CN102516266B - Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases - Google Patents
Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases Download PDFInfo
- Publication number
- CN102516266B CN102516266B CN201110401839.2A CN201110401839A CN102516266B CN 102516266 B CN102516266 B CN 102516266B CN 201110401839 A CN201110401839 A CN 201110401839A CN 102516266 B CN102516266 B CN 102516266B
- Authority
- CN
- China
- Prior art keywords
- preparation
- thiazole quinoline
- copper
- organocopper compound
- thiazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases. The thiazole quinoline organic copper compound is prepared by adding 2-mercaptobenzothiazole, 8-hydroxyquinoline and a cupric salt in an organic solvent for a reaction for 1 to 3 h and sequentially carrying out separation, rinsing and drying after the reaction is finished. The preparation method provided in the invention has the advantages of simpleness, easy practicability, low cost and no environmental pollution; the prepared novel thiazole quinoline organic compound copper-2-mercaptobenzothiazole-8-hydroxyquinoline has stable properties and a broad fungicide spectrum and can be widely used for control of agricultural plant diseases like tomato late blight, cucumber downy mildew, lichee downy mildew, apple ring rot, etc.
Description
Technical field
The invention belongs to pesticide chemical technical field, particularly a kind of thiazole quinoline organocopper compound and preparation method thereof, preparation and the purposes in control agricultural plants disease.
Background technology
2-mercaptobenzothiazole molecular formula is C
7h
5nS
2, molecular weight is 167.24, pale yellow powder is dissolved in the basic solutions such as propyl alcohol, ethanol, chloroform, ammoniacal liquor, sodium hydroxide and sodium carbonate, is slightly soluble in benzene, water insoluble and gasoline.Main as vulcanizer (captax), also, as agricultural bactericide, be commonly called as mercaptobenzothiaz01e or M agent, but its activity is lower, fail to be used widely.2-mercaptobenzothiazole is also by the industrial inhibiter as metallic copper, and for inquiring into the inhibition mechanism of 2-mercaptobenzothiazole, 2-mercaptobenzothiazole and copper effect are widely studied.Literature research finds that 2-mercaptobenzothiazole comes from 2-mercaptobenzothiazole to the provide protection of metallic copper and monovalence copper forms title complex (Qian Wenying etc., the inhibition principle of spectrochemistry research alpha-mercapto benzothiazole to copper, Chinese Journal of Inorganic Chemistry, 1999,15 (06): 756-760; I.P.Khullar, and U.Agarewala, Can.J.Chem.1975,53,1165).
Oxine molecular formula is C
9h
7nO, molecular weight is 145.16, is white or faint yellow crystallization or crystalline powder, water insoluble and ether, be dissolved in ethanol, acetone, chloroform, benzene or diluted acid, it is amphoteric substance, can be dissolved in strong acid, highly basic, is ionized into negative ion in alkali, energy binding hydrogen ions in acid,, easily there is the reactions such as nitrated, sulfonation, oxidation in solvability minimum in the time of PH=7, is the useful intermediates of organic synthesis (as medicine).Also can be used as rna synthesis inhibitor, beard and hair trichobacteria, myrothecium verrucaria and trichoderma viride are had to sterilization restraining effect, its mantoquita complex compound is good sterilant.
Copper fungicide is as a kind of tradition, important sterilant; have the Application and Development time the earliest, duration of service is the longest, use the maximum and 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, forbid or limit use at florescence and young fruit period; 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, in a disguised form 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, at present still take 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, many agricultural chemicals producer of China 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 " that be 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.Wherein these three organic copper preparations of Thiodiazole-copper, oxinecopper and 30% nonylphenolsulfonate copper microemulsion, 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 that uses: 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 can not cause chemical reaction with most sterilant, miticide, sterilant and plant-growth regulator phase mixture, 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 " medicine Zhiduo County disease ".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 " it is neutral that great majority are organic copper preparation, has better affinity and mixture, 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, and the florescence on farm crop and young fruit period impact are less, 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 in the time of 10mg/L, in the time that its concentration reaches 30mg/L, can make poisoning to sensitive plant.Have not yet to see the relevant report of novel thiazole quinolines copper-2-mercaptobenzothiazole-oxine and preparation method thereof, more do not find the relevant report for agricultural plants disease control by this novel thiazole quinolines copper-2-mercaptobenzothiazole-oxine.
