CN103788119A - Thiadiazole metal complex and application thereof in control of agricultural plant diseases - Google Patents
Thiadiazole metal complex and application thereof in control of agricultural plant diseases Download PDFInfo
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Abstract
The invention discloses application of a thiadiazole metal complex in control of plant fungal and bacterial diseases in agriculture. The experimental result proves that the compound is capable of effectively inhibiting fungal disease pathogenic bacteria such as fusarium asiaticum, pepper oxysporum, cytospora mandshurica and the like as well as bacterial disease pathogenic bacteria such as bacterial blight of rice, tobacco bacterial wilt and the like. Furthermore, the compound can be used for controlling the fungal and bacterial diseases of crops, and is simple in structure and preparation technology, low in production cost and wide in application scope. The thiadiazole metal complex has the formula I or II shown in the specification, wherein M is Cu, Zn or Mn.
Description
Technical field
The present invention relates to chemical industry and agricultural chemicals, concrete technology is the application that a class thiadiazoles metal complex is prevented and treated plant epiphyte and bacterial disease in agricultural.
Background technology
Bacterial wilt be a kind of by Ralstonia solanacearum (
r. solanacearum) the crushing soil-borne disease that causes, morbidity plant stem-leaf is wilted sagging until all withered, be endanger in the world maximum, distribute the widest, one of the most serious Plant diseases that causes damage, still there is no so far effective chemical pesticide and other prevention and treatment methods.
Bacterial blight of rice is commonly called as white leaf pest, is one of Major Diseases on paddy rice, this disease the whole nation distribute and spread very wide, very large to rice hazard, be a kind of quarantine disease.Once bacterial blight of rice occurs, generally can the underproduction 10% left and right, serious can underproduction 50%-60%, even 90%.
Metal sterilant 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, be a class wide-spectrum bactericide, in the agriculture bacterium of control and fungal disease, have purposes widely.Metal current sterilant mainly comprises inorganic metal and has metal preparation.Wherein common inorganic metal preparation has copper hydroxide, Basic Chrome Sulphate (Bordeaux mixture), copper oxychloride.In organo-metallic preparation, at present still take organic copper preparation as main.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, are all the product innovations with Chinese independent intellectual property right, and market potential is very considerable.Other organo-metallic preparation also has zinc thiazole, ziram, zineb, zinc manganese ethylenebisdithiocarbamate etc.
1,3,4-thiadiazoles is that a class contains the heteroatomic five member ring heterocyclic compound of S, N, and its cyclic skeleton has obvious conjugative effect and aromaticity, thereby has biological activity widely.Substituting group on 2,5 of 1,3,4-thiadiazoles and derivative thereof can participate in numerous chemical reactions, is usually introduced in pesticide molecule as active group, is the hot subject of modernization agronomy discipline research.
Therefore, based on previous work, we are to this seminar 2-sulfydryl-5-substituting group-1 of synthesized in earlier stage, 3,4-thiadiazole compound carries out further structure of modification, prepare and a series ofly contained 1,3, the metal complex of 4-thiadiazoles, and synthetic compound is adopted to opacity method, carry out bioactivity screening for the bacterial pathogen such as bacterial blight of rice and tobacco bacterial wilt, result shows that part of compounds all has extraordinary activity to bacterial blight of rice and tobacco bacterial wilt pathogenic bacteria.
Summary of the invention
The object of the invention is to 2-sulfydryl-5-substituting group-1 to synthesized in this problem early stage, 3,4-thiadiazole compound carries out further structure of modification, prepared a series of 1,3, the metal complex of 4-thiadiazoles, and for the control of crop virus.
The present invention's one class is prevented and treated the thiadiazoles metal complex of plant epiphyte and bacterial disease in agricultural, and structural formula is suc as formula (I) or formula (II):
In formula (I) or formula (II): R
1be selected from hydrogen, halogen; M is selected from Cu, Zn, Mn metal ion, and halogen is fluorine, chlorine.
Above-mentioned formula (I) indication part target compound is: 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate,
Above-mentioned formula (II) indication part target compound is: 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate.
An above-mentioned class thiadiazoles metal complex is used as the control of agricultural plants fungoid and bacterial disease as Fungicidal compounds medicine or medicament.
