CN103214474A - 5-methyl-1,2,3-thiadiazole derivatives containing 4,5-dihydrothiazole alcohol acid esters and preparation methods and application thereof - Google Patents
5-methyl-1,2,3-thiadiazole derivatives containing 4,5-dihydrothiazole alcohol acid esters and preparation methods and application thereof Download PDFInfo
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Abstract
The invention provides a kind of 5-methyl-1,2,3-thiadiazole derivatives containing 4,5-dihydrothiazole alcohol acid esters and preparation methods and application thereof, and relates to heterocyclic compounds containing 1,2,3-thiadiazole. The derivatives have a chemical structural general formula V shown in the specification. The invention discloses the structural general formulas and synthetic methods of the compounds and application of the compounds as pesticides, acaricides and bactericides. Mixed with agriculturally acceptable auxiliaries or synergists, the compounds are used for the processing technology of preparing the pesticides, acaricides and bactericides. The invention also discloses application of the compositions of the compounds and the commercial pesticides, acaricides, bactericides, anti-plant-virus agents and plant activators in control of agricultural, forestry and horticultural diseases, insect pests, mites and virus diseases, and preparation methods of the compounds.
Description
Technical field
Technical scheme of the present invention relates to and contains the 1,2-diazole compound, is specially 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative, i.e. 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound.
Background technology
Virus, fungi, bacterium etc. are to influence one of important factor that modern agriculture produces, and the various diseases that caused by these pathogenic agent have a strong impact on the output associating quality of agricultural-food.Various chemical bactericides are to guarantee to reduce disease to guarantee one of important means of agricultural-food productive rate and quality.Yet in recent years, the extensively and not science of various sterilant is used, make China farmland various pathogenic bacterias to existing traditional sterilant produced tangible resistance (Jia Junchao, Ma Lin, Fan Zhijin, etc. Pesticide Science journal, 2008,10 (1): 1-9.).Methoxy acrylic bactericide once was at one of China's the most widely used sterilant in farmland, also produced in China farmland at present tangible resistance (Zhao Ping, Yan Qiuxu, Li Xin, etc. agricultural chemicals, 2011,50 (8): 547-542.).Therefore development structure is novel more, simple, and the sterilant with different binding modes is extremely urgent.The thiazoline compounds that Japanese firm contains trifluoromethyl has preferably, and fungicidal activity has certain insecticidal activity (JP 2005330258) simultaneously.
1,2, the 3-thiadiazole compound has wide biological activity, early stage patent and document are summed up and are seen Bakulev, et al.Newyork:John Wiley﹠Sons, Inc, 2004 monograph, 1,2,3-thiadiazoles derivative commercial kind in medicine and agricultural chemicals is few, agriculture field application have only cotton defoliant--disleave spirit (N-phenyl-N '-1,2,3-thiadiazoles-5-urea, TDZ), plant activator--Acibenzolar (phendioxin, 2,3-thiadiazoles-7-thiocarboxylic acid methyl esters, BTH), rice field sterilant--tiadinil (3 '-chloro-4,4 '-dimethyl-1,2,3-thiadiazoles-5-formylaniline, TDL).Contriver's research and design in earlier stage is synthetic and found that the first thiophene lures the inducing anti-disease activity of amine, at present just in the industrialization development process.
, wide spectrum more efficient, low toxicity, low ecological risk in order to seek and to find and with existing sterilant do not have the new type bactericide of cross resistance and more high biological activity 1,2,3-thiadiazole new compound, the present invention designs and has synthesized a class and contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the 3-thiadiazoles derivative, carried out the bioactive screening and the evaluation of system simultaneously, provide the candidate compound in the hope of initiative research for novel pesticide
Summary of the invention
Technical problem to be solved by this invention is: provide a class new contain 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the synthetic method of 5-thiazoline-4-polyol carboxylic acid ester derivative, the biological activity and the measuring method thereof of this compounds regulation and control agricultural, gardening and health and the 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 the technical scheme that is adopted: what have that 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 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the chemical structure of general formula of 3-thiadiazoles derivative is seen formula V:
Wherein, R is selected from: cyclohexyl, o-tolyl, between tolyl, p-methylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, the ortho-nitrophenyl base, the m-nitro base, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, the acetparaminosalol phenyl, to N, N dimethylamine base phenyl, furans-2-base, thiophene-2-base, 5-methyl-3-Chloro-O-Phenyl-isoxazole-4-bases, 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the synthetic method of 3-thiadiazoles derivative V is as follows:
Wherein: R is selected from: cyclohexyl, o-tolyl, a tolyl, p-methylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, acetparaminosalol phenyl, to N, N dimethylamine base phenyl, furans-2-base, thiophene-2-base, 5-methyl-3-Chloro-O-Phenyl-isoxazole-4-base;
Part of compounds adopts direct method of condensing to prepare according to following formula:
Wherein, R is selected from: 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
Specifically be divided into following steps:
A.5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl ammonia II
In 250 milliliters of single necked round bottom flask, once add 80 milliliters of ethanol, 5-methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate 17.2 grams, promptly 100 mmoles, the 25% strong aqua aqueous solution are 80 milliliters, and stirring at room 12 hours is cooled to 0 degree centigrade, filter, wash with small amount of ethanol with getting white solid, with the pure product calculated yield of gained, yield 99%; The 5-methyl isophthalic acid, 2, the 3-thiadiazoles-amount of 4-formyl ammonia II preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle.
B. intermediate 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-sulfo-formyl ammonia III:
In 250 milliliters of three mouthfuls of round-bottomed flasks, add initial reactant 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl ammonia II14.3 gram, promptly 100 mmoles, 150 milliliters of toluene, lawesson reagent are Lawesson ' s Reagent24.2 gram, i.e. 60 mmoles, nitrogen protection was stirred stirring and refluxing 4 hours, after reaction finishes reaction solution concentrated and remove toluene, resistates obtains faint yellow solid 5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-sulfo-formyl ammonia III, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 3: 1; With the pure product calculated yield of gained, yield 76%; Intermediate 5-methyl isophthalic acid, 2, the 3-thiadiazoles-amount of 4-sulfo-formyl ammonia III and the volume of reaction vessel enlarge by corresponding proportion or dwindle.
C. intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol IV:
In 100 milliliters of three mouthfuls of round-bottomed flasks, add the 5-methyl isophthalic acid, 2,3-thiadiazoles-4-sulfo-formyl ammonia III7.96 gram, i.e. 50 mmoles, 60 milliliters of stirrings of dehydrated alcohol of handling, 3-bromo-1,1,1-trifluoroacetone 9.6 gram, i.e. 50 mmoles, nitrogen protection was stirred stirring and refluxing 16 hours, after reaction finishes reaction solution concentrated and remove toluene, resistates obtains faint yellow solid 5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, and 2,3-thiadiazoles-4-sulfo-formyl ammonia III, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 10: 1; With the pure product calculated yield of gained, yield 62%; Intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-alcohol IV preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle.
D.2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method one:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, 8 milliliters of exsiccant methylene dichloride, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice-water bath is cooled to 0 degree centigrade, slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine 1.2 mmoles then, reaction solution slowly rises to room temperature and stirred 4～10 hours according to the difference of substrate.After reacting completely, methylene dichloride is diluted to 30 milliliters, use dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing successively, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, yield 61-93%; Described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, the ortho-nitrophenyl formyl chloride, m-nitrobenzoyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, acetaminol chlorine, to N, N dimethylamine base Benzoyl chloride, furans-2-formyl chloride, thiophene-2-formyl chloride, 5-methyl-3-Chloro-O-Phenyl-isoxazoles-4-formyl chloride; 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-polyol carboxylic acid ester V preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle; Chemical structure and the physical and chemical parameter of compound V see Table 1;
E.2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method two:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid; 2; 3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4; 5-thiazoline-4-alcohol IV0.27 gram; promptly 1.0 mmoles, 8 milliliters of exsiccant methylene dichloride, triethylamine 0.15 restrain; i.e. 1.0 mmoles, various heterocyclic substituted formic acid 1.2 mmoles; stirring also is cooled to 0 degree centigrade; under nitrogen protection, drip dicyclohexyl carbon imide 0.25 gram then by syringe; promptly the dichloromethane solution of 1.2 mmoles dropwised in 10 minutes.Reaction solution rises to room temperature and stirs and spend the night; Reaction finishes and removes insolubles, rotary evaporation removes and desolvates, thick product gets faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-and 4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, productive rate 61-93%.Described heterocyclic substituted formic acid is selected from: 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 2-chloropyridine-3-formic acid; 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-polyol carboxylic acid ester V preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle; Chemical structure and the physical and chemical parameter of compound V see Table 1.
F.2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester cpds are to the mensuration of mythimna separata cytotoxicity:
2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester cpds is as follows to the insecticidal activity screening method of aphid larva: adopt the blade medicine embrane method; Sample carries out active primary dcreening operation with 200 μ g/mL earlier; Test compound is earlier with the small amount of acetone dissolving, and with 0.5 ‰ Triton-100 dilution, 0.5 ‰ Triton-100 water are contrast then, and every test compound repeats for 4 times, 10 examinations of each re-treatment worm; Get fresh free of contamination maize leaf, in the soup for preparing, soak 10s, in indoor dry about 2h after, put into the culture dish of diameter 9cm, insert 2 initial stage in age of the mythimna separata larva of big or small basically identical respectively; Tighten with bungee and to be placed in the mythimna separata constant temperature insectary check result and calculation correction mortality ratio behind the 72h; Touching polypide with little writing brush or tweezers, can not coordinated movement be dead; With the clear water is contrast, the positive contrast of Provado, calculation correction mortality ratio.
G. of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the fungicidal activity that 3-thiadiazoles derivative V is right is measured:
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, V sterilization of 3-thiadiazoles derivative or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in an amount of dimethyl formamide, then with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, reagent agent is respectively drawn under aseptic condition in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, make 50 mcg/ml pastille flat boards after shaking up, do blank with the flat board that adds 1 milliliter of aqua sterilisa, punch tool with 4 millimeters of diameters cuts the bacterium dish along the mycelia outer rim, move on the pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed on cultivation in 24 ± 1 degrees centigrade of constant incubators, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively handles bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, for trying the kind that bacterial classification comprises most of phytopathogen of the actual generation in multiple representative field in China's agriculture production, 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: ring rot of apple bacterium (Physalospora piricola), PS: Rhizoctonia solani Kuhn (Pellicularia sasakii), RC: cereal rhizoctonia (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
H. of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V inducing anti-disease activity is measured:
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the active screening method of 3-thiadiazoles derivative V evoking tobacco resisting tobacco mosaic virus (TMV) is:
(1). standard plant activator: selecting tiadinil (TDL) (purity is greater than 99.5%) is the plant activator of standard;
(2). contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the active screening method of the anti-TMV of 3-thiadiazoles derivative V evoking tobacco: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; It is common cigarette with the seedling age unanimity that live body is induced, 3 basins are one group, cigarette seedling respectively at inoculation pre-treatment in preceding 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 mcg/ml, and the 7th day frictional inoculation TMV on the tobacco leaf that newly grows places its growth optimal temperature and the following cultivation of illumination after 3 days the cigarette seedling, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, and 3 repetitions are established in each processing, and water and TDL are selected in blank and the contrast of standard medicament respectively:
Wherein, R is the induce effect of new compound to the anti-TMV of tobacco, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is for inducing the average withered spot number of handling rear blade, unit: individual through compound;
Except the mensuration of carrying out above-mentioned induced activity, contain 4 simultaneously, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the active mensuration of therapeutic activity, inactivate activity and protection of the anti-TMV of 3-thiadiazoles derivative V.
The invention has the beneficial effects as follows: contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V has carried out guide's optimization, and the synthetic new compound has been carried out 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 used to prevent and treat agriculture field and the plant pest in field of forestry and gardening field and the control of virus disease.
The present invention specifies more by specific preparation and biological activity determination embodiment and contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, synthetic and biological activity and the application of 3-thiadiazoles derivative V, described embodiment only is used to specify the present invention and unrestricted the present invention, especially biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Embodiment 1
The 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl ammonia II:
In 250 milliliters of single necked round bottom flask, once add 80 milliliters of ethanol, 5-methyl isophthalic acid, 2, (80 milliliters of 3-thiadiazoles-4-ethyl formate (17.2 grams, 100 mmoles), strong aquas, 25% aqueous solution), stirring at room 12 hours is cooled to 0 degree centigrade, filters, wash with small amount of ethanol, vacuum-drying obtains white solid 15.7 grams, with the pure product calculated yield of gained, yield 99%;
1HNMR (400MHz, CDCl
3): δ 5.90 (s, br, 2H), 2.90 (s, 3H).
