by weight percentage and the conventional auxiliary material of water dispersible granules according to a conventional method Zhi are Chenged oxazole class organocopper compound water dispersible granules and are measured for the conventional bacteriostatic test of garlic ash arrhizus bacteria, garlic ash arrhizus bacteria is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, to make reference sample containing 50% water dispersible granules (auxiliary material and content thereof are all with the present embodiment Zhong oxazole class organocopper compound water dispersible granules) of disliking mould spirit or derosal.Result shows: 3g oxazole class organocopper compound water dispersible granules is put in the water of 1000mL, to the bacteriostasis rate of test organisms, be 97%, and 3g dislikes the water dispersible granules of mould spirit or derosal, put in the water of 1000mL, the bacteriostasis rate of test organisms is respectively to 26% and 58%.
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 9.
Copper-3-hydroxy-5-methyl-isoxazole prepared by the present embodiment that is 60% by weight percentage is Chenged oxazole class organocopper compound water dispersible granules for the conventional bacteriostatic test mensuration of pear tree purple root rot (Helicobasidium mompa) bacterium with the conventional auxiliary material of water dispersible granules according to ordinary method Zhi, pear tree purple root rot (Helicobasidium mompa) Jun You Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo provides, and with the water dispersible granules (auxiliary material and content thereof are all with the oxazole class organocopper compound water dispersible granules in the present embodiment) that contains the mould spirit of 60% evil or derosal, makes reference sample.Result shows: 3g oxazole class organocopper compound water dispersible granules is put in the water of 1000mL, to the bacteriostasis rate of test organisms, be 98%, and 3g dislikes the water dispersible granules of mould spirit or derosal, put in the water of 1000mL, the bacteriostasis rate of test organisms is respectively to 33% and 48%.
Embodiment 11
Get in the mould spirit of evil of the commercial purity 98% of 5.5g and the disposable input 500ml reaction flask of aqueous ethanolic solution that 280ml massfraction is 85%, heating for dissolving at the temperature of 68 ℃, obtain solution A, a water acetic acid copper that is 99% by 3.0g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 25 ℃, after treating that neutralized verdigris dissolves completely in water, under the effect of stirring, solution A dropwise (every 0.02～0.04ml) drip in the aqueous solution of neutralized verdigris, within 24min, dropwise, then temperature control is at 58 ℃, stirring reaction 1h, after reaction, staticly settle 4.2h, fully after layering, remove upper solution, lower floor's green precipitate thing is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 103 ℃, dry, obtain green powder and be copper-3-hydroxy-5-methyl-isoxazole.
Copper-3-hydroxy-5-methyl-isoxazole prepared by the present embodiment that is 20% by weight percentage and the conventional auxiliary material of suspension concentrate according to a conventional method Zhi are Chenged oxazole class organocopper compound suspension concentrate and are measured for the conventional bacteriostatic test of Peach canker disease bacterium, Peach canker disease Jun You Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo provides, to make reference sample containing 20% suspension concentrate (auxiliary material and content thereof are all with the oxazole class organocopper compound suspension concentrate in the present embodiment) of disliking mould spirit or derosal.Result shows that: oxazole class organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 1000ppm), to the bacteriostasis rate of test organisms, be 95%, and the suspension concentrate of disliking mould spirit or derosal is the in the situation that of dilution 200 times (ultimate density is 1000ppm), the bacteriostasis rate of test organisms is respectively to 25% and there is no fungistatic effect.
Embodiment 12
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 11.
Copper-3-hydroxy-5-methyl-isoxazole prepared by the present embodiment that is 30% by weight percentage is made into according to a conventional method oxazole class organocopper compound suspension concentrate with the conventional auxiliary material of suspension concentrate and is measured for the conventional bacteriostatic test of tomato early epidemic germ, tomato early epidemic germ is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, with the suspension concentrate (auxiliary material and content thereof are all with the oxazole class organocopper compound suspension concentrate in the present embodiment) that contains the mould spirit of 30% evil or derosal, makes reference sample.Result shows that: oxazole class organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 1500ppm), to the bacteriostasis rate of test organisms, be 96%, and the suspension concentrate of disliking mould spirit or derosal is the in the situation that of dilution 200 times (ultimate density is 1500ppm), the bacteriostasis rate of test organisms is respectively to 34% and 35%.
Embodiment 13
The preparation method of copper-3-hydroxy-5-methyl-isoxazole is with embodiment 11.
Copper-3-hydroxy-5-methyl-isoxazole prepared by the present embodiment that is 40% by weight percentage and the conventional auxiliary material of suspension concentrate according to a conventional method Zhi are Chenged oxazole class organocopper compound suspension concentrate and are measured for the conventional bacteriostatic test of cucumber fusarium axysporum, cucumber fusarium axysporum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, with the suspension concentrate (auxiliary material and content thereof are all with the present embodiment Zhong oxazole class organocopper compound suspension concentrate) that contains the mould spirit of 40% evil or derosal, makes reference sample.Result shows that: oxazole class organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 2000ppm), to the bacteriostasis rate of test organisms, be 94%, and derosal or the suspension concentrate of disliking mould spirit be the in the situation that of dilution 200 times (ultimate density is 2000ppm), the bacteriostasis rate of test organisms is respectively to 30% and there is no fungistatic effect.
