CN103232448B - One class contains 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles and its production and use - Google Patents
One class contains 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles and its production and use Download PDFInfo
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Abstract
The invention provides a class containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles and its production and use, the present invention relates to the heterogeneous ring compound containing 1,2,3-thiadiazoles, they have the chemical structure of general formula as shown in V.
Description
Technical field
Technical scheme of the present invention relates to containing 1,2-diazole compounds, be specially 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles, i.e. 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound.
Background technology
Virus, fungi, bacterium etc. are one of important factors affecting modern agricultural production, and the various diseases caused by these pathogenic agent have a strong impact on the output associating quality of agricultural-food.Various chemical bactericide ensures that reducing disease ensures one of important means of agricultural-food productive rate and quality.But in recent years, the extensively and not scientifical use of various sterilant, makes the various pathogenic bacterias in China farmland create obvious resistance (Jia Junchao to existing conventional sterilants, Ma Lin, Fan Zhijin, etc. Pesticide Science journal, 2008,10 (1): 1-9.).Methoxy acrylic bactericide was once at one of the most widely used sterilant in China farmland, also created obvious resistance (Zhao Ping, Yan Qiuxu at present in China farmland, Li Xin, Deng. agricultural chemicals, 2011,50 (8): 547-542.).Therefore development structure is more novel, simple, and the sterilant with different binding mode is extremely urgent.Japanese firm has good fungicidal activity containing the thiazoline compounds of trifluoromethyl and has certain insecticidal activity (JP2005330258) simultaneously.
1, 2, 3-thiadiazole compound has biological activity widely, early stage patent and document are summed up and are seen Bakulev, etal.Newyork:JohnWiley & Sons, Inc, the monograph of 2004, 1, 2, 3-thiadiazoles derivative commercial kind in medicine and agricultural chemicals is few, what agriculture field was applied only has cotton defoliant--disleave spirit (N-phenyl-N '-1, 2, 3-thiadiazoles-5-urea, TDZ), activating plants agent--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 is in earlier stage synthesized and has found that first thiophene lures the inducing anti-disease activity of amine, at present just in industrialization development process.
In order to find and find more efficient, wide spectrum, low toxicity, low ecological risk and with existing sterilant without the new type bactericide of cross resistance and more high biological activity 1,2,3-thiadiazole new compound, design and synthesis of the present invention one class is containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles, carry out the bioactive screening and evaluation of system simultaneously, provide candidate compounds to the innovative research for novel pesticide
Summary of the invention
Technical problem to be solved by this invention is: provide a class new containing 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4, the synthetic method of 5-thiazoline-4-polyol carboxylic acid ester derivative, this kind of compound modulates agricultural, the biological activity of gardening and health and forestry plant insect and the phytopathy original and measuring method thereof are provided, provide these compounds to apply in agriculture field, horticultural field, field of forestry and health field simultaneously.
The present invention solves this technical problem adopted technical scheme: there is agriculture field, horticultural field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant produce anti-disease activity, insect growth regulator activity containing 4-methyl isophthalic acid, 2, the chemical structure of general formula of 4,5-thiazoline carboxylic ester derivatives of 3-thiadiazoles is shown in formula V:
Wherein, R is selected from: cyclohexyl, o-tolyl, between tolyl, p-methylphenyl, to ethylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, O-Nitrophenylfluorone, 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, the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
Of the present invention containing 4-methyl isophthalic acid, the synthetic method of 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles is as follows:
Wherein: R is selected from: cyclohexyl, o-tolyl, a tolyl, p-methylphenyl, to ethylphenyl, p-methoxy-phenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, O-Nitrophenylfluorone, 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 to be prepared according to the following formula with the direct method of condensing of acid:
Wherein, R is selected from: the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
Specifically be divided into following steps:
A.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl ammonia II
Ethanol 80 milliliters, 5-methyl isophthalic acid is once added in 250 milliliters of single necked round bottom flask, 2,3-thiadiazoles-4-ethyl formate 17.2 grams, i.e. 100 mmoles, the 25% strong aqua aqueous solution 80 milliliters, stirring at room temperature 12 hours, be cooled to 0 degree Celsius, filter to obtain white solid, use a small amount of washing with alcohol, by gained sterling calculated yield, yield 98%; The volume of amount prepared by above-claimed cpd II and reaction vessel expands by corresponding proportion or reduces.
B. intermediate 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-sulfo-formyl ammonia III:
Initial reactant 4-methyl isophthalic acid is added in 250 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-formyl ammonia II14.3 gram, i.e. 100 mmoles, toluene 150 milliliters, lawesson reagent and Lawesson ' sReagent24.2 gram, i.e. 60 mmoles, nitrogen protection stirring and refluxing 4 hours, by reaction solution concentrated removing toluene after reaction terminates, resistates obtains faint yellow solid 4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 3: 1; By gained sterling calculated yield, yield 75%; The volume of amount prepared by intermediate III and reaction vessel expands by corresponding proportion or reduces.
C. the preparation of intermediate 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV:
4-methyl isophthalic acid is added, 2,3-thiadiazoles-5-sulfo-formyl ammonia III7.96 gram, i.e. 50 mmoles, the dehydrated alcohol 60 milliliters that processed in 100 milliliters of three mouthfuls of round-bottomed flasks, stir, then add 3-bromo-1,1,1-trifluoroacetone 9.6 grams, i.e. 50 mmoles, nitrogen protection stirring and refluxing 16 hours; By reaction solution concentrated removing toluene after reaction terminates, resistates obtains faint yellow solid 4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 10: 1; By gained sterling calculated yield, yield 70%; The volume of amount prepared by intermediate compound IV and reaction vessel expands by corresponding proportion or reduces.