Embodiment 2
Intermediate 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-sulfo-formyl ammonia III:
In 250 milliliters of three mouthfuls of round-bottomed flasks, add initial reactant 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl ammonia II (14.3 grams, 100 mmoles), 150 milliliters of toluene, lawesson reagent (Lawesson ' s Reagent) (24.2 grams, 60 mmoles), nitrogen protection was stirred stirring and refluxing 4 hours, after reaction finishes reaction solution concentrated and remove toluene, resistates obtains faint yellow solid 5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-sulfo-formyl ammonia III12.1 gram, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 3: 1; With the pure product calculated yield of gained, yield 76%;
1H NMR (400MHz, CDCl
3): δ 7.00 (s, br, 2H), 2.37 (s, 3H).
Embodiment 3
Intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol IV:
In 100 milliliters of three mouthfuls of round-bottomed flasks, add the 5-methyl isophthalic acid, 2,3-thiadiazoles-4-sulfo-formyl ammonia III (7.96 grams; 50 mmoles), 60 milliliters of the dehydrated alcohols handled, 3-bromo-1,1; 1-trifluoroacetone (9.6 grams, 50 mmoles), nitrogen protection was stirred stirring and refluxing 16 hours.After reaction finishes reaction solution concentrated and remove toluene, resistates obtains 9.4 gram faint yellow solid 5-methyl isophthalic acids, 2,3-thiadiazoles-4-sulfo-formyl ammonia III through 200～300 order purification by silica gel column chromatography, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 10: 1; Obtain yellow solid 9.4 grams, with the pure product calculated yield of gained, yield 62%.
1HNMR(400MHz，CDCl
3)：δ3.69(s，2H)，3.00(s，3H)。
Embodiment 4
2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-polyol carboxylic acid ester V:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV (0.27 gram, 1.0 mmole), 8 milliliters of exsiccant methylene dichloride, triethylamine (0.15 gram, 1.5 mmoles), ice-water bath is cooled to 0 degree centigrade, slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine (1.2 mmole) then, reaction solution slowly rises to room temperature and stirred 4～10 hours according to the difference of substrate.After reacting completely, methylene dichloride is diluted to 30 milliliters, use dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing successively, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, yield 61-93%.Its physical and chemical parameter and structural parameter see Table 1.Described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, the ortho-nitrophenyl formyl chloride, m-nitrobenzoyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, acetaminol chlorine, to N, N dimethylamine base Benzoyl chloride, furans-2-formyl chloride, thiophene-2-formyl chloride, 5-methyl-3-Chloro-O-Phenyl-isoxazoles-4-formyl chloride.
Embodiment 5
2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-polyol carboxylic acid ester V:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid; 2; 3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4; 5-thiazoline-4-alcohol IV (0.27 gram; 1.0 mmole), 8 milliliters of exsiccant methylene dichloride, triethylamine (0.15 gram; 1.0 various heterocyclic substituted formic acid (1.2 mmole) mmole); stirring also is cooled to 0 degree centigrade; under nitrogen protection, drip dicyclohexyl carbon imide (0.25 gram then by syringe; 1.2 dichloromethane solution mmole) dropwised in 10 minutes.Reaction solution rises to room temperature and stirs and spend the night.Reaction finishes and removes insolubles, rotary evaporation removes and desolvates, thick product gets faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-and 4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 61～93 degrees centigrade a sherwood oil: ethyl acetate, according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, productive rate 60-90%.Its physical and chemical parameter and structural parameter see Table 1.Described heterocyclic substituted formic acid is selected from: 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 2-chloropyridine-3-formic acid.
Embodiment 6
2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound V bacteriostatic activity measurement result
The 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: ring rot of apple bacterium (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: cereal rhizoctonia (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that the field takes place in the agriculture production.Thalli growth rate method measurement result sees Table 2, table 2 shows, when 50 mcg/ml, all compounds of synthetic of the present invention all have fungicidal activity in various degree, remove mt008-49-7, outer all compounds of mt008-48-13 are higher than 40% to the fungicidal activity of AS, compound mt008-48-2 wherein, mt008-49-9, mt008-48-5, mt008-48-6, mt008-48-7, mt008-48-8, mt008-48-9, mt008-49-4, mt008-48-1, mt008-49-6, mt008-49-2, mt008-48-10, mt008-48-11, mt008-48-12, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-16, mt008-48-17, mt008-48-18, mt008-48-19, mt008-49-11, more than 50%, activity is higher than contrast medicament Azoxystrobin to mt008-49-10 to the fungicidal activity of AS; Remove mt008-49-7, outer all compounds of mt008-48-13 are higher than 40% to the fungicidal activity of CA, compound mt008-48-2 wherein, mt008-48-3, mt008-48-4, mt008-49-9, mt008-48-6, mt008-48-7, mt008-48-1, mt008-49-6, mt008-49-2, mt008-48-11, mt008-48-12, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-16, mt008-48-15, mt008-48-17, mt008-48-18, mt008-49-10, mt008-49-11, more than 55%, activity is better than contrasting the medicament Azoxystrobin to mt008-48-19 to the fungicidal activity of CA bacterium; All compounds of synthetic of the present invention all are higher than 40% to the fungicidal activity of GZ, wherein more than 80%, activity is higher than contrast medicament Azoxystrobin to the fungicidal activity of GZ bacterium for compound mt008-49-9, mt008-49-6, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-16, mt008-48-19, mt008-49-11, mt008-49-10; Except that mt008-49-1, all compounds of synthetic of the present invention are higher than 40% to the fungicidal activity of PP, wherein mt008-49-9, mt008-49-5, mt008-48-7, mt008-49-4, mt008-49-2, mt008-49-5, mt008-49-1, mt008-48-15, mt008-48-16, mt008-48-17, mt008-48-18, mt008-48-19, mt008-49-10 are higher than 90% to the fungicidal activity of PP, and activity is higher than or approaching contrast medicament Azoxystrobin; Institute of the present invention compound is higher than 40% to the fungicidal activity of BC, mt008-48-2 wherein, mt008-48-3, mt008-48-4, mt008-49-9, mt008-48-5, mt008-48-6, mt008-48-7, mt008-48-8, mt008-48-9, mt008-49-4, mt008-48-1, mt008-49-6, mt008-49-7, mt008-49-2, mt008-48-13, mt008-48-11, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-15, mt008-48-16, mt008-48-17, mt008-48-18, mt008-48-19, mt008-49-11, mt008-49-10 to the equal fungicidal activity of BC more than 70%, because contrast medicament