Above-mentioned agricultural plants comprises farm crop, fruit tree or vegetables; Described farm crop are paddy rice, wheat, corn, soybean, cotton, peanut, watermelon, rape, capsicum, rape, potato or sesame; Described fruit tree is apple tree, pear tree, litchi, citrus trees or peach; Described vegetables are tomato or cucumber.
Above-mentioned fungal disease is the plant epiphyte venereal disease evils such as wheat scab, the late blight of potato, canker of apple fruit, capsicum wilt, rice sheath blight disease, sclerotinia rot of colza.
Above-mentioned bacterial disease is the bacterial diseases of plants such as tobacco bacterial wilt, bacterial wilt of tomato, pepper ralstonia solanacearum, potato bacterial wilt, strawberry bacterial wilt, eggplant bacterial wilt, tomato macula disease, bacterial blight of rice, paddy bacterial brown spot, bacterial leaf streak of rice, cotton bacterial angular leaf spot, Chinese cabbage leaf spot, watermelon bacterial angular leaf spot, cucumber bacterial angular leaf spot, capsicum bacterial leaf spot and Chinese cabbage bacterial angular leaf spot.
The above-mentioned thiadiazoles metal complex with control plant epiphyte and bacterial disease maybe needs to prevent and treat material, crop, the soil of fungi or bacteria attack, the purposes of seed for the treatment of fungi or bacterium, fungi or bacterium habitat.
Invention effect
(1), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, effect is better.
(2), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, specifically, can prevent and treat the evil such as the plant epiphyte venereal disease that suppresses fusarium graminearum, capsicum wilt bacterium and Valsa mali, the bacterial diseases of plants such as tobacco bacterial wilt, bacterial blight of rice, bacterial leaf streak of rice.
(3), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, simple in structure, preparation technology is simple, production cost is low, has a extensive future.
Embodiment
Embodiment mono-: the preparation of target compound
With compound 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3, the preparation of 4-thiadiazoles zineb illustrates the preparation of this target compound, wherein 2,4 dichloro benzene methyl acetate, 2,4-dichlorobenzene acethydrazide, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles and 2-sulfydryl-5-(2,4-dichloro benzyl)-1, the synthetic of 3,4-thiadiazoles zineb is all with reference to existing document (Chen, Z.
et al.molecules. 2010. Xu, W. M.
et al.Pesticide Biochemistry and Physiology. 2011. Wang Zhenjun, etc. Chinese invention patent
2012).R
1it is cited 2 that group is not limited to, 4-bis-chlorine substituents.Can also be the substituting groups such as hydrogen, 4-fluorine, 4-chlorine.
synthesizing of fenac methyl esters
In tri-mouthfuls of round-bottomed bottles of 50 mL, add 2,4 dichloro benzene acetic acid (0.01 mol), anhydrous methanol 25 mL.Open and stir, dropwise add 98% H
2sO
4(0.008 mol), opens heating, TCL tracking reaction (
v sherwood oil:
v ethyl acetate=3:1), 7 ~ 8 h reactions are complete.Remove unnecessary anhydrous methanol, use 10% NaHCO
3solution is removed H
2sO
4, the product obtaining is oily matter, water extracts, and retains organic phase, obtains product 2,4 dichloro benzene methyl acetate, yield 94%.
synthesizing of dichlorobenzene acethydrazide
In tri-mouthfuls of round-bottomed bottles of 50 mL, add 2,4 dichloro benzene methyl acetate (0.01 mol), anhydrous methanol 20 mL, then mixed, open and stir, TLC tracking reaction (
v sherwood oil:
v ethyl acetate=3:1), back flow reaction 4 ~ 5 h, stopped reaction, unnecessary hydrazine hydrate and anhydrous methanol are removed in decompression, obtain white solid, filter, and dry, and use dehydrated alcohol recrystallization, obtain white solid.Yield 73%, 168 ~ 170 ℃ of fusing points.
sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles synthetic
2,4 dichloro benzene acethydrazide (0.003 mol) is thrown in tri-mouthfuls of round-bottomed flasks of 50 mL, added 20 mL dehydrated alcohols, repeated hydrogenation potassium oxide (0.003 mol), stirring and dissolving.Control temperature and be less than 25 ℃, drip dithiocarbonic anhydride (0.004 mol), rapid stirring 5 h.Suction filtration, with absolute ethanol washing, obtains white solid.Under cryosel is bathed, draw the 10 mL vitriol oils and join in tri-mouthfuls of round-bottomed flasks of 50 mL.Under agitation drop into sylvite (0.01 mol), reaction is violent, a large amount of heat releases, temperature control <3 ℃.After adding, treat that all solids dissolves, then stir 90 min, then reactant is slowly poured into thread shape in the frozen water of 200 mL, product is precipitated out, and suction filtration washs by suitable quantity of water, solid dissolves with 10% NaOH solution, and elimination insolubles is used 5% dilute hydrochloric acid acidifying again, obtains white solid.By recrystallizing methanol, obtain colourless acicular crystal.Yield 76%, 132 ~ 134 ℃ of fusing points.
sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles zineb synthetic
By 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles (0.003 mol) drops in tri-mouthfuls of round-bottomed flasks of 50 mL, adds 20 mL water, then adds 0.0036 mol sodium hydroxide, treats that solid dissolves completely.Take zinc sulfate (0.0015 mol), then use 10 mL water dissolution, solution dropwise joins in there-necked flask with constant pressure funnel.Stopped reaction after reaction 2 ~ 4 h, suction filtration, water and acetone difference washing leaching cake 3 times, obtain white powder solid.Yield 95%, fusing point: be greater than 250 ℃.
Embodiment bis-: the indoor Antifungi venereal disease evil of part of compounds determination of activity
Adopt isolated growth rate method to measure the bacteriostatic activity of compound.Heating potato dextrose agar (PDA substratum: potato 200 g, agar 20 g, glucose 20 g, distilled water 1000 mL), to dissolving state (40-60 ℃), is mixed with respectively 500 by the compound of synthesized and commercial References medicament
μthe liquid of g/mL.Then 10 mL liquids (liquids of 10 times of final concentrations) are poured in 90 mL PDA substratum, fully shaken up, evenly pour in the culture dish of diameter 9 cm, horizontal positioned, to be cooled solidifying.Play at the fresh pathogenic bacteria colony edge punch tool of cultivating 4 d the bacterium dish that cut-off footpath is 4 mm, bacterium dish is inverted in to the dull and stereotyped central authorities containing medicament PDA, then be placed in 27 ℃ of fixed temperature and humidity incubators and be inverted cultivation, start observation when approaching plate 2/3rds place until blank colony growth, right-angled intersection method is measured colony diameter, averages.Blank is adding medicine not, but the solvent that contains same concentration and 0.1% Tween solution, each processing is in triplicate.Calculate the inhibiting rate of medicament to mycelial growth by following formula, the results are shown in
table 1.
I=(C-T)/(C-0.4)*100%
Wherein I is inhibiting rate, and C is blank diameter (cm), and T is for processing diameter (cm).
table 1part target compound is 50
μantifungi activity under g/mL concentration
From
table 1in can find out: 50
μunder g/mL concentration, compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate all has certain bacteriostatic activity to fusarium graminearum, capsicum wilt bacterium and the rotten germ of apple, because the thiadiazoles structure of metal complex in the present invention is closely similar, can predict, other compounds also have the effect of certain inhibition fusarium graminearum, capsicum wilt bacterium and Valsa mali.
Embodiment tri-: the indoor anti-bacteria venereal disease evil of part of compounds determination of activity
(1). the determination of activity of the indoor inhibition bacterial blight of rice of part of compounds pathogenic bacteria
By former bacterial blight of rice bacterium at M210(enzymic hydrolysis casein: 8 g, sucrose: 5 g, yeast extract: 4 g, K
2hPO
4: 3 g, MgSO
47H
2o:0.3 g, agar: 15 g, intermediate water: 1 L, pH=7.0) above solid medium, rule, at 28 ℃, cultivate until grow single bacterium colony.On picking M210 solid medium, the single bacterium colony of the former bacterium of bacterial blight of rice is to M210 liquid nutrient medium (enzymic hydrolysis casein: 8 g, sucrose: 5 g, yeast extract: 4 g, K
2hPO
4: 3 g, MgSO
47H
2o:0.3 g, intermediate water: 1 L, pH=7.0) in, for subsequent use to growth logarithmic phase at 28 ℃, 180 rpm constant-temperature table shaking culture.