D.2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method one:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, dry methylene dichloride 8 milliliters, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice-water bath is cooled to 0 degree Celsius, then slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine 1.2 mmole, reaction solution slowly rises to room temperature and stirs 4 ~ 10 hours according to the difference of substrate, after reacting completely, dchloromethane to 30 milliliter, 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-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1 ~ 3: 1, by gained sterling calculated yield, yield 60-90%, described substituted formyl chlorine is selected from: cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, p-ethylbenzoyl chloride, methoxy benzoyl chloride, meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, 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-isoxazole-4-formyl chloride, the volume of amount prepared by compound V and reaction vessel expands by corresponding proportion or reduces, the chemical structure of compound V and physical and chemical parameter are in table 1,
E.2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method two:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, dry methylene dichloride 8 milliliters, triethylamine 0.15 gram, i.e. 1.0 mmoles, various heterocyclic substituted formic acid 1.2 mmole, stir, dicyclohexylcarbodiimide 0.25 gram is dripped by syringe under nitrogen protection after being cooled to 0 degree Celsius, the i.e. dichloromethane solution of 1.2 mmoles, dropwises for 10 minutes; Reaction solution rises to rt while stirring overnight; React complete removing insolubles, rotary evaporation is except desolventizing, thick product obtains faint yellow solid 2-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, according to the difference of product, volume ratio is between 15: 1 ~ 3: 1; By gained sterling calculated yield, productive rate 60-90%; Described heterocyclic substituted formic acid is selected from: the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-formic acid, pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 2-chloropyridine-3-formic acid; The volume of amount prepared by compound V and reaction vessel expands by corresponding proportion or reduces;
F.2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester cpds is to the mensuration of mythimna separata cytotoxicity:
2-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-base) the insecticidal activity screening method of-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester cpds to aphid larva is as follows: adopt blade medicine embrane method; Sample first carries out active primary dcreening operation with 200 μ g/mL; Test compound first uses a small amount of acetone solution, and then with 0.5 ‰ Triton-100 dilutions, 0.5 ‰ Triton-100 water are contrast, and every test compound repeats for 4 times, each re-treatment 10 examination worm; Get fresh free of contamination maize leaf, soak 10 seconds in the liquid prepared, after about 2h is dried in indoor, put into the culture dish of diameter 9cm, access basically identical mythimna separata 2 Initial instar larvae in age of size respectively; Tightening with bungee is placed in mythimna separata constant temperature insectary, check result after 72h calculation correction mortality ratio; Touching polypide with little writing brush or tweezers, can not coordinated movement be dead; Take clear water as contrast, Provado is positive control, calculation correction mortality ratio.
G. of the present invention containing 4-methyl isophthalic acid, the fungicidal activity that 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles are right measures:
Of the present invention containing 4-methyl isophthalic acid, 2, 4 of 3-thiadiazoles, the derivative V sterilization of 5-thiazoline carboxylic ester or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with the medicament being diluted to 500 mcg/ml containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent is aseptically respectively drawn in 1 milliliter of injection culture dish, add 9 milliliters of substratum more respectively, 50 mcg/ml pastilles are made dull and stereotyped after shaking up, blank is done with the flat board adding 1 milliliter of aqua sterilisa, bacterium dish is cut along mycelia outer rim with the punch tool of diameter 4 millimeters, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivates, treat that contrast colony diameter expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate, the kind of the majority of plant pathogenic bacteria of the actual generation in multiple representative field in China's agriculture production is comprised for examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternariasolani), BC: botrytis cinerea pers (Botrytiscinerea), CA: peanut Cercospora bacteria (Cercosporaarachidicola), GZ: fusarium graminearum (Gibberellazeae), PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary), PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola), PS: Rhizoctonia solani Kuhn (pelliculariasasakii), RC: Rhizoctonia cerealis (Rhizoctoniacerealis), SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum).
H. of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V inducing anti-disease activities of 2,3-thiadiazoles measure:
Of the present invention containing 4-methyl isophthalic acid, the screening method that 4,5-thiazoline carboxylic ester derivatives V evoking tobacco resisting tobacco mosaic virus (TMV) of 2,3-thiadiazoles are active is:
(1). standard plant activator: select the activating plants agent that tiadinil (TDL) (purity is greater than 99.5%) is standard;
(2). containing 4-methyl isophthalic acid, the screening method of the anti-TMV activity of 4,5-thiazoline carboxylic ester derivative V evoking tobacco of 2,3-thiadiazoles: the mensuration of in vitro directly antiviral activity adopts half leaf method to carry out, live body induction is by common cigarette consistent for seedling age, 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in first 7 days, processing mode comprises: spray test compounds solution 2 to 3 times, each 10 milliliters, or soil treatment, each 10 milliliters, measuring concentration is 50 mcg/ml, 7th day frictional inoculation TMV on the tobacco leaf newly grown, cultivate under cigarette seedling being placed in its growth optimal temperature and illumination after 3 days, check incidence, comprehensive scab number is calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV, 3 repetitions are established in each process, blank and standard agent contrast select water and TDL respectively:
Wherein, R is the inducing effect of new compound to Resistance In Tobacco TMV, unit: %; CK is the average withered spot number of clear water contrast blade, unit: individual; I is the average withered spot number through compound induction process rear blade, unit: individual;
Except carrying out the mensuration of above-mentioned induced activity, carry out containing 4-methyl isophthalic acid, the mensuration of the therapeutic activity of the anti-TMV of 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles, inactivate activity and prolection simultaneously.
The invention has the beneficial effects as follows: containing 4-methyl isophthalic acid, 2,4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V has carried out guide's optimization, and the new compound of synthesis has been carried out to the screening of insecticidal activity and bacteriostatic activity and antiviral activity, carried out the research that itself and common pestsides synthesis use, this compounds may be used for control agriculture field and the plant pest of field of forestry and horticultural field and the control of virus disease simultaneously.
