CN103483288B - One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use - Google Patents

One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use Download PDF

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CN103483288B
CN103483288B CN201310481691.7A CN201310481691A CN103483288B CN 103483288 B CN103483288 B CN 103483288B CN 201310481691 A CN201310481691 A CN 201310481691A CN 103483288 B CN103483288 B CN 103483288B
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chloroisothiazole
bis
agent
sterilant
bishydrazide
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CN103483288A (en
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范志金
宗广宁
李岳东
李娟娟
李凤云
姬晓恬
朱玉洁
陈来
刘超伦
程胜名
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Nankai University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

The invention provides class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use, the present invention relates to the heterogeneous ring compound containing 1,2,3-thiadiazoles, they have the chemical structure of general formula as shown in I.

Description

One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use
Technical field
Technical scheme of the present invention relates to containing 1; the heterogeneous ring compound of 2-isothiazole; be specifically related to containing 3; 4-bis-chloroisothiazole bishydrazide derivative; more specifically relate to N-(3; 4-bis-chloroisothiazole-5-formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound and N-(3,4-bis-chloroisothiazole-5-formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound.
Background technology
Insect growth regulator(IGR) (IGRs), as sterilant of new generation, is grown to regulate the normal growth of insect and is carried out optionally Control pests with metamorphosis, have that security is high, selectivity good, nuisanceless, low residue and biological activity advantages of higher.20th century the mid-80, Rohm-Hass company of the U.S. first reported the N-tertiary butyl bishydrazide compounds RH-5849 of synthesis and it intends moulting hormone effect accordingly, and is successfully developed to commodity and presses down food hydrazine.Rohm-Hass company with N-tertiary butyl bishydrazide for guide's active structure, utilize row's principles such as molecule, adopt the method for roughly the same synthesizing, structural modification is carried out to RH-5849, successfully develops again RH-5992, RH-2485, RH-0345 tri-biological activitys comparatively better industrialization product of RH-5849.Wherein, the former medicine of RH-5992 and 24% suspension agent (rice is full), the former medicine of RH-2485 and 24% suspension agent (happiness) are registered in China, be respectively used to control forest dendrolimus punctatus and rice-stem borer (synthesis of Zhang Xiangning .N-tertiary butyl bishydrazide new compound and bioactivity research [D]. Agricultural University Of Nanjing, 2003,14-16).
Have 1, the biological activity of the compound of 2-isothiazole is the focus studied in recent years, if isotianil (isotianil) is the isothiazole series bactericidal agent that Bayer and Sumitomo Chemical research and develop jointly for preventing and treating rice blast, its IUPAC name is called 3,4-dichloro-2 '-cyano-1,2-thiazole-5-carboxanilide.Its feature is not produce direct anti-microbial effect to pathogenic bacteria, and the object (AssmannL by exciting the natural immunology defense of paddy rice self to rice blast to reach opposing rice blast, etal.Preparationofisothiazolecarboxamidesasplantprotecta nts:WO9924413 [P], 1999-05-20).
Produce with inducing plant the lead compound that system resume has insecticidal activity simultaneously to find, design and synthesis of the present invention one class 3,4-bis-chloroisothiazole bishydrazide compounds, and carried out the bioactive screening of system, to providing candidate compounds for New pesticides discovery research.
Summary of the invention
Technical problem to be solved by this invention is: provide new 3,4-bis-chloroisothiazole bishydrazide compounds synthetic method, there is provided this compounds to suppress agricultural and gardening and forestry plant pathogen, insect and do harm to biological activity and the measuring method of mite, providing these compounds to apply in agriculture field and horticultural field and field of forestry simultaneously.
The present invention solves this technical problem adopted technical scheme: have agriculture field, the chemical structure of general formula of 3,4-bis-chloroisothiazole bishydrazide compounds that horticultural field, field of forestry desinsection, acaricidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity is shown in formula I:
Wherein, R 1be selected from: hydrogen or the tertiary butyl, R 2be selected from: hydrogen or the tertiary butyl, R 3be selected from: 3-chlorinated benzene-1-base, 2-chlorinated benzene-1-base, 1-chlorinated benzene-1-base, 3-trifluoromethylbenzene-1-base, 4-trifluoromethylbenzene-1-base, 2-anisole-1-base, 2-oil of mirbane-1-base, 3-oil of mirbane-1-base, 3-fluorobenzene-1-base, 4-methyl-3-(2-chloro-phenyl-)-Ji-4-oxazolyl, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazole-4-bases.