Summary of the invention
The object of the present invention is to provide a kind of novel thiazole quinoline organocopper compound, provide that a kind of preparation method is simple, cost is low, the preparation method of the novel thiazole quinoline organocopper compound of environmental protection simultaneously, the thiazole quinoline organocopper compound stable in properties of preparation, fungicidal spectrum is wide, extensively the control of agricultural plants disease.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of thiazole quinoline organocopper compound, concrete name is called copper-2-mercaptobenzothiazole-oxine, and this compound has chemical structural formula as shown in Equation 1:
The preparation method of above-mentioned thiazole quinoline organocopper compound, comprises the following steps:
It is in the methanol aqueous solution or aqueous ethanolic solution of 75-95% that the oxine of the 2-mercaptobenzothiazole of 6.5-7.0g purity 99% and 5.3-5.8g purity 98% is added to 140-260ml massfraction, heating for dissolving, obtain solution A, the cupric salt that is 95-99% by 2.5-3.0g 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, stir 1h in 55-70 ℃, stirring staticly settles after finishing, precipitation separation, to precipitate by washing with alcohol, then wash with water, washing post-drying obtains blackish green Powdered thiazole quinoline organocopper compound.
The addition of described methanol aqueous solution or aqueous ethanolic solution is can dissolve 2-mercaptobenzothiazole and oxine is as the criterion; In the time that cupric salt is water-soluble, the addition of water is as the criterion can dissolve cupric salt, and in the time that cupric salt is water insoluble, the addition of water is being as the criterion by moistening cupric salt.
Described cupric salt includes but not limited to copper sulfate, cupric chloride, copper hydroxide, cupric nitrate or neutralized verdigris.
Described solution A dropwises in 22-30min.
The preparation of above-mentioned thiazole quinoline organocopper compound, said preparation comprises the thiazole quinoline organocopper compound of 20-90% 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% thiazole quinoline organocopper compound, 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 above-mentioned thiazole quinoline 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, soybean, cotton, peanut, watermelon, rape or sesame; Described fruit tree is apple tree, litchi, pear tree, citrus trees or peach; Described vegetables are tomato or cucumber; Described bacterial disease is rice leaf spot bacteria or ulcer bacteria; Described fungal disease is rust, phytophthora root rot bacterium, Pseudoperonospora cubensis, wheel line bacterium disease, leaf spot fungi, stem point rot bacterium, sheath blight fungus, wilt or sclerotium germ.
The invention has the advantages that: first, main raw material 2-mercaptobenzothiazole of the present invention and oxine are with low cost, raw material is easy to get, for prepared thiazole quinoline organocopper compound copper-2-mercaptobenzothiazole-oxine provides 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, thiazole quinoline organocopper compound copper-2-mercaptobenzothiazole-oxine stable in properties of preparation, chance strong acid, highly basic do not decompose, can be mixed with Multiple Pesticides, solve Inorganic Copper and the poor drawback of organic copper fungicide compounding in the past; The 4th, thiazole quinoline organocopper compound prepared by the present invention forms coordination compound with organic molecule and cupric ion, make the release of cupric ion can reach the concentration of kill pathogenic organisms, can not cause poisoning to crop again, therefore possess the potentiality of the novel organic copper sterilant that is developed to efficient, nontoxic, lasting and environmental protection simultaneously; The 5th, the sterilant that adopts thiazole quinoline organocopper compound of the present invention to be prepared from, fungicidal spectrum is wide, bacterium and the microbial disease of fungoid disease are had to prevention effect, can be widely used in the control of the agricultural plants diseases such as tomato late blight, cucumber downy mildew, downy mildew of lichee, ring rot of apple, in addition also can be used as, the mould inhibitor of rope, line, leather, vinyl plastics.