The present invention illustrates containing 4-methyl isophthalic acid by specific preparation and biological activity determination embodiment more, 2,4 of 3-thiadiazoles, the synthesis of 5-thiazoline carboxylic ester derivative V and biological activity and application, described embodiment is only for illustrating the present invention and unrestricted the present invention, especially biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Embodiment 1
Intermediate 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl ammonia II:
Ethanol 80 milliliters, 5-methyl isophthalic acid is once added in 250 milliliters of single necked round bottom flask, 2,3-thiadiazoles-4-ethyl formate (17.2 grams, 100 mmoles), strong aqua (80 milliliters, 25% aqueous solution), stirring at room temperature 12 hours, is cooled to 0 degree Celsius, filters, wash with a small amount of ethanol, vacuum-drying obtains white solid 15.6 grams, by gained sterling calculated yield, and yield 98%;
1hNMR (400MHz, CDCl
3): δ 5.92 (s, br, 2H), 2.95 (s, 3H); 4-methyl isophthalic acid, the chemical structure of 2,3-thiadiazoles-5-formyl ammonia II and physical and chemical parameter are in table 1.
Embodiment 2
Intermediate 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-sulfo-formyl ammonia III:
Initial reactant 4-methyl isophthalic acid is added in 250 milliliters of three mouthfuls of round-bottomed flasks, 2, 3-thiadiazoles-5-formyl ammonia II (14.3 grams, 100 mmoles), toluene 150 milliliters, lawesson reagent (Lawesson ' sReagent) (24.2 grams, 60 mmoles), nitrogen protection stirring and refluxing 4 hours, by reaction solution concentrated removing toluene after reaction terminates, resistates obtains faint yellow solid 4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2, 3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, according to the difference of product, volume ratio is 3: 1, by gained sterling calculated yield, yield 75%,
1hNMR (400MHz, CDCl
3): δ 6.12 (s, br, 2H), 2.95 (s, 3H).
Embodiment 3
The preparation of intermediate 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV:
4-methyl isophthalic acid is added in 100 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-sulfo-formyl ammonia III (7.96 grams, 50 mmoles), the dehydrated alcohol 60 milliliters that processed, the bromo-TFK of 3-(9.6 grams, 50 mmoles), nitrogen protection stirring and refluxing 16 hours; By reaction solution concentrated removing toluene after reaction terminates, resistates obtains 9.4 grams of faint yellow solid 4-methyl isophthalic acids through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 10: 1; By gained sterling calculated yield, yield 70%;
1hNMR (400MHz, CDCl
3): δ 3.65 (s, 2H), 3.00 (s, 3H).
Embodiment 4
The preparation of 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV (0.27 gram, 1.0 mmoles), dry methylene dichloride 8 milliliters, triethylamine (0.15 gram, 1.5 mmoles), ice-water bath is cooled to 0 degree Celsius, then slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine (1.2 mmole), reaction solution slowly rises to room temperature and stirs 4 ~ 10 hours according to the difference of substrate; After reacting completely, dchloromethane to 30 milliliter, 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-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1 ~ 3: 1; By gained sterling calculated yield, yield 60-90%.Its physical and chemical parameter and structural parameter are in table 1.Described substituted formyl chlorine is selected from: cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, methoxy benzoyl chloride, meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, 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-isoxazole-4-formyl chloride.
Embodiment 5
The preparation of 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks; 2; 3-thiadiazoles-5-base)-4-(trifluoromethyl)-4; 5-thiazoline-4-alcohol IV (0.27 gram; 1.0 mmoles), dry methylene dichloride 8 milliliters, triethylamine (0.15 gram; 1.0 mmoles), various heterocyclic substituted formic acid (1.2 mmole); stir and be cooled to 0 degree Celsius; then dicyclohexylcarbodiimide (0.25 gram is dripped by syringe under nitrogen protection; 1.2 mmoles) dichloromethane solution, within 10 minutes, dropwise.Reaction solution rises to rt while stirring overnight.React complete removing insolubles, rotary evaporation is except desolventizing, thick product obtains faint yellow solid 2-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, according to the difference of product, volume ratio is between 15: 1 ~ 3: 1; By gained sterling calculated yield, productive rate 60-90%.Its physical and chemical parameter and structural parameter are in table 1.Described heterocyclic substituted formic acid is selected from: the bromo-1-of 3-(3-chloropyridine-2-base)-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 (4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound V to mythimna separata insecticidal activity assay result
We have selected 4 representational 2-of the present invention (4-methyl isophthalic acids, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester insecticidal activity assay the results are shown in Table 2, table 2 is visible: when reagent agent concentration is 200mg/L, after observation acts on 72 hours, the activity of compound mt008-44-18, mt008-46-1 is higher, is respectively 35%, 40% to sticky lethality rate.
