CN103497182A - 3,4-dichloro isothiazole derivative containing 4,5-dihydro thiazole alkyd resin and preparation method and application thereof - Google Patents

3,4-dichloro isothiazole derivative containing 4,5-dihydro thiazole alkyd resin and preparation method and application thereof Download PDF

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CN103497182A
CN103497182A CN201310512189.8A CN201310512189A CN103497182A CN 103497182 A CN103497182 A CN 103497182A CN 201310512189 A CN201310512189 A CN 201310512189A CN 103497182 A CN103497182 A CN 103497182A
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plant
bis
chloroisothiazoles
dichloro
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CN103497182B (en
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范志金
宗广宁
李凤云
李岳东
李娟娟
姬晓恬
陈来
朱玉洁
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
    • 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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
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Abstract

The invention relates to a heterocyclic compound containing 1,2,3-thiadiazole, and provides a 3,4-dichloro isothiazole derivative containing 4,5-dihydro thiazole alkyd resin and a preparation method and application of the 3,4-dichloro isothiazole derivative. The heterocyclic compound containing 1,2,3-thiadiazole has a chemical construction general formula shown as VI. The invention discloses the structural general formula, a synthetic method and the application as insecticide, acaricide and bactericide of the compound. The 3,4-dichloro isothiazole derivative containing the 4,5-dihydro thiazole alkyd resin can be used for processing techniques for preparing the insecticide, the acaricide and the bactericide after being mixed with agriculturally acceptable auxiliaries or synergist. The invention further discloses the application of the compound at the aspects of preventing diseases, insect attacks, acarid attacks and virus disasters in agriculture, forestry and horticulture, and the preparation method the compound when the compound is combined with commercial insecticide, acaricide, bactericide, agents resisting against plant viruses and plant activating agents for use.

Description

One class contains 3 of 4,5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives and its production and use
Technical field
Technical scheme of the present invention relates to containing isothiazole compounds, is specially 3 of 4,5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives, be 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound.
Background technology
Heterogeneous ring compound has biological activity widely, and the bioactive compounds major part of patent literature is all heterogeneous ring compounds.Different thiazoles compound has biological activity widely, as far back as 1988, Melnikov has noticed the potential biological activity widely of isothiazole compounds (Mel ' nikov, N.N.Zhurnal Vsesoyuznogo Khimic hesk-ogo Obshchestva im.D.I. Mendeleeva.1988,33 (6), 602-609).Isothiazole compounds is widely used in research and development (Engel, the Stefan of agricultural chemicals and pharmaceutical prod; Et al. WO9738987.1997-10-23), the chloro-5-carboxylic acid of 3,4-bis-and derivative thereof have fungicidal action (US P.5188663; Chem.Abstr.11988937 (1993)).Different thiazoles compound PBZ (B) plays great role in the control rice blast, its meta-bolites 1,2-benzisothiazole-3 (2H) 1,1-dioxide BIT (C) can produce systemic acquired resistance by inducing plant, resist the immersion of external pathogenic bacteria, therefore can be used as a kind of activating plants agent (Yoshioka, Keiko; Et al.Plant Journal.2001,25 (2), 149-157).Isotianil (isotianil) is (D) 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 title: 3,4-dichloro-2 '-cyano-1,2-thiazole-5-carboxanilide, it can not produce direct anti-microbial effect to pathogenic bacteria, by exciting paddy rice self, the natural immunology defense of rice blast is reached to purpose (the Assmann L of opposing rice blast invasion; Et al.WO 9924413.1999-05-20).It is low consumption activeconstituents that the inducing anti-disease effect is arranged (Yan Zhiyan. medicine research and application, 2005:9 (5): 41), be applicable to very much the use in growth process of riceplant, this compound also has certain insecticidal activity in addition.
, wide spectrum more efficient in order to find and to find, low toxicity, low ecological risk and with existing sterilant without the new type bactericide of cross resistance and the isothiazole class new compound of high biological activity more, the present invention designs and has synthesized a class containing 4,3 of 5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives, carry out the bioactive screening and evaluation of system simultaneously, to the research of the initiative for novel pesticide, provide the candidate compound
Summary of the invention
Technical problem to be solved by this invention is: provide a class new containing 2-(3,4-bis-chloroisothiazoles-4-yl)-4-(trifluoromethyl)-4, the synthetic method of 5-thiazoline-4-polyol carboxylic acid ester derivative, biological activity and the measuring method thereof of this compounds regulation and control agricultural, gardening and health and forestry plant insect and the phytopathy original are provided, the middle application of these compounds at agriculture field, gardening field, field of forestry and health field is provided simultaneously.
The present invention solves this technical problem adopted technical scheme: have agriculture field, gardening field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity, insect growth regulator activity containing 4,3 of 5-thiazoline carboxylic ester, the chemical structure of general formula of 4-dichloro Isothizole derivatives is shown in formula VI:
Figure BSA0000096728360000021
Wherein, R is selected from: cyclohexyl, a tolyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, adjacent fluoroform phenyl, m-benzotrifluoride base, to fluoroform phenyl, O-Nitrophenylfluorone, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, furans-2-base, thiophene-2-base, the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 6-chloropyridine-3-base.
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the synthetic method of 4-dichloro Isothizole derivatives VI is as follows:
Figure BSA0000096728360000022
Wherein: R is selected from: cyclohexyl, a tolyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, adjacent fluoroform phenyl, m-benzotrifluoride base, to fluoroform phenyl, O-Nitrophenylfluorone, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, furans-2-base;
According to following method of condensing, prepared by part of compounds:
Wherein, R is selected from: the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 6-chloropyridine-3-base, thiophene-2-base.