Accompanying drawing explanation
Fig. 1 is the mass spectrum of the thiazole quinoline organocopper compound prepared of the present invention.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the thiazole quinoline organocopper compound prepared of the present invention.
Fig. 3 is thiazole quinoline organocopper compound prepared by the present invention fungistatic effect figure while measuring for citrus ulcer bacteria 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 derosal is commercial product.
The 2-mercaptobenzothiazole that is 99% by 6.6g purity, 5.4g purity is in 98% oxine and the 260ml massfraction disposable input 500ml reaction flask of aqueous ethanolic solution that is 75%, heating for dissolving at the temperature of 74 ℃, obtain solution A, the cupric sulfate pentahydrate that is 99% by 2.5g 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 28min, dropwise, then temperature control is at 70 ℃, stirring reaction 1h, after reaction, staticly settle 4.5h, fully after layering, remove upper solution, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 105 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine, structure is shown below,
As Fig. 1, shown in 2, detecting m/z in mass spectrum and be 373 characteristic peak and NMR hydrogen spectrogram intermediate value is 7.03,7.53,7.61,7.64,7.70,8.01,8.18,8.39 and 8.89 characteristic peak.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 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% thiazole quinoline organocopper compound wettable powder.
The 50% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to bacteriostatic test mensuration, make reference sample, the citrus ulcer bacteria that strains tested provides for Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo with the wettable powder that contains 50% derosal (auxiliary material and content thereof are all with the 50% thiazole quinoline organocopper compound wettable powder of the present embodiment).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 ℃, after 24h, and observations, record.Fungistatic effect is as Fig. 3, in figure left side be the wettable powder (667ppm) of derosal to citrus ulcer bacteria fungistatic effect, right side is that thiazole quinoline organocopper compound wettable powder (667ppm) is to citrus ulcer bacteria fungistatic effect.The restraining and sterilizing bacteria successful of thiazole quinoline organocopper compound wettable powder is better than contrasting pesticide carbendazim as can be seen from Figure 3, and inhibition zone is roughly 3 times of derosal control group.
Embodiment 2
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 1.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 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% thiazole quinoline organocopper compound wettable powder.
Strains tested is rice leaf spot bacteria, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 20% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, do reference sample with the wettable powder that contains 20% derosal (auxiliary material and content thereof are all with the 20% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 20% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 500 times (ultimate density is 400ppm), be 89% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 500 times (ultimate density is 400ppm), test organisms be there is no to fungistatic effect.
Embodiment 3
The 2-mercaptobenzothiazole that is 99% by 6.5g purity, 5.6g purity is in 98% oxine and the 140ml massfraction disposable input 500ml reaction flask of methanol aqueous solution that is 95%, heating for dissolving at the temperature of 85 ℃, obtain solution A, the cupric sulfate pentahydrate that is 99% by 2.5g purity and 25ml distilled water join in 500ml reaction flask, heating, and stir it is fully dissolved at the temperature of 30 ℃, 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, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 110 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 90.0%, Nonyl pheno base ether 3.5%, novalgin formaldehyde condensation products 1.0%, wilkinite 5.5% prepared by the present embodiment, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 90% thiazole quinoline organocopper compound wettable powder.
Strains tested is Botryosphaeria berengeriana f. sp, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 90% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, make reference sample with the wettable powder that contains 90% derosal (auxiliary material and content thereof are all with the 90% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 90% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density is 900ppm), be 97% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 1000 times (ultimate density is 900ppm), the inhibiting rate of test organisms is respectively to 44%.
Embodiment 4
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 3.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 70.0%, octylphenol polyethylene oxyethylene group ether sulfate 10.0%, sodium dibutyl naphthalene sulfonate formaldehyde condensation products 5.5%, attapulgite 14.5% prepared by the present embodiment, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 70% thiazole quinoline organocopper compound wettable powder.
Strains tested is downy mildew of lichee bacterium, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 70% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, make reference sample with the wettable powder that contains 70% derosal (auxiliary material and content thereof are all with the 70% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 70% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density is 700ppm), be 96% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 1000 times (ultimate density is 700ppm), be 46% to the bacteriostasis rate of test organisms.