Embodiment 7
2-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound V Antibacterial Activity result
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternariasolani); BC: botrytis cinerea pers (Botrytiscinerea); CA: peanut Cercospora bacteria (Cercosporaarachidicola); GZ: fusarium graminearum (Gibberellazeae); PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (Pelliculariasasakii); RC: Rhizoctonia cerealis (Rhizoctoniacerealis); SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that field occurs in agriculture production.Thalli growth rate method measurement result is in table 3, and table 3 shows, when 50 mcg/ml, all compounds of the present invention's synthesis all have fungicidal activity in various degree, mt008-44-7 to the fungicidal activity of AS higher than 40%, mt008-44-1, mt008-44-7, mt008-44-21 to the fungicidal activity of CA higher than 40%, mt008-43-2, mt008-46-4, mt008-44-21, mt008-44-22 to the fungicidal activity of GZ higher than 40%, mt008-44-16, mt008-44-8, mt008-43-2, mt008-44-6, mt008-44-10, mt008-44-4, mt008-44-2, mt008-44-1, mt008-44-7, mt008-44-5, mt008-44-3, mt008-46-9, mt008-44-12, mt008-46-8, mt008-46-4, mt008-46-2, mt008-44-19, mt008-44-11, mt008-44-18, mt008-46-3, mt008-46-7, mt008-46-5, mt008-44-20, mt008-44-21, mt008-44-22 to the fungicidal activity of PP higher than 40%, institute compound thing mt008-44-16 of the present invention, mt008-44-9, mt008-44-8, mt008-43-2, mt008-44-6, mt008-44-10, mt008-44-4, mt008-44-2, mt008-44-1, mt008-44-7, mt008-44-5, mt008-44-17, mt008-44-3, mt008-46-9, mt008-44-12, mt008-46-8, mt008-46-4, mt008-46-2, mt008-44-19, mt008-44-11, mt008-44-15, mt008-44-18, mt008-46-3, mt008-46-7, mt008-46-5, mt008-46-6, mt008-46-1, mt008-44-20, mt008-44-21, mt008-44-22 to the fungicidal activity of BC higher than 50%, mt008-44-16, mt008-44-8, mt008-43-2, mt008-44-6, mt008-44-10, mt008-44-4, mt008-44-2, mt008-44-7, mt008-44-17, mt008-44-3, mt008-46-8, mt008-46-5, mt008-46-6, mt008-44-20 to the fungicidal activity of SS higher than 40%, mt008-44-16, mt008-44-8, mt008-43-2, mt008-44-6, mt008-44-10, mt008-44-4, mt008-44-2, mt008-44-1, mt008-44-7, mt008-44-5, mt008-44-17, mt008-44-3, mt008-46-9, mt008-44-12, mt008-46-8, mt008-46-4, mt008-46-2, mt008-44-19, mt008-44-11, mt008-44-15, mt008-44-18, mt008-46-3, mt008-46-7, mt008-46-5, mt008-46-6, mt008-46-1, mt008-44-20, mt008-44-21, mt008-44-22 to the fungicidal activity of RC higher than 40%, mt008-44-16, mt008-44-9, mt008-44-8, mt008-43-2, mt008-44-6, mt008-44-10, mt008-44-4, mt008-44-2, mt008-44-1, mt008-44-7, mt008-44-5, mt008-44-17, mt008-44-3, mt008-46-9, mt008-44-12, mt008-46-8, mt008-46-4, mt008-46-2, mt008-44-19, mt008-44-11, mt008-44-15, mt008-46-3, mt008-46-7, mt008-46-5, mt008-46-6, mt008-46-1, mt008-44-20, mt008-44-21, mt008-44-22 to the fungicidal activity of PS higher than 40%.Especially compound mt008-44-16, mt008-44-8, mt008-44-10, mt008-44-17, mt008-44-12, mt008-46-8, mt008-46-2, mt008-46-7, mt008-46-5, mt008-46-6, mt008-46-1f that the present invention that outstanding is synthesizes are to the fungicidal activity of BC higher than 75%, and more commercial Azoxystrobin activity is good; Therefore, this compounds shows good fungicidal activity.
Embodiment 8
The anti-TMV active of 2-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester compound V:
The measurement result of TMV activity is in table 4, and table 4 shows, majority of compounds of the present invention has the activity of good anti-TMV; When 100 μ g/mL, although compound mt008-46-3, mt008-44-16, mt008-44-12, mt008-43-2, in the therapeutic mode to the inhibiting rate of TMV not as good as Ningnanmycin, but all higher than contrast medicament virazole, illustrate that they have direct antiviral activity in live body preferably.Under passivation pattern, the inhibiting rate of compound mt008-44-21 is greater than 40%.In protected mode, compound mt008-44-4, mt008-44-5, mt008-46-1, also show the inhibiting rate more than 40%.And under induction pattern, compound mt008-44-12, mt008-46-6, show the inhibiting rate more than 40%, illustrate that these have the activity of certain anti-TMV of induction plant.Therefore, this compounds shows good anti-plant tobacco mosaic virus activity.
Embodiment 9
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and insecticide composition prevent and treat the application in agriculture and forestry and gardening plant insect pest
Of the present invention all containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V and existing sterilants of 2,3-thiadiazoles: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, its No. CAS is 121451-02-3, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Baysir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, BaySIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or two kinds in emaricins etc. combinationally use for preventing and treating agricultural and forestry and gardening plant insect pest, of the present invention containing 4-methyl isophthalic acid, 2,4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V mass percentage is in the composition 1%-90%, of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and the ratio of above-mentioned sterilant are mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, comprise agriculturally acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc. in the preparation of composition, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, the insect pest that can prevent and treat mainly contains red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), singly sting mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane flat angle plant hopper, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, small white, pyrameis indica, the yellow a kind of butterfly harmful to crop plants of ramie, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the little buprestid beetle of oranges and tangerines, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hangs cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, Soybean stem borer, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, plant in control agricultural and forestry and gardening plant insect pest comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition improves the defence capability of plant while desinsection, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 10
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and miticide combine prevent and treat agriculture and forestry and gardening plant mite do harm in application
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and agriculturally acceptable auxiliary agent and be selected from azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, monocrotophos, naled, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, Phosalone, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, acephatemet, propetamphos, dialifos, R-1504, acrinathrin, bifenthrin, cyhalothrin, essence lambda-cyhalothrin, Fenvalerate, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, aldicarb, butocarboxim, oxamyl, Talcord, thiofanox, F-1991, sok, carbofuran, carbosulfan, meta-tolyl-N-methylcarbamate (MTMC), promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, any one or two kinds of pharmaceutical agent combinations in pyridaben are prepared into miticide and do harm to for preventing and treating agricultural and forestry and gardening plant mite, of the present invention containing 4-methyl isophthalic acid, 2,4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V total mass percentage is in the composition 1%-90%, of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and the ratio of above-mentioned medicament are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, plant during composition for preventing and controlling agricultural and forestry and gardening plant mite do harm to is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape, the mite evil that composition is suitable for is phytophagy evil mite, phytophagy evil mite be selected from tetranychid and Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae harmful mite and Panonychus citri belongs to, tetranychus telarius belongs to and these global Agricultural Mites of itch mite of Eriophyidae, forestry harmful mites, the harmful mite of gardening and the harmful mite of health.