The fungistatic effect that the present invention prepares oxazole class organic copper compound (copper-3-hydroxy-5-methyl-isoxazole) is obviously better than disliking mould spirit and derosal, fungistatic effect is 3-4 times of the mould spirit of evil, be the 2-5 of derosal doubly, be to bacillary or the restraining and sterilizing bacteria effect of fungoid germ is all very remarkable.
Claims (10)
1. Yi Zhong oxazole class organocopper compound, is characterized in that: this compound has chemical structural formula as shown in Equation 1:
2. prepare a method of stating oxazole class organocopper compound as claim 1, it is characterized in that: comprise the following steps:
It is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that 2.4-5.4g3-hydroxy-5-methyl-isoxazole is added to 140-280ml massfraction, heating for dissolving, obtain solution A, the cupric salt that is 95-99% by 1.2-3.0g purity adds in 25ml water, obtain the mixture of cupric salt and water, solution A is added drop-wise in the mixture of cupric salt and water, after dropwising, in 55-65 ℃, stir 1h, stirring staticly settles after finishing, precipitation separation, to precipitate by washing with alcohol, and then wash with water, washing post-drying obtains green flour powder oxazole class organocopper compound.
3. a kind of method of Bei oxazole class organocopper compound processed according to claim 2, is characterized in that: the preparation method of described 3-hydroxy-5-methyl-isoxazole, comprises the following steps:
The oxammonium hydrochloride that is 98% by 9.6g purity is dissolved in 100ml pure water, stirring is cooled to and after 0-5 ℃, adds the aqueous sodium hydroxide solution of 50ml massfraction 30% to neutralize to obtain mixed solution, mixed solution is dripped within 15-20min in 100ml methyl aceto acetate, after dropwising, in 0-5 ℃, stir 1.5h, the vitriol oil that adds 30ml massfraction 98% after stirring, then at 25 ℃, stir 2h, stir final vacuum and concentrate to obtain light yellow crystal, by benzene reflux 2h for light yellow crystal, after refluxing, steam and desolventize, then use normal hexane recrystallization, obtain 3-hydroxy-5-methyl-isoxazole.
4. a kind of method of Bei oxazole class organocopper compound processed according to claim 2, is characterized in that: described cupric salt is selected from copper sulfate, cupric chloride, copper hydroxide, cupric nitrate or neutralized verdigris.
5. a kind of method of Bei oxazole class organocopper compound processed according to claim 2, is characterized in that: described solution A dropwises in 20-30min.
6. state the preparation of oxazole class organocopper compound as claim 1 for one kind, it is characterized in that: said preparation comprises 20-90% oxazole class organocopper compound by massfraction, surplus is auxiliary material, and the formulation of said preparation is selected from wettable powder, water dispersible granules or suspension concentrate.
7. the preparation of Yi Zhong oxazole class organocopper compound according to claim 6, is characterized in that: the component of described wettable powder comprises that by massfraction 20～90% oxazole class organocopper compounds, 1～10% wetting agent, 1～10% dispersion agent, surplus are filler.
8. the preparation of an oxazole class organocopper compound according to claim 7, is characterized in that: described wetting agent is one or more the composition in Sodium dodecylbenzene sulfonate, sodium dibutyl naphthalene sulfonate, octyl phenol polyoxyethylene ether, Nonyl pheno base ether or octylphenol polyethylene oxyethylene group ether sulfate; Described dispersion agent is one or more the composition 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 sulfonate or carboxymethyl cellulose; Described filler is one or more the composition in diatomite, white carbon black, wilkinite, light calcium carbonate or attapulgite.
9. state the purposes of oxazole class organocopper compound in the bacillary and fungal disease of control agricultural plants as claim 1 for one kind.
10. the purposes of Yi Zhong oxazole class organocopper compound in the bacillary and fungal disease of control agricultural plants according to claim 9, is characterized in that: described agricultural plants is selected from farm crop, fruit tree or vegetables; Described farm crop are paddy rice, wheat, corn, beans, cotton, tobacco, watermelon, beet or Chinese cabbage; Described fruit tree is apple tree, pear tree, citrus or peach; Described vegetables are tomato, paprike, eggplant, cucumber or green onion, garlic; Described bacterial disease is ralstonia solanacearum, rice leaf spot bacteria or ulcer bacteria; Described fungal disease is gibberellic hypha, seedling maize ear rot bacterium, rotten mildew fungus, silk core germ, root shell germ, avenges micro-germ, sheath blight fungus, wilt or sclerotium germ.
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| CN1329827A (en) * | 1992-05-07 | 2002-01-09 | 三共株式会社 | 3-hydroxy-5-methyl-isoxazole pesticide composition and using method |
| CN1348692A (en) * | 2001-09-05 | 2002-05-15 | 黑龙江企达农药开发有限公司 | Hymexazol and its water phase synthesis process |
| CN1927847A (en) * | 2005-09-08 | 2007-03-14 | 沈阳化工研究院 | Application of isoxazole compounds as bactericide |
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| CN1329827A (en) * | 1992-05-07 | 2002-01-09 | 三共株式会社 | 3-hydroxy-5-methyl-isoxazole pesticide composition and using method |
| CN1348692A (en) * | 2001-09-05 | 2002-05-15 | 黑龙江企达农药开发有限公司 | Hymexazol and its water phase synthesis process |
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