Specifically be divided into following steps:
A.3, the preparation of 4-bis-chloroisothiazoles-5-methyl-formiate II
Add successively 80 milliliters of methyl alcohol, 3 in 250 milliliters of single necked round bottom flask, 4-bis-chloroisothiazoles-5-formic acid I (10.7 grams, 53.8 mmole), drip gradually thionyl chloride (9.6 grams under condition of ice bath, 80.7 mmole), drip to finish and to be heated to 40 degrees centigrade and to stir 5 hours, reacting completely after concentrated adds acetic acid ethyl dissolution and filters, and filtrate is used respectively distilled water, saturated NaHCO 3saturated NaCl washes one time, anhydrous magnesium sulfate drying, concentrated white solid 11.2 grams, yield 98%; 3,4-, bis-chloroisothiazoles-amount prepared by 5-methyl-formiate II and the volume of reaction vessel enlarge or dwindle by corresponding proportion.
B.3, the preparation of 4-bis-chloroisothiazoles-5-methane amide III:
Add initial reactant 3 in 250 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methyl-formiate II (10.0 grams, 47.16 mmole), 100 milliliters of anhydrous methanols, drip ammoniacal liquor gradually under room temperature condition, drip complete room temperature and continue to stir 5 hours, filter, filtration cakes torrefaction, obtain white solid III9.1 gram, yield 98%; 3,4-, bis-chloroisothiazoles-amount of 5-methane amide III and the volume of reaction vessel enlarge or dwindle by corresponding proportion.
C. intermediate 3, the preparation of 4-bis-chloroisothiazoles-5-thioformamide IV:
Add successively 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methane amide III (4.6 grams, 23.5 mmole), 40 milliliters of toluene, lawesson reagent, English name is: Lawesson ' s Reagent5.7 gram, i.e. 14.1 mmoles, nitrogen protection stirring and refluxing 4 hours, after reaction finishes, reaction solution is concentrated and removes toluene, resistates obtains yellow solid 3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-thioformamide IV, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 10:1; With gained sterling calculated yield, yield 75%; Intermediate 3,4-bis-chloroisothiazoles-amount prepared by 5-thioformamide IV and the volume of reaction vessel enlarge or dwindle by corresponding proportion.
D. intermediate 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol V:
Add successively 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 40 milliliters of 4-bis-chloroisothiazoles-5-thioformamide IV (1.7 grams, 7.9 mmoles), the dehydrated alcohols processed, 3-bromo-1,1,1-trifluoroacetone (1.7 grams, 8.7 mmoles), nitrogen protection is stirred stirring and refluxing 25 hours, after reaction finishes, reaction solution is concentrated and removes ethanol, resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, and volume ratio is 20:1; Obtain light red solid 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V0.8 gram, yield 31%; Intermediate 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the amount that the 5-thiazoline-prepared by 4-alcohol V and the volume of reaction vessel enlarge or dwindle by corresponding proportion.
E.2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation method one:
Add intermediate 2-(3 in 50 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V0.32 gram, i.e. 0.98 mmole, then vacuum nitrogen filling gas triplicate, add 5 milliliters of dry methylene dichloride, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice bath is cooled to 0 degree centigrade, then slowly drip the 5mL dichloromethane solution of various substituted formyl chlorine 1.2 mmoles, reaction solution slowly rises to room temperature and stirs 4～10 hours according to the difference of substrate.After reacting completely, methylene dichloride is diluted to 30 milliliters, use successively dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or pink solid 2-(3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to the difference of product, volume ratio is 15:1～5:1, with gained sterling calculated yield, yield 70-95%, described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, between toluyl chlorine, Butyltriphenylphosphonium chloride, o-methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, adjacent phenylfluoroform formyl chloride, the m-benzotrifluoride formyl chloride, to the phenylfluoroform formyl chloride, the ortho-nitrophenyl formyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, furans-2-formyl chloride, 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-amount prepared by 4-polyol carboxylic acid ester VI and the volume of reaction vessel enlarge or dwindle by corresponding proportion, the chemical structure of compound VI and physical and chemical parameter are in Table 1,
F.2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation method two:
Add successively various heterocyclic substituted formic acid 0.12 grams in 50 milliliters of three mouthfuls of round-bottomed flasks, i.e. 0.93 mmole, dicyclohexyl carbon imines, be called for short: DCC, 0.26 gram, i.e. 1.24 mmoles, the DMAP of catalytic amount, then vacuum nitrogen filling gas triplicate, add 10 milliliters of dry dichloros, under the nitrogen protection atmosphere, stirring at room is 2 hours, then add gradually intermediate 2-(3 under condition of ice bath, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-alcohol, then continue stirring at room 2 hours, remove by filter insolubles after reacting completely, the evaporating column chromatography purification obtains white or yellow solid 2-(3, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-polyol carboxylic acid ester VI, difference according to product, volume ratio is 10:1～5:1, with gained sterling calculated yield, productive rate 80-96%, described heterocyclic substituted formic acid is selected from: pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 6-chloropyridine-3-formic acid, the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, 2-thiophenic acid, 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-amount prepared by 4-polyol carboxylic acid ester VI and the volume of reaction vessel enlarge or dwindle by corresponding proportion, the chemical structure of compound VI and physical and chemical parameter are in Table 1.
G.2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the mensuration of 5-thiazoline-4-polyol carboxylic acid ester VI compound to the mythimna separata cytotoxicity:
2-of the present invention (3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI compound is as follows to the insecticidal activity screening method of mythimna separata: adopt the blade medicine embrane method; Sample first carries out active primary dcreening operation by 200 ug/ml; Test compound is first used a small amount of acetone solution, and then, with 0.5 ‰ Triton-100 dilutions, 0.5 ‰ Triton-100 water are contrast, and every test compound repeats for 4 times, 10 examination worms of each re-treatment; Get fresh free of contamination maize leaf, soak in the liquid prepared 10 seconds, in indoor dry approximately 2 hours after, put into the culture dish of 9 centimetres of diameters, the mythimna separata Initial instar larvae in 2 age that access size respectively is basically identical; Tighten and be placed in mythimna separata constant temperature insectary with bungee, check result calculation correction mortality ratio after 72 hours; Touching polypide with little writing brush or tweezers, can not coordinated movement be dead; Take clear water as contrast, the positive contrast of Provado, calculation correction mortality ratio.