It is 200,100 that the compound of synthesized is configured to respectively to concentration with contrast medicament
μthe toxic M210 liquid nutrient medium of g/mL, adds 40
μthe M210 liquid nutrient medium that contains the former bacterium of bacterial blight of rice of the above-mentioned preparation of L at 28 ℃, 180 rpm constant-temperature table shaking culture 24 ~ 48 h, is measured OD value (OD by the bacterium liquid of each concentration in microplate reader
595).And measuring in addition concentration is 200,100
μthe M210 liquid nutrient medium OD value of g/mL medicament and contrast medicament, the OD value that medicament itself is caused is proofreaied and correct.The calculation formula of proofreading and correct OD value and inhibiting rate is as follows:
Correction OD value=containing bacterium culture medium OD value-aseptic culture medium OD value
Inhibiting rate=(the toxic substratum OD value of control medium bacterium liquid OD value-proofread and correct after proofreading and correct)/proofread and correct control medium bacterium liquid OD value × 100% afterwards
Measure according to above method, the inhibition activity of part target compound is shown in
table 2.
table 2the inhibition activity of part of compounds to bacterial blight of rice pathogenic bacteria
By
table 2can find out: under test concentrations, target compound all has certain inhibition activity to the former bacterium of bacterial blight of rice.200
μunder g/mL concentration, compound 2-sulfydryl-5-phenyl-1 of wherein testing, 3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is 100% to the inhibiting rate of bacterial blight of rice pathogenic bacteria.The inhibition activity to the former bacterium of bacterial blight of rice higher than commercial References medicament bismerthiazol and Thiodiazole-copper.Because the thiadiazoles structure of metal complex in the present invention is closely similar, can predict, other compounds also have the effect of certain former bacterium of inhibition bacterial blight of rice.
(2). the determination of activity of the indoor inhibition tobacco bacterial wilt of part of compounds pathogenic bacteria
By tobacco bacterial wilt pathogenic bacteria at NA(extractum carnis: 3 g, peptone: 5 g, yeast extract: 1 g, glucose: 10 g, intermediate water: 1 L; With 5 mol/L NaOH solution tune pH=7 left and right, 121 ℃ of sterilizing 20 min.) above solid medium, rule, at 28 ℃, cultivate until grow single bacterium colony.On picking NA solid medium, the single bacterium colony of tobacco bacterial wilt pathogenic bacteria is to NB liquid nutrient medium (extractum carnis: 3 g, peptone: 5 g, yeast extract: 1 g, glucose: 10 g, intermediate water: 1 L; Adjust about pH=7,121 ℃ of sterilizing 20 min with 5 mol/L NaOH solution) in, for subsequent use to growth logarithmic phase at 30 ℃, 180 rpm constant-temperature table shaking culture.
It is 200,100 that synthetic compound is configured to respectively to concentration with contrast medicament
μthe toxic NB liquid nutrient medium of g/mL, adds 40
μthe NB liquid nutrient medium that contains tobacco bacterial wilt pathogenic bacteria of the above-mentioned preparation of L at 30 ℃, 180 rpm constant-temperature table shaking culture 24 ~ 48 h, is measured OD value (OD by the bacterium liquid of each concentration in microplate reader
595).And measuring in addition concentration is 200,100
μthe NB liquid nutrient medium OD value of g/mL medicament and contrast medicament, the OD value that medicament itself is caused is proofreaied and correct.The calculation formula of proofreading and correct OD value and inhibiting rate is as follows:
Correction OD value=containing bacterium culture medium OD value-aseptic culture medium OD value
Inhibiting rate=(the toxic substratum OD value of control medium bacterium liquid OD value-proofread and correct after proofreading and correct)/proofread and correct control medium bacterium liquid OD value × 100% afterwards
Measure according to above method, the inhibition activity of part target compound is shown in
table 3.