The 2-mercaptobenzothiazole that is 99% by 6.7g purity, 5.7g purity is in 98% oxine and the 220ml massfraction disposable input 500ml reaction flask of methanol aqueous solution that is 75%, heating for dissolving at the temperature of 80 ℃, obtain solution A, the cupric chloride that is 95% by 2.6g 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 22min, dropwise, then temperature control is at 62 ℃, stirring reaction 1h, after reaction, staticly settle 5h, fully after layering, remove upper solution, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 102 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 80%, sodium dibutyl naphthalene sulfonate 4%, succinate sodium sulfonate (a kind of alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfonate) 10%, light calcium carbonate 6% prepared by the present embodiment, after by said ratio, each material fully being mixed, ground, cross 320 mesh sieves and obtain 80% thiazole quinoline organocopper compound wettable powder.
Strains tested is Germ To Soybean Frogeye Leaf Spot, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 80% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to bacteriostatic test mensuration according to ordinary method, make reference sample with the wettable powder that contains 80% derosal (auxiliary material and content thereof are all with the 80% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 80% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 1000 times (ultimate density 800ppm), be 98% to the inhibiting rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 1000 times (ultimate density is 800ppm), be 33% to the bacteriostasis rate of test organisms.
Embodiment 6
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 5.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 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%, carboxymethyl cellulose 3%, diatomite and attapulgite 3) 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% thiazole quinoline organocopper compound wettable powder.
Strains tested is cotton-wilt fusarium, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 60% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, do reference sample with the wettable powder that contains 60% derosal (auxiliary material and content thereof are all with the 60% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 60% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 200 times (ultimate density is 3000ppm), be 98% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 200 times (ultimate density is 3000ppm), test organisms be there is no to fungistatic effect.
Embodiment 7
The 2-mercaptobenzothiazole that is 99% by 7.0g purity, 5.8g purity is in 98% oxine and the 200ml massfraction disposable input 500ml reaction flask of aqueous ethanolic solution that is 95%, heating for dissolving at the temperature of 60 ℃, obtain 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 65 ℃, stirring reaction 1h, after reaction, staticly settle 4.2h, fully after layering, remove upper solution, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 100 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 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: octylphenol polyethylene oxyethylene group ether sulfate=1: 1: 1) composition 10%, 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% thiazole quinoline organocopper compound wettable powder.
Strains tested is peanut Cercospora bacteria, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 30% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, make reference sample with the wettable powder that contains 30% derosal (auxiliary material and content thereof are all with the 30% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 30% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 400 times (ultimate density is 750ppm), be 97% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 400 times (ultimate density is 750ppm), be 42% to the bacteriostasis rate of test organisms.
Embodiment 8
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 7.
Get each material of following weight percent: copper-2-mercaptobenzothiazole-oxine 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: alkylphenol-polyethenoxy base ether formaldehyde condensation products sulfonate=2: 1: 3: 4) composition 10%, 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% thiazole quinoline organocopper compound wettable powder.
Strains tested is Sclerotinia sclerotiorum, provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, the 40% thiazole quinoline organocopper compound wettable powder being mixed with is carried out to conventional bacteriostatic test mensuration according to ordinary method, make reference sample with the wettable powder that contains 40% derosal (auxiliary material and content thereof are all with the 40% thiazole quinoline organocopper compound wettable powder of the present embodiment).Result shows: 40% thiazole quinoline organocopper compound wettable powder is the in the situation that of dilution 400 times (ultimate density is 1000ppm), be 95% to the bacteriostasis rate of test organisms, and the wettable powder of derosal is the in the situation that of dilution 400 times (ultimate density is 1000ppm), be 32% to the bacteriostasis rate of test organisms.
Embodiment 9
The 2-mercaptobenzothiazole that is 99% by 6.8g purity, 5.5g purity is in 98% oxine and the 180ml massfraction disposable input 500ml reaction flask of methanol aqueous solution that is 85%, heating for dissolving at the temperature of 70 ℃, obtain solution A, the cupric nitrate that is 95% by 2.5g 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, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 108 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine.