H. 3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the fungicidal activity that 4-dichloro Isothizole derivatives VI is right is measured:
Of the present invention 4, 3 of 5-thiazoline carboxylic ester, the VI sterilization of 4-dichloro Isothizole derivatives 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).
I. 3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, 4-dichloro Isothizole derivatives VI inducing anti-disease activity is measured:
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the active screening method of 4-dichloro Isothizole derivatives VI 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). containing 3 of 4,5-thiazoline carboxylic ester, the screening method of the anti-TMV activity of 4-dichloro Isothizole derivatives VI 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;
Except the mensuration of carrying out above-mentioned induced activity, contain 3 of 4,5-thiazoline carboxylic ester, the mensuration of therapeutic activity, inactivate activity and the prolection of the anti-TMV of 4-dichloro Isothizole derivatives VI simultaneously.
The invention has the beneficial effects as follows: containing 4,3 of 5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives VI has carried out guide's optimization, and synthetic new compound has been carried out to the screening of insecticidal activity and bacteriostatic activity and antiviral 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 containing 4 more by specific preparation and biological activity determination embodiment, 3 of 5-thiazoline carboxylic ester, synthetic and biological activity and the application of 4-dichloro Isothizole derivatives VI, described embodiment is unrestricted the present invention for illustrating the present invention only, especially biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Embodiment 1
The preparation of 3,4-, bis-chloroisothiazoles-5-methyl-formiate II:
Add successively 80 milliliters of methyl alcohol, 3 in 250 milliliters of single necked round bottom flask, 4-bis-chloroisothiazoles-5-formic acid (10.7 grams, 53.8 mmole), drip gradually thionyl chloride (9.6 grams under condition of ice bath, 80.7 mmole), drip complete 40 degrees centigrade of stirrings 5 hours that are heated to, the rear concentrated acetic acid ethyl dissolution that adds that reacts completely filters, and filtrate is used respectively distilled water, saturated NaHCO 3saturated NaCl washes one time, anhydrous magnesium sulfate drying, and concentrated, vacuum-drying obtains white solid 11.2 grams, yield 98%;
Embodiment 2
Intermediate 3, the preparation of 4-bis-chloroisothiazoles-5-methane amide III:
Add initial reactant 3 in 250 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methyl-formiate II (10.0 grams, 47.16 mmole), 100 milliliters of anhydrous methanols, drip ammoniacal liquor gradually under room temperature condition, drip complete room temperature and continue to stir 5h, filter, filtration cakes torrefaction, obtain white solid 9.1 grams, yield 98%; 1h NMR (400MHz, DMSO-d 6): δ 8.35 (s, br, 1H), 8.08 (s, br, 1H).
Embodiment 3
Intermediate 3, the preparation of 4-bis-chloroisothiazoles-5-thioformamide IV:
Add successively 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methane amide III (4.6 grams, 23.5 mmole), 40 milliliters of toluene, lawesson reagent (Lawesson ' s Reagent) (5.7 grams, 14.1 mmole), nitrogen protection stirring and refluxing 4 hours, after reaction finishes, reaction solution is concentrated and removes toluene, resistates obtains yellow solid 3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-thioformamide IV, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 10:1; With gained sterling calculated yield, yield 75%; 1h NMR (400MHz, CDCl 3): δ 6.80 (s, br, 1H), 6.24 (s, br, 1H).
Embodiment 4
Intermediate 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol V:
Add successively 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 40 milliliters of 4-bis-chloroisothiazoles-5-thioformamide IV (1.7 grams, 7.9 mmoles), the dehydrated alcohols processed, 3-bromo-1,1,1-trifluoroacetone (1.7 grams, 8.7 mmoles), nitrogen protection is stirred stirring and refluxing 25 hours, after reaction finishes, reaction solution is concentrated and removes ethanol, resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, and volume ratio is 20:1; Obtain light red solid 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V0.8 gram, yield 31%; 1hNMR (400MHz, CDCl 3): δ 3.85 (dd, J=15.6Hz, 12.4Hz, 2H)
Embodiment 5
2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation
Add intermediate 2-(3 in 50 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V (0.32 gram, 0.98 mmole), then vacuum nitrogen filling gas triplicate, add 5 milliliters of dry methylene dichloride, triethylamine (0.15 gram, 1.5 mmole), ice bath is cooled to 0 degree centigrade, then slowly drip 5 milliliters of dichloromethane solutions of various substituted formyl chlorine 1.2 mmoles, reaction solution slowly rises to room temperature and stirs 4～10 hours according to the difference of substrate.After reacting completely, methylene dichloride is diluted to 30 milliliters, use successively dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or pink solid 2-(3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to the difference of product, volume ratio is between 15:1～5:1; With gained sterling calculated yield, yield 70-95%; Its physical and chemical parameter and structural parameter are in Table 1.Described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, between toluyl chlorine, Butyltriphenylphosphonium chloride, o-methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, adjacent phenylfluoroform formyl chloride, the m-benzotrifluoride formyl chloride, to the phenylfluoroform formyl chloride, the ortho-nitrophenyl formyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, furans-2-formyl chloride,
Embodiment 6
2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation
Add successively various heterocyclic substituted formic acid (0.12 grams in 50 milliliters of three mouthfuls of round-bottomed flasks, 0.93 mmole), dicyclohexyl carbon imines (DCC, 0.26 gram, 1.24 mmole), the DMAP of catalytic amount, then vacuum nitrogen filling gas triplicate, add 10 milliliters of dry dichloros, under the nitrogen protection atmosphere, stirring at room is 2 hours, then add gradually intermediate 2-(3 under condition of ice bath, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-alcohol, then continue stirring at room 2 hours, remove by filter insolubles after reacting completely, the evaporating column chromatography purification obtains white or yellow solid 2-(3, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-polyol carboxylic acid ester VI, difference according to product, volume ratio is between 10:1～5:1, with gained sterling calculated yield, productive rate 80-96%, its physical and chemical parameter and structural parameter are in Table 1.Described heterocyclic substituted formic acid is selected from: pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 6-chloropyridine-3-formic acid, the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, 2-thiophenic acid.