table 3the inhibition activity of part of compounds to tobacco bacterial wilt pathogenic bacteria
By
table 3can find out: under test concentrations, target compound all has certain inhibition activity to tobacco bacterial wilt pathogenic bacteria.200
μunder g/mL concentration, compound 2-sulfydryl-5-phenyl-1 of wherein testing, 3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is 100% to the inhibiting rate of tobacco bacterial wilt pathogenic bacteria.Inhibition activity higher than contrast medicament Thiodiazole-copper to tobacco bacterial wilt pathogenic bacteria.Because the thiadiazoles structure of metal complex in the present invention is closely similar, can predict, other compounds also have the effect of certain inhibition tobacco bacterial wilt pathogenic bacteria.
Embodiment tetra-: high-activity compound virulence regression equation and EC
50the mensuration of value
(1). compound is to fungal disease pathogen virulence regression equation and EC
50the mensuration of value
Adopt isolated growth rate method to measure the bacteriostatic activity of compound.Heating potato dextrose agar (PDA substratum: potato 200 g, agar 20 g, glucose 20 g, distilled water 1000 mL) is to dissolving state (40-60 ℃), synthetic compound and commercial References medicament are configured to respectively to liquid 10 mL of 5 respective concentration, 10 mL liquids (liquids of 10 times of final concentrations) are poured in 90 mL PDA substratum, fully shake up, evenly pour in the culture dish of diameter 9 cm, horizontal positioned, to be cooled solidifying.Play at the fresh pathogenic bacteria colony edge punch tool of cultivating 4 d the bacterium dish that cut-off footpath is 4 mm, bacterium dish is inverted in to the dull and stereotyped central authorities containing medicament PDA, then be placed in 27 ℃ of fixed temperature and humidity incubators and be inverted cultivation, start observation when approaching plate 2/3rds place until blank colony growth, right-angled intersection method is measured colony diameter, averages.Blank is adding medicine not, but the solvent that contains same concentration and 0.1% Tween solution, each processing is in triplicate.Calculate the inhibiting rate of medicament to mycelial growth by following formula
I=(C-T)/(C-0.4)*100%
Wherein I is inhibiting rate, and C is blank diameter (cm), and T is for processing diameter (cm).
By inhibiting rate data-switching become probit value (y), drug concentration (
μg/mL) convert logarithmic value (x) to, in Excel data processing software, carry out regression analysis, obtain virulence regression equation (y=ax+b) and relation conefficient (R), calculate medicament to concentration (EC in pathogenic bacteria inhibition
50), result is shown in respectively
table 4, table 5with
table 6.
table 4part target compound is to concentration in the inhibition of fusarium graminearum
From
table 4in can find out: compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is to concentration (EC in the inhibition of fusarium graminearum
50) be respectively 32.13 ± 2.11,35.83 ± 3.56 and 18.67 ± 1.45
μg/mL, and commercial References medicament kresoxim-methyl and the EC of azoles bacterium ester to fusarium graminearum
50value is respectively 41.61 ± 5.92 and 65.41 ± 4.78
μg/mL.Can find out that this type of thiadiazoles metal complex has good biological activity to fusarium graminearum.
table 5part target compound is to concentration in the inhibition of capsicum wilt bacterium
From
table 5in can find out: compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is to concentration (EC in the inhibition of capsicum wilt bacterium
50) be respectively 28.83 ± 2.12,27.48 ± 1.67 and 25.09 ± 1.09
μg/mL, and commercial References medicament kresoxim-methyl and the EC of azoles bacterium ester to capsicum wilt bacterium
50value is respectively 25.25 ± 1.31 and 93.90 ± 4.67
μg/mL.Can find out that this type of thiadiazoles metal complex has good biological activity to capsicum wilt bacterium.
table 6part target compound is to concentration in the inhibition of Valsa mali
From
table 6in can find out: compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is to concentration (EC in the inhibition of Valsa mali
50) be respectively 29.69 ± 2.65,22.53 ± 1.25 and 21.50 ± 1.08
μg/mL, and commercial References medicament kresoxim-methyl and the EC of azoles bacterium ester to Valsa mali
50value is respectively 38.66 ± 4.54 and 47.33 ± 3.31
μg/mL.Can find out that this type of thiadiazoles metal complex has good biological activity to Valsa mali.