Chemical structure of general formula is that 3, the 4-bis-chloroisothiazole bishydrazide compounds of formula I are specifically divided into IV and VII kind form:
The synthetic method of 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention is as follows:
Work as R 1for hydrogen, R 2during for the tertiary butyl, R 3be selected from: 3-chlorinated benzene-1-base, 2-chlorinated benzene-1-base, 1-chlorinated benzene-1-base, 3-trifluoromethylbenzene-1-base, 4-trifluoromethylbenzene-1-base, 2-anisole-1-base, 2-oil of mirbane-1-base, 3-oil of mirbane-1-base, 3-fluorobenzene-1-base, 4-methyl-3-(2-chloro-phenyl-)-Ji-4-oxazolyl, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazole-4-bases;
Work as R 1for the tertiary butyl, R 2during for hydrogen, R 3be selected from: 3-chlorinated benzene-1-base, 2-chlorinated benzene-1-base, 1-chlorinated benzene-1-base, 3-trifluoromethylbenzene-1-base, 4-trifluoromethylbenzene-1-base, 2-anisole-1-base, 2-oil of mirbane-1-base, 3-oil of mirbane-1-base, 3-fluorobenzene-1-base, 4-methyl-3-(2-chloro-phenyl-)-Ji-4-oxazolyl, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazole-4-bases.
Specifically be divided into following steps:
A.3, the preparation of 4-dichloro isothiazollylacyl tertiary butyl hydrazine III
In 50 milliliters of there-necked flasks, add 0.016 mole of i.e. 2g Tertiary butyl hydrazine hydrochloride, 10 milliliters of methylene dichloride, stir after being cooled to 0 degree Celsius, drip the aqueous sodium hydroxide solution 0.016 mole namely 6.4 grams of 10%, dropwise rear stirring 30 minutes; Drip containing 3,4-dichloro isothiazolo acyl chloride 0.004 mole i.e. 10 milliliters of dichloromethane solutions of 0.84 gram and sodium hydroxide 0.004 molar solution 1.6 grams of 10% at 0 degree Celsius simultaneously; Control rate of addition, make both add simultaneously.Dropwise, slowly rise to room temperature, 25 degrees Celsius of reactions 5 hours; After completion of the reaction, collecting by filtration organic layer, after washing with water, anhydrous magnesium sulfate drying, steams solvent, with silicagel column successively drip washing obtain two kinds of hydrazides, eluent volume ratio: petrol ether/ethyl acetate=3/1 of 60 ~ 90 degrees Celsius, that first drip washing goes out is 3,4-bis-chloroisothiazole formyl tertiary butyl hydrazine III0.32 gram, and productive rate is 30%; The amount of synthesis above-claimed cpd III expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces.
B.3, the preparation of 4-bis-chloroisothiazole bishydrazide derivative I V
In 50 milliliters of there-necked flasks, add 3,4-bis-chloroisothiazole formyl tertiary butyl hydrazine III0.4 gram, i.e. 1.5 mmoles, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, i.e. 2.2 mmoles, under ice bath, drip 1.5 mmole R 3cOCl, after stirring at room temperature react 2 hours; After completion of the reaction, by system dilute with water, with dichloromethane extraction, collected organic layer, with anhydrous magnesium sulfate drying, except product thick after desolventizing is through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, its volume ratio of difference according to product is 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthesis above-claimed cpd IV expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces; The chemical structure of above-claimed cpd IV and physical and chemical parameter are in table 1.
C. the preparation of intermediate substituted aryl formyl radical tertiary butyl hydrazine VI
In 50 milliliters of there-necked flasks, add Tertiary butyl hydrazine hydrochloride 2 grams, namely 0.016 mole, add 10 milliliters of methylene dichloride, stir and be cooled to 0 degree Celsius, drip the aqueous sodium hydroxide solution 6.4 grams of 10%, namely 0.016 mole, dropwise rear stirring 30 minutes; Drip 0.004 mole of R at 0 degree Celsius simultaneously 310 milliliters of dichloromethane solutions of COClV and the aqueous sodium hydroxide solution 1.6g of 10%, namely 0.004 mole; Control rate of addition, make both add simultaneously; Dropwise, slowly rise to room temperature, 25 degrees Celsius of reactions 5 hours; Filter, the rear anhydrous magnesium sulfate drying of organic layer washing, steam solvent, thick product is through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, its volume ratio of difference according to product is 10:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-50%; The amount of synthesis above-claimed cpd VI expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces.
D.3, the preparation of 4-bis-chloroisothiazole bishydrazide derivative VII
1.5 mmole intermediate substituted aryl formyl radical tertiary butyl hydrazine VI are added in 50 milliliters of there-necked flasks, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, i.e. 2.2 mmoles, 3 are dripped under ice bath, 4-bis-chloroisothiazole formyl chloride 0.32 gram, i.e. 1.5 mmoles, after stirring at room temperature react 2 hours; After completion of the reaction, by system dilute with water, with dichloromethane extraction, collected organic layer, with anhydrous magnesium sulfate drying, steam solvent, thick product compound VII is through 200 ~ 300 order purification by silica gel column chromatography, and eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and its volume ratio of difference according to product is 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthesis above-claimed cpd VII expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces; The chemical structure of above-claimed cpd VII and physical and chemical parameter are in table 1.