Embodiment 7
2-of the present invention (3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound VI Antibacterial Activity result
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 (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); 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 synthetic majority of compounds of the present invention has fungicidal activity in various degree, compound zgn002-17-2 wherein, zgn002-22-3, zgn002-8-1, zgn001-28-1, zgn001-25-1, zgn003-5-1, zgn003-5-2, zgn003-8-1, zgn003-8-3, zgn001-29-1, zgn003-5-3, zgn003-8-2 to the fungicidal activity of AS higher than 30%, compound zgn003-8-3, zgn001-29-1, zgn003-5-3, zgn003-8-2 to the fungicidal activity of AS more than 40%, compound zgn002-23-3, zgn002-16-3, zgn002-22-3, zgn002-8-1, zgn001-28-1, zgn002-16-2, zgn001-29-1, zgn001-25-1, zgn03-5-1, zgn03-5-2, zgn03-5-3, zgn003-8-1, zgn003-8-2, zgn003-8-3 to the fungicidal activity of CA higher than 30%, compound zgn001-29-1, zgn003-5-1, zgn003-5-3, zgn003-8-3 to the fungicidal activity of CA higher than 50%, majority of compounds of the present invention is better to the fungicidal activity of GZ, compound zgn002-12-1 wherein, zgn002-15-2, zgn002-16-3, zgn002-26-1, zgn002-22-3, zgn001-43-1, zgn002-8-1, zgn001-28-1, zgn002-23-2, zgn001-29-1, zgn003-5-1, zgn003-5-2, zgn003-5-3, zgn003-8-1, zgn003-8-2, zgn003-8-3 to the fungicidal activity of GZ higher than 30%, compound zgn002-16-3 particularly, zgn001-28-1, zgn001-29-1 is to the fungicidal activity of GZ more than 70%, higher than or approach contrast medicament Azoxystrobin, except zgn002-23-3, zgn002-17-2, compound of the present invention is to the fungicidal activity of PP higher than 30%, and wherein compound zgn001-29-1 approaches contrast medicine Azoxystrobin to the fungicidal activity of PP, all chemical combination that the present invention synthesizes to the fungicidal activity of BC all higher than 44%, particularly compound zgn002-23-3, zgn002-17-2, zgn002-16-1, zgn002-16-3, zgn002-15-1, zgn002-10-1, zgn002-22-1, zgn002-29-1, zgn001-25-1, zgn003-8-2 higher than 70%, are better than contrasting the medicine Azoxystrobin to the fungicidal activity of BC, compound zgn002-26-2, zgn002-23-3, zgn002-17-2, zgn002-28-1, zgn002-15-2, zgn002-16-1, zgn002-16-3, zgn002-26-1, zgn002-15-1, zgn002-22-3, zgn002-22-1, zgn001-43-1, zgn001-28-1, zgn002-16-2, zgn002-17-1, zgn001-29-1, zgn001-25-1, zgn003-8-2, zgn003-8-3 to the fungicidal activity of SS higher than 80%, all compounds that the present invention synthesizes are to the fungicidal activity of RC higher than 40%, and wherein compound zgn002-22-3, zgn002-17-1, zgn001-29-1, zgn001-25-1, zgn001-26-1 higher than 70%, approach contrast medicine Azoxystrobin to the fungicidal activity of RC, except compound zgn002-10-1, zgn002-22-1, zgn002-17-3, all compounds that the present invention synthesizes to the fungicidal activity of PS all higher than 30%, wherein compound zgn002-23-3, zgn002-17-2, zgn002-22-3, zgn001-29-1, zgn003-5-1, zgn003-8-1, zgn003-8-2, zgn003-8-3 to the fungicidal activity of PS higher than 60%, compound zgn002-23-3, zgn002-17-2, zgn002-16-1, zgn002-16-3, zgn002-9-1, zgn002-22-3, zgn002-16-2, zgn002-17-1, zgn001-29-1, zgn001-25-1, zgn001-26-1, zgn003-5-1, zgn003-8-1, zgn003-8-2 to the fungicidal activity of PI higher than 30%.Therefore, this compounds has fungicidal activity preferably.
Embodiment 8
2-of the present invention (3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the anti-TMV of 5-thiazoline-4-polyol carboxylic acid ester compound VI is active:
The measurement result of TMV activity is in Table 3, and table 3 shows, majority of compounds of the present invention has the activity of anti-TMV preferably; When 100 ug/ml, all compounds that the present invention synthesizes all have anti-TMV activity in various degree.Under the passivation pattern, the inhibiting rate of compound zgn002-26-2, zgn002-22-3, zgn002-17-3, zgn001-26-1, zgn003-5-2 is greater than 40%, active in contrast medicament tiadinil, suitable with virazole and Ningnanmycin; Under the treatment pattern, the inhibiting rate of compound zgn002-23-3, zgn002-16-1, zgn002-26-1, zgn002-15-1, zgn002-22-3, zgn002-22-1, zgn003-8-3, zgn002-8-3 approaches or is greater than 40%, active in contrast medicament tiadinil, approach contrast medicament virazole; Under protected mode, the inhibiting rate of compound zgn002-26-2, zgn002-17-2, zgn002-12-1, zgn002-16-3, zgn002-8-3, zgn002-17-1, zgn001-26-1, zgn003-5-3 approaches or is greater than 40%, active or approaching higher than contrast medicament tiadinil, virazole and Ningnanmycin; Under induction pattern, the inhibiting rate of compound zgn002-23-3, zgn002-15-2, zgn002-15-1, zgn002-8-3, zgn001-29-1, zgn003-5-1 approaches or is greater than 40%, active in contrast medicament virazole, with to contrast the medicament tiadinil substantially suitable.Visible, 2-of the present invention (3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound VI has anti-TMV activity preferably.