In sum: from
table 4, table 5with
table 6in can find out compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate all has good biological activity to fusarium graminearum, capsicum wilt bacterium and Valsa mali.Because the thiadiazoles structure of metal complex in the present invention is closely similar, can predict, other compounds also have the effect of the plant epiphyte venereal disease evil pathogenic bacterias such as certain inhibition fusarium graminearum, capsicum wilt bacterium and Valsa mali.
(2). compound is to the former bacterium virulence regression equation of bacterial blight of rice and EC
50the mensuration of value
Synthetic compound and commercial References medicament are configured to respectively to the toxic M210 liquid nutrient medium of 5 respective concentration, get 5 mL in test tube, measure toxic aseptic liquid nutrient medium OD value (OD by microplate reader
595), add 40
μthe M210 liquid nutrient medium that L contains the former bacterium of bacterial blight of rice, then at 30 ℃, 180 rpm constant-temperature table shaking culture 24 h, measures the OD value (OD of each concentration bacterium liquid by microplate reader
595).And the OD value of each concentration bacterium liquid after the OD value of the toxic aseptic M210 liquid nutrient medium of mensuration contrast medicament and 24 h, proofreaies and correct the OD value causing due to medicament itself in addition.By inhibiting rate data-switching become probit value (y), drug concentration (
μg/mL) convert logarithmic value (x) to, in Excel data processing software, carry out regression analysis, obtain virulence regression equation (y=ax+b) and relation conefficient (R), calculate medicament to concentration (EC in pathogenic bacteria inhibition
50), the results are shown in
table 7.
table 7part of compounds is to concentration in the inhibition of the former bacterium of bacterial blight of rice
From
table 7in can find out: compound 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is to concentration (EC in the inhibition of the former bacterium of bacterial blight of rice
50) be respectively 57.40 ± 2.78,41.66 ± 3.54 and 50.80 ± 1.69
μg/mL, and commercial References medicament bismerthiazol and the Thiodiazole-copper EC to the former bacterium of bacterial blight of rice
50be respectively 92.61 ± 2.15 and 121.82 ± 3.59
μg/mL.Can find out that compound thiadiazoles metal complex has good biological activity to the former bacterium of bacterial blight of rice, be better than commercially available medicine contrast medicament bismerthiazol and Thiodiazole-copper.
(3). compound is to tobacco bacterial wilt pathogen virulence regression equation and EC
50the mensuration of value
Synthetic compound and commercial References medicament are configured to respectively to the toxic NB liquid nutrient medium of 5 respective concentration, get 5 mL in test tube, measure toxic aseptic liquid nutrient medium OD value (OD by microplate reader
595), add 40
μthe NB liquid nutrient medium that L contains tobacco bacterial wilt pathogenic bacteria, then at 28 ℃, 180 rpm constant-temperature table shaking culture 48 h, measures the OD value (OD of each concentration bacterium liquid by microplate reader
595).And the OD value of each concentration bacterium liquid after the OD value of the toxic aseptic NB liquid nutrient medium of mensuration contrast medicament and 48 h, proofreaies and correct the OD value causing due to medicament itself in addition.By inhibiting rate data-switching become probit value (y), drug concentration (
μg/mL) convert logarithmic value (x) to, in Excel data processing software, carry out regression analysis, obtain virulence regression equation (y=ax+b) and relation conefficient (R), calculate medicament to concentration (EC in pathogenic bacteria inhibition
50), the results are shown in
table 8.
table 8part of compounds is to concentration in the inhibition of tobacco bacterial wilt pathogenic bacteria
By
table 8result can be found out: compound 2-sulfydryl-5-phenyl-1, and 3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate is to concentration (EC in the inhibition of tobacco bacterial wilt pathogenic bacteria
50) be respectively 31.40 ± 1.13,136.35 ± 5.87 and 51.07 ± 3.48
μg/mL, and commercial References medicament bismerthiazol and the Thiodiazole-copper EC to tobacco bacterial wilt pathogenic bacteria
50be respectively 151.66 ± 5.98 and 269.80 ± 7.11
μg/mL.Can find out that compound thiadiazoles metal complex has good biological activity to tobacco bacterial wilt pathogenic bacteria, be better than commercially available medicine contrast medicament bismerthiazol and Thiodiazole-copper.