The conventional auxiliary material of copper-2-mercaptobenzothiazole-oxine prepared by the present embodiment that is 50% by weight percentage and water dispersible granules is measured for the conventional bacteriostatic test of stalk of sesame point rot bacterium after making according to a conventional method thiazole quinoline organocopper compound water dispersible granules, stalk of sesame point rot bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, makes reference sample with the water dispersible granules that contains 50% derosal (auxiliary material and content thereof are all with the thiazole quinoline organocopper compound water dispersible granules of the present embodiment).Result shows: 3g thiazole quinoline organocopper compound water dispersible granules is put in 1000mL water, be 98%, and the water dispersible granules of 3g derosal is put in 1000mL water, is 45% to the bacteriostasis rate of test organisms to the bacteriostasis rate of test organisms.
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 9.
The conventional auxiliary material of copper-2-mercaptobenzothiazole-oxine prepared by the present embodiment that is 60% by weight percentage and water dispersible granules is measured for the conventional bacteriostatic test of pear tree alternaria after making thiazole quinoline organocopper compound water dispersible granules according to ordinary method, pear tree alternaria is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, makes reference sample with the water dispersible granules that contains 60% derosal (auxiliary material and content thereof are all with the thiazole quinoline organocopper compound water dispersible granules of the present embodiment).Result shows: 3g thiazole quinoline organocopper compound water dispersible granules is put in 1000mL water, be 97%, and the water dispersible granules of 3g derosal is put in 1000mL water, is 33% to the bacteriostasis rate of test organisms to the bacteriostasis rate of test organisms.
Embodiment 11
The 2-mercaptobenzothiazole that is 99% by 6.9g purity, 5.3g purity is in 98% oxine and the 240ml massfraction disposable input 500ml reaction flask of aqueous ethanolic solution that 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 40 ℃, 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 25min, dropwise, then temperature control is at 64 ℃, stirring reaction 1h, after reaction, staticly settle 4.6h, fully after layering, remove upper solution, the blackish green throw out of lower floor is used dehydrated alcohol (or ethanol) and water washing successively, then in thermostatic drying chamber, at 106 ℃, dry, obtain blackish green powder and be copper-2-mercaptobenzothiazole-oxine.
The conventional auxiliary material of copper-2-mercaptobenzothiazole-oxine prepared by the present embodiment that is 20% by weight percentage and suspension concentrate is measured for the conventional bacteriostatic test of Peach canker disease bacterium after making according to a conventional method thiazole quinoline organocopper compound suspension concentrate, Peach canker disease bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, makes reference sample with the suspension concentrate that contains 20% derosal (auxiliary material and content thereof are all with the thiazole quinoline organocopper compound suspension concentrate of the present embodiment).Result shows: thiazole quinoline organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 1000ppm), be 98% to the bacteriostasis rate of test organisms, and the suspension concentrate of derosal is the in the situation that of dilution 200 times (ultimate density is 1000ppm), test organisms be there is no to fungistatic effect.
Embodiment 12
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 11.
The conventional auxiliary material of copper-2-mercaptobenzothiazole-oxine prepared by the present embodiment that is 30% by weight percentage and suspension concentrate is measured for the conventional bacteriostatic test of tomato late blight bacterium after making according to a conventional method thiazole quinoline organocopper compound suspension concentrate, tomato late blight bacterium is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, makes reference sample with the suspension concentrate that contains 30% derosal (auxiliary material and content thereof are all with the thiazole quinoline organocopper compound suspension concentrate of the present embodiment).Result shows: thiazole quinoline organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 1500ppm), be 97% to the bacteriostasis rate of test organisms, and the suspension concentrate of derosal is the in the situation that of dilution 200 times (ultimate density is 1500ppm), be 52% to the bacteriostasis rate of test organisms.
Embodiment 13
The preparation method of copper-2-mercaptobenzothiazole-oxine is with embodiment 11.