Embodiment 9
2-of the present invention (3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the insecticidal activity assay result of 5-thiazoline-4-polyol carboxylic acid ester compound VI
2-(3 of the present invention, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-polyol carboxylic acid ester compound VI the results are shown in Table 4 to the insecticidal activity assay of mythimna separata, table 4 shows: when reagent agent concentration is 200mg/L, after observation effect 72 hours, zgn001-26-1, zgn001-29-1, zgn002-8-3, zgn002-10-1, zgn002-16-1, zgn002-22-1, zgn002-22-3, zgn002-23-2, zgn002-28-1, zgn003-5-1, zgn003-5-2 is greater than 20% lower than contrast medicament cyanogen insect amide and Provado to the toxic action of mythimna separata.Compound of the present invention has certain toxic action to mythimna separata.
Embodiment 10
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the application in 4-dichloro Isothizole derivatives VI and insecticide composition control agricultural and forestry and gardening plant insect pest
All 3 of 4,5-thiazoline carboxylic esters that contains of the present invention, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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, sorghum 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 11
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the application in 4-dichloro Isothizole derivatives VI and miticide combination control agricultural and forestry and gardening plant mite evil
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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 12
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the application in 4-dichloro Isothizole derivatives VI and sterilant combination control agricultural and forestry and gardening plant disease
All 3 of 4,5-thiazoline carboxylic esters that contains of the present invention, 4-dichloro Isothizole derivatives VI 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: isotianlil, 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI and aforementioned sterilant is that mass percent arrives 99%:1% at 1%: 99%, 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, 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.
Embodiment 13
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, 4-dichloro Isothizole derivatives VI and antiviral agent are combined in the application in control agricultural and forestry and gardening plant virus disease
Of the present inventionly contain 4, 3 of 5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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 14
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, complete processing and the stability of 4-dichloro Isothizole derivatives VI and commercially available agricultural chemical compound preparation
Of the present inventionly contain 4, 3 of 5-thiazoline carboxylic ester, the mixture complete processing of 4-dichloro Isothizole derivatives VI and commercially available agricultural chemical is in Table 5, from table 5, most medicament all can be processed according to the method for statement, 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.
Figure BSA0000096728360000171
Figure BSA0000096728360000181
Figure BSA0000096728360000191
Table 2 the present invention contains 3 of 4,5-thiazoline carboxylic ester, the bacteriostatic activity (/ %) of 4-dichloro Isothizole derivatives VI
Compound AS CA GZ PP BC SS RC PS PI
zgn002-26-2 17.24 20.00 5.88 32.08 64.58 89.33 60.47 51.56 22.22
zgn002-23-3 27.59 36.00 2.94 28.30 75.00 85.33 65.12 68.75 37.04
zgn002-17-2 31.03 28.00 14.71 11.32 77.08 98.67 62.79 65.63 40.74
zgn002-28-1 17.24 16.00 0 35.85 60.42 100 60.47 57.81 25.93
zgn002-12-1 24.24 13.79 47.06 51.28 66.67 52.11 64.52 50.60 25.93
zgn002-15-2 21.21 24.14 58.82 57.69 61.54 94.37 74.19 49.40 29.63
zgn002-16-1 18.18 17.24 29.41 47.44 76.92 84.51 72.58 34.94 33.33
zgn002-16-3 27.27 34.48 70.59 41.03 74.36 92.96 70.97 48.19 37.04
zgn002-26-1 15.15 13.79 52.94 51.28 69.23 88.73 66.13 49.40 25.93
zgn002-9-1 21.21 10.34 17.65 50.00 64.10 71.83 70.97 26.51 37.04
zgn002-15-1 18.18 24.14 23.53 60.26 76.92 83.10 74.19 38.55 18.52
zgn002-22-3 39.39 41.38 35.29 66.67 48.72 88.73 77.42 60.24 44.44
zgn002-10-1 18.18 20.69 11.76 39.74 71.79 64.79 61.29 28.92 29.63
zgn002-22-1 21.21 27.59 0 42.31 79.49 80.28 66.13 22.89 25.93
zgn001-43-1 18.18 13.79 41.18 50.00 69.23 90.14 72.58 37.35 29.63
zgn002-8-1 33.33 31.03 58.82 58.97 66.67 73.24 70.97 49.40 25.93
zgn001-28-1 30.30 37.93 70.59 51.28 51.28 81.69 67.74 48.19 29.63
zgn002-23-2 12.12 24.14 52.94 64.10 74.36 54.93 70.97 39.76 25.93