Azoxystrobin; Mt008-48-2, mt008-48-3, mt008-48-4, mt008-49-9, mt008-48-5, mt008-48-6, mt008-48-7, mt008-48-8, mt008-48-9, mt008-49-4, mt008-48-1, mt008-49-6, mt008-49-2, mt008-48-13, mt008-48-10, mt008-48-11, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-15, mt008-48-16, mt008-48-17, mt008-48-19, mt008-49-11, mt008-49-10 is higher than 80% to the fungicidal activity of SS, and is active in contrast medicament Azoxystrobin; All compounds of synthetic of the present invention are higher than 40% to the fungicidal activity of RC, and wherein mt008-49-5, mt008-48-5, mt008-49-5, mt008-49-10 more than 88%, are better than contrasting the medicament Azoxystrobin to the fungicidal activity of RC bacterium; All compounds of synthetic of the present invention are higher than 75% to the fungicidal activity of PS, and activity is close to or higher than the contrast medicament; Compound mt008-49-9, mt008-48-5, mt008-49-4, mt008-48-1, mt008-49-6, mt008-49-3, mt008-49-5, mt008-49-1, mt008-48-15, mt008-48-16, mt008-48-17, mt008-48-18, mt008-49-11, mt008-49-10 are higher than 40% to the fungicidal activity of PI bacterium.Therefore, this compounds is showing that excellent fungicidal activity is arranged.
Embodiment 7
2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the anti-TMV of 5-thiazoline-4-polyol carboxylic acid ester compound V is active:
The active measurement result of TMV sees Table 3, and table 3 shows that majority of compounds of the present invention has the activity of anti-TMV preferably; When 100 mcg/ml, all compounds of synthetic of the present invention all have anti-TMV activity in various degree.Under the treatment pattern, the inhibiting rate of compound mt008-48-18, mt008-48-16, mt008-48-3, mt008-49-10 is approaching or greater than 40%, activity is higher than contrast medicament virazole; Under the passivation pattern, the inhibiting rate of compound mt008-48-6, mt008-49-5 is greater than 40%; Under protected mode, the inhibiting rate of compound mt008-48-18, mt008-48-9, mt008-49-11 is greater than 40%; Inducing under the pattern, the inhibiting rate of compound mt008-48-5, mt008-48-8, mt008-49-11, mt008-49-6, mt008-49-5 is greater than 40%.As seen, 2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound V has anti-preferably TMV activity.
Embodiment 8
2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the insecticidal activity assay result of 5-thiazoline-4-polyol carboxylic acid ester compound V
2-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester the results are shown in Table 4 to the insecticidal activity assay of mythimna separata, table 4 is as seen: when reagent agent concentration is 200mg/L, after the observation effect 72 hours, all compounds all show certain insecticidal activity, the insecticidal activity that individual compound does well.Wherein, compound mt008-48-5, mt008-48-6, mt008-48-7, mt008-48-16, mt008-48-17, mt008-48-13, mt008-49-6, mt008-49-7, mt008-49-2, mt008-49-3, mt008-49-11, mt008-49-5 are higher than 40% to the lethality rate of mythimna separata; Particularly compound mt008-48-10, mt008-48-15, mt008-48-19, mt008-48-11 are 100% to the lethality rate of mythimna separata, have showed excellent insecticidal activity.
Embodiment 9
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the application in 3-thiadiazoles derivative V and sterilant combination control agricultural and forestry and the gardening plant insect pest
Of the present invention all contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), more visit rhzomorph, 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, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, fluorine bell urea, flufenoxuron, the pyridine worm is grand, the Acarus tritici urea, the poisonous insect urea, penfluron, Noviflumuron is a noviflumuron, and its CAS number is 121451-02-3, flucycloxuron, Novaluron is a Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-two 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, promptly two three flufenoxuron of Bistrifluron, furans worm hydrazides, 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, azoles mite ester, pyridaben, four mite piperazines, alkynes mite spy, the butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, fluorine worm nitrile, the desinsection list, disosultap, the chlorine insect amide, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, the azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, the pyrrole propyl ether, in the emaricin etc. any one or two kinds are used in combination and are used for control agricultural and forestry and gardening plant insect pest; Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and above-mentioned sterilant is mass percent 1%: 99% to 99%: 1%; Spray after can directly converting water, comprise agricultural in the preparation of composition and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; 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, the hard a red-spotted lizard of Korea's ball, pear lace bug, the banana lace bug, thin corner piece stinkbug, little minute pirate bugs, 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, intend smaller apple leaf roller, 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, big 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, black dull cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big 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 the 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, genseng, 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 is in the parasiticidal defence capability that improves plant simultaneously, makes plant produce defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 10
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the application during 3-thiadiazoles derivative V and miticide combination control agricultural and forestry and gardening plant mite do harm to
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and agricultural go up acceptable assistant 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, the Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, smart 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, fourth fluorine mite ester, the mite quinone goes out, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, the Ai Pulinuo rhzomorph, ivermectin, rhzomorph is drawn in match, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, azoles mite ester, four mite piperazines, alkynes mite spy, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, in the pyridaben any one or two kinds of medicament combined preparation become miticide to be used for control agricultural and forestry and gardening plant mite evil; Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; The formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; Plant in composition for preventing and controlling agricultural and forestry and the 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, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape; The mite evil that composition is suitable for is phytophagy evil mite, 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 evil mites of the itch mite of Eriophyidae, forestry evil mite, the harmful mite of gardening and the harmful mite of health that phytophagy evil mite is selected from tetranychid.
