CN103483288A - 3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof - Google Patents

3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof Download PDF

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CN103483288A
CN103483288A CN201310481691.7A CN201310481691A CN103483288A CN 103483288 A CN103483288 A CN 103483288A CN 201310481691 A CN201310481691 A CN 201310481691A CN 103483288 A CN103483288 A CN 103483288A
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agent
bis
plant
chloroisothiazole
oil
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CN103483288B (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

Abstract

The invention provides 3,4-dichloroisothiazole containing bishydrazide compounds as well as a preparation method and an application thereof. The invention relates to 1,2,3-thiadiazole containing heterocyclic compounds. The heterocyclic compounds have a chemical structural general formula shown in a figure I in the specification. The invention discloses the structural general formula, a synthesis method and application of the compounds as pesticides, acaricides and bactericides as well as a processing technology for preparing the pesticides, the acaricides and the bactericides by mixing the compounds with agriculturally acceptable auxiliaries or synergists. The invention also discloses combined application of the compounds and the commodities such as the pesticides, the acaricides, the bactericides, anti-plant-virus agents and plant activators to control of diseases, insect pests, pest mites and virus diseases in agriculture, forestry and horticulture and a preparation method of the compounds.

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 derivatives; more specifically relate to N-(3; 4-bis-chloroisothiazoles-5-formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound and N-(3,4-, bis-chloroisothiazoles-5-formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound.
Background technology
Insect growth regulator(IGR) (IGRs) is as sterilant of new generation, with the normal growth of regulating insect, grows with metamorphosis and carrys out optionally Control pests, have safe, selectivity good, nuisanceless, low residue and biological activity advantages of higher.20th century the mid-80, U.S. Rohm-Hass company at first reported synthetic N-tertiary butyl bishydrazide compounds RH-5849 with and intend accordingly the moulting hormone effect, and successfully it is developed to commodity and presses down the food hydrazine.N-tertiary butyl bishydrazide be take as guide's active structure in Rohm-Hass company, utilize row's principles such as molecule, adopt roughly the same synthetic method, RH-5849 carried out to structural modification, again develop RH-5992, RH-2485, tri-biological activitys of RH-0345 than the 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 prevent and treat forest dendrolimus punctatus and rice-stem borer (the synthetic and bioactivity research [D] of Zhang Xiangning .N-tertiary butyl bishydrazide new compound. Agricultural University Of Nanjing, 2003,14-16).
Figure BSA0000096198280000011
Have 1, the biological activity of the compound of 2-isothiazole is the focus of studying in recent years, as isotianil (isotianil) is the isothiazole series bactericidal agent that the common research and development of Bayer and Sumitomo Chemical are used for preventing and treating rice blast, its IUPAC name is called 3,4-dichloro-2 '-cyano-1,2-thiazole-5-carboxanilide.Its characteristics are pathogenic bacteria not to be produced to direct anti-microbial effect, and by exciting paddy rice self natural immunology defense of rice blast to be reached to purpose (the Assmann L of opposing rice blast, et al.Preparation of isothiazolecarboxamides as plant protectants:WO9924413[P], 1999-05-20).
Obtain in order to find with inducing plant generation system the lead compound that disease resistance has insecticidal activity simultaneously, the present invention designs and has synthesized a class 3,4-bis-chloroisothiazole bishydrazide compounds, and carried out the bioactive screening of system, to for novel pesticide initiative research, providing the candidate compound.
Summary of the invention
Technical problem to be solved by this invention is: provide new 3,4-bis-chloroisothiazole bishydrazide compounds synthetic methods, provide this compounds to suppress biological activity and the measuring method of agricultural and gardening and forestry plant pathogen, insect and evil mite, the middle application of these compounds in agriculture field and gardening field and field of forestry is provided simultaneously.
The present invention solves this technical problem adopted technical scheme: have agriculture field, gardening field, field of forestry desinsection, acaricidal activity, fungicidal activity, anti-phytoviral activity, inducing plant and produce 3 of anti-disease activity, the chemical structure of general formula of 4-bis-chloroisothiazole bishydrazide compounds is shown in formula I:
Figure BSA0000096198280000021
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-chloroisothiazoles-4-base.