Embodiment 11
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and antimicrobial combination prevent and treat the application in agriculture and forestry and gardening plant disease
Of the present invention all containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and existing sterilant are as diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, it is English general by name: isotianil, 3,4-bis-chloroisothiazole-5-formic acid, 3,4-bis-chloroisothiazole-5-sodium formiate, 3,4-bis-chloroisothiazole-5-ethyl formate, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole combinationally use for preventing and treating agricultural and forestry and gardening plant disease, of the present invention containing 4-methyl isophthalic acid, 2,4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V total mass percentage is in the composition 1%-90%, of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and the ratio of aforementioned sterilant are mass percent 1%: 99% to 99%: 1%, the prevention effect of composition is good, and these compositions have certain synergism and summation action, does not find the composition with antagonistic action, above-mentioned composition may be used for the control of agricultural plants disease and gardening plant disease, the Achyla, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora etc. more than 20 that controlling object comprises Oomycete belongs to the disease produced, as other diseases etc. of the plurality of cereals crops such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose, cash crop, gardening plant and forestry plant, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent.These compositions comprise cereal for preventing and treating plant applicable in agricultural and forestry and gardening plant disease: paddy, wheat, barley, oat, corn, millet, Chinese sorghum; Tuber crops: sweet potato, potato, cassava; Beans: soybean, broad bean, pea, mung bean, red bean and fiber: cotton, crudefiber crop, silkworm and mulberry; Oil plant: peanut, rape, sesame, soybean, Sunflower Receptacle; Sugar material: beet, sugarcane; Beverage: tealeaves, coffee, cocoa; Hobby: tobacco leaf; Medicinal: ginseng, the bulb of fritillary; The torrid zone: rubber, coconut, oil palm, sisal hemp; Food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, Chinese medicinal materials cash crop and plant melon, really, tea, silkworm and mulberry, vegetables, containing various wild vegetable, bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, seedling and other garden crop garden crops as tobacco: flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco; Vegetables, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, melon: watermelon, muskmelon, hami melon, pawpaw; Beans: soybean, broad bean, pea-pods; Potato, wheat, corn, paddy rice, peanut, fruit tree: apple, banana, citrus, peach, papaya; Flowers: orchid; Potted landscape; Composition improves the defence capability of plant while sterilization, makes plant create defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 12
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and antiviral agent are combined in the application prevented and treated in agriculture and forestry and gardening plant virus disease
Of the present invention containing 4-methyl isophthalic acid, 2, 4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V and existing Antiphytoviral medicament diazosulfide, tiadinil, be abbreviated as TDL, isotianil, it is English general by name: isotianil, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate, 3, 4-bis-chloroisothiazole-5-formic acid, 3, 4-bis-chloroisothiazole-5-sodium formiate, 3, 4-bis-chloroisothiazole-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, in jingganmycin, any 1 or 2 compound combinations are for preventing and treating agricultural and forestry and gardening plant virus disease, the disease of control agricultural and forestry and gardening plant virus disease is selected from tobacco mosaic virus disease, various melon virus disease, various solanaceous vegetables virus disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any one in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any one in cybidium ring spot virus.These compositions are selected from paddy for the plant preventing and treating agricultural and forestry and gardening plant virus disease, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions makes the immunizing power of crop self improve, while producing the control of insect especially infection insect, produce the defence capability to viral diseases of plants induction of plant, also can produce the direct prevention effect of virus disease, therefore, these compositions may be used for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Of the present invention containing 4-methyl isophthalic acid, 2,4 of 3-thiadiazoles, 5-thiazoline carboxylic ester derivative V total mass percentage is in the composition 1%-90%, of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and the ratio of aforementioned Antiphytoviral medicament are mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, granule, microemulsion, finish, with the seed of coated pesticidal, suspended emulsion agent, soluble thick agent, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule suspension, dispersible dense dose, missible oil, electrostatic spray agent, water-in-oil emulsion, seed treatment agent, oil-in-water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog rod, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, ointment, thermal fog, the agent of solid-liquid mixing dress, liquid/liquid mixing dress agent, cold mist agent, Gu Gu/mixing dress agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, tablet, follow the trail of pulvis, ultra low volume liquids, any one in steam releasing agent, all show addition or synergism between these compositions, while maintenance insecticidal activity, its antiviral activity is all greater than the effect that any one compound is used alone, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
Embodiment 13
Of the present invention containing 4-methyl isophthalic acid, 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and the complete processing of commercially available agricultural chemical compound preparation and stability
Of the present invention containing 4-methyl isophthalic acid, 2, 4 of 3-thiadiazoles, the mixture complete processing of 5-thiazoline carboxylic ester derivative V and commercially available agricultural chemical is in table 5, from table 5, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes effect composition, other agriculturally acceptable adjuvant components such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation places 1 week without Precipitation at 0 ± 2 degree Celsius, solid preparation is placed 2 weeks at 54 ± 2 degrees Celsius, there is not caking phenomenon in medicament, all formulation storage place the medicament drug effect of front and back without significant difference, the rate of decomposition of composition effective constituent is within 5%, composite preparation qualified stability.