Embodiment 11
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the application in 3-thiadiazoles derivative V and sterilant combination control agricultural and forestry and the gardening plant disease
of the present invention all contain the 5-methyl isophthalic acid of 4,5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing bactericide such as diazosulfide, tiadinil is 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 formate, 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-, two chloroisothiazoles-5-formic acid, 3,4-, two chloroisothiazoles-5-sodium formate, 3,4-, two chloroisothiazoles-5-Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, frost urea cyanogen, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metalaxyl, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, glyoxalin, plant the bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, the Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the hot salt of biguanides, iminoctadine, botran, the benzene flusulfamide, the toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in bactericide such as allyl isothiazole are used in combination for control agricultural and forestry and gardening plant disease, of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, the ratio of 2,3-thiadiazoles derivative V and aforementioned bactericide are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergistic effect and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be used for the control of agricultural plant 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, industrial crops, 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 agent, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspension emulsion, 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, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke agent, 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, fine granule, 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, liniment, the fritter poison bait, suspending agent, suspended 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 are used for preventing and treating agricultural and forestry and the suitable plant of gardening plant disease and comprise cereal: 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: genseng, 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 crop such 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 is in the germ-resistant defence capability that improves plant simultaneously, makes plant produce defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 12
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, different metsulfovax, 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-two chloroisothiazoles-5-formic acid, 3,4-two chloroisothiazoles-5-sodium formiate, 3,4-two 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, any 1 or the combination of 2 compounds are used for control agricultural and forestry and gardening plant virus disease in the jingganmycin; The disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus diseases, various solanberry viroid diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any in cotton virus disease and the various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, the paddy rice virus disease comprises rice dwarf virus disease, yellow dwart, stripe virus disease, the fern leaf of tomato viral disease, sick and the tobacco veinal necrosis virus disease of chilli pepper mosaic virus, the corn short mosaic disease, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in the cybidium ring spot virus.The plant that these compositions are used to prevent and treat agricultural and forestry and gardening plant virus disease 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, genseng, 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, agriculturals such as potted landscape, gardening, economical, plants such as forestry; The use of these compositions makes the immunizing power of crop self improve, and has induced the defence capability of plant generation to viral diseases of plants when producing the control of insect especially infection insect; Also can produce the direct prevention effect of virus disease; Therefore, these compositions can be used for Antiphytoviral medicament and inducing plant Antiphytoviral medicaments preparation and purposes.Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and aforementioned Antiphytoviral medicament is mass percent 1%: 99% to 99%: 1%; The formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; All show addition or synergism between these compositions, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 13
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the complete processing and the stability of 3-thiadiazoles derivative V and commercially available agricultural chemical compound preparation
Of the present inventionly contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the mixture complete processing of 3-thiadiazoles derivative V and commercially available agricultural chemical sees Table 5, by table 5 as seen, 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 component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes the effect composition, other agriculturals such as tensio-active agent and filler go up the acceptable adjuvant component, the cold storage test of process preparation, liquid preparation is placed 1 week not have to precipitate at 0 ± 2 degree centigrade and is separated out, solid preparation placed for 2 weeks at 54 ± 2 degrees centigrade, caking phenomenon does not appear in medicament, the medicament drug effect that all preparations store before and after placing does not have significant difference, the rate of decomposition of composition effective constituent in 5%, the composite preparation qualified stability.
Table 3 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the activity of 3-thiadiazoles derivative V resisting tobacco mosaic virus (inhibiting rate of 50 μ g/mL/%)
| Sequence number | Compound | Treatment | Passivation | Protection | Induce |
| 1 | mt008-48-2 | 31.86±5.95 | 19.05±4.20 | 37.44±5.40 | 38.38±3.81 |
| 2 | mt008-48-3 | 39.22±4.50 | 19.58±642 | 25.13±5.40 | 32.83±5.32 |
| 3 | mt008-48-4 | 23.53±6.74 | 39.15±2.42 | 22.05±5.40 | 38.38±3.81 |
| 4 | mt008-49-9 | 19.05±4.76 | 34.36±5.40 | 23.48±5.69 | 39.80±5.65 |
| 5 | mt008-48-15 | 29.69±4.69 | 35.00±5.00 | 10.22±5.66 | 6.77±3.93 |
| 6 | mt008-48-14 | 28.65±3.94 | 27.78±4.20 | 19.36±5.82 | 29.17±4.78 |
| 7 | mt008-48-5 | 24.02±3.70 | 28.04±4.85 | 36.41±4.70 | 41.41±2.32 |
| 8 | mt008-48-6 | 35.78±3.70 | 41.80±3.99 | 6.15±3.08 | 24.75±6.22 |
| 9 | mt008-48-7 | 31.86±6.63 | 34.92±3.18 | 13.85±4.62 | 31.82±4.55 |
| 10 | mt008-48-16 | 40.10±3.25 | 32.78±6.94 | 34.41±4.06 | 28.13±6.25 |
| 11 | mt008-48-17 | 36.98±4.78 | 31.11±4.19 | 24.19±5.82 | 36.46±3.94 |
| 12 | mt008-48-18 | 41.67±3.25 | 39.44±4.19 | 42.47±2.46 | 36.46±5.92 |
| 13 | mt008-48-19 | 35.42±4.78 | 30.00±3.33 | 10.22±5.66 | 21.88±5.64 |