Chemical structure of general formula is 3 of formula I, and 4-bis-chloroisothiazole bishydrazide compounds specifically are divided into IV and VII kind form:
Figure BSA0000096198280000022
Of the present invention 3, the synthetic method of 4-bis-chloroisothiazole bishydrazide compounds I is as follows:
Figure BSA0000096198280000023
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-chloroisothiazoles-4-base;
Figure BSA0000096198280000024
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-chloroisothiazoles-4-base.
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 to be 2g tertiary butyl hydrazine hydrochloride, 10 milliliters of methylene dichloride, after stirring and being cooled to 0 degree centigrade, drip i.e. 6.4 grams of 0.016 mole of 10% aqueous sodium hydroxide solution, dropwises rear stirring 30 minutes; Drip simultaneously and contain 0.004 mole of 3,4-dichloro isothiazolo acyl chloride i.e. 10 milliliters of dichloromethane solutions of 0.84 gram and 10% sodium hydroxide 0.004 molar solution 1.6 grams at 0 degree centigrade; Control rate of addition, both are added simultaneously.Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; After completion of the reaction, filter collected organic layer, after washing with water, anhydrous magnesium sulfate drying, steam solvent, with silicagel column successively drip washing obtain two kinds of hydrazides, eluent volume ratio: the petrol ether/ethyl acetate of 60～90 degrees centigrade=3/1, what first drip washing went out is 3,4-, bis-chloroisothiazole formyl tertiary butyl hydrazine III0.32 grams, and productive rate is 30%; The amount of synthetic above-claimed cpd III enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion.
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 grams, 1.5 mmoles, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, and 2.2 mmoles drip 1.5 mmole R under ice bath 3cOCl, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, except thick product after desolventizing through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd IV enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion; 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
Add tertiary butyl hydrazine hydrochloride 2 grams in 50 milliliters of there-necked flasks, 0.016 mole, add 10 milliliters of methylene dichloride, stir and be cooled to 0 degree centigrade, drip 10% aqueous sodium hydroxide solution 6.4 grams, 0.016 mole, dropwise rear stirring 30 minutes; Drip 0.004 mole of R at 0 degree centigrade simultaneously 310 milliliters of dichloromethane solutions of COCl V and 10% aqueous sodium hydroxide solution 1.6g, 0.004 mole; Control rate of addition, both are added simultaneously; Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; Filter, use anhydrous magnesium sulfate drying after the organic layer washing, steam solvent, thick product is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 10:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-50%; The amount of synthetic above-claimed cpd VI enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion.
D.3, the preparation of 4-bis-chloroisothiazole bishydrazide derivative VII
Add 1.5 mmole intermediate substituted aryl formyl radical tertiary butyl hydrazine VI 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, drip 3 under ice bath, 4-bis-chloroisothiazole formyl chloride 0.32 grams, i.e. 1.5 mmoles, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, steam solvent, thick product compound VII is through 200～300 order purification by silica gel column chromatography, and the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate is 20:1-1:1 according to its volume ratio of difference of product, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd VII enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion; The chemical structure of above-claimed cpd VII and physical and chemical parameter are in Table 1.
E.3, the mensuration of 4-bis-chloroisothiazole bishydrazide compounds I to the pathogenic fungi growth activity:
Of the present invention 3, 4-bis-chloroisothiazole bishydrazide compounds I sterilizations or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 ug/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add respectively again 9 milliliters of substratum, make 50 ug/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, cut the bacterium dish with the punch tool of 4 millimeters of diameters along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed in 24 ± 1 degrees centigrade of constant incubators and cultivates, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, the kind that comprises multiple representative majority of plant pathogenic bacteria of the actual generation in field in China's agriculture production for the examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani), BC: botrytis cinerea pers (Botrytis cinerea), CA: peanut Cercospora bacteria (Cercospora arachidicola), GZ: fusarium graminearum (Gibberella zeae), PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary), PP: Botryosphaeria berengeriana f. sp (Physalospora piricola), PS: Rhizoctonia solani Kuhn (Pellicularia sasakii), RC: Rhizoctonia cerealis (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
F. of the present invention 3, the mensuration of 4-bis-chloroisothiazole bishydrazide compounds I inducing anti-disease activities:
Of the present invention 3, the active screening method of 4-bis-chloroisothiazole bishydrazide compounds I evoking tobacco resisting tobacco mosaic virus (TMV) is:
(1). the agent of standard activating plants: selecting tiadinil (TDL) (purity is greater than 99.5%) is the activating plants agent of standard;
(2) .3, the screening method of the anti-TMV activity of 4-bis-chloroisothiazole bishydrazide compounds I evoking tobacco: the mensuration of in vitro directly antiviral activity adopts half leaf method to carry out, it is the common cigarette that seedling age is consistent that live body is induced, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in first 7 days, processing mode comprises: spray test compound solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 ug/ml, the 7th day frictional inoculation TMV on the tobacco leaf newly grown, after the cigarette seedling is placed under its growth optimal temperature and illumination and cultivates 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 processing, water and TDL are selected respectively in blank and the contrast of standard medicament:
R = CK - I CK × 100
Wherein, R is the induce effect of new compound to Resistance In Tobacco TMV, unit: %; The average withered spot number that CK is clear water contrast blade, unit: individual; I is for inducing the average withered spot number of processing rear blade, unit: individual through compound.