zgn002-16-2 15.15 31.03 11.76 44.87 56.41 84.51 69.35 56.63 37.04
zgn002-17-3 18.18 20.69 23.53 56.41 66.67 69.01 70.97 22.89 22.22
zgn002-17-1 15.15 20.69 29.41 52.56 69.23 92.96 77.42 63.86 40.74
zgn001-29-1 51.52 51.72 82.35 91.03 87.18 95.77 88.71 87.95 48.15
zgn001-25-1 33.33 31.03 5.88 51.28 79.49 85.92 74.19 59.04 33.33
zgn001-26-1 12.12 20.69 0 47.44 48.72 70.42 75.81 53.01 40.74
zgn003-5-1 38.30 51.43 32.79 45.68 64.81 74.63 56.86 63.29 44.44
zgn003-5-2 42.55 45.71 31.15 29.63 44.44 77.61 52.94 58.23 22.22
zgn003-5-3 51.06 51.43 37.70 58.02 50.00 65.67 50.98 56.96 25.93
zgn003-8-1 36.17 31.43 36.07 40.74 53.70 59.70 47.06 77.22 40.74
zgn003-8-2 48.94 42.86 63.93 72.84 85.19 94.03 54.90 70.89 48.15
zgn003-8-3 70.21 74.29 63.93 49.38 53.70 80.60 54.90 62.03 22.22
Azoxystrobin 46.88 55.56 75.00 91.18 71.43 100 88.10 84.06 80.77
[0087]table 3 contains 3 of 4,5-thiazoline carboxylic ester, the activity (inhibiting rate/% of 100 μ g/mL) of 4-dichloro Isothizole derivatives VI resisting tobacco mosaic virus
Compound Passivation Treatment Protection Induce
zgn002-26-2 42.92±4.11 32.89±5.47 41.88±2.83 27.03±3.46
zgn002-23-3 14.58±5.32 39.56±2.87 17.52±3.86 41.44±2.52
zgn002-17-2 34.58±4.61 18.22±3.64 42.31±3.51 31.08±3.73
zgn002-28-1 35.42±5.10 14.22±4.44 31.62±3.51 18.47±4.17
zgn002-12-1 35.83±6.57 10.22±4.76 43.16±3.14 4.50±3.31
zgn002-15-2 15.00±3.75 9.78±8.13 21.79±6.27 39.64±3.96
zgn002-16-1 22.08±4.92 39.56±3.38 35.47±3.46 17.57±2.86
zgn002016-3 39.17±5.07 32.44±2.15 40.60±5.42 27.48±2.48
zgn002-26-1 30.00±6.09 42.22±2.31 32.91±6.09 31.53±4.06
zgn002-9-1 23.33±5.42 32.44±4.47 18.80±4.24 13.51±4.23
zgn002-15-1 22.92±6.92 38.22±6.56 9.40±3.39 40.09±4.44
zgn002-22-3 40.83±3.40 32.00±6.55 29.06±2.84 17.57±5.75
zgn002-10-1 36.25±4.55 32.00±4.65 9.40±3.40 31.53±4.41
zgn002-22-1 27.92±5.91 39.11±2.44 20.09±5.62 11.26±3.43
zgn001-43-1 29.17±5.87 27.11±4.25 22.22±5.51 25.23±6.04
zgn002-8-3 36.25±8.06 39.56±5.84 39.74±5.59 42.79±3.48
zgn001-28-1 10.83±5.35 16.44±4.43 9.83±4.12 31.98±4.34
zgn002-23-2 36.25±3.50 9.78±4.39 28.21±3.95 14.41±7.43
zgn002-16-2 22.92±6.48 30.67±5.53 34.62±4.89 25.23±3.41
zgn002-17-3 43.75±2.68 23.56±4.28 19.23±5.43 27.93±5.78
zgn002-17-1 27.92±4.35 20.00±4.93 41.88±3.17 29.28±5.67
zgn001-29-1 8.33±2.86 16.89±6.97 14.53±3.39 39.64±4.46
zgn001-25-1 33.75±4.56 5.33±4.47 35.04±3.44 23.42±5.23
zgn001-26-1 42.92±2.02 32.44±5.54 38.89±3.40 5.86±3.19
zgn003-5-1 25.33±2.76 31.20±3.28 37.40±4.47 42.92±3.16
zgn003-5-2 40.44±2.85 17.95±3.26 38.62±4.40 35.83±1.91
zgn003-5-3 32.44±1.97 11.11±2.85 44.31±3.44 30.83±3.95
zgn003-8-1 24.44±4.01 9.83±2.94 8.94±3.31 10.83±5.18
zgn003-8-2 31.56±6.59 22.65±4.01 15.04±3.63 21.25±5.98
zgn003-8-3 16.89±3.37 41.45±3.46 30.49±5.28 25.00±5.32
Cyanogen insect amide 18.30±1.83 19.11±3.53 18.38±5.71 31.53±3.42
TDL 24.17±5.28 14.67±4.19 32.05±4.91 45.50±1.79
Virazole 43.33±1.79 44.44±3.87 40.17±4.94 23.87±3.49
Ningnanmycin 44.17±2.50 28.89±3.43 44.02±2.48 17.57±4.73
[0089]table 43 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, the activity of 4-dichloro Isothizole derivatives VI to mythimna separata
Compound Mortality ratio % Compound Mortality ratio % Compound Mortality ratio %
zgn001-25-1 0 zgn002-15-2 0 zgn002-23-3 15
zgn001-26-1 20 zgn002-16-1 45 zgn002-26-1 0
zgn001-28-1 15 zgn002-16-2 0 zgn002-26-2 0
zgn001-29-1 35 zgn002-16-3 0 zgn002-28-1 20
zgn001-43-1 10 zgn002-17-1 15 zgn003-5-1 30
zgn002-8-3 25 zgn002-17-2 5 zgn003-5-2 40
zgn002-9-1 30 zgn002-17-3 0 zgn003-5-3 5
zgn002-10-1 20 zgn002-22-1 25 zgn003-8-1 10
zgn002-12-1 5 zgn002-22-3 35 zgn003-8-2 5
zgn002-15-1 15 zgn002-23-2 25 zgn003-8-3 0
Provado 65 Cyanogen insect amide 100 ? ?
72 hours measurement results; Measure concentration: 200 μ g/mL; Measuring method: blade medicine embrane method
Table 5 contains 3 of 4,5-thiazoline carboxylic ester, the 4-dichloro Isothizole derivatives VI working method mixed with commercially available agricultural chemical
Figure BSA0000096728360000221

Claims (10)

1. a class is containing 3 of 4,5-thiazoline carboxylic ester, and 4-dichloro Isothizole derivatives is characterized in that having the chemical structure of general formula suc as formula shown in VI:
Figure FSA0000096728350000011
Wherein: R is selected from: cyclohexyl, between tolyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, adjacent fluoroform phenyl, the m-benzotrifluoride base, to the fluoroform phenyl, O-Nitrophenylfluorone, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, furans-2-base, thiophene-2-base, the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 6-chloropyridine-3-base.