Table 2 is of the present invention containing 4-methyl isophthalic acid, and 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles are to the activity of mythimna separata
| Sequence number | Compound | Mortality ratio (%) | Sequence number | Compound | Mortality ratio (%) |
| 1 | mt008-44-8 | 0 | 3 | mt008-44-18 | 38 |
| 2 | mt008-44-12 | 5 | 4 | mt008-46-1 | 45 |
72 hours measurement results; Measure concentration: 200mg/L; Measuring method: blade medicine embrane method
Table 3 is of the present invention containing 4-methyl isophthalic acid, the fungicidal activity (%) (50 μ g/mL) of 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles
| Sequence number | Compound | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| 1 | mt008-44-16 | 33.33 | 27.78 | 7.41 | 50.68 | 91.67 | 67.44 | 64.44 | 72.84 | 22.22 |
| 2 | mt008-44-9 | 28.57 | 27.78 | 3.70 | 32.88 | 50.00 | 0 | 35.56 | 46.91 | 14.81 |
| 3 | mt008-44-8 | 38.10 | 38.89 | 7.41 | 64.38 | 81.25 | 44.19 | 57.78 | 72.84 | 22.22 |
| 4 | mt008-43-2 | 0 | 18.52 | 40.63 | 60.29 | 69.39 | 52.78 | 66.67 | 63.77 | 26.92 |
| 5 | mt008-44-6 | 43.33 | 24.00 | 25.64 | 50.00 | 80.77 | 61.25 | 63.89 | 66.27 | 20.00 |
| 6 | mt008-44-21 | 17.55 | 37.21 | 42.12 | 44.43 | 55.10 | 25.28 | 47.62 | 65.22 | 15.66 |
| 7 | mt008-44-20 | 25.00 | 48.00 | 34.09 | 69.57 | 83.93 | 75.00 | 69.23 | 70.69 | 29.17 |
| 8 | mt008-44-10 | 33.33 | 32.00 | 7.69 | 48.33 | 76.92 | 50.00 | 61.11 | 68.67 | 11.43 |
| 9 | mt008-44-4 | 23.81 | 16.67 | 0 | 41.10 | 70.83 | 48.84 | 46.67 | 49.38 | 11.11 |
| 10 | mt008-44-2 | 38.10 | 22.22 | 18.52 | 42.47 | 75.00 | 51.16 | 68.89 | 72.84 | 22.22 |
| 11 | mt008-44-22 | 22.50 | 27.41 | 50.00 | 44.12 | 65.10 | 15.28 | 47.62 | 65.22 | 12.33 |
| 12 | mt008-44-1 | 33.33 | 44.44 | 11.11 | 60.27 | 70.83 | 32.56 | 57.78 | 80.25 | 25.93 |
| 13 | mt008-44-7 | 42.86 | 44.44 | 14.81 | 43.84 | 64.58 | 86.05 | 60.00 | 76.54 | 18.52 |
| 14 | mt008-44-5 | 33.33 | 33.33 | 0 | 41.10 | 72.92 | 32.56 | 48.89 | 76.54 | 11.11 |
| 15 | mt008-44-17 | 23.81 | 22.22 | 0 | 39.73 | 93.75 | 53.49 | 46.67 | 70.37 | 14.81 |
| 16 | mt008-44-3 | 36.67 | 28.00 | 2.56 | 43.33 | 82.69 | 62.50 | 59.72 | 67.47 | 17.14 |
| 17 | mt008-46-9 | 25.00 | 14.81 | 28.13 | 52.94 | 69.39 | 34.72 | 50.00 | 66.67 | 15.38 |
| 18 | mt008-44-12 | 31.43 | 21.43 | 4.26 | 33.33 | 82.76 | 4.08 | 54.55 | 67.65 | 21.74 |
| 19 | mt008-46-8 | 28.13 | 25.93 | 0 | 47.06 | 87.76 | 45.83 | 50.00 | 72.46 | 23.08 |
| 20 | mt008-46-4 | 12.50 | 7.41 | 50.00 | 44.12 | 55.10 | 15.28 | 47.62 | 65.22 | 7.69 |
| 21 | mt008-46-2 | 21.88 | 22.22 | 25.00 | 35.29 | 91.84 | 31.94 | 61.90 | 68.12 | 11.54 |
| 22 | mt008-44-19 | 30.00 | 32.00 | 10.26 | 55.00 | 63.46 | 42.50 | 54.17 | 59.04 | 17.14 |
| 23 | mt008-44-11 | 34.29 | 35.71 | 23.40 | 47.83 | 81.03 | 14.29 | 63.64 | 73.53 | 17.39 |
| 24 | mt008-44-15 | 22.86 | 17.86 | 0 | 34.78 | 60.34 | 16.33 | 52.27 | 66.18 | 21.74 |
| 26 | mt008-44-18 | 31.43 | 21.43 | 10.64 | 39.13 | 65.52 | 28.57 | 63.64 | 30.88 | 13.04 |
| 27 | mt008-46-3 | 12.30 | 32.00 | 45.23 | 24.12 | 55.80 | 20.43 | 60.09 | 35.22 | 13.69 |
| 28 | mt008-46-7 | 25.00 | 18.52 | 0 | 39.71 | 81.63 | 37.50 | 54.76 | 72.46 | 19.23 |
| 29 | mt008-46-5 | 31.25 | 22.22 | 0 | 51.47 | 91.84 | 31.94 | 57.14 | 79.71 | 30.77 |
| 30 | mt008-46-6 | 28.13 | 22.22 | 0 | 42.65 | 83.67 | 48.61 | 47.62 | 78.26 | 19.23 |
| 31 | mt008-46-1 | 28.13 | 11.11 | 12.50 | 36.76 | 89.80 | 36.11 | 52.38 | 71.01 | 15.38 |