G. the mensuration of 3,4-, bis-chloroisothiazole bishydrazide derivative Is to the small cabbage moth insecticidal activity that contains of the present invention:
Of the present invention 3,4-bis-chloroisothiazole bishydrazide derivative Is are as follows to the screening method of the insecticidal activity of small cabbage moth: adopt the blade medicine embrane method; The solution that sample to be tested is mixed with 400 ug/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, 10 examination worms of each re-treatment; Get fresh free of contamination cabbage leaves, soaked for 10 seconds in liquid, in indoor dry approximately 2 hours after, put into the culture dish of 9 centimetres of diameters, small cabbage moth 2 instar larvaes that access size respectively is basically identical, tighten and be placed in small cabbage moth constant temperature insectary with bungee, check result after 96 hours or 120 hours, touch polypide with little writing brush or tweezers, can not coordinated movement as death; With the positive contrast of methoxyfenozide.
The invention has the beneficial effects as follows: the present invention is to 3,4-bis-chloroisothiazole bishydrazide compounds I have carried out guide's optimization, and synthetic new compound has been carried out to the screening of insecticidal activity and bacteriostatic activity and inducing anti-disease activity, carried out it simultaneously and mixed the research of using with common agricultural chemicals, this compounds can be for the plant pest of preventing and treating agriculture field and field of forestry and gardening field and the control of virus disease.
The present invention illustrates 3 more by specific preparation and biological activity determination embodiment, synthetic and biological activity and the application thereof of 4-bis-chloroisothiazole bishydrazide compounds I, described embodiment is unrestricted the present invention for illustrating the present invention only, especially its biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Figure BSA0000096198280000061
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, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3, the group of 4-bis-chloroisothiazoles-4-base.
Embodiment 1.3, the preparation of 4-dichloro isothiazollylacyl tertiary butyl hydrazine III
In 50 milliliters of there-necked flasks, add 0.016 mole to be 2g tertiary butyl hydrazine hydrochloride, 10 milliliters of methylene dichloride, after stirring and being cooled to 0 degree centigrade, drip i.e. 6.4 grams of 0.016 mole of 10% aqueous sodium hydroxide solution, dropwises rear stirring 30 minutes; Drip simultaneously and contain 0.004 mole of 3,4-dichloro isothiazolo acyl chloride i.e. 10 milliliters of dichloromethane solutions of 0.84 gram and 10% sodium hydroxide 0.004 molar solution 1.6 grams at 0 degree centigrade; Control rate of addition, both are added simultaneously.Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; After completion of the reaction, filter collected organic layer, after washing with water, anhydrous magnesium sulfate drying, steam solvent, with silicagel column successively drip washing obtain two kinds of hydrazides, eluent volume ratio: the petrol ether/ethyl acetate of 60～90 degrees centigrade=3/1, what first drip washing went out is 3,4-, bis-chloroisothiazole formyl tertiary butyl hydrazine III0.32 grams, and productive rate is 30%; The amount of synthetic above-claimed cpd III enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion.
Synthetic and the Structural Identification of embodiment 2.N-(3,4-, bis-chloroisothiazoles-5-formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine class compound IV
In 50 milliliters of there-necked flasks, add 3,4-, bis-chloroisothiazole formyl tertiary butyl hydrazine III0.4 grams, 1.5 mmoles, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, and 2.2 mmoles drip 1.5 mmole R under ice bath 3cOCl, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, except thick product after desolventizing through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd IV enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion; The chemical structure of above-claimed cpd IV and physical and chemical parameter are in Table 1.