E.3,4-bis-chloroisothiazole bishydrazide compounds I is to the mensuration of pathogenic fungi growth activity:
Of the present invention 3, the bishydrazide compounds I sterilization of 4-bis-chloroisothiazole or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with the medicament being diluted to 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, 50 mcg/ml pastilles are made dull and stereotyped after shaking up, blank is done with the flat board adding 1 milliliter of aqua sterilisa, bacterium dish is cut along mycelia outer rim with the punch tool of diameter 4 millimeters, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivates, treat that contrast colony diameter expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate, the kind of the majority of plant pathogenic bacteria of the actual generation in multiple representative field in China's agriculture production is comprised for examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternariasolani), BC: botrytis cinerea pers (Botrytiscinerea), CA: peanut Cercospora bacteria (Cercosporaarachidicola), GZ: fusarium graminearum (Gibberellazeae), PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary), PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola), PS: Rhizoctonia solani Kuhn (Pelliculariasasakii), RC: Rhizoctonia cerealis (Rhizoctoniacerealis), SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum).
F. the mensuration of 3,4-bis-chloroisothiazole bishydrazide compounds I inducing anti-disease activities of the present invention:
The screening method of 3,4-bis-chloroisothiazole bishydrazide compounds I evoking tobacco resisting tobacco mosaic virus (TMV) activity of the present invention is:
(1). standard plant activator: select the activating plants agent that tiadinil (TDL) (purity is greater than 99.5%) is standard;
(2) screening method of the anti-TMV activity of .3,4-bis-chloroisothiazole bishydrazide compounds I evoking tobacco: the mensuration of in vitro directly antiviral activity adopts half leaf method to carry out, live body induction is by common cigarette consistent for seedling age, 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in first 7 days, processing mode comprises: spray test compounds solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 mcg/ml, 7th day frictional inoculation TMV on the tobacco leaf newly grown, cultivate under cigarette seedling being placed in its growth optimal temperature and illumination after 3 days, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each process, blank and standard agent contrast select water and TDL respectively:
R = CK - I CK × 100
Wherein, R is the inducing effect of new compound to Resistance In Tobacco TMV, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is the average withered spot number through compound induction process rear blade, unit: individual.
G. 3, the 4-bis-chloroisothiazole bishydrazide derivative I that contains of the present invention is to the mensuration of small cabbage moth insecticidal activity:
The screening method of 3,4-bis-chloroisothiazole bishydrazide derivative Is of the present invention to the insecticidal activity of small cabbage moth is as follows: adopt blade medicine embrane method; The solution that sample to be tested is mixed with 400 mcg/ml carries out, get former medicine sample and first use a small amount of acetone solution, then with 0.5 ‰ Triton-100 aqueous solution dilutions, the 0.5 ‰ Triton-100 aqueous solution are contrast, each concentration repeats for 3 times, each re-treatment 10 examination worm; Get fresh free of contamination cabbage leaves, soaked for 10 seconds in liquid, after indoor dry about 2 hours, put into the culture dish of diameter 9 centimetres, access basically identical small cabbage moth 2 instar larvae of size respectively, tighten with bungee and be placed in small cabbage moth constant temperature insectary, check result after 96 hours or 120 hours, touch polypide with little writing brush or tweezers, can not coordinated movement as death; Take methoxyfenozide as positive control.
The invention has the beneficial effects as follows: the present invention is to 3,4-bis-chloroisothiazole bishydrazide compounds I has carried out guide's optimization, and the new compound of synthesis has been carried out to the screening of insecticidal activity and bacteriostatic activity and inducing anti-disease activity, carried out the research that itself and common pestsides synthesis use, this compounds may be used for control agriculture field and the plant pest of field of forestry and horticultural field and the control of virus disease simultaneously.
The present invention illustrates 3 more by specific preparation and biological activity determination embodiment, the synthesis of 4-bis-chloroisothiazole bishydrazide compounds I and biological activity and application thereof, described embodiment is only for illustrating the present invention and unrestricted the present invention, especially its biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Wherein, R 3be selected from 3-chlorinated benzene-1-base, 2-chlorinated benzene-1-base, 1-chlorinated benzene-1-base, 3-trifluoromethylbenzene-1-base, 4-trifluoromethylbenzene-1-base, 2-anisole-1-base, 2-oil of mirbane-1-base, 3-oil of mirbane-1-base, 3-fluorobenzene-1-base, 4-methyl-3-(2-chloro-phenyl-)-Ji-4-oxazolyl, 2, the group of 2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazole-4-bases.
The preparation of embodiment 1.3,4-dichloro isothiazollylacyl tertiary butyl hydrazine III
In 50 milliliters of there-necked flasks, add 0.016 mole of i.e. 2g Tertiary butyl hydrazine hydrochloride, 10 milliliters of methylene dichloride, stir after being cooled to 0 degree Celsius, drip the aqueous sodium hydroxide solution 0.016 mole namely 6.4 grams of 10%, dropwise rear stirring 30 minutes; Drip containing 3,4-dichloro isothiazolo acyl chloride 0.004 mole i.e. 10 milliliters of dichloromethane solutions of 0.84 gram and sodium hydroxide 0.004 molar solution 1.6 grams of 10% at 0 degree Celsius simultaneously; Control rate of addition, make both add simultaneously.Dropwise, slowly rise to room temperature, 25 degrees Celsius of reactions 5 hours; After completion of the reaction, collecting by filtration organic layer, after washing with water, anhydrous magnesium sulfate drying, steams solvent, with silicagel column successively drip washing obtain two kinds of hydrazides, eluent volume ratio: petrol ether/ethyl acetate=3/1 of 60 ~ 90 degrees Celsius, that first drip washing goes out is 3,4-bis-chloroisothiazole formyl tertiary butyl hydrazine III0.32 gram, and productive rate is 30%; The amount of synthesis above-claimed cpd III expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces.
The synthesis of embodiment 2.N-(3,4-bis-chloroisothiazole-5-formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound IV and Structural Identification thereof
In 50 milliliters of there-necked flasks, add 3,4-bis-chloroisothiazole formyl tertiary butyl hydrazine III0.4 gram, i.e. 1.5 mmoles, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, i.e. 2.2 mmoles, under ice bath, drip 1.5 mmole R 3cOCl, after stirring at room temperature react 2 hours; After completion of the reaction, by system dilute with water, with dichloromethane extraction, collected organic layer, with anhydrous magnesium sulfate drying, except product thick after desolventizing is through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, its volume ratio of difference according to product is 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthesis above-claimed cpd IV expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces; The chemical structure of above-claimed cpd IV and physical and chemical parameter are in table 1.
Wherein, R 2for being selected from 3-chlorinated benzene-1-base, 2-chlorinated benzene-1-base, 1-chlorinated benzene-1-base, 3-trifluoromethylbenzene-1-base, 4-trifluoromethylbenzene-1-base, 2-anisole-1-base, 2-oil of mirbane-1-base, 3-oil of mirbane-1-base, 3-fluorobenzene-1-base, 4-methyl-3-(2-chloro-phenyl-)-Ji-4-oxazolyl, 2, the group of 2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazole-4-bases.
The preparation of embodiment 3. intermediate substituted aryl formyl radical tertiary butyl hydrazine VI
In 50 milliliters of there-necked flasks, add Tertiary butyl hydrazine hydrochloride 2 grams, namely 0.016 mole, add 10 milliliters of methylene dichloride, stir and be cooled to 0 degree Celsius, drip the aqueous sodium hydroxide solution 6.4 grams of 10%, namely 0.016 mole, dropwise rear stirring 30 minutes; Drip 0.004 mole of R at 0 degree Celsius simultaneously 310 milliliters of dichloromethane solutions of COClV and the aqueous sodium hydroxide solution 1.6g of 10%, namely 0.004 mole; Control rate of addition, make both add simultaneously; Dropwise, slowly rise to room temperature, 25 degrees Celsius of reactions 5 hours; Filter, the rear anhydrous magnesium sulfate drying of organic layer washing, steam solvent, thick product is through 200 ~ 300 order purification by silica gel column chromatography, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, its volume ratio of difference according to product is 10:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-50%; The amount of synthesis above-claimed cpd VI expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces.
The synthesis of embodiment 4.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound VII and Structural Identification thereof
1.5 mmole intermediate substituted aryl formyl radical tertiary butyl hydrazine VI are added in 50 milliliters of there-necked flasks, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, i.e. 2.2 mmoles, 3 are dripped under ice bath, 4-bis-chloroisothiazole formyl chloride 0.32 gram, i.e. 1.5 mmoles, after stirring at room temperature react 2 hours; After completion of the reaction, by system dilute with water, with dichloromethane extraction, collected organic layer, with anhydrous magnesium sulfate drying, steam solvent, thick product compound VII is through 200 ~ 300 order purification by silica gel column chromatography, and eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and its volume ratio of difference according to product is 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthesis above-claimed cpd VII expands by corresponding proportion or reduces, and the volume of reaction vessel expands by corresponding proportion or reduces; The chemical structure of above-claimed cpd VII and physical and chemical parameter are in table 1.
Antibacterial or the fungicidal activity of embodiment 5. 3,4-bis-chloroisothiazole bishydrazide derivative Is of the present invention:
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternariasolani); BC: botrytis cinerea pers (Botrytiscinerea); CA: peanut Cercospora bacteria (Cercosporaarachidicola); GZ: fusarium graminearum (Gibberellazeae); PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (Pelliculariasasakii); RC: Rhizoctonia cerealis (Rhizoctoniacerealis); SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that field occurs in agriculture production.Thalli growth rate method measurement result is in table 2, table 2 shows, when 50 mcg/ml, all 3 of the present invention's synthesis, 4-bis-chloroisothiazole bishydrazide derivative I all has fungicidal activity in various degree, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree, the compound of the present invention's synthesis to the fungicidal activity of AS below 30%; Most of between 10%-20% to the fungicidal activity of CA; To the fungicidal activity of GZ between 10%-50%, wherein compound L Y6-22-1 is 68.42% preferably; To the fungicidal activity of PP between 10%-60%, wherein the fungicidal activity of LY6-41-5, LY6-41-3, LY6-42-4, LY6-45-4, LY6-39-9 is higher than 50%; Most of between 40%-70% to the fungicidal activity of BC, wherein LY6-39-5, LY6-22-1 are higher than 70%; Most of between 30%-60% to the fungicidal activity of SS, wherein LY6-39-9, LY6-22-1, LY6-43-3, LY6-22-12, LY6-22-15 are higher than 70%; Most of between 40%-60% to the fungicidal activity of RC, wherein LY6-39-9 is 67.61%; Most of between 40%-60% to the activity of PS, LY6-42-6, LY6-40-3, LY6-22-1, LY6-43-6, LY6-43-5 are higher than 60%; To the active major part of PI bacterium between 20%-40%.
The insecticidal activity of embodiment 6. 3,4-bis-chloroisothiazole bishydrazide derivative Is of the present invention
Bioassay results is in table 3, table 3 shows, the majority of compounds that the present invention synthesizes has activity in various degree, when 200 mcg/ml to small cabbage moth, LY6-39-5 poisoning rate of the present invention is 80%, LY6-41-9 poisoning rate is 100%, LY6-42-2 poisoning rate be 100%, LY6-22-3 poisoning rate is 90%, LY6-44-5 poisoning rate is 90%, LY6-22-9 poisoning rate is 100%, and wherein contrasting medicine Rynaxypyr is 100%, and Provado is 0%.Therefore, the part of compounds of the present invention's synthesis has good cytotoxicity to small cabbage moth.
The effect of embodiment 7. 3, the 4-bis-anti-TMV of chloroisothiazole bishydrazide derivative I or the anti-TMV of evoking tobacco of the present invention
The measurement result of antiviral activity and induced activity is in table 4, table 4 shows, induced resistance of plant activiator tiadinil (TDL) amine of standard has the resistance of good evoking tobacco generation to TMV, antiviral agent virazole and Ningnanmycin have well directly antiviral activity, but almost do not have induced activity.3,4-bis-chloroisothiazole bishydrazide compounds I parts of the present invention have the activity of the anti-TMV of better evoking tobacco.Wherein: the therapeutic activity of LY6-41-9, LY6-45-3, LY6-40-3, LY6-22-1, LY6-22-12 between 35%-40%, LY6-43-4, LY6-44-4, LY6-43-3 therapeutic activity higher than 40%; The prolection of LY6-22-3, LY6-43-3, LY6-22-12, LY6-22-9 is about 40%; The inactivate activity of LY6-44-3, LY6-45-4, LY6-22-3 is higher than 40%.The good compound of inducing anti-disease activity: LY6-42-6, LY6-44-3, LY6-39-9, LY6-43-2, LY6-43-4, LY6-44-5, LY6-43-6 to the induced activity of tobacco between 40%-50%, and its direct antiviral activity is very weak, induced activity, with to contrast medicine tiadinil TDL (induced activity is 47%) suitable, meets inducing anti-disease activity feature.
Embodiment 8. 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and insecticide composition prevent and treat the application in agricultural and forestry and gardening plant insect pest
All 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and existing sterilant: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its No. CAS is 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Baysir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, BaySIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or two kinds in emaricins etc. combinationally use for preventing and treating agricultural and forestry and gardening plant insect pest, of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I mass percentage is in the composition 1%-90%, the ratio of 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and above-mentioned sterilant is mass percent 1%:99% to 99%:1%, can directly be watered rear spraying, comprise agriculturally acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc. in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane flat angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hangs cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, plant in control agricultural and forestry and gardening plant insect pest comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition improves the defence capability of plant while desinsection, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 9. 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and miticide combine prevent and treat agricultural and forestry and gardening plant mite do harm in application
3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and agriculturally acceptable auxiliary agent and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one or two kinds of pharmaceutical agent combinations in pyridaben are prepared into miticide and do harm to for preventing and treating agricultural and forestry and gardening plant mite, of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I total mass percentage is in the composition 1%-90%, the ratio of 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and above-mentioned medicament is mass percent 1%:99% to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, plant during composition for preventing and controlling agricultural and forestry and gardening plant mite do harm to is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the mite evil that composition is suitable for is phytophagy evil mite, phytophagy evil mite be selected from tetranychid and Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae harmful mite and Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health.
Embodiment 10. 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and antimicrobial combination prevent and treat the application in agricultural and forestry and gardening plant disease
All 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and existing sterilant are as diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-bis-chloroisothiazole-5-formic acid, 3,4-bis-chloroisothiazole-5-sodium formiate, 3,4-bis-chloroisothiazole-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, tears go out into, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole combinationally use for preventing and treating agricultural and forestry and gardening plant disease, of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I total mass percentage is in the composition 1%-90%, the ratio of 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and aforementioned sterilant is mass percent 1%:99% to 99%:1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find the composition with antagonistic action, above-mentioned composition may be used for the control of agricultural plants disease and gardening plant disease, the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora etc. more than 20 that controlling object comprises Oomycete belongs to the disease produced, as other diseases etc. of the plurality of cereals crops such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose, cash crop, gardening plant and forestry plant, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent.These compositions comprise cereal for preventing and treating plant applicable in agricultural and forestry and gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum; Tuber crops: sweet potato, potato, cassava; Beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry; Oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle; Sugar material: beet, sugarcane; Beverage: tealeaves, coffee, cocoa; Hobby: tobacco leaf; Medicinal: ginseng, the bulb of fritillary; The torrid zone: rubber, coconut, oil palm, sisal hemp; Food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, the bitter edible plant, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, containing various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco; Vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw; Beans: soybean, broad bean, pea-pods; Potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya; Flowers: orchid; Potted landscape; Composition improves the defence capability of plant while sterilization, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 11. 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and antiviral agent are combined in the application prevented and treated in agricultural and forestry and gardening plant virus disease
Of the present invention 3, 4-bis-chloroisothiazole bishydrazide compounds I and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are for preventing and treating agricultural and forestry and gardening plant virus disease, the disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus disease, various solanaceous vegetables virus disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any one in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any one in cybidium ring spot virus.These compositions are selected from paddy for the plant preventing and treating agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions makes the immunizing power of crop self improve, while producing the control of insect especially infection insect, produce the defence capability to viral diseases of plants induction of plant, also can produce the direct prevention effect of virus disease, therefore, these compositions may be used for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I total mass percentage is in the composition 1%-90%, the ratio of 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and aforementioned Antiphytoviral medicament is mass percent 1%:99% to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, all show addition or synergism between these compositions, while maintenance insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used alone, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
The complete processing of embodiment 12. 3,4-bis-chloroisothiazole bishydrazide compounds I of the present invention and commercially available agricultural chemical compound preparation and stability
Of the present invention 3, the mixed preparation complete processing of 4-bis-chloroisothiazole bishydrazide compounds I and commercially available agricultural chemical is in table 5, from table 5, most medicament all can be processed according to the method described in upper table, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes effect composition, other agriculturally acceptable adjuvant components such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation places 1 week without Precipitation at 0 ± 2 degree Celsius, solid preparation is placed 2 weeks at 54 ± 2 degrees Celsius, there is not caking phenomenon in medicament, all formulation storage place the medicament drug effect of front and back without significant difference, the rate of decomposition of composition effective constituent is within 5%, composite preparation qualified stability.Commercially available agricultural chemical of the present invention is aforesaid sterilant, miticide, sterilant, anti-plant virus agent.
The bacteriostatic activity (/ %) of table 23,4-bis-chloroisothiazole bishydrazide compounds I of the present invention
Compound AS CA GZ PP BC SS RC PS PI
LY6-39-5 25.00 13.04 43.90 43.75 73.91 47.37 43.66 40.48 13.51
LY6-41-5 18.75 8.70 7.32 68.75 47.83 34.21 46.48 50.00 16.22
LY6-44-2 12.50 0 34.15 16.67 32.61 34.21 46.48 41.67 2.70
LY6-41-3 21.88 0 43.90 56.25 56.52 50.00 57.75 51.19 40.54
LY6-41-9 9.68 11.54 5.56 36.73 27.66 20.69 47.62 4.76 7.89
LY6-42-6 28.13 4.35 51.22 41.67 36.96 60.53 60.56 63.10 37.84
LY6-42-4 12.50 17.39 2.44 85.42 32.61 28.95 60.56 30.95 10.81
LY6-44-3 18.75 4.35 41.46 20.83 47.83 28.95 46.48 47.62 48.65
LY6-45-4 12.50 0 4.88 66.67 32.61 39.47 50.70 55.95 13.51
LY6-42-2 12.50 8.70 29.27 22.92 43.48 26.32 54.93 44.05 43.24
LY6-39-9 28.13 8.70 36.59 58.33 60.87 81.58 67.61 48.81 32.43
LY6-43-2 15.63 0 14.63 33.33 34.78 39.47 61.97 48.81 54.05
LY6-45-3 19.35 15.38 2.00 32.08 45.00 23.33 37.50 25.00 32.50
LY6-40-3 21.88 4.35 46.34 37.50 43.48 39.47 59.15 66.67 21.62
LY6-22-1 25.00 27.78 68.42 37.50 82.00 69.77 39.58 69.88 31.43
LY6-43-4 18.75 0 17.07 37.50 50.00 26.32 60.56 39.29 48.65
LY6-22-3 15.63 13.04 26.83 25.00 52.17 21.05 49.30 45.24 40.54
LY6-44-4 15.63 0 19.51 29.17 36.96 31.58 52.11 19.05 40.54
LY6-43-3 31.25 13.04 34.15 52.08 65.22 68.42 57.75 70.24 35.14
LY6-22-4 18.75 4.35 26.83 22.92 39.13 26.32 38.03 21.43 45.95
LY6-22-12 12.50 0 17.07 31.25 47.83 81.58 59.15 44.05 45.95
LY6-22-5 28.13 4.35 48.78 16.67 54.35 65.79 50.70 41.67 27.03
LY6-44-5 12.50 8.70 26.83 22.92 41.30 65.79 49.30 41.67 45.95
LY6-22-9 21.88 44.3.5 29.27 14.58 32.61 55.26 43.66 32.14 13.51
LY6-43-6 18.75 0 39.02 41.67 58.70 39.47 71.83 64.29 24.32
LY6-43-5 31.25 13.04 48.78 41.67 52.17 57.89 54.93 60.71 43.24
LY6-22-15 15.63 4.35 17.07 39.58 56.52 73.68 50.70 35.71 48.65
LY6-44-6 15.63 0 12.20 27.08 39.13 34.21 18.31 46.43 43.24
Data are the measurement result of 50 mcg/ml; AS: tomato early blight bacterium (Alternariasolani); BC: botrytis cinerea pers (Botrytiscinerea); CA: peanut Cercospora bacteria (Cercosporaarachidicola); GZ: fusarium graminearum (Gibberellazeae); PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (Pelliculariasasakii); RC: Rhizoctonia cerealis (Rhizoctoniacerealis); SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum).
3,4-bis-chloroisothiazole bishydrazide compounds I of table 3 the present invention synthesis are to the insecticidal activity (200 mg/litre) of small cabbage moth
Numbering Poisoning rate, % Numbering Poisoning rate, % Numbering Poisoning rate, %
LY6-39-5 80 LY6-39-9 0 LY6-22-12 0
LY6-41-5 0 LY6-43-2 70 LY6-22-5 0
LY6-44-2 0 LY6-45-3 0 LY6-44-5 90
LY6-41-3 40 LY6-40-3 0 LY6-22-9 100
LY6-41-9 100 LY6-22-1 0 LY6-43-6 40
LY6-42-6 30 LY6-43-4 0 LY6-43-5 60
LY6-42-4 0 LY6-22-3 90 LY6-22-15 50
LY6-44-3 0 LY6-44-4 0 LY6-44-6 0
LY6-45-4 0 LY6-43-3 20 Provado 0
LY6-42-2 100 LY6-22-4 0 Rynaxypyr 100
Antiviral activity (inhibiting rate/%) (100 mg/litre) of table 43,4-bis-chloroisothiazole bishydrazide compounds I of the present invention
Compound Therapeutic activity Prolection Inactivate activity Induced activity
LY6-39-5 23.53±8.18 30.73±3.94 6.67±4.94 34.17±5.64
LY6-41-5 17.65±6.74 8.33±3.93 22.05±6.94 14.58±5.64
LY6-44-2 25.00±6.41 23.96±3.94 29.74±3.88 38.33±5.64
LY6-41-3 30.39±5.16 27.51±2.42 32.82±6.94 36.25±5.00
LY6-41-9 35.29±3.89 35.45±6.42 10.77±4.07 8.75±5.73
LY6-42-6 10.78±5.17 8.99±7.15 22.56±4.70 40.00±3.75
LY6-42-4 9.80±5.17 12.70±5.72 32.31±5.55 25.83±4.39
LY6-44-3 31.86±6.12 20.83±5.48 41.03±3.88 42.92±5.64
LY6-45-4 11.76±4.42 17.19±3.13 42.57±2.35 36.25±5.73
LY6-42-2 22.55±7.54 24.87±6.42 37.44±5.40 34.17±6.41
LY6-39-9 34.80±3.70 18.52±4.85 24.61±5.55 44.58±3.15
LY6-43-2 34.31±5.17 26.46±4.85 36.92±3.08 40.83±2.60
LY6-45-3 39.71±2.95 31.75±7.28 36.92±3.08 14.58±5.20
LY6-40-3 36.27±6.63 35.42±4.78 21.54±4.62 34.58±5.05
LY6-22-1 38.23±3.89 17.99±3.99 30.77±4.62 30.42±3.15
LY6-43-4 43.63±3.70 18.23±5.49 37.44±3.87 43.75±2.50
LY6-22-3 19.12±5.30 43.75±6.25 40.00±4.07 35.42±5.64
LY6-44-4 40.69±4.50 15.87±4.20 29.74±3.88 16.67±5.05
LY6-43-3 41.67±3.70 40.11±3.93 18.46±4.62 19.58±4.39
LY6-22-4 24.51±5.94 33.86±6.32 13.84±7.05 15.42±5.05
LY6-22-12 38.73±5.17 43.91±2.42 12.82±6.41 33.33±4.02
LY6-22-5 25.49±6.12 17.71±5.49 43.59±3.87 18.33±4.39
LY6-44-5 26.47±4.41 14.82±7.15 7.69±4.07 41.25±3.75
LY6-22-9 10.78±5.17 44.79±3.93 6.67±5.40 7.50±4.51
LY6-43-6 32.35±2.94 30.73±5.49 35.90±5.40 45.42±3.15
LY6-43-5 35.29±7.36 22.92±6.31 19.49±6.21 18.75±3.75
LY6-22-15 25.00±6.74 27.08±5.48 18.98±6.22 10.83±5.05
LY6-44-6 23.04±5.94 29.17±6.31 35.90±3.87 39.58±4.39
TDL 23.53±4.41 20.11±6.41 20.51±3.88 47.50±3.75
Virazole 44.12±2.94 46.03±4.20 25.64±3.87 27.08±4.39
Ningnanmycin 41.67±2.25 42.86±1.59 43.08±4.07 25.00±3.75
The working method that 3, the 4-bis-chloroisothiazole bishydrazide compounds I that table 5 the present invention synthesizes are mixed with commercially available agricultural chemical

Claims (4)

1. class 3, a 4-bis-chloroisothiazole bishydrazide compounds, is characterized in that having following code and chemical structural formula:
2. LY6-41-5, LY6-41-3, LY6-42-4, LY6-45-4, LY6-43-3 in 3,4-bis-chloroisothiazole bishydrazide compounds according to claim 1 and agriculturally acceptable auxiliary agent are preparing sterilant for preventing and treating the purposes of Botryosphaeria berengeriana f. sp, LY6-39-9, LY6-22-12 and agriculturally acceptable auxiliary agent are preparing sterilant for preventing and treating the purposes of Sclerotinia sclerotiorum, compound L Y6-39-5 in claim 1, LY6-41-5, LY6-44-2, LY6-41-3, LY6-41-9, LY6-42-6, LY6-42-4, LY6-44-3, LY6-45-4, LY6-42-2, LY6-39-9, LY6-43-2, LY6-43-4, LY6-22-3, LY6-44-4, LY6-43-3, LY6-22-4, LY6-22-12, LY6-44-5, LY6-22-9, LY6-43-6, LY6-43-5, LY6-22-15 and agriculturally acceptable auxiliary agent are preparing sterilant for preventing and treating the purposes of Rhizoctonia cerealis, LY6-44-3, LY6-42-2, LY6-43-2, LY6-43-4, LY6-22-3, LY6-44-4, LY6-22-4, LY6-22-12, LY6-44-5, LY6-43-5, LY6-22-15, LY6-44-6 and agriculturally acceptable auxiliary agent are preparing sterilant for preventing and treating the purposes of phytophthora infestans.
3. the purposes of killing in small cabbage moth medicament prepared by LY6-39-5, LY6-41-3, LY6-41-9, LY6-42-6, LY6-42-2, LY6-43-2, LY6-22-3, LY6-43-3, LY6-44-5, LY6-22-9, LY6-43-6, LY6-43-5, LY6-22-15 in 3,4-bis-chloroisothiazole bishydrazide compounds according to claim 1 and agriculturally acceptable auxiliary agent.
4. the purposes of activating plants agent of evoking tobacco resisting tobacco mosaic virus prepared by LY6-43-4, LY6-44-5, LY6-43-6, LY6-42-6, LY6-44-3, LY6-39-9, LY6-43-2 in 3,4-bis-chloroisothiazole bishydrazide compounds according to claim 1 and agriculturally acceptable auxiliary agent.
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