2. described 3 of 4, the 5-thiazoline carboxylic ester that contains of claim 1, the synthetic method of 4-dichloro Isothizole derivatives VI:
Figure FSA0000096728350000012
Wherein: cyclohexyl, a tolyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, adjacent fluoroform phenyl, m-benzotrifluoride base, to fluoroform phenyl, O-Nitrophenylfluorone, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, furans-2-base;
According to following method of condensing, prepared by part of compounds:
Figure FSA0000096728350000013
Wherein: R is selected from: the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 6-chloropyridine-3-base, thiophene-2-base
Concrete synthetic route is as follows:
A.3, the preparation of 4-bis-chloroisothiazoles-5-methyl-formiate II
Add successively 80 milliliters of methyl alcohol, 3 in 250 milliliters of single necked round bottom flask, 4-bis-chloroisothiazoles-5-formic acid I10.7 gram, i.e. 53.8 mmoles, drip gradually thionyl chloride 9.6 grams under condition of ice bath, i.e. 80.7 mmoles, drip to finish and to be heated to 40 degrees centigrade and to stir 5 hours, reacting completely after concentrated adds acetic acid ethyl dissolution and filters, and filtrate is used respectively distilled water, saturated NaHCO 3saturated NaCl washes one time, anhydrous magnesium sulfate drying, concentrated white solid 11.2 grams, yield 98%; 3,4-, bis-chloroisothiazoles-amount prepared by 5-methyl-formiate II and the volume of reaction vessel enlarge or dwindle by corresponding proportion;
B.3, the preparation of 4-bis-chloroisothiazoles-5-methane amide III:
Add initial reactant 3 in 250 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methyl-formiate II10.0 gram, i.e. 47.16 mmoles, 100 milliliters of anhydrous methanols, drip ammoniacal liquor gradually under room temperature condition, drip complete room temperature and continue to stir 5 hours, filter, filtration cakes torrefaction, obtain white solid III9.1 gram, yield 98%; 3,4-, bis-chloroisothiazoles-amount of 5-methane amide III and the volume of reaction vessel enlarge or dwindle by corresponding proportion;
C. intermediate 3, the preparation of 4-bis-chloroisothiazoles-5-thioformamide IV:
Add successively 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-methane amide III4.6 gram, i.e. 23.5 mmoles, 40 milliliters of toluene, lawesson reagent, English name is: Lawesson ' s Reagent5.7 gram, i.e. 14.1 mmoles, nitrogen protection stirring and refluxing 4 hours, after reaction finishes, reaction solution is concentrated and removes toluene, resistates obtains yellow solid 3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-thioformamide IV, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, volume ratio is 10:1; With gained sterling calculated yield, yield 75%; Intermediate 3,4-bis-chloroisothiazoles-amount prepared by 5-thioformamide IV and the volume of reaction vessel enlarge or dwindle by corresponding proportion;
D. intermediate 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol V:
Add 3 in 100 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-thioformamide IV1.7 gram, 7.9 mmoles, the dehydrated alcohol processed are 40 milliliters, and 3-bromo-1,1,1-trifluoroacetone 1.7 grams, i.e. 8.7 mmoles, nitrogen protection is stirred stirring and refluxing 25 hours, after reaction finishes, reaction solution is concentrated and removes ethanol, resistates is through 200～300 order purification by silica gel column chromatography, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, and volume ratio is 20:1; Obtain light red solid 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V0.8 gram, yield 31%; Intermediate 2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, the amount that the 5-thiazoline-prepared by 4-alcohol V and the volume of reaction vessel enlarge or dwindle by corresponding proportion;
E.2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation method one:
Add intermediate 2-(3 in 50 milliliters of three mouthfuls of round-bottomed flasks, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol V0.32 gram, i.e. 0.98 mmole, then vacuum nitrogen filling gas triplicate, add 5 milliliters of dry methylene dichloride, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice bath is cooled to 0 degree centigrade, then slowly drip the 5mL dichloromethane solution of various substituted formyl chlorine 1.2 mmoles, reaction solution slowly rises to room temperature and stirs 4～10 hours according to the difference of substrate, after reacting completely, methylene dichloride is diluted to 30 milliliters, use successively dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or pink solid 2-(3 through 200～300 order purification by silica gel column chromatography, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI, the sherwood oil that eluent is 60～90 degrees centigrade: ethyl acetate, according to the difference of product, volume ratio is 15:1～5:1, with gained sterling calculated yield, yield 70-95%, described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, between toluyl chlorine, Butyltriphenylphosphonium chloride, o-methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, adjacent phenylfluoroform formyl chloride, the m-benzotrifluoride formyl chloride, to the phenylfluoroform formyl chloride, the ortho-nitrophenyl formyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, furans-2-formyl chloride, 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-amount prepared by 4-polyol carboxylic acid ester VI and the volume of reaction vessel enlarge or dwindle by corresponding proportion,
F.2-(3,4-, bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester VI preparation method two:
Add successively various heterocyclic substituted formic acid 0.12 grams in 50 milliliters of three mouthfuls of round-bottomed flasks, i.e. 0.93 mmole, dicyclohexyl carbon imines, be called for short: DCC, 0.26 gram, i.e. 1.24 mmoles, the DMAP of catalytic amount, then vacuum nitrogen filling gas triplicate, add 10 milliliters of dry dichloros, under the nitrogen protection atmosphere, stirring at room is 2 hours, then add gradually intermediate 2-(3 under condition of ice bath, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-alcohol, then continue stirring at room 2 hours, remove by filter insolubles after reacting completely, the evaporating column chromatography purification obtains white or yellow solid 2-(3, 4-bis-chloroisothiazoles-5-yl)-4-(trifluoromethyl)-4, 5-thiazoline-4-polyol carboxylic acid ester VI, difference according to product, volume ratio is 10:1～5:1, with gained sterling calculated yield, productive rate 80-96%, described heterocyclic substituted formic acid is selected from: pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 6-chloropyridine-3-formic acid, the bromo-1-of 3-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, 2-thiophenic acid, 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-amount prepared by 4-polyol carboxylic acid ester VI and the volume of reaction vessel enlarge or dwindle by corresponding proportion.
3. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1,4-dichloro Isothizole derivatives VI and the upper purposes of acceptable auxiliary agent in preparing sterilant of agricultural.
4. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1,4-dichloro Isothizole derivatives VI and the upper purposes of acceptable auxiliary agent in preparing sterilant of agricultural.
5. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1,4-dichloro Isothizole derivatives VI and the upper purposes of acceptable auxiliary agent in preparing anti-plant virus agent of agricultural.
6. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1, the application in 4-dichloro Isothizole derivatives VI and insecticide composition control agricultural and forestry and gardening plant insect pest:
All 3 of 4,5-thiazoline carboxylic esters that contains of the present invention, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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, the oil Lay, 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. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1, the application during 4-dichloro Isothizole derivatives VI and miticide combination control agricultural and forestry and gardening plant mite do harm to:
3 of 4, the 5-thiazoline carboxylic ester that contains of the present invention, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1, the application in 4-dichloro Isothizole derivatives VI and sterilant combination control agricultural and forestry and gardening plant disease:
All 3 of 4,5-thiazoline carboxylic esters that contains of the present invention, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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, jowar, 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, 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. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1, the application in 4-dichloro Isothizole derivatives VI and anti-plant virus agent combination control agricultural and forestry and gardening plant virus disease:
Of the present inventionly contain 4, 3 of 5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives VI 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 inventionly contain 4,3 of 5-thiazoline carboxylic ester, the total quality percentage composition of 4-dichloro Isothizole derivatives VI in composition is 1%-90%, of the present inventionly contain 4,3 of 5-thiazoline carboxylic ester, the ratio of 4-dichloro Isothizole derivatives VI 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. 3 of 4, the 5-thiazoline carboxylic ester that contains claimed in claim 1,4-dichloro Isothizole derivatives VI and common pesticide combination form the complete processing of pesticide preparation.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103975931A (en) * 2014-06-04 2014-08-13 吴文君 Application of thiazoline compound as agricultural bactericide
CN105777727A (en) * 2014-12-26 2016-07-20 沈阳中化农药化工研发有限公司 2-thiophene pyridine compound, and applications thereof
CN106632301A (en) * 2016-11-14 2017-05-10 云南大学 Method for synthesizing pyridine bithiazole carboxylic acid derivative
CN107619408A (en) * 2014-12-17 2018-01-23 南开大学 A kind of aminothiazole carboxylic acid derivates and its production and use
CN108047199A (en) * 2017-12-21 2018-05-18 中国医药集团总公司四川抗菌素工业研究所 A kind of thiazole spirocyclopropane skeleton object and its crystal and preparation method
CN109439685A (en) * 2018-12-26 2019-03-08 菏泽学院 A kind of construction method of the plant expression vector that can express gypsymoth USP gene dsRNA and its application
CN111039904A (en) * 2019-12-25 2020-04-21 西华大学 2-cyano-3-furan substituted ethyl valerate compound and application thereof
CN112480103A (en) * 2021-01-05 2021-03-12 南开大学 Coumarin derivatives containing 3, 4-dichloroisothiazole and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942565A (en) * 2012-11-06 2013-02-27 江西天人生态股份有限公司 3,4-dichloro isothiazole derivatives, their preparation method and application
CN103214474A (en) * 2013-05-02 2013-07-24 南开大学 5-methyl-1,2,3-thiadiazole derivatives containing 4,5-dihydrothiazole alcohol acid esters and preparation methods and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102942565A (en) * 2012-11-06 2013-02-27 江西天人生态股份有限公司 3,4-dichloro isothiazole derivatives, their preparation method and application
CN103214474A (en) * 2013-05-02 2013-07-24 南开大学 5-methyl-1,2,3-thiadiazole derivatives containing 4,5-dihydrothiazole alcohol acid esters and preparation methods and application thereof

Cited By (13)

* Cited by examiner, † Cited by third party
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CN103975931A (en) * 2014-06-04 2014-08-13 吴文君 Application of thiazoline compound as agricultural bactericide
CN107619408A (en) * 2014-12-17 2018-01-23 南开大学 A kind of aminothiazole carboxylic acid derivates and its production and use
CN105777727B (en) * 2014-12-26 2019-04-16 沈阳中化农药化工研发有限公司 2- thiophene pyridine compounds and their and application thereof
CN105777727A (en) * 2014-12-26 2016-07-20 沈阳中化农药化工研发有限公司 2-thiophene pyridine compound, and applications thereof
CN106632301B (en) * 2016-11-14 2020-03-17 云南大学 Synthesis method of pyridine-bis-thiazole carboxylic acid derivative
CN106632301A (en) * 2016-11-14 2017-05-10 云南大学 Method for synthesizing pyridine bithiazole carboxylic acid derivative
CN108047199A (en) * 2017-12-21 2018-05-18 中国医药集团总公司四川抗菌素工业研究所 A kind of thiazole spirocyclopropane skeleton object and its crystal and preparation method
CN108047199B (en) * 2017-12-21 2019-09-03 中国医药集团总公司四川抗菌素工业研究所 A kind of thiazole spirocyclopropane skeleton object and its crystal and preparation method
CN109439685A (en) * 2018-12-26 2019-03-08 菏泽学院 A kind of construction method of the plant expression vector that can express gypsymoth USP gene dsRNA and its application
CN111039904A (en) * 2019-12-25 2020-04-21 西华大学 2-cyano-3-furan substituted ethyl valerate compound and application thereof
CN111039904B (en) * 2019-12-25 2021-03-02 西华大学 2-cyano-3-furan substituted ethyl valerate compound and application thereof
CN112480103A (en) * 2021-01-05 2021-03-12 南开大学 Coumarin derivatives containing 3, 4-dichloroisothiazole and preparation method and application thereof

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