Figure BSA0000096198280000071
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, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3, the group of 4-bis-chloroisothiazoles-4-base.
The preparation of embodiment 3. intermediate substituted aryl formyl radical tertiary butyl hydrazine VI
Add tertiary butyl hydrazine hydrochloride 2 grams in 50 milliliters of there-necked flasks, 0.016 mole, add 10 milliliters of methylene dichloride, stir and be cooled to 0 degree centigrade, drip 10% aqueous sodium hydroxide solution 6.4 grams, 0.016 mole, dropwise rear stirring 30 minutes; Drip 0.004 mole of R at 0 degree centigrade simultaneously 310 milliliters of dichloromethane solutions of COCl V and 10% aqueous sodium hydroxide solution 1.6g, 0.004 mole; Control rate of addition, both are added simultaneously; Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; Filter, use anhydrous magnesium sulfate drying after the organic layer washing, steam solvent, thick product is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 10:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-50%; The amount of synthetic above-claimed cpd VI enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion.
Synthetic and the Structural Identification of embodiment 4.N-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl radical)-N-tertiary butyl-N '-substituted formyl hydrazine class compound VII
Add 1.5 mmole intermediate substituted aryl formyl radical tertiary butyl hydrazine VI 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, drip 3 under ice bath, 4-bis-chloroisothiazole formyl chloride 0.32 grams, i.e. 1.5 mmoles, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, steam solvent, thick product compound VII is through 200～300 order purification by silica gel column chromatography, and the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate is 20:1-1:1 according to its volume ratio of difference of product, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd VII enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion; The chemical structure of above-claimed cpd VII and physical and chemical parameter are in Table 1.
Embodiment 5. is of the present invention 3, the antibacterial or fungicidal activity of 4-bis-chloroisothiazole bishydrazide derivative Is:
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberellazeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that in agriculture production, field occurs.Thalli growth rate method measurement result is in Table 2, table 2 shows, when 50 ug/ml, the present invention synthesizes all 3,4-bis-chloroisothiazole bishydrazide derivative Is all have fungicidal activity in various degree, when 50 ug/ml, all compounds that the present invention synthesizes all have fungicidal activity in various degree, the synthetic compound of the present invention to the fungicidal activity of AS below 30%; To the fungicidal activity major part of CA between 10%-20%; 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%; To the fungicidal activity major part of BC, between 40%-70%, wherein LY6-39-5, LY6-22-1 are higher than 70%; To the fungicidal activity major part of SS, between between 30%-60%, wherein LY6-39-9, LY6-22-1, LY6-43-3, LY6-22-12, LY6-22-15 are higher than 70%; To the fungicidal activity major part of RC, between 40%-60%, wherein LY6-39-9 is 67.61%; To the activity major part of PS, between 40%-60%, LY6-42-6, LY6-40-3, LY6-22-1, LY6-43-6, LY6-43-5 are higher than 60%; Active most of between 20%-40% to the PI bacterium.
Embodiment 6. is of the present invention 3, the insecticidal activity of 4-bis-chloroisothiazole bishydrazide derivative Is
Bioassay results is in Table 3, table 3 shows, the synthetic majority of compounds of the present invention has activity in various degree to small cabbage moth, when 200 ug/ml, LY6-39-5 poisoning rate of the present invention is 80%, LY6-41-9 poisoning rate is that 100%, LY6-42-2 poisoning rate is that 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 the medicine Rynaxypyr is 100%, and Provado is 0%.Therefore, the synthetic part of compounds of the present invention has cytotoxicity preferably to small cabbage moth.
Embodiment 7. is of the present invention 3, the effect of the 4-bis-anti-TMV of chloroisothiazole bishydrazide derivative I or the anti-TMV of evoking tobacco
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 good evoking tobacco and produces the resistance to TMV, antiviral agent virazole and Ningnanmycin have well directly antiviral activity, but almost there is no induced activity.Of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I partly 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 is 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 in 40% left and right; The inactivate activity of LY6-44-3, LY6-45-4, LY6-22-3 is higher than 40%.Inducing anti-disease activity is compound preferably: 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 the inducing anti-disease activity characteristics.
Embodiment 8. is of the present invention 3, the application in 4-bis-chloroisothiazole bishydrazide compounds I and insecticide composition control agricultural and forestry and gardening plant insect pest
Of the present invention all 3,4-bis-chloroisothiazole bishydrazide compounds I and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the 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, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, the pyridine worm is grand, lufenuron, the poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, the 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, the desinsection list, disosultap, chlorantraniliprole, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin etc. or two kinds are used in combination for preventing and treating agricultural and forestry and gardening plant insect pest, of the present invention 3, the quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and above-mentioned sterilant is that mass percent 1%:99% is to 99%:1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural 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, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages 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, the flat angle of sugarcane 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, the 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, the 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), the 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, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the 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, the 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, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks Agricultural pests such as must posting 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 has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 9. is of the present invention 3, the application during 4-bis-chloroisothiazole bishydrazide compounds I and miticide combination control agricultural and forestry and gardening plant mite do harm to
Of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I and the upper acceptable auxiliary agent of agricultural 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, the 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 in pyridaben or two kinds of medicament combinations are prepared into miticide for preventing and treating agricultural and forestry and gardening plant mite evil, of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and above-mentioned medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, plant in composition for preventing and controlling agricultural and forestry and gardening plant mite evil 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 applicable mite of composition evil is phytophagy evil mite, and it is that the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that 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 that phytophagy evil mite is selected from tetranychid.
Embodiment 10. is of the present invention 3, the application in 4-bis-chloroisothiazole bishydrazide compounds I and sterilant combination control agricultural and forestry and gardening plant disease
Of the present invention all 3,4-bis-chloroisothiazole bishydrazide compounds I and existing sterilant are as diazosulfide, tiadinil, be abbreviated as TDL, tisocromide, the first thiophene lures amine, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the 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, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant the 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, the 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, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the 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 hot salt of biguanides, iminoctadine, dicloran, the benzene flusulfamide, the 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 are used in combination for preventing and treating agricultural and forestry and gardening plant disease, of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and aforementioned sterilant is that mass percent 1%:99% is to 99%:1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants 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 etc., the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent.These compositions comprise cereal for preventing and treating agricultural and forestry and the applicable plant of 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, contain 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 has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 11. is of the present invention 3, and 4-bis-chloroisothiazole bishydrazide compounds I and antiviral agent are combined in the application in control 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, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazoles-5-formic acid, 3, 4-bis-chloroisothiazoles-5-sodium formiate, 3, 4-bis-chloroisothiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the 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 diseases, various solanaceous vegetables virus diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any 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, the fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus.These compositions are selected from paddy for the plant that prevents and treats 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, and when producing the control of insect especially infection insect, has induced plant to produce the defence capability to viral diseases of plants, also can produce the direct prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and aforementioned Antiphytoviral medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, all show addition or synergism between these compositions, when keeping insecticidal activity, its antiviral activity all is greater than the effect that any one compound is used separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 12. is of the present invention 3, complete processing and the stability of 4-bis-chloroisothiazole bishydrazide compounds I and commercially available agricultural chemical compound preparation
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 described method of 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 the effect composition, the upper acceptable adjuvant component of other agriculturals such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation is placed 1 week without Precipitation at 0 ± 2 degree centigrade, solid preparation is placed 2 weeks at 54 ± 2 degrees centigrade, caking phenomenon does not appear in medicament, all preparations store the medicament drug effect of placement front and back without significant difference, the rate of decomposition of composition effective constituent is in 5%, the composite preparation qualified stability.Commercially available agricultural chemical of the present invention is aforesaid sterilant, miticide, sterilant, anti-plant virus agent.
Figure BSA0000096198280000161
Figure BSA0000096198280000171
Figure BSA0000096198280000181
Table 2 is of the present invention 3, the bacteriostatic activity (/ %) of 4-bis-chloroisothiazole bishydrazide compounds I
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
The measurement result that data are 50 ug/ml; AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
Table 3 the present invention synthesize 3, the insecticidal activity (200 mg/litre) of 4-bis-chloroisothiazole bishydrazide compounds I to small cabbage moth
Numbering The poisoning rate, % Numbering The poisoning rate, % Numbering The 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
[0074]table 4 is of the present invention 3, the antiviral activity (inhibiting rate/%) (100 mg/litre) of 4-bis-chloroisothiazole bishydrazide compounds I
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
Table 5 the present invention synthesize 3, the 4-bis-chloroisothiazole bishydrazide compounds I working method mixed with commercially available agricultural chemical
Figure BSA0000096198280000201

Claims (10)

1. a class 3,4-bis-chloroisothiazole bishydrazide compounds is characterized in that having the chemical structure of general formula suc as formula shown in I:
Figure FSA0000096198270000011
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-chloroisothiazoles-4-base.
2. claim 1 is described 3, the synthetic method of 4-bis-chloroisothiazole bishydrazide compounds I, and chemical structure of general formula is 3 of formula I, 4-bis-chloroisothiazole bishydrazide compounds specifically are divided into IV and VII kind form:
Figure FSA0000096198270000012
Concrete synthetic route is as follows:
Figure FSA0000096198270000013
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, 2,2-dimethyl-3-(2-methyl-propyl-1-thiazolinyl) cyclopropane base, 4-ethylbenzene-1-base, 3,4-bis-chloroisothiazoles-4-base;
A.3, the preparation of 4-dichloro isothiazollylacyl tertiary butyl hydrazine III
In 50 milliliters of there-necked flasks, add 0.016 mole to be 2g tertiary butyl hydrazine hydrochloride, 10 milliliters of methylene dichloride, after stirring and being cooled to 0 degree centigrade, drip i.e. 6.4 grams of 0.016 mole of 10% aqueous sodium hydroxide solution, dropwises rear stirring 30 minutes; Drip simultaneously and contain 0.004 mole of 3,4-dichloro isothiazolo acyl chloride i.e. 10 milliliters of dichloromethane solutions of 0.84 gram and 10% sodium hydroxide 0.004 molar solution 1.6 grams at 0 degree centigrade; Control rate of addition, both are added simultaneously; Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; After completion of the reaction, filter collected organic layer, after washing with water, anhydrous magnesium sulfate drying, steam solvent, with silicagel column successively drip washing obtain two kinds of hydrazides, eluent volume ratio: the petrol ether/ethyl acetate of 60～90 degrees centigrade=3/1, what first drip washing went out is 3,4-, bis-chloroisothiazole formyl tertiary butyl hydrazine III0.32 grams, and productive rate is 30%; The amount of synthetic above-claimed cpd III enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion;
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 grams, 1.5 mmoles, after dissolving with 20 milliliters of methylene dichloride, add triethylamine 0.22 gram, and 2.2 mmoles drip 1.5 mmole R under ice bath 3cOCl, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, except thick product after desolventizing through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 20:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd IV enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion;
C. the preparation of intermediate substituted aryl formyl radical tertiary butyl hydrazine VI
Add tertiary butyl hydrazine hydrochloride 2 grams in 50 milliliters of there-necked flasks, 0.016 mole, add 10 milliliters of methylene dichloride, stir and be cooled to 0 degree centigrade, drip 10% aqueous sodium hydroxide solution 6.4 grams, 0.016 mole, dropwise rear stirring 30 minutes; Drip 0.004 mole of R at 0 degree centigrade simultaneously 310 milliliters of dichloromethane solutions of COCl V and 10% aqueous sodium hydroxide solution 1.6g, 0.004 mole; Control rate of addition, both are added simultaneously; Dropwise, slowly rise to room temperature, 25 degrees centigrade of reactions 5 hours; Filter, use anhydrous magnesium sulfate drying after the organic layer washing, steam solvent, thick product is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to its volume ratio of difference of product, be 10:1-1:1, by gained sterling calculated yield, according to its yield of difference of product at 10-50%; The amount of synthetic above-claimed cpd VI enlarges or dwindles by corresponding proportion;
D.3, the preparation of 4-bis-chloroisothiazole bishydrazide derivative VII
Add 1.5 mmole intermediate substituted aryl formyl radical tertiary butyl hydrazine VI 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, drip 3 under ice bath, 4-bis-chloroisothiazole formyl chloride 0.32 grams, i.e. 1.5 mmoles, after stirring at room reaction 2 hours; After completion of the reaction, by the system dilute with water, use dichloromethane extraction, collected organic layer, use anhydrous magnesium sulfate drying, steam solvent, thick product compound VII is through 200～300 order purification by silica gel column chromatography, and the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate is 20:1-1:1 according to its volume ratio of difference of product, by gained sterling calculated yield, according to its yield of difference of product at 10-90%; The amount of synthetic above-claimed cpd VII enlarges or dwindles by corresponding proportion, and the volume of reaction vessel enlarges or dwindles by corresponding proportion.
3. claimed in claim 13,4-bis-chloroisothiazole bishydrazide compounds I and the upper purposes of acceptable auxiliary agent in preparing sterilant of agricultural.
4. claimed in claim 13,4-bis-chloroisothiazole bishydrazide compounds I and the upper purposes of acceptable auxiliary agent in preparing sterilant of agricultural.
5. claimed in claim 13,4-bis-chloroisothiazole bishydrazide compounds I and the upper purposes of acceptable auxiliary agent in preparing anti-plant virus agent of agricultural.
6. claimed in claim 13, the application in 4-bis-chloroisothiazole bishydrazide compounds I and insecticide composition control agricultural and forestry and gardening plant insect pest:
Of the present invention all 3,4-bis-chloroisothiazole bishydrazide compounds I and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, the Beta-cyfloxylate, cyfloxylate, the 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, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, the pyridine worm is grand, lufenuron, the poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, the 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, the desinsection list, disosultap, chlorantraniliprole, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, any one in emaricin etc. or two kinds are used in combination for preventing and treating agricultural and forestry and gardening plant insect pest, of the present invention 3, the quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and above-mentioned sterilant is that mass percent 1%:99% is to 99%:1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural 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, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, clouding car locust, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, the east mole cricket, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian manages 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, the flat angle of sugarcane 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, the 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, the 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), the 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, the straight burr rice hesperiidae, pelopidas mathias, the oranges and tangerines swallowtail butterfly, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, the beans blister beetle, the 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, the 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, the yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged the cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, the melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, plant fly, onion fly, the radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks Agricultural pests such as must posting 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 has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
7. claimed in claim 13, the application during 4-bis-chloroisothiazole bishydrazide compounds I and miticide combination control agricultural and forestry and gardening plant mite do harm to:
Of the present invention 3,4-bis-chloroisothiazole bishydrazide compounds I and the upper acceptable auxiliary agent of agricultural 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, the 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 in pyridaben or two kinds of medicament combinations are prepared into miticide for preventing and treating agricultural and forestry and gardening plant mite evil, of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and above-mentioned medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, plant in composition for preventing and controlling agricultural and forestry and gardening plant mite evil 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 applicable mite of composition evil is phytophagy evil mite, and it is that the harmful mite of Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae is that 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 that phytophagy evil mite is selected from tetranychid.
8. claimed in claim 13, the application in 4-bis-chloroisothiazole bishydrazide compounds I and sterilant combination control agricultural and forestry and gardening plant disease:
Of the present invention all 3,4-bis-chloroisothiazole bishydrazide compounds I and existing sterilant are as diazosulfide, tiadinil, be abbreviated as TDL, tisocromide, the first thiophene lures amine, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-, bis-chloroisothiazoles-5-formic acid, 3,4-, bis-chloroisothiazoles-5-sodium formiate, 3,4-, bis-chloroisothiazoles-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the 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, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant the 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, the 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, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the 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 hot salt of biguanides, iminoctadine, dicloran, the benzene flusulfamide, the 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, aldicarb, 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 are used in combination for preventing and treating agricultural and forestry and gardening plant disease, of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and aforementioned sterilant is that mass percent 1%:99% is to 99%:1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants 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 etc., the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, these compositions comprise cereal for preventing and treating agricultural and forestry and the applicable plant of 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: bitter edible plant leaf, 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, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, contain 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 has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
9. claimed in claim 13, the application in 4-bis-chloroisothiazole bishydrazide compounds I and anti-plant virus agent combination control 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, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, the 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazoles-5-formic acid, 3, 4-bis-chloroisothiazoles-5-sodium formiate, 3, 4-bis-chloroisothiazoles-5-ethyl formate, the DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, the 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 diseases, various solanaceous vegetables virus diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any 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, the fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus, these compositions are selected from paddy for the plant that prevents and treats 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, and when producing the control of insect especially infection insect, has induced plant to produce the defence capability to viral diseases of plants, also can produce the direct prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament, of the present invention 3, the total quality percentage composition of 4-bis-chloroisothiazole bishydrazide compounds I in composition is 1%-90%, of the present invention 3, the ratio of 4-bis-chloroisothiazole bishydrazide compounds I and aforementioned Antiphytoviral medicament is that mass percent 1%:99% is to 99%:1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, can disperse dense dose, missible oil, the electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke substance, the smog ball, granular poison bait, foaming agent, ointment, thermal fog, solid-liquid mixes the dress agent, liquid/liquid mixes the dress agent, cold mist agent, Gu Gu/mix filling agent, the medicine paint, the seed treatment liquor, microgranules, oil suspending agent, finish, the oil-dispersing property pulvis, paste, the sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, the fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, the film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in the steam releasing agent, all show addition or synergism between these compositions, when keeping insecticidal activity, its antiviral activity all is greater than the effect that any one compound is used separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
10. claimed in claim 13,4-bis-chloroisothiazole bishydrazide compounds I and common pesticide combination form the complete processing of pesticide preparation.