Conclusion
(1), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, effect is better.
(2), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, specifically, can prevent and treat the evil such as the plant epiphyte venereal disease that suppresses fusarium graminearum, capsicum wilt bacterium and Valsa mali, the bacterial diseases of plants such as tobacco bacterial wilt, bacterial blight of rice, bacterial leaf streak of rice.
(3), a class thiadiazoles metal complex is applied to control plant epiphyte and bacterial disease, simple in structure, preparation technology is simple, production cost is low, has a extensive future.
Claims (7)
1. an Anilidothiobiazole metal complex, is characterized in that indication Anilidothiobiazole metal complex structural formula is suc as formula (I) or formula (II):
In formula (I) or formula (II): R
1be selected from hydrogen, halogen; M is selected from Cu, Zn, Mn metal ion, and halogen is fluorine, chlorine.
2. Anilidothiobiazole metal complex according to claim 1, is characterized in that formula (I) indication part target compound is: 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-phenyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-fluorophenyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(2,4 dichloro benzene base)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-chloro-phenyl-)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate,
Formula (II) indication part target compound is: 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles zineb, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles gloomy copper of generation, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles maneb, 2-sulfydryl-5-benzyl-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-luorobenzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(2,4-dichloro benzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate, 2-sulfydryl-5-(4-chlorobenzyl)-1,3,4-thiadiazoles zinc manganese ethylenebisdithiocarbamate.
3. according to claim 1 or 2, the application of described thiadiazoles metal complex, is characterized in that a described class thiadiazoles metal complex is as medicine or the preparation of preparing Fungicidal compounds, as the control of agricultural plants fungoid and bacterial disease.
4. thiadiazoles metal complex according to claim 3, in the application of control agricultural plants fungus and bacterium disease, 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, capsicum, rape, potato or sesame; Described fruit tree is apple tree, pear tree, litchi, citrus trees or peach; Described vegetables are tomato or cucumber.
5. thiadiazoles metal complex according to claim 3, in the application of control crop fungus and bacterium disease, is characterized in that described fungal disease is the plant epiphyte venereal disease evils such as wheat scab, the late blight of potato, canker of apple fruit, capsicum wilt, rice sheath blight disease, sclerotinia rot of colza.
6. thiadiazoles metal complex according to claim 3 is in the application of control crop fungus and bacterium disease, it is characterized in that described bacterial disease is tobacco bacterial wilt, bacterial wilt of tomato, pepper ralstonia solanacearum, potato bacterial wilt, strawberry bacterial wilt, eggplant bacterial wilt, tomato macula disease, bacterial blight of rice, paddy bacterial brown spot, bacterial leaf streak of rice, cotton bacterial angular leaf spot, Chinese cabbage leaf spot, watermelon bacterial angular leaf spot, cucumber bacterial angular leaf spot, the bacterial diseases of plants such as capsicum bacterial leaf spot and Chinese cabbage bacterial angular leaf spot.
7. the application of thiadiazoles metal complex according to claim 3, the metal complex that it is characterized in that the described thiadiazoles with control plant epiphyte and bacterial disease maybe needs to prevent and treat material, crop, the soil of bacterium or fungal attack, the purposes of seed for the treatment of bacterium or fungi, bacterium or fungi habitat.
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| CN111423472A (en) * | 2018-12-24 | 2020-07-17 | 刘力 | Broad-spectrum sterilization low-toxicity low-residue growth-promoting Thisen manganese zinc compound and composition thereof |
| CN113563281A (en) * | 2021-07-06 | 2021-10-29 | 贵州大学 | Benzophenone compound containing 1,3, 4-thiadiazole thioether structure and application thereof |
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| CN113563281A (en) * | 2021-07-06 | 2021-10-29 | 贵州大学 | Benzophenone compound containing 1,3, 4-thiadiazole thioether structure and application thereof |
| CN113563281B (en) * | 2021-07-06 | 2023-11-24 | 贵州大学 | Benzophenone compound containing 1,3, 4-thiadiazole thioether structure and application thereof |
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