| 32 | Azoxystrobin | 46.88 | 55.56 | 75.00 | 91.18 | 71.43 | 100 | 88.10 | 84.06 | 80.77 |
Table 4 contains 4-methyl isophthalic acid, the activity (inhibiting rate/% of 50 μ g/mL) of 4,5-thiazoline carboxylic ester derivative V resisting tobacco mosaic virus of 2,3-thiadiazoles
| Sequence number | Compound | Treatment | Passivation | Protection | Induction |
| 1 | mt008-44-16 | 10.05±7.16 | 23.59±4.94 | 37.56±4.30 | 37.31±5.97 16 --> |
| 2 | mt008-44-9 | 25.92±9.03 | 22.56±3.87 | 22.07±3.54 | 28.36±2.99 |
| 3 | mt008-44-8 | 13.23±5.57 | 27.69±5.55 | 33.80±2.82 | 29.85±5.38 |
| 4 | mt008-43-2 | 36.51±6.35 | 16.41±6.41 | 30.98±5.08 | 35.82±5.97 |
| 5 | mt008-44-6 | 34.92±5.72 | 21.03±8.47 | 14.55±4.95 | 24.38±6.73 |
| 6 | mt008-44-21 | 20.84±3.93 | 40.00±4.07 | 41.94±3.54 | 8.33±3.11 |
| 7 | mt008-44-20 | 30.84±6.51 | 20.17±1.67 | 21.22±1.62 | 18.33±3.93 |
| 8 | mt008-44-10 | 32.28±6.42 | 23.08±7.05 | 12.68±4.23 | 32.84±5.97 |
| 9 | mt008-44-4 | 10.05±6.42 | 18.97±8.47 | 40.38±4.95 | 29.85±5.97 |
| 10 | mt008-44-2 | 23.28±5.10 | 34.36±7.75 | 29.58±4.23 | 30.84±6.73 |
| 11 | mt008-44-22 | 23.28±6.42 | 25.64±4.70 | 23.12±3.54 | 27.86±6.03 |
| 12 | mt008-44-1 | 23.28±3.99 | 28.72±4.70 | 14.55±4.95 | 25.87±4.56 |
| 13 | mt008-44-7 | 24.34±4.85 | 23.59±6.42 | 25.82±4.30 | 15.92±6.21 |
| 14 | mt008-44-5 | 16.40±5.57 | 26.15±7.05 | 41.79±4.30 | 21.40±6.73 |
| 15 | mt008-44-17 | 11.64±7.16 | 31.80±6.93 | 34.27±5.69 | 22.89±5.65 |
| 16 | mt008-44-3 | 20.63±5.72 | 35.39±5.55 | 23.47±6.35 | 26.87±6.84 |
| 17 | mt008-46-9 | 29.10±5.57 | 25.64±5.40 | 23.48±2.93 | 32.84±4.48 |
| 18 | mt008-44-12 | 34.39±6.42 | 27.69±5.55 | 22.07±3.54 | 38.81±4.48 |
| 19 | mt008-46-8 | 20.10±2.42 | 23.08±4.07 | 35.68±2.94 | 21.39±3.11 |
| 20 | mt008-46-4 | 16.93±7.16 | 29.74±3.88 | 25.35±5.08 | 16.92±3.76 |
| 21 | mt008-46-2 | 27.51±6.42 | 23.59±3.87 | 21.13±5.64 | 20.90±5.38 |
| 22 | mt008-44-19 | 23.28±3.99 | 25.64±6.22 | 21.13±4.23 | 27.86±6.03 |
| 23 | mt008-44-11 | 16.40±5.57 | 22.56±5.40 | 13.61±3.54 | 24.87±5.24 |
| 24 | mt008-44-15 | 17.46±7.28 | 20.51±7.74 | 14.55±3.54 | 19.90±4.56 |
| 25 | mt008-44-18 | 18.52±2.42 | 13.84±3.87 | 25.82±2.93 | 21.89±4.48 |
| 26 | mt008-46-3 | 26.47±5.30 | 9.52±6.35 | 23.08±5.55 | 22.73±4.55 |
| 27 | mt008-46-7 | 31.22±5.57 | 20.00±5.55 | 28.17±4.23 | 29.35±6.03 |
| 28 | mt008-46-5 | 31.75±4.77 | 28.72±7.89 | 15.02±3.54 | 27.86±5.24 |
| 29 | mt008-46-6 | 19.05±5.72 | 18.46±7.05 | 38.50±5.69 | 39.30±3.75 |
| 30 | mt008-46-1 | 15.87±7.28 | 20.51±6.21 | 40.38±4.30 | 37.81±6.03 |
| 31 | Virazole | 34.39±7.99 | 40.51±3.21 | 44.60±4.30 | 24.88±4.56 |
| 32 | Ningnanmycin | 27.08±5.48 | 45.64±2.35 | 43.19±3.54 | 28.36±2.99 |
| 33 | TDL | 31.75±4.77 | 26.15±3.08 | 26.76±5.07 | 43.28±2.99 |
Table 5 containing 4-methyl isophthalic acid, the working method that 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles are mixed with commercially available agricultural chemical
。
Claims (3)
1. a class is containing 4-methyl isophthalic acid, and 4,5-thiazoline carboxylic ester derivatives of 2,3-thiadiazoles, is characterized in that having the chemical structure of general formula such as formula shown in V:
Wherein: R is selected from cyclohexyl, o-tolyl, between tolyl, p-methylphenyl, to ethylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, O-Nitrophenylfluorone, 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, the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base.