The conventional auxiliary material of copper-2-mercaptobenzothiazole-oxine prepared by the present embodiment that is 40% by weight percentage and suspension concentrate is measured for the conventional bacteriostatic test of cucumber fusarium axysporum after making according to a conventional method thiazole quinoline organocopper compound suspension concentrate, cucumber fusarium axysporum is provided by Inst. of Pesticides, Xibei Univ. of Agricultural &. Forestry Science &. Technolo, makes reference sample with the suspension concentrate that contains 40% derosal (auxiliary material and content thereof are all with the thiazole quinoline organocopper compound suspension concentrate of the present embodiment).Result shows: thiazole quinoline organocopper compound suspension concentrate is the in the situation that of dilution 200 times (ultimate density is 2000ppm), be 95% to the bacteriostasis rate of test organisms, and the suspension concentrate of derosal is the in the situation that of dilution 200 times (ultimate density is 2000ppm), test organisms be there is no to fungistatic effect.
The fungistatic effect of thiazole quinoline organocopper compound (copper-2-mercaptobenzothiazole-oxine) prepared by the present invention is obviously better than derosal, fungistatic effect be derosal 2-5 doubly, be to bacillary or the restraining and sterilizing bacteria effect of fungoid germ is all very remarkable.
Claims (8)
1. a thiazole quinoline organocopper compound, is characterized in that: this compound has chemical structural formula as shown in Equation 1:
2. prepare a method for thiazole quinoline organocopper compound as claimed in 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 the oxine of the 2-mercaptobenzothiazole of 6.5-7.0g purity 99% and 5.3-5.8g purity 98% is added to 140-260ml massfraction, heating for dissolving, obtain solution A, the cupric salt that is 95-99% by 2.5-3.0g 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, stir 1h in 55-70 ℃, stirring staticly settles after finishing, precipitation separation, to precipitate by washing with alcohol, then wash with water, washing post-drying obtains blackish green Powdered thiazole quinoline organocopper compound,
Described cupric salt is selected from copper sulfate, cupric chloride, copper hydroxide, cupric nitrate or neutralized verdigris.
3. a kind of method of thiazole quinoline organocopper compound according to claim 2, is characterized in that: described solution A dropwises in 22-30min.
4. a preparation, is characterized in that: said preparation comprises 20-90% thiazole quinoline as claimed in claim 1 organocopper compound by massfraction, and surplus is auxiliary material, and the formulation of said preparation comprises wettable powder, water dispersible granules or suspension concentrate.
5. preparation according to claim 4, is characterized in that: the component of described wettable powder comprises that by massfraction 20～90% thiazole quinoline organocopper compounds as claimed in claim 1,1～10% wetting agent, 1～10% dispersion agent, surplus are filler.
6. preparation according to claim 5, 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.
7. the purposes of thiazole quinoline organocopper compound in the bacillary and fungal disease of control agricultural plants as claimed in claim 1.
8. the purposes of a kind of thiazole quinoline organocopper compound in the bacillary and fungal disease of control agricultural plants according to claim 7, is characterized in that: described agricultural plants comprises farm crop, fruit tree or vegetables; Described farm crop are paddy rice, wheat, corn, soybean, cotton, peanut, watermelon, rape or sesame; Described fruit tree is apple tree, litchi, pear tree, citrus trees or peach; Described vegetables are tomato or cucumber; Described bacterial disease is rice leaf spot bacteria or ulcer bacteria; Described fungal disease is rust, phytophthora root rot bacterium, Pseudoperonospora cubensis, wheel line bacterium disease, leaf spot fungi, stem point rot bacterium, sheath blight fungus, wilt or sclerotium germ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110401839.2A CN102516266B (en) | 2011-12-06 | 2011-12-06 | Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110401839.2A CN102516266B (en) | 2011-12-06 | 2011-12-06 | Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102516266A CN102516266A (en) | 2012-06-27 |
| CN102516266B true CN102516266B (en) | 2014-07-02 |
Family
ID=46287384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110401839.2A Expired - Fee Related CN102516266B (en) | 2011-12-06 | 2011-12-06 | Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516266B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104115869B (en) * | 2014-06-12 | 2016-08-31 | 中国水稻研究所 | A kind of ternary built pesticide containing Copper hydrate, trifloxystrobin and Tebuconazole |
-
2011
- 2011-12-06 CN CN201110401839.2A patent/CN102516266B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Complexes of 2-Mercaptobenzothiazole with Cu(II), Ni(II), Co(II), Cd(II), Zn(II), Pb(II), Ag(I), and Ti(I);I.P. Khullar, et al.;《CAN. J. CHEM.》;19751231;第53卷;第1165-1171页 * |
| I.P.Khullar et al..Complexes of 2-Mercaptobenzothiazole with Cu(II) |
| 光谱电化学研究α-巯基苯并噻唑对铜的缓蚀机理;钟文英等;《无机化学学报》;19991130;第15卷(第6期);第756-760页 * |
| 钟文英等.光谱电化学研究α-巯基苯并噻唑对铜的缓蚀机理.《无机化学学报》.1999,第15卷(第6期),第756-760页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102516266A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100422153C (en) | N-(2-substituted phenyl)-N-methoxy carbamate compounds and their preparation and use | |
| TW200911753A (en) | Novel fungicides | |
| Sharma et al. | Biomedical and antifungal application of Cu (II) soaps and its urea complexes derived from various oils | |
| CN102630691A (en) | Pesticide composition containing cyflumetofen | |
| CN102516265B (en) | Thiadiazole quinoline organic copper compound, preparation method thereof, preparation thereof, and application thereof in controlling agricultural plant diseases | |
| CN106117064B (en) | A kind of (anti-)-β-farnesene analog of acid groups containing jasmine and its preparation and application | |
| CN101946802B (en) | Bactericide composition with synergistic effect | |
| CN102516267B (en) | Thiodiazole copper compound, and its preparation method, preparation and application | |
| CN102516266B (en) | Thiazole quinoline organic copper compound and its preparation method, preparation and application in controlling agricultural plant diseases | |
| CN102516268B (en) | Oxazole thiadiazole organic copper compound, its preparation method, preparation and application in controlling agricultural plant diseases | |
| CN107200712A (en) | One class yl pyrimidines aryl containing substitution amidine compound, its preparation method and application | |
| CN102516190B (en) | Oxazolyl quinoline organic copper compound, preparation method of oxazolyl quinoline organic copper compound, oxazolyl quinoline organic copper compound agent, and use of oxazolyl quinoline organic copper compound in prevention and treatment of crop diseases | |
| CN102516189B (en) | Oxazole organic copper compound, and preparation method and preparation thereof and purpose thereof in control of agricultural plant disease | |
| CN102516269B (en) | Thiazole oxazoles organic copper compound, its preparation method, its preparation and its purpose for preventing and treating plant diseases in agriculture | |
| CN104542653A (en) | Antibacterial composition containing polyoxin and oxine-copper | |
| CN108719288A (en) | Application of the farnesol in plant botrytis prevention as sterilizing synergistic agent | |
| JPS6025402B2 (en) | Fungicide for agriculture and horticulture | |
| CN102986741A (en) | Application of euphorbiaceous acid to biopesticides | |
| MXPA06011190A (en) | Sulphur-containing oils for controlling plant pathogens and stimulating nutrient uptake. | |
| CN103385244A (en) | Bactericidal composition comprising fluxapyroxad and thiocarbamate | |
| CN102715182A (en) | Sterilization composition containing active components Bellkute and imazalil | |
| CN102369938B (en) | Sterilization composition containing zineb and chunleimeisu | |
| CN101747290A (en) | N-substituent thiazolone derivative and preparation method and applications thereof | |
| CN100515202C (en) | Gadolinium nitrate berberine complex pesticides sterilizing emulsion agent and preparation method thereof | |
| CN109776545A (en) | A kind of triazolo pyrimidine antibacterial agent and its composition pesticide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140702 Termination date: 20171206 |