| 14 | mt008-48-8 | 33.82±5.31 | 20.11±6.41 | 37.44±3.87 | 40.40±4.63 |
| 15 | mt008-48-9 | 13.23±6.41 | 25.93±6.42 | 40.51±5.40 | 20.71±5.32 |
| 16 | mt008-49-4 | 24.34±5.57 | 25.13±7.27 | 18.78±3.55 | 17.41±2.28 |
| 17 | mt008-48-1 | 23.53±5.30 | 20.10±4.00 | 23.08±5.55 | 23.74±4.63 |
| 18 | mt008-49-6 | 25.93±7.15 | 28.21±6±.22 | 14.08±2.82 | 40.30±5.38 |
| 19 | mt008-49-7 | 23.81±4.76 | 29.74±3.88 | 35.21±4.23 | 27.36±4.56 |
| 20 | mt008-49-2 | 17.46±7.28 | 18.98±5.82 | 26.29±4.95 | 25.37±4.48 |
| 21 | mt008-48-13 | 21.16±5.57 | 20.00±5.55 | 32.39±5.08 | 37.81±5.24 |
| 22 | mt008-48-10 | 26.47±3.70 | 9.52±2.42 | 23.08±3.08 | 22.73±5.32 |
| 23 | mt008-48-11 | 24.02±5.16 | 28.04±4.85 | 7.18±2.35 | 31.82±3.03 |
| 24 | mt008-48-12 | 21.57±5.16 | 10.58±5.57 | 14.87±3.20 | 14.65±4.63 |
| 25 | mt008-49-3 | 17.99±4.85 | 22.05±6.94 | 39.44±4.23 | 30.35±6.03 |
| 26 | mt008-49-11 | 19.79±7.04 | 23.33±7.64 | 43.01±2.46 | 41.15±3.25 |
| 27 | mt008-49-5 | 24.87±7.16 | 40.51±4.70 | 15.49±5.64 | 39.80±6.21 |
| 28 | mt008-49-10 | 38.02±2.39 | 33.89±2.55 | 36.02±2.46 | 8.85±4.77 |
| 29 | mt008-49-1 | 35.45±4.85 | 22.56±6.22 | 10.33±4.95 | 35.32±3.76 |
| 30 | Virazole | 34.39±7.99 | 40.51±3.21 | 44.60±4.30 | 24.88±4.56 |
| 31 | Ningnanmycin | 27.08±5.48 | 45.64±2.35 | 43.19±3.54 | 28.36±2.99 |
| 32 | TDL | 31.75±4.77 | 26.15±3.08 | 26.76±5.07 | 43.28±2.99 |
[0084]Table 4 is of the present invention to contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V is to the activity of mythimna separata
| Sequence number | Compound | Mortality ratio (%) | Sequence number | Compound | Mortality ratio (%) |
| 1 | mt008-48-2 | 5 | 16 | mt008-49-4 | 10 |
| 2 | mt008-48-3 | 20 | 17 | mt008-48-1 | 5 |
| 3 | mt008-48-4 | 25 | 18 | mt008-49-6 | 70 |
| 4 | mt008-49-9 | 5 | 19 | mt008-49-7 | 60 |
| 5 | mt008-48-15 | 100 | 20 | mt008-49-2 | 45 |
| 6 | mt008-48-14 | 20 | 21 | mt008-48-13 | 60 |
| 7 | mt008-48-5 | 65 | 22 | mt008-48-10 | 100 |
| 8 | mt008-48-6 | 55 | 23 | mt008-48-11 | 100 |
| 9 | mt008-48-7 | 65 | 24 | mt008-48-12 | 20 |
| 10 | mt008-48-16 | 40 | 25 | mt008-49-3 | 60 |
| 11 | mt008-48-17 | 80 | 26 | mt008-49-11 | 50 |
| 12 | mt008-48-18 | 10 | 27 | mt008-49-5 | 50 |
| 13 | mt008-48-19 | 100 | 28 | mt008-49-10 | 10 |
| 14 | mt008-48-8 | 5 | 29 | mt008-49-1 | 15 |
| 15 | mt008-48-9 | 25 | 30 | The chlorine insect amide | 100 |
72 hours measurement results; Measure concentration: 200 μ g/mL; Measuring method: blade medicine embrane method
Table 5 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the working method that 3-thiadiazoles derivative V and commercially available agricultural chemical are used with
Table 4 is of the present invention to contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V is to the activity of mythimna separata
| Sequence number | Compound | Mortality ratio (%) | Sequence number | Compound | Mortality ratio (%) |
| 1 | mt008-48-2 | 5 | 16 | mt008-49-4 | 10 |
| 2 | mt008-48-3 | 20 | 17 | mt008-48-1 | 5 |
| 3 | mt008-48-4 | 25 | 18 | mt008-49-6 | 70 |
| 4 | mt008-49-9 | 5 | 19 | mt008-49-7 | 60 |
| 5 | mt008-48-15 | 100 | 20 | mt008-49-2 | 45 |
| 6 | mt008-48-14 | 20 | 21 | mt008-48-13 | 60 |
| 7 | mt008-48-5 | 65 | 22 | mt008-48-10 | 100 |
| 8 | mt008-48-6 | 55 | 23 | mt008-48-11 | 100 |
| 9 | mt008-48-7 | 65 | 24 | mt008-48-12 | 20 |
| 10 | mt008-48-16 | 40 | 25 | mt008-49-3 | 60 |
| 11 | mt008-48-17 | 80 | 26 | mt008-49-11 | 50 |
| 12 | mt008-48-18 | 10 | 27 | mt008-49-5 | 50 |
| 13 | mt008-48-19 | 100 | 28 | mt008-49-10 | 10 |
| 14 | mt008-48-8 | 5 | 29 | mt008-49-1 | 15 |
| 15 | mt008-48-9 | 25 | 30 | The chlorine insect amide | 100 |
72 hours measurement results; Measure concentration: 200 μ g/mL; Measuring method: blade medicine embrane method
Table 5 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the working method that 3-thiadiazoles derivative V and commercially available agricultural chemical are used with
Claims (10)
1. a class contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the 3-thiadiazoles derivative is characterized in that having the chemical structure of general formula suc as formula shown in the V:
Wherein: R is selected from cyclohexyl, o-tolyl, between tolyl, p-methylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, the ortho-nitrophenyl base, the m-nitro base, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, the acetparaminosalol phenyl, to N, N dimethylamine base phenyl, furans-2-base, thiophene-2-base, 5-methyl-3-Chloro-O-Phenyl-isoxazole-4-bases, 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
2. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the synthetic method of 3-thiadiazoles derivative V, concrete synthetic route is as follows:
Wherein: R is selected from: cyclohexyl, o-tolyl, a tolyl, p-methylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, o-bromophenyl, to cyano-phenyl, acetparaminosalol phenyl, to N, N dimethylamine base phenyl, furans-2-base, thiophene-2-base, 5-methyl-3-Chloro-O-Phenyl-isoxazole-4-base;
Part of compounds adopts with the direct method of condensing of carboxylic acid and prepares according to following formula:
Wherein, R is selected from: 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base;
Specifically be divided into following steps:
A.5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl ammonia II
In 250 milliliters of single necked round bottom flask, once add 80 milliliters of ethanol, 5-methyl isophthalic acid, 2,3-thiadiazoles-4-ethyl formate 17.2 grams, promptly 100 mmoles, the 25% strong aqua aqueous solution are 80 milliliters, and stirring at room 12 hours is cooled to 0 degree centigrade, filter, wash with small amount of ethanol with getting white solid, with the pure product calculated yield of gained, yield 99%; The 5-methyl isophthalic acid, 2, the 3-thiadiazoles-amount of 4-formyl ammonia II preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle;
B. intermediate 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-sulfo-formyl ammonia III:
In 250 milliliters of three mouthfuls of round-bottomed flasks, add initial reactant 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl ammonia II14.3 gram, promptly 100 mmoles, 150 milliliters of toluene, lawesson reagent are Lawesson ' s Reagent24.2 gram, i.e. 60 mmoles, nitrogen protection was stirred stirring and refluxing 4 hours, after reaction finishes reaction solution concentrated and remove toluene, resistates obtains faint yellow solid 5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-sulfo-formyl ammonia III, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 3: 1; With the pure product calculated yield of gained, yield 76%; Intermediate 5-methyl isophthalic acid, 2, the 3-thiadiazoles-amount of 4-sulfo-formyl ammonia III and the volume of reaction vessel enlarge by corresponding proportion or dwindle;
C. intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the preparation of 5-thiazoline-4-alcohol IV:
In 100 milliliters of three mouthfuls of round-bottomed flasks, add the 5-methyl isophthalic acid, 2,3-thiadiazoles-4-sulfo-formyl ammonia III7.96 gram, i.e. 50 mmoles, 60 milliliters of stirrings of dehydrated alcohol of handling, 3-bromo-1,1,1-trifluoroacetone 9.6 gram, i.e. 50 mmoles, nitrogen protection was stirred stirring and refluxing 16 hours, after reaction finishes reaction solution concentrated and remove toluene, resistates obtains faint yellow solid 5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, and 2,3-thiadiazoles-4-sulfo-formyl ammonia III, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, volume ratio are 10: 1; With the pure product calculated yield of gained, yield 62%; Intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-alcohol IV preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle;
D.2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method one:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, 8 milliliters of exsiccant methylene dichloride, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice-water bath is cooled to 0 degree centigrade, slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine 1.2 mmoles then, reaction solution slowly rises to room temperature and stirred 4～10 hours according to the difference of substrate; After reacting completely, methylene dichloride is diluted to 30 milliliters, use dilute hydrochloric acid, saturated sodium bicarbonate aqueous solution, saturated common salt water washing successively, anhydrous magnesium sulfate drying, removal of solvent under reduced pressure, resistates obtains white or faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, yield 61-93%; Described substituted formyl chlorine is selected from: the cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, methoxy benzoyl chloride, the meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, the ortho-nitrophenyl formyl chloride, m-nitrobenzoyl chloride, paranitrobenzoyl chloride, adjacent bromo-benzoyl chloride, to cyano-benzoyl chloride, acetaminol chlorine, to N, N dimethylamine base Benzoyl chloride, furans-2-formyl chloride, thiophene-2-formyl chloride, 5-methyl-3-Chloro-O-Phenyl-isoxazoles-4-formyl chloride; 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-polyol carboxylic acid ester V preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle;
E.2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method two:
In 50 milliliters of three mouthfuls of round-bottomed flasks, add intermediate 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, promptly 1.0 mmoles, 8 milliliters of exsiccant methylene dichloride, triethylamine 0.15 restrain, i.e. 1.0 mmoles, various heterocyclic substituted formic acid 1.2 mmoles, stirring also is cooled to 0 degree centigrade, under nitrogen protection, drip dicyclohexyl carbon imide 0.25 gram then by syringe, promptly the dichloromethane solution of 1.2 mmoles dropwised in 10 minutes; Reaction solution rises to room temperature and stirs and spend the night; Reaction finishes and removes insolubles, rotary evaporation removes and desolvates, thick product gets faint yellow solid 2-(5-methyl isophthalic acid through 200～300 order purification by silica gel column chromatography, 2,3-thiadiazoles-4-yl)-and 4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is 60～90 degrees centigrade a sherwood oil: ethyl acetate, according to the difference of product, volume ratio is between 15: 1～3: 1; With the pure product calculated yield of gained, productive rate 61-93%; Described heterocyclic substituted formic acid is selected from: 3-bromo-1-(3-chloropyridine-2-yl)-pyrazoles-5-formic acid, pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 2-chloropyridine-3-formic acid; 2-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-yl)-4-(trifluoromethyl)-4, the 5-thiazoline-amount of 4-polyol carboxylic acid ester V preparation and the volume of reaction vessel enlarge by corresponding proportion or dwindle.
3. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V goes up the purposes of acceptable assistant in the preparation sterilant with agricultural.
4. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V goes up the purposes of acceptable assistant in the preparation sterilant with agricultural.
5. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V goes up the purposes of acceptable assistant in the preparation anti-plant virus agent with agricultural.
6. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the application in 3-thiadiazoles derivative V and sterilant combination control agricultural and forestry and the gardening plant insect pest:
All classes of the present invention contain 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing sterilant: Chlorpyrifos 94, the inferior Nong in ground, acetamiprid, Affirm (Merck Co.), more visit rhzomorph, 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, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, fluorine bell urea, flufenoxuron, the pyridine worm is grand, the Acarus tritici urea, the poisonous insect urea, penfluron, Noviflumuron is a noviflumuron, and its CAS number is 121451-02-3, flucycloxuron, Novaluron is a Rimon, fluorine pyridine urea, Bay sir6874 i.e. { 1-[(3.5-two 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, promptly two three flufenoxuron of Bistrifluron, furans worm hydrazides, 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, azoles mite ester, pyridaben, four mite piperazines, alkynes mite spy, the butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, fluorine worm nitrile, the desinsection list, disosultap, the chlorine insect amide, Flubendiamide, the fluorine cyanogen insect amide, cyanogen insect amide, the azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, the pyrrole propyl ether, in the emaricin etc. any one or two kinds are used in combination and are used for control agricultural and forestry and gardening plant insect pest; A class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, a class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and above-mentioned sterilant is mass percent 1%: 99% to 99%: 1%; Spray after can directly converting water, comprise agricultural in the preparation of composition and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; 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, the hard a red-spotted lizard of Korea's ball, pear lace bug, the banana lace bug, thin corner piece stinkbug, little minute pirate bugs, 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, intend smaller apple leaf roller, 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, big 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, black dull cockchafer, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big 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 the 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, genseng, 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 is in the parasiticidal defence capability that improves plant simultaneously, makes plant produce defence capability to pathogenic fungi, bacterium and virus infection.
7. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the application in 3-thiadiazoles derivative V and miticide combination control agricultural and forestry and the gardening plant mite evil:
A class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and agricultural go up acceptable assistant 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, the Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, smart 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, fourth fluorine mite ester, the mite quinone goes out, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, the Ai Pulinuo rhzomorph, ivermectin, rhzomorph is drawn in match, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, azoles mite ester, four mite piperazines, alkynes mite spy, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, in the pyridaben any one or two kinds of medicament combined preparation become miticide to be used for control agricultural and forestry and gardening plant mite evil; A class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, a class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; The formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; Plant in composition for preventing and controlling agricultural and forestry and the 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, genseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape; The mite evil that composition is suitable for is phytophagy evil mite, 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 evil mites of the itch mite of Eriophyidae, forestry evil mite, the harmful mite of gardening and the harmful mite of health that phytophagy evil mite is selected from tetranychid.
8. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the application in 3-thiadiazoles derivative V and sterilant combination control agricultural and forestry and the gardening plant disease:
all classes of the present invention contain the 5-methyl isophthalic acid of 4,5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing bactericide such as diazosulfide, tiadinil is 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 formate, 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-, two chloroisothiazoles-5-formic acid, 3,4-, two chloroisothiazoles-5-sodium formate, 3,4-, two chloroisothiazoles-5-Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, frost urea cyanogen, thiram, ziram, Mancozeb, aliette, thiophanate-methyl, Bravo, the enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, efficient metalaxyl, efficient M 9834, two chlorine zarilamids, flusulfamide, the first flusulfamide, thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, the pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, oxime bacterium ester, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, Cyproconazole, Difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, own azoles alcohol, glyoxalin, plant the bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, Fenamidone, the Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, the fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, the benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, IBP, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the hot salt of biguanides, iminoctadine, botran, the benzene flusulfamide, the toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in bactericide such as allyl isothiazole are used in combination for control agricultural and forestry and gardening plant disease, a class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, a class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, the ratio of 2,3-thiadiazoles derivative V and aforementioned bactericide are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergistic effect and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be used for the control of agricultural plant 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, industrial crops, 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 agent, pulvis, micro-capsule suspension, the dispersible body preparation, the dispersible solid preparation, Seed Treatment emulsion, aqueous emulsion, granule, microemulsion, finish, seed with coated pesticidal, suspension emulsion, 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, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, the smog rod, the smog sheet, smoke agent, 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, fine granule, 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, liniment, the fritter poison bait, suspending agent, suspended 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 are used for control agricultural and forestry and the applicable plant of gardening plant disease and comprise cereal: 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, 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, cereal crops and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicine industrial crops and plant melon, really, tea, silkworm and mulberry, vegetables, contain various wild vegetables, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crops such 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, garden pea, 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, make plant produce defence capability to disease fungus, bacterium and virus infection.
9. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2, the application in 3-thiadiazoles derivative V and anti-plant virus agent combination control agricultural and forestry and the gardening plant virus disease:
A class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative V and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, different metsulfovax, 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-two chloroisothiazoles-5-formic acid, 3,4-two chloroisothiazoles-5-sodium formiate, 3,4-two 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, any 1 or the combination of 2 compounds are used for control agricultural and forestry and gardening plant virus disease in the jingganmycin; The disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus diseases, various solanberry viroid diseases, the beans virus disease, the Cruciferae virus disease, the grain and oil crop virus disease, any in cotton virus disease and the various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, the paddy rice virus disease comprises rice dwarf virus disease, yellow dwart, stripe virus disease, the fern leaf of tomato viral disease, sick and the tobacco veinal necrosis virus disease of chilli pepper mosaic virus, the corn short mosaic disease, cauliflower mosaic virus, the oranges and tangerines virus disease, cymbidium mosaic virus, any in the cybidium ring spot virus; The plant that these compositions are used to prevent and treat agricultural and forestry and gardening plant virus disease 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, genseng, 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, agriculturals such as potted landscape, gardening, economical, plants such as forestry; The use of these compositions makes the immunizing power of crop self improve, and has induced the defence capability of plant generation to viral diseases of plants when producing the control of insect especially infection insect; Also can produce the direct prevention effect of virus disease; Therefore, these compositions can be used for Antiphytoviral medicament and inducing plant Antiphytoviral medicaments preparation and purposes; A class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the total quality percentage composition of 3-thiadiazoles derivative V in composition is 1%-90%, a class of the present invention contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, 2, the ratio of 3-thiadiazoles derivative V and aforementioned Antiphytoviral medicament is mass percent 1%: 99% to 99%: 1%; The formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, 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 and adorn agent, the medicine lacquer, 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, plant the clothing 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, in the steam releasing agent any one; All show addition or synergism between these compositions, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Find no the composition of antagonistic action, the drug effect lasting period of composition is long.
10. the described class of claim 1 contains 4, the 5-methyl isophthalic acid of 5-thiazoline carboxylic ester, and 2,3-thiadiazoles derivative V and common pesticide combination form the complete processing of pesticide preparation.
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| CN103975931A (en) * | 2014-06-04 | 2014-08-13 | 吴文君 | Application of thiazoline compound as agricultural bactericide |
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| CN103497182A (en) * | 2013-10-25 | 2014-01-08 | 南开大学 | 3,4-dichloro isothiazole derivative containing 4,5-dihydro thiazole alkyd resin and preparation method and application thereof |
| CN103497182B (en) * | 2013-10-25 | 2016-05-11 | 南开大学 | One class contains 3 of 4,5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives and its production and use |
| CN103975931A (en) * | 2014-06-04 | 2014-08-13 | 吴文君 | Application of thiazoline compound as agricultural bactericide |
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