2. a class described in claim 1 is containing 4-methyl isophthalic acid, the synthetic method of 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles, and concrete synthetic route is as follows:
Wherein: R is selected from cyclohexyl, o-tolyl, between tolyl, p-methylphenyl, to ethylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, Chloro-O-Phenyl, between chloro-phenyl-, rubigan, adjacent fluorophenyl, between fluorophenyl, to fluorophenyl, O-Nitrophenylfluorone, 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, the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base,
Part of compounds adopts to be prepared according to the following formula with the direct method of condensing of acid:
Wherein, R is selected from: the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-base, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 2-chloropyridine-3-base;
Specifically be divided into following steps:
A.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formyl ammonia II
Ethanol 80 milliliters, 5-methyl isophthalic acid is once added in 250 milliliters of single necked round bottom flask, 2,3-thiadiazoles-4-ethyl formate 17.2 grams, i.e. 100 mmoles, the 25% strong aqua aqueous solution 80 milliliters, stirring at room temperature 12 hours, be cooled to 0 degree Celsius, filter to obtain white solid, use a small amount of washing with alcohol, by gained sterling calculated yield, yield 98%;
B. intermediate 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-sulfo-formyl ammonia III:
Initial reactant 4-methyl isophthalic acid is added in 250 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-formyl ammonia II14.3 gram, i.e. 100 mmoles, toluene 150 milliliters, lawesson reagent and Lawesson ' sReagent24.2 gram, i.e. 60 mmoles, nitrogen protection stirring and refluxing 4 hours, by reaction solution concentrated removing toluene after reaction terminates, resistates obtains faint yellow solid 4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 3: 1; By gained sterling calculated yield, yield 75%;
C. the preparation of intermediate 2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV:
4-methyl isophthalic acid is added, 2,3-thiadiazoles-5-sulfo-formyl ammonia III7.96 gram, i.e. 50 mmoles, the dehydrated alcohol 60 milliliters that processed in 100 milliliters of three mouthfuls of round-bottomed flasks, stir, then add 3-bromo-1,1,1-trifluoroacetone 9.6 grams, i.e. 50 mmoles, nitrogen protection stirring and refluxing 16 hours; By reaction solution concentrated removing toluene after reaction terminates, resistates obtains faint yellow solid 4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-sulfo-formyl ammonia III, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and volume ratio is 10: 1; By gained sterling calculated yield, yield 70%;
D.2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method one:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, dry methylene dichloride 8 milliliters, triethylamine 0.15 gram, i.e. 1.5 mmoles, ice-water bath is cooled to 0 degree Celsius, then slowly drip the 7mL dichloromethane solution of various substituted formyl chlorine 1.2 mmole, reaction solution slowly rises to room temperature and stirs 4 ~ 10 hours according to the difference of substrate, after having reacted, dchloromethane to 30 milliliter, 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-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, and according to the difference of product, volume ratio is between 15: 1 ~ 3: 1, by gained sterling calculated yield, yield 60-90%, described substituted formyl chlorine is selected from: cyclohexyl formyl chloride, adjacent toluyl chlorine, between toluyl chlorine, Butyltriphenylphosphonium chloride, p-ethylbenzoyl chloride, methoxy benzoyl chloride, meta-methoxy Benzoyl chloride, anisoyl chloride, o-chlorobenzoyl chloride, m-chlorobenzoyl chloride, parachlorobenzoyl chloride, o-fluoro-benzoyl chloride, between fluorobenzoyl chloride, to fluorobenzoyl chloride, 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-isoxazole-4-formyl chloride,
E.2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V preparation method two:
Intermediate 2-(4-methyl isophthalic acid is added in 50 milliliters of three mouthfuls of round-bottomed flasks, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-alcohol IV0.27 gram, i.e. 1.0 mmoles, dry methylene dichloride 8 milliliters, triethylamine 0.15 gram, i.e. 1.0 mmoles, various heterocyclic substituted formic acid 1.2 mmole, stir, dicyclohexylcarbodiimide 0.25 gram is dripped by syringe under nitrogen protection after being cooled to 0 degree Celsius, the i.e. dichloromethane solution of 1.2 mmoles, dropwises for 10 minutes; Reaction solution rises to rt while stirring overnight; React complete removing insolubles, rotary evaporation is except desolventizing, thick product obtains faint yellow solid 2-(4-methyl isophthalic acid through 200 ~ 300 order purification by silica gel column chromatography, 2,3-thiadiazoles-5-base)-4-(trifluoromethyl)-4,5-thiazoline-4-polyol carboxylic acid ester V, eluent is the sherwood oil of 60 ~ 90 degrees Celsius: ethyl acetate, according to the difference of product, volume ratio is between 15: 1 ~ 3: 1; By gained sterling calculated yield, productive rate 60-90%; Described heterocyclic substituted formic acid is selected from: the bromo-1-of 3-(3-chloropyridine-2-base)-pyrazoles-5-formic acid, pyridine-2-formic acid, Nicotinicum Acidum, pyridine-4-formic acid, 2-chloropyridine-3-formic acid.
3. a class according to claim 1 is containing 4-methyl isophthalic acid, and the purposes in anti-plant virus agent prepared by 4,5-thiazoline carboxylic ester derivative V of 2,3-thiadiazoles and agriculturally acceptable auxiliary agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072657C (en) * | 1996-09-30 | 2001-10-10 | 日本农药株式会社 | 1,2,3-thiadiazole derivs. and salts thereof, disease agent for agricultural and horticultural use and method for use thereof |
| WO1999052882A1 (en) * | 1998-04-13 | 1999-10-21 | Nihon Nohyaku Co., Ltd. | 1,2,3-thiadiazole derivative or salt thereof and pest control agent, and method of use thereof |
| CN1346827A (en) * | 2001-10-26 | 2002-05-01 | 南开大学 | 1,2,3-thiadiazole compounds, and their preparing process and bioactivity |
| JP2005330258A (en) * | 2004-04-23 | 2005-12-02 | Sumitomo Chemical Co Ltd | Thiazoline compound and its use for controlling plant disease |
| CN101343269A (en) * | 2008-08-28 | 2009-01-14 | 南开大学 | 1,2,3-thiadiazoles derivants, synthesis and use thereof |
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