CN201310481691.7A 2013-10-12 2013-10-12 One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use Expired - Fee Related CN103483288B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105622597A (en) * 2016-01-26 2016-06-01 南开大学 Chloroisothiazole neonicotine compound, as well as preparation method and application thereof
CN105837517A (en) * 2016-04-07 2016-08-10 浙江工业大学 Novel hydroxypyrimidine-containing acethydrazide derivatives and preparing method and applications thereof
CN110066256A (en) * 2019-05-31 2019-07-30 中国烟草总公司郑州烟草研究院 A kind of method of purification of 5-Chloro-2-methyl-4-isothiazolin-3-one

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261755A2 (en) * 1986-09-26 1988-03-30 Rohm And Haas Company Five-membered heterocyclic derivatives of N'-substituted-N,N'-Diacylhydrazines
US4906280A (en) * 1987-10-14 1990-03-06 Pennwalt Corporation Tertiary butylhydrazides as plant growth regulators
EP2000029A1 (en) * 2007-06-06 2008-12-10 Bayer CropScience AG Insecticide and fungicide active agent combinations
CN101591308A (en) * 2009-06-26 2009-12-02 南开大学 A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use
CN102633746A (en) * 2012-04-05 2012-08-15 南开大学 Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole
CN102633747A (en) * 2012-04-05 2012-08-15 南开大学 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0261755A2 (en) * 1986-09-26 1988-03-30 Rohm And Haas Company Five-membered heterocyclic derivatives of N'-substituted-N,N'-Diacylhydrazines
US4906280A (en) * 1987-10-14 1990-03-06 Pennwalt Corporation Tertiary butylhydrazides as plant growth regulators
EP2000029A1 (en) * 2007-06-06 2008-12-10 Bayer CropScience AG Insecticide and fungicide active agent combinations
CN101591308A (en) * 2009-06-26 2009-12-02 南开大学 A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use
CN101891708A (en) * 2009-06-26 2010-11-24 南开大学 Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof
CN102633746A (en) * 2012-04-05 2012-08-15 南开大学 Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole
CN102633747A (en) * 2012-04-05 2012-08-15 南开大学 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WANG H ET AL: "Synthesis and insecticidal activity of N-tert-butyl-N, N′-diacylhydrazines containing 1, 2, 3-thiadiazoles", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 *
柯少勇 等: "具有生物活性的酰肼衍生物的研究进展", 《有机化学》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105622597A (en) * 2016-01-26 2016-06-01 南开大学 Chloroisothiazole neonicotine compound, as well as preparation method and application thereof
CN105622597B (en) * 2016-01-26 2018-08-17 南开大学 A kind of chloro isothiazole anabasine compound and its preparation method and application
CN105837517A (en) * 2016-04-07 2016-08-10 浙江工业大学 Novel hydroxypyrimidine-containing acethydrazide derivatives and preparing method and applications thereof
CN105837517B (en) * 2016-04-07 2019-08-06 浙江工业大学 A kind of hydrazide derivatives and the preparation method and application thereof of hydroxyl pyrimidine
CN110066256A (en) * 2019-05-31 2019-07-30 中国烟草总公司郑州烟草研究院 A kind of method of purification of 5-Chloro-2-methyl-4-isothiazolin-3-one
CN110066256B (en) * 2019-05-31 2022-03-08 中国烟草总公司郑州烟草研究院 Purification method of 5-chloro-2-methyl-4-isothiazolin-3-one

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