CN102633747A - 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof - Google Patents
5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102633747A CN102633747A CN2012100970780A CN201210097078A CN102633747A CN 102633747 A CN102633747 A CN 102633747A CN 2012100970780 A CN2012100970780 A CN 2012100970780A CN 201210097078 A CN201210097078 A CN 201210097078A CN 102633747 A CN102633747 A CN 102633747A
- Authority
- CN
- China
- Prior art keywords
- agent
- thiadiazoles
- isophthalic acid
- methyl isophthalic
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as a preparation method and application thereof and relates to heterocyclic compounds containing 1, 2, 3-thiadiazole which have the chemical structure general formula as shown in I. The invention discloses the structure general formula and the synthetic method of the compounds, the application of the compounds as insecticides, bactericides, plant virtues resisting agents and plant activators and a processing technology for preparing the insecticides, the bactericides, the plant virtues resisting agents and the plant activators by mixing the compounds with agriculturally acceptable auxiliaries or synergists. The invention further discloses the application of combination of the compounds, commercial insecticides, miticides, the bactericides, the plant virtues resisting agent and the plant activators in the aspects of preventing and controlling agricultural, forestry and horticultural diseases, insect pests, mite damages and virus diseases and the preparation method of the compounds.
Description
Technical field
Technical scheme of the present invention relates to the 1,2-diazole compound, is specifically related to the 5-methyl isophthalic acid, and 2,3-thiadiazoles bishydrazide verivate.
Background technology
The scientists of Rohm-Hass company in 1988 finds that bishydrazide compounds RH-5849 can cause phenomenons such as tested insect is precocious, abnormal not exclusively, lethality is casted off a skin; One type of new insect growth regulator(IGR)-moulting hormone antagonist thus has been born; Make the moulting hormone analogue move towards practicability (Wing K D.RH 5849, a nonsteroidal ecdysone agonist:effects on a drosophila cell line, Sci.; 1988,241:467-469.).Subsequently on the basis of RH-5849, Rohm-Hass company successively develops RH-5992, RH-0345, RH-2485, and (Le D.P. is etc., RH-2485:a new selective insecticide for caterpillar control; Brighton Crop Prot Conf Pests Dis.Farnham, Surrey, UK:BCPC, 1996; 2:481-486.), Japanese Nippon Kayaku Co.Ltd and Sankyo Co.Ltd develop ANS-118 cooperatively (Yanagi M are etc., ANS-118:A novel insecticide.Brighton Crop Prot Conf Pests Dis.Farnham; Surrey, UK:BCPC, 2000,2:27-32.); People such as Zhang Xiangning formulate out JS-118, and (Zhang Xiangning is etc., the synthetic and biological activity of innovation bishydrazide insect growth regulator(IGR) JS118; Agricultural chemicals, 2003,42 (12): 18-20.).This compounds becomes after neotonin, chitin synthesis inhibitor, and another type commercial insect growth regulator(IGR) is widely used in the control of insect, has good development prospect.
There is different opinions in the different research groups of the research of relevant bishydrazide compounds structure structure activity relationship; The Qian Xuhong of East China University of Science once utilized the molecular simulation method; Adopt the single argument parameter interatomic distance R relevant with 3-d modelling; Established the quantitative structure-activity relation that halogen list on the aromatic ring substitutes onto the two acylhydrazine insect growth regulator(IGR)s of polysubstituted N-tertiary butyl (quantitative structure-activity relation of Qian Xuhong .N-tertiary butyl dibenzoyl hydrazine insect growth regulator(IGR). chemistry world, 1995,36 (supplementary issues): 35.); Japan three altogether companies is added to the structure of RH-5992 on the steroid structure; (Yoshihiro Sawada is etc., Synthesis and insecticidal activity of benzoheterocyclic analogues of N '-benzoyl-N-(tert-butyl) benzohydrazide to obtain simple two-dimensional stack model; Pest Manag.Sci.2003,1:49-57.).
1,2, the 3-thiadiazole compound has wide biological activity equally, and relevant patent and document are summed up and seen Bakulev, et al.Newyork:John Wiley & Sons; Inc, 2004 monograph, the research of relevant thiadiazoles mainly concentrates on 1,3; 4-thiadiazoles derivative, 1,2,5-thiadiazoles derivative and 1,2; On the 4-thiadiazoles derivative, and for 1,2, the active research report of 3-thiadiazoles derivative is but less relatively; With 1,2,3-thiadiazoles group is introduced the synthetic rarely seen report of new compound of bishydrazide structure; Contriver seminar early-stage Study is found, with 4-methyl isophthalic acid, 2; The 3-thiadiazoles is introduced bishydrazide structure synthetic new compound and is had excellent insecticidal activity (Fan Zhijin; Deng, the patent No.: ZL 201010187048.X, Granted publication number: CN 101891708B).1,2,3-thiadiazoles derivative commercial kind in medicine and agricultural chemicals is few, and agriculture field is used has only cotton defoliant--the clever (N-phenyl-N '-1 of disleave; 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.
In order to seek 1,2 of high biological activity more, 3-thiadiazole new compound; The present invention is the 5-methyl isophthalic acid, and 2, the 3-thiadiazoles is introduced in the bishydrazide molecule; One type of 5-methyl isophthalic acid has been synthesized in design, and 2,3-thiadiazoles bishydrazide verivate; And carried out the bioactive screening of system, in the hope of the candidate compound being provided for novel pesticide initiative research.
Summary of the invention
Technical problem to be solved by this invention is: new 5-methyl isophthalic acid is provided; 2; The compound method of 3-thiadiazoles bishydrazide verivate; 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: the 5-methyl isophthalic acid with agriculture field, gardening field, forestry and health field insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, insect growth regulator activity; 2, the chemical structure of general formula of 3-thiadiazoles bishydrazide verivate is seen formula I:
General formula I:
Wherein, R
1Be selected from: o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, to cyano-phenyl, 3; 5-3,5-dimethylphenyl, 3-methoxyl group-2-aminomethyl phenyl, 3; 5-dichlorophenyl, 2; 6-dichlorophenyl, 3; The 5-dinitrophenyl, to chlorophenylmethyl, 2; 4-dichlorobenzene methyl, 1-naphthyl, 2-chloropyridine-3-base, 2-chloropyridine-5-base, 2; 5-dichloropyridine-6-base, furans-2-base, thiophene-2-base, 2-methyl ethylene, cyclopropyl, cyclohexyl, 1-cyclopentyl ethyl, 5-ethyl-1-methylpyrazole-3-base, 5-methyl isophthalic acid, 2, the group of 3-thiadiazoles-4-base.
The compound method of N-of the present invention (5-methyl isophthalic acid, 2,3-thiadiazoles-4-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine compound I is following:
Wherein, R
1Be selected from: o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, to cyano-phenyl, 3; 5-3,5-dimethylphenyl, 3-methoxyl group-2-aminomethyl phenyl, 3; 5-dichlorophenyl, 2; 6-dichlorophenyl, 3; The 5-dinitrophenyl, to chlorophenylmethyl, 2; 4-dichlorobenzene methyl, 1-naphthyl, 2-chloropyridine-3-base, 2-chloropyridine-5-base, 2; 5-dichloropyridine-6-base, furans-2-base, thiophene-2-base, 2-methyl ethylene, cyclopropyl, cyclohexyl, 1-cyclopentyl ethyl, 5-ethyl-1-methylpyrazole-3-base, 5-methyl isophthalic acid, 2, the group of 3-thiadiazoles-4-base.
Specifically be divided into following steps:
A. midbody 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl chloride:
With the 5-methyl isophthalic acid of 67 mmoles, 2,3-thiadiazoles-4-formic acid and 30 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks; 80 degrees centigrade of following reflux 6 hours remove excessive thionyl chloride under reduced pressure, and underpressure distillation is collected 94-96 degree centigrade cut and got faint yellow product 9.25 grams under 2000Pa; Yield 85%, midbody 5-methyl isophthalic acid, 2; The 3-thiadiazoles-sealing of 4-formyl chloride is kept in the moisture eliminator subsequent use; The 5-methyl isophthalic acid, 2, the amount of 3-thiadiazoles-4-formyl chloride preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles.
B. the preparation of intermediate N (5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine:
In 250 milliliters two-mouth bottle, add 31 mmole tertiary butyl hydrazonium salt hydrochlorates, add 60 milliliters of methylene dichloride again and make solvent, under condition of ice bath, add 10 ml water solution of 31 mmole sodium hydroxide; Stir after 20 minutes the 5-methyl isophthalic acid that is dissolved in 26 mmoles in 30 milliliters of dichloromethane solutions, 2,3-thiadiazoles-4-formyl chloride slowly is added drop-wise in the reaction flask; Remove ice bath, room temperature reaction 5 hours closes organic layer after the reaction solution washing and spends the night with anhydrous sodium sulfate drying; Suction filtration is removed SODIUM SULPHATE ANHYDROUS 99PCT, and rotary evaporation removes and desolvates, and obtains faint yellow blocks of solid 4.05g; Yield 72%; Be intermediate N (5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine; The amount of synthetic compound enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles, commercially available 5-methyl isophthalic acid, and 2,3-thiadiazoles-4-formyl chloride has same effect.
C. the preparation of substituted formyl chlorine:
The replacing acid that in 50 milliliters of round-bottomed flasks, adds 0.2 mmole adds the sulfur oxychloride of 1.2 mmoles again, and with oil bath reflux 3-4 hour, air distillation obtained substituted formyl chlorine after going out unreacted sulfur oxychloride with reaction mixture, and the sealing preservation is subsequent use; The amount of substituted formyl chlorine preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles, and commercially available substituted formyl chlorine has same effect.
D.5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles bishydrazide verivate: N-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine compound I:
Get 0.1 mmole N-(5-methyl isophthalic acid; 2; 3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; Join in 50 milliliters of round-bottomed flasks, add 0.12 mmole acid binding agent triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole substituted formyl chlorine down; At room temperature continued stirring reaction after dripping 4 hours, after reaction finished, reaction mixture was with washing 3 times; Anhydrous sodium sulfate drying spends the night, and filters back decompression precipitation, and crude product is with the ethyl acetate petroleum ether recrystallization or with 200-300 order purification by silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE volume ratio 3: 1 gets N-(5-methyl isophthalic acid, 2; 3-thiadiazoles-4-formyl radical)-the N '-tertiary butyl-N '-pure article of substituted formyl hydrazine class compound I, carry out fusing point,
1The mensuration of HNMR is confirmed its chemical structure, and the amount of compound I preparation enlarges by corresponding proportion or dwindles; The structure of compound I is seen table 1.
E. 5-methyl isophthalic acid of the present invention, 2,3-thiadiazoles bishydrazide derivative I is to the mensuration of small cabbage moth insecticidal activity:
5-methyl isophthalic acid of the present invention, 2,3-thiadiazoles bishydrazide derivative I is following to the screening method of the insecticidal activity of small cabbage moth: adopt the blade medicine embrane method; The solution that sample to be tested is mixed with 400 mcg/ml carries out; Get former medicine sample earlier with the small amount of acetone dissolving, then with the dilution of the 0.5 ‰ Triton-100 aqueous solution, the 0.5 ‰ Triton-100 aqueous solution are contrast; Each concentration repeats for 3 times, 10 examinations of each re-treatment worm; Get fresh free of contamination cabbage leaves, in soup, soaked for 10 seconds, after indoor drying (about 2 hours); Put into the petridish of 9 centimetres of diameters; Insert small cabbage moth 2 instar larvaes of big or small basically identical respectively, tighten with bungee and be placed in the small cabbage moth constant temperature insectary check result after 96 hours or 120 hours; Touch polypide with little writing brush or tweezers, can not coordinated movement as death; With the positive contrast of methoxyfenozide.
F. 5-methyl isophthalic acid of the present invention, 2,3-thiadiazoles bishydrazide derivative I is to the mensuration of pathogenic fungi fungicidal activity:
5-methyl isophthalic acid of the present invention, 2, derivative I sterilization of 3-thiadiazoles bishydrazide or bacteriostatic activity adopt thalli growth rate assay method; Detailed process is: get 5 milligrams of sample dissolution in an amount of N, with containing the medicament that a certain amount of polysorbas20 emulsifier aqueous solution is diluted to 500 mcg/ml, will supply the reagent agent under aseptic condition, respectively to draw in 1 milliliter of injection petridish then; Add 9 milliliters of substratum more respectively, it is dull and stereotyped to process 50 mcg/ml pastilles after shaking up, and does 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, be equilateral triangle and put, every processing repetition 3 times; Petridish 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, averages, and relatively calculates relative bacteriostasis rate with blank; Supply the examination bacterial classification to comprise the kind of most of phytopathogen of the actual generation in multiple representative field in China's agriculture prodn, 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).
G. 5-methyl isophthalic acid of the present invention, 2, the mensuration of 3-thiadiazoles bishydrazide derivative I inducing anti-disease activity:
5-methyl isophthalic acid of the present invention, 2, the active screening method of 3-thiadiazoles bishydrazide derivative I 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) .5-methyl isophthalic acid, 2, the active screening method of the 3-thiadiazoles bishydrazide anti-TMV of derivative I evoking tobacco: the mensuration of the direct antiviral activity that exsomatizes adopts half leaf method to carry out; It is the common cigarette that seedling age is consistent that live body is induced, and 3 basins are one group, respectively at the cigarette seedling of inoculation pre-treatment in preceding 7 days; Processing mode comprises: spray test compound solution 2 to 3 times, and each 10 milliliters, or soil treating; Each 10 milliliters, measuring concentration is 50 mcg/ml, the 7th day frictional inoculation TMV on the tobacco leaf that newly grows; The cigarette seedling is placed its growth optimal temperature and illumination, and cultivation is after 3 days down, and inspection incidence, comprehensive scab number are calculated as follows out the inducing anti-disease toxic effect fruit of test compound to TMV; 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.
The invention has the beneficial effects as follows: the present invention is to the 5-methyl isophthalic acid; 2; 3-thiadiazoles bishydrazide derivative I has carried out the optimization of first guide structure; And the synthetic new compound carried out the mensuration of desinsection, antibacterial and inducing anti-disease activity, anti-phytoviral activity and mixed the research of using, this compounds can be used for disease, insect pest and the virus disease control in agriculture field, field of forestry, gardening field.
The present invention will use the formulation of complete processing and selection as embodiment the 5-methyl isophthalic acid to be described more specifically through specific preparation and biological activity determination and with the commercially available agricultural chemical combination; 2; Synthetic and the biological activity and the application thereof of 3-thiadiazoles bishydrazide derivative I, unrestricted the present invention, especially its biological activity and complete processing only illustrate but said embodiment only is used for bright specifically the present invention; And unrestricted this patent, embodiment is following:
Embodiment 1
Midbody 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl chloride:
With the 5-methyl isophthalic acid of 67 mmoles, 2,3-thiadiazoles-4-formic acid and 30 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks; 80 degrees centigrade of following reflux 6 hours remove excessive thionyl chloride under reduced pressure, and underpressure distillation is collected 94-96 degree centigrade cut and got faint yellow product 9.25 grams under 2000Pa; Yield 85%; Midbody 5-methyl isophthalic acid, 2, the 3-thiadiazoles-sealing of 4-formyl chloride is kept in the moisture eliminator subsequent use.
Embodiment 2
The preparation of intermediate N (5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine:
In 250 milliliters two-mouth bottle, add 31 mmole tertiary butyl hydrazonium salt hydrochlorates, add 60 milliliters of methylene dichloride again and make solvent, under condition of ice bath, add 10 ml water solution of 31 mmole sodium hydroxide; Stir after 20 minutes the 5-methyl isophthalic acid that is dissolved in 26 mmoles in 30 milliliters of dichloromethane solutions, 2,3-thiadiazoles-4-formyl chloride slowly is added drop-wise in the reaction flask; Remove ice bath, room temperature reaction 5 hours closes organic layer after the reaction solution washing and spends the night with anhydrous sodium sulfate drying; Suction filtration is removed SODIUM SULPHATE ANHYDROUS 99PCT; Rotary evaporation removes and desolvates, and gets intermediate N (5-methyl isophthalic acid, 2; 3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine is faint yellow blocks of solid 4.05g, yield 72%.
Embodiment 3
The preparation of substituted formyl chlorine:
The replacing acid that in 50 milliliters of round-bottomed flasks, adds 0.2 mmole adds the sulfur oxychloride of 1.2 mmoles again, and with oil bath reflux 3-4 hour, air distillation obtained substituted formyl chlorine after going out unreacted sulfur oxychloride with reaction mixture, and the sealing preservation is subsequent use.
Embodiment 4
The 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles bishydrazide verivate: N-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine compound I:
Get 0.1 mmole N-(5-methyl isophthalic acid; 2; 3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; Join in 50 milliliters of round-bottomed flasks, add 0.12 mmole acid binding agent triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole substituted formyl chlorine down; At room temperature continued stirring reaction after dripping 4 hours, after reaction finished, reaction mixture was with washing 3 times; Anhydrous sodium sulfate drying spends the night, and filters back decompression precipitation, and crude product is with the ethyl acetate petroleum ether recrystallization or with 200-300 order purification by silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE volume ratio 3: 1 gets N-(5-methyl isophthalic acid, 2; 3-thiadiazoles-4-formyl radical)-the N '-tertiary butyl-N '-pure article of substituted formyl hydrazine class compound I, carry out fusing point,
1The mensuration of HNMR is confirmed its chemical structure; The structure of compound I is seen table 1.
Embodiment 5: 5-methyl isophthalic acid of the present invention, 2, the bacteriostatic activity of 3-thiadiazoles bishydrazide derivative I
The title and the code name of frequently seen plants pathogenic fungi comprise AS on the agricultural of the present invention's test: tomato early blight bacterium (Alternariasolani); CA: peanut Cercospora bacteria (Cercosporaarachidicola); GZ: fusarium graminearum (Gibberellazeae); PP: ring rot of apple bacterium (Physalosporapiricola); BC: botrytis cinerea pers (Botrytiscinerea); SS: Sclerotinia sclerotiorum (Sclerotiasclerotium); RC: cereal rhizoctonia (Rhizoctoniacerealis); PS: Rhizoctonia solani Kuhn (Pelliculariasasakii); PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary), these bacterial classifications can be represented the kind of most of pathogenic bacteria that the field takes place in the agriculture prodn.Thalli growth rate method is measured the result and is seen table 3; Table 3 shows; When 50 mcg/ml, most of 5-methyl isophthalic acid of the present invention, 2; 3-thiadiazoles bishydrazide derivative I has restraining effect in various degree to the growth of most of pathogenic fungi of mensuration, and especially outstanding is that synthetic compound WH-6-19-1 of the present invention, WH-5-40 are higher than 80% to the fungicidal activity of SS; WH-6-28-2 is higher than 70% to the fungicidal activity of PP; WH-5-45-3, WH-6-25-2, WH-7-10-1-(2), WH-6-34-2-(1), WH-7-6-2, WH-7-7-1-(1), WH-6-45-2-(2), WH-7-7-2-(1), WH-7-8-2, WH-7-10-2-(2) are higher than 70% to the fungicidal activity of SS; WH-6-8-A,, WH-6-20-2, WH-6-28-2, WH-6-4-(2) be higher than 60% to the fungicidal activity of SS; WH-6-4-(2), WH-6-39-2-(2) are higher than 60% to the fungicidal activity of RC; WH-5-42, WH-6-22-2, WH-6-48-2, WH-6-39-2-(2), WH-6-47-1-(2) are higher than 50% to the fungicidal activity of BC; WH-6-47-1-(2), WH-7-8-1 are higher than 50% to the fungicidal activity of SS; WH-6-15, WH-6-17, WH-6-25-2, WH-6-28-2, WH-6-48-2, WH-6-35-2, WH-6-40-2, WH-7-8-2, WH-6-43-2-(1) are higher than 50% to the fungicidal activity of RC; WH-6-28-2 is higher than 50% to the fungicidal activity of PS; WH-5-42 is higher than 40% to the fungicidal activity of GZ; WH-5-38, WH-5-47, WH-6-19-1, WH-6-24-2, WH-6-4-(2), WH-6-34-2-(1), WH-6-48-1WH-6-39-2-(2), WH-7-7-2-(1) are higher than 40% to the fungicidal activity of PP; WH-5-34, WH-5-50, WH-5-45-3, WH-6-8-A, WH-6-24-2, WH-6-29-2, WH-6-30-2, WH-6-35-2, WH-6-48-1, WH-6-43-2-(1) are higher than 40% to the fungicidal activity of BC; WH-6-40-2 is higher than 40% to the fungicidal activity of SS; WH-5-34, WH-5-38, WH-5-42, WH-5-45-3, WH-6-8-A, WH-6-20-2, WH-6-19-1, WH-6-22-2, WH-6-29-2, WH-6-30-2, WH-6-31-2, WH-7-10-1-(2), WH-6-33-2, WH-6-48-1, WH-6-46-2, WH-7-7-1-(1), WH-6-44-2, WH-6-47-1-(2), WH-7-8-1 are higher than 40% to the fungicidal activity of RC; WH-5-42, WH-6-17, WH-6-22-2, WH-6-35-2, WH-6-46-2 are higher than 40% to the fungicidal activity of PS; Therefore, this compounds has shown fungicidal activity preferably.
Embodiment 6: 5-methyl isophthalic acid of the present invention, 2, the effect of 3-thiadiazoles bishydrazide derivative I evoking tobacco resisting tobacco mosaic virus
The mensuration result of antiviral activity and induced activity sees table 4; Table 4 shows; The plant inducing anti-disease activator tiadinil of standard has the activity of good protection and passivation TMV; Well evoking tobacco produces the resistance to TMV, but the antiviral agent virazole has well directly antiviral activity, but does not almost have induced activity; Most of 5-methyl isophthalic acid of the present invention, 2,3-thiadiazoles bishydrazide derivative I has the activity of direct anti-TMV preferably, and the therapeutic activity of WH-6-31-2 is higher than 70%; The induced activity of WH-5-50 is higher than 70%; The therapeutic activity of WH-5-50, WH-6-35-2, WH-6-33-2 is higher than 60%; The inactivate activity of WH-5-50, WH-6-8-A, WH-6-24-2, WH-6-48-2, WH-6-35-2, WH-6-33-2, WH-6-39-2-(2), WH-5-40 is higher than 60%; The induced activity of WH-6-8-A, WH-6-24-2, WH-6-30-2, WH-6-4-(2) is higher than 60%; The therapeutic activity of WH-5-47, WH-6-17, WH-6-30-2, WH-6-4-(2), WH-6-40-2, WH-6-44-2 is higher than 50%; The inactivate activity of WH-6-29-2, WH-6-40-2, WH-6-47-1-(2), WH-6-43-2-(1) is higher than 50%; The protection activity of WH-5-42, WH-6-20-2, WH-6-19-1, WH-6-30-2, WH-6-47-1-(2) is higher than 50%; The induced activity of WH-5-34, WH-6-22-2, WH-6-25-2, WH-6-46-2, WH-5-40 is higher than 50%; The therapeutic activity of WH-5-42, WH-6-22-2, WH-6-48-2, WH-6-34-2-(1), WH-6-46-2, WH-6-45-2-(2), WH-6-43-2-(1) is higher than 40%; The inactivate activity of WH-5-34, WH-6-17, WH-6-20-2, WH-6-25-2, WH-6-31-2, WH-6-44-2 is higher than 40%; The protection activity of WH-5-50, WH-6-15, WH-7-10-1-(2), WH-7-7-1-(1) is higher than 40%; The induced activity of WH-5-42, WH-5-47, WH-6-15, WH-6-17, WH-6-34-2-(1), WH-6-48-1, WH-6-40-2, WH-7-6-2, WH-7-7-1-(1), WH-6-44-2, WH-6-47-1-(2) is higher than 40%; The half leaf activity that the half leaf activity of WH-6-34-2-(1) is higher than 30%WH-5-34, WH-5-42, WH-5-50, WH-6-8-A, WH-6-30-2, WH-6-31-2, WH-7-10-1-(2), WH-6-4-(2), WH-6-39-2-(2), WH-6-46-2, WH-7-7-1-(1), WH-7-10-2-(2), WH-5-40 is higher than 20%; Other compounds all have in various degree directly antiviral activity and induced activity.Above-claimed cpd has become to have the 5-methyl isophthalic acid of inducing anti-disease cytotoxic activity at the tobacco vivo degradation; 2,3-thiadiazoles-4-formic acid is seen from chemical structure; C=O in the 4-position all can be by water molecules or the attack of OH-ion in plant materials for all compounds of the present invention; Thereby hydrolysis goes out the 5-methyl isophthalic acid, 2, and 3-thiadiazoles-4-formic acid.Therefore, compound of the present invention has Antiphytoviral and inducing plant and produces the effect that viral diseases of plants is produced resistance.
Embodiment 7: 5-methyl isophthalic acid of the present invention, 2, the insecticidal activity of 3-thiadiazoles bishydrazide derivative I
Bioassay results is seen table 2; Table 2 shows, the most of 5-methyl isophthalic acid of synthetic of the present invention, 2; 3-thiadiazoles bishydrazide derivative I has insecticidal activity preferably; Activity as far as small cabbage moth: when 400 mcg/ml, compound WH-6-8-A, WH-6-15, WH-6-25-2, WH-6-24-2, WH-6-48-2, WH-6-4-(2), WH-6-40-2, WH-6-45-2-(2), WH-6-47-1-(2) have certain insecticidal activity, and wherein the insecticidal activity of WH-6-15 is higher than 20%; The insecticidal activity of WH-6-8-A, WH-6-4-(2), WH-6-40-2 is higher than 10%, is lower than the insecticidal activity of positive control medicament methoxyfenozide.
Embodiment 8
5-methyl isophthalic acid of the present invention, 2, the application in 3-thiadiazoles bishydrazide derivative I and sterilant combination control agricultural and forestry and the gardening plant insect pest
All 5-methyl isophthalic acids of the present invention; 2; 3-thiadiazoles bishydrazide derivative I and existing sterilant: Chlorpyrifos 94, inferior Nong, acetamiprid, Affirm (Merck Co.), more visit that rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, PP-383, beta_cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-FCR-1272, FCR-1272, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, WL 43479, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, the young urea that goes out, Teflubenzuron, deinsectization are grand, fluorine bell urea, WL 115110, pyridine worm are grand, Acarus tritici urea, poisonous insect urea, penfluron, Noviflumuron are noviflumuron, its CAS number for 121451-02-3, flucycloxuron, Novaluron be Rimon, fluorine pyridine urea, Bay sir 6874 promptly { 1-[(3.5-two chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 promptly [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, promptly two three WL 115110s of Bistrifluron, furans worm hydrazides, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, PP-062, MTMC, isoprocarb, cartap, fenobucarb, leaf disperse, any one or two kinds of combination uses in the carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite Te, butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, PP618, ethoprophos, fluorine worm nitrile, desinsection list, disosultap, chlorine insect amide, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, pyrrole propyl ether, emaricin etc.; 5-methyl isophthalic acid of the present invention; 2, the quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%, 5-methyl isophthalic acid of the present invention; 2, the ratio of 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; Spray after can directly converting water; Comprise agricultural in its preparation and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc., Gu the formulation of compsn processing be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, 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, seed treatment suspension agent, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, big granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mix dress agent, liquid/liquid mix dress agent, cold mist agent, admittedly/mixing adorns agent, medicine lacquer, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, bold and vigorously waters in agent, stylus, the agent of kind clothing, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, tracking pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, the wet-mixing kind water-dispersible powder 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, east mole cricket, 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, 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, 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, apple Spilonota lechriaspis, brown belt length leaf roller, intends smaller apple leaf roller, 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 selects diamond drill, black cutworm, big cutworm, yellow cutworm, robber poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, oranges and tangerines swallowtail butterfly, 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, golden edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, 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, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, the outstanding cocoon ichneumon wasp of corn earworm, 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, melon trypetid, wheat leaf ash are dived fly, Americal rice leaf miner, the black fly of diving of beans stalk, frit fly, kind fly, onion fly, radish fly, full skirt chase after and post that fly, Pyrausta nubilalis (Hubern). are strictly posted fly, armyworm lacks Agricultural pests, forestry pest, gardening pest insect and sanitary insect pests such as must posting fly, and the controlling mode while also comprises double controlling; The control effect of compsn is good, and drug effect plays stably, and has certain synergism and summation action, finds to have the compsn of antagonistic action; The crop that these compsns are suitable for comprise paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, 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, yam, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
Compsn makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection in the parasiticidal defence capability that improves plant simultaneously.
Embodiment 9
5-methyl isophthalic acid of the present invention, 2, the application in 3-thiadiazoles bishydrazide derivative I and sterilant combination control agricultural and forestry and the gardening plant disease
All the present invention is 5 - methyl-1, 2,3 - thiadiazole dihydrazide derivative (I) with existing fungicides such as benzo-thiadiazole, thiazole acid bacteria amines, amides thiophene, methyl thiophene induced amine, 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid 4 - methyl-1, 2,3 - thiadiazole-5 - Sodium 4 - methyl-1, 2,3 - thiadiazole oxadiazol-5 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, Isotianil (isotianil), ribavirin, An Tuofen, Ningnanmycin or salicylic acid, Cymoxanil, thiram, ziram , mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone, Fenpropidine, thiophanate, thiophanate, metalaxyl, salicylic acid, fluorine morpholine, Dimethomorph, efficient metalaxyl, efficient Benalaxyl, double cypermethrin bacteria amine, flusulfamide, A flusulfamide, thiophene bacteria amine fluoride, fluorine amide, leaf blight phthalocyanine, cyclopropyl amine acid bacteria , cyflufenamid, cycloalkyl amine acid bacteria, cyano bacteria amine, amine silica thiabendazole, furosemide topiramate amine bacteria, penthiopyrad, diacetylene amine acid bacteria, zoxamide, ofurace, carboxin, B Bacteria Lee, iprodione, azoxystrobin, Kresoxim amines, fluoxastrobin, kresoxim, phenoxy bacteria amines, amine oxime ether bacteria, picoxystrobin, pyraclostrobin, trifloxystrobin, allyl oxime bacteria esters, allyl amine oxime bacteria, oxygen propiconazole, bromuconazole, cyproconazole, difenoconazole azole, Diniconazole, efficient diniconazole, Epoxiconazole, fenbuconazole, fluorine quinazoline, fluorosilicone azole, Flutriafol, Hexaconazole, imines azole, Ipconazole, Metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, PTFE ether , triazole alcohol, sterilization azole, Bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, triflumizole, Cyazofamid, imidazole cycloheximide, evil imidazole, pefurazoate, Famoxadone, pyridine bacteria oxazole, hymexazol oxadixyl, thiophene pyraclostrobin, earth benomyl, Xin chlorthalidone, benzoth thiocyanate, twelve morpholine ring, SBR do morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, piperidine oxime plaque, bacteria amine piperidine ring, boscalid, fluorine boscalid, piperidine amine bacteria, cyprodinil, fluoro-ethyl bacteria amine, ferimzone, mepanipyrim, pyrimethanil, fenarimol, nuarimol, Chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, quinoline propoxy, phenoxy quinoline, diethofencarb, isopropyl bacteria amines, benzene thiabendazole amines Propamocarb, sulfur bacteria Granville, edifenphos, iprobenfos, topiramate bacteria phosphorus, tolclofos, blasticidin, Jubilee mildew Su, Polyoxin, Polyoxin, validamycin, Jinggangmycin, streptomycin, metalaxyl, furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim, benomyl , thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethyl ethyl phenol, ethirimol, captafol, captan, folpet, vinclozolin, chlorofluorocarbons sclerotia Lee, Dimetachlone, chlorothalonil, Isoprothiolane, kitazine, leaf blight, PCNB, mancozeb, Propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper, oxygen cupric chloride, cuprous oxide, copper hydroxide, benzene cycloheximide, Pencycuron, da cycloheximide, tetrachlorophthalide, pyroquilon, Spiro bacteria amines, Tricyclazole, triforine, more fruit pyridine, Iminoctadine salts, biguanides octylamine, Dicloran, flusulfamide benzene, toluene, flusulfamide, indole ester, Fenaminosulf, oxolinic acid, allyl benzene, thiazole, bronopol, methyl iodide, metham, enemy lines esters, dazomet, dichloro-isopropyl ether, Fosthiazate, Cadusafos, fensulfothion, insects fenamiphos, fenamiphos, Ethoprophos, in addition to line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, kill line K, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene, isonicotinic acid chloride, allyl isothiazole and the like using any one or combination of the two; the present invention is 5 - methyl-1 , 2,3 - thiadiazole dihydrazide derivative (I) in the composition in mass percent of the total content of 1% -90%, the present invention is 5 - methyl-1, 2,3 - thiadiazole bis hydrazide derivative (I) with the product ratio of weight percentage of pesticide 1%: 99% to 99%: 1%; composition control effect is good, these compositions have a synergistic effect and the additive effect, we have not found to have antagonistic the role of composition; said composition can be used for agricultural and horticultural plant disease plant disease prevention, control objects include Oomycete the genus Achlya, Aphanomyces spp, Pythium, Phytophthora, referring Terrier spp, Plasmopara genus false downy mildew genus Peronospora spp produced more than twenty genera diseases, such as cotton seedlings rot, root rot of tomato, potato late blight, tobacco black shank, millet powdery mildew, grape cream mildew, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose and other food crops, cash crops, horticultural and forestry plants, other diseases, etc.; processing composition is selected from a wettable powder formulations, controlled release agents, powders, microcapsule suspensions, dispersible liquid formulations, dispersible solid preparation, seed treatment, emulsions, aqueous emulsion, large grain, granules, micro-emulsions, oil suspensions, oil, seed coated with a pesticide, suspension emulsion, water-soluble granules, soluble concentrate agent, water dispersible granules, poison Valley, aerosols, block bait, release block, concentrated bait, capsules granules, capsules suspensions, dispersible concentrate, powder, dry mix kinds of powders, emulsifiable concentrates, electrostatic sprays, oil-in-water emulsion, seed treatment agent, water-in-oil emulsions, aerosol cans, fine granules, smoke candle, smoke cartridges, smoke stick, suspension for seed treatment, smoke tablet, aerosol, smoke pellet, granular bait, gas evolution agents, large granules, drifting powders, granules, ointments, thermal fog, solid / liquid mixing device agent, a liquid / liquid mixing device agents, fog agent, a solid / solid mixing device agent , medicine paint, seed treatment liquid, particulates, oils suspending agents, oil, oil dispersible powders, creams, flaky baits, thick glue, sprinkling agents, stick agents, seed coating, bait, liniment, small bait, suspensions, emulsions suspensions, water-soluble granule, soluble concentrate agents, film oil, soluble powders, water soluble powder for seed treatment, ultra low volume suspension, tablet, tracking powder, ultra low volume liquid , steam release agents, water-dispersible granules, wettable powders, water dispersible powder wet dressing of any one.The crop that these compsns are suitable for comprise cereal (comprising paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprising sweet potato, yam, cassava etc.), beans (comprising soybean, broad bean, pea, mung bean, red bean etc.) and fiber (cotton, crudefiber crop, silkworm and mulberry etc.), oil plant (peanut, rape, sesame, soybean, Sunflower Receptacle etc.), sugar material (beet, sugarcane etc.), beverage (tealeaves, coffee, cocoa etc.), hobby (tobacco leaf etc.), medicinal (genseng, the bulb of fritillary etc.), the torrid zone (rubber, coconut, oil palm, the sisal hemp etc.) food crop of etc.ing and fruit, flowers, oil plant, sugared expect and cash crop such as cotton, fiber crops, tea, tobacco, Chinese medicinal materials and plant melon, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and garden crop such as tobacco (flue-cured tobaccos such as ornamental plant, hops, medicinal material, pepper, seedling and other garden crops; Air-curing of tobacco leaves, suncured tabacco), vegetables, (tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), yam, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (like orchid), potted landscape etc.
Compsn makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection in the germ-resistant defence capability that improves plant simultaneously.
Embodiment 10
5-methyl isophthalic acid of the present invention, 2,3-thiadiazoles bishydrazide derivative I and antiviral agent are combined in the application in control agricultural and forestry and the gardening plant virus disease
All 5-methyl isophthalic acids of the present invention; 2; 3-thiadiazoles bishydrazide derivative I and existing Antiphytoviral medicament diazosulfide, tiadinil (TDL), different metsulfovax (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, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure any 1 or 2 compounds combinations in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, the jingganmycin; Be used to prevent and treat the agricultural plants virus disease; These virus diseases are selected from tobacco mosaic virus disease, various melon virus disease, various solanberry viroid disease, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, cotton virus disease and the various fruit tree virus disease any, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, paddy rice virus disease comprise in rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, chilli pepper mosaic virus disease and tobacco veinal necrosis virus disease, corn short mosaic disease, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, the cybidium ring spot virus any.The crop that these compsns are suitable for be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, 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, yam, paddy rice, pepper, apple, banana, citrus, plants such as agricultural, gardening, economy, forestry such as peach, papaya, orchid, potted landscape; The use of these compsns makes the immunizing power of crop self be improved, and when producing the control of insect especially infection insect, has induced plant to produce the control to viral diseases of plants; Also can produce the direct control effect of virus disease; Therefore, these compsns can be used for Antiphytoviral medicament and inducing plant Antiphytoviral preparation of medicaments and purposes.5-methyl isophthalic acid of the present invention; 2, the total quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%, 5-methyl isophthalic acid of the present invention; 2, the ratio of 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; The formulation of compsn processing is selected from wettable powder; Sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Granule; Microemulsion; Oil-suspending agent; Finish; Seed with coated pesticidal; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Can disperse dense dose; Pulvis; Dry mixing kind pulvis; 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 seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; Big granula; The drift pulvis; Granula; 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; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; Water-dispersible granules; Wettable powder; In the wet-mixing kind water-dispersible powder any one; All show addition or synergism between these compsns, when keeping insecticidal activity, the effect that its antiviral activity all uses separately greater than any one compound; Do not find to have the compsn of antagonistic action, the drug effect lasting period of compsn is long.
Can know 5-methyl isophthalic acid, 2 from the basic principles of chemistry; Thereby 3-thiadiazoles bishydrazide derivative I can produce 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formic acid from the carbonyl fracture in plant with after the water molecules effect; Confirm also that through relevant software prediction and test compound of the present invention can produce 5-methyl isophthalic acid, 2,3-thiadiazoles-4-formic acid in the degraded of plant materials intracellular metabolite; Bibliographical information confirms the 5-methyl isophthalic acid; 2,3-thiadiazoles-4-formic acid has inducing plant and produces the resistance to the phytopathy original, can be used in the control of Plant diseases and viral diseases of plants.Therefore, these compsns can be used in preparation Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Compsn has improved the defence capability of plant in Antiphytoviral, make plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 11
5-methyl isophthalic acid of the present invention, 2, the application in 3-thiadiazoles bishydrazide derivative I and miticide combination control agricultural and forestry and the gardening plant mite evil
All 5-methyl isophthalic acids of the present invention; 2,3-thiadiazoles bishydrazide derivative I can with the following miticide of group: azocyclotin, cyhexatin, fenbutatin oxide, three phosphor tins, Zaprawa enolofos, dimethylvinphos, crotoxyphos, SD-1750, heptenopos, Phosdrin, SD-9129, RE-4355, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, RP-11974, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, SRA-5172, 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, MTMC, promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, fourth fluorine mite ester, the mite quinone that goes out, Nissol, WL 115110, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, Ai Pulinuo rhzomorph, ivermectin, match draw in rhzomorph, CL-301423, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, azoles mite ester, four mite piperazines, alkynes mite spy, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, the pyridaben etc. one or more to mix use; 5-methyl isophthalic acid of the present invention; 2, the total quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%, 5-methyl isophthalic acid of the present invention; 2, the ratio of 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%; Spray after can directly converting water; Comprise agricultural in its preparation and go up acceptable solvent and emulsifying agent and solubility promoter and synergistic agent etc., Gu the formulation of compsn processing be selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, big granula, granule, microemulsion, oil-suspending agent, finish, the seed with coated pesticidal, suspended emulsion agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, block poison bait, sustained-release block, dense poison bait, capsule granula, capsule suspension, can disperse dense dose, pulvis, dry mixing kind pulvis, 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, seed treatment suspension agent, smog sheet, smoke substance, smog ball, granular poison bait, foaming agent, big granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mix dress agent, liquid/liquid mix dress agent, cold mist agent, admittedly/mixing adorns agent, medicine lacquer, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, bold and vigorously waters in agent, stylus, the agent of kind clothing, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, tracking pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, the wet-mixing kind water-dispersible powder any one; The mite that can prevent and treat evil mainly contain phytophagy mite tetranychid (Tetranychidae, Tenuipalpidae), furan line mite, Eriophyidae like Panonychus citri belong to, tetranychus telarius belongs to and global agricultural evil mite, forestry evil mite, gardening evil mite and the health evil mites such as itch mite of Eriophyidae; The common carmine spider mite Tetranychus cinnabarinus that comprises; Tetranychus urticae T.urticae; Truncate leaf mite T.truncatus; Turkestan tetranychid T.turkestani and Dunhuang tetranychid T.dunhuangensis and refreshing Ze Shi tetranychid T.kanzawai; Citrus red mite (crm) Panonychus citri (McGregor); East amblyseius as predatory mite Amblyseius brientalis Ehara and Nissl amblyseius as predatory mite Amblyseius nicholsi Ehara et Lee; Matrimony vine goitre acariasis Aceri macrodonis Keifer; Controlling mode also comprises double controlling simultaneously; Controlling mode also comprises double controlling simultaneously; The control effect of compsn is good, all shows addition or synergism between each compsn, finds to have the compsn of antagonistic action, and the drug effect lasting period length of compsn, drug effect are played stably.The crop that these compsns are suitable for comprise paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, 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, yam, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.
Compsn has improved the defence capability of plant when killing mite, make plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 12
5-methyl isophthalic acid of the present invention, 2, the complete processing and the stability of 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical compound preparation
5-methyl isophthalic acid of the present invention; 2, the mixed preparation complete processing of 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical is seen table 5, and is visible by table 5; Most medicament all can be processed according to the method for statement; The main component of liquid preparation is other a component etc. of effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, thickening material or permeate agent etc., and the composition of solid preparation mainly includes imitates other agriculturals such as composition, tensio-active agent and filler and go up acceptable adjuvant components, 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, and caking phenomenon does not appear in medicament, and the medicament drug effect that all preparations store before and after placing does not have significant difference; The rate of decomposition of compsn effective constituent in 5%, the composite preparation qualified stability.
Table 1 5-methyl isophthalic acid of the present invention, 2, the chemical structure and the physical and chemical parameter of 3-thiadiazoles bishydrazide derivative I: N-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine compound
General formula I:
R
1For be selected from o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, to cyano-phenyl, 3; 5-3,5-dimethylphenyl, 3-methoxyl group-2-aminomethyl phenyl, 3; 5-dichlorophenyl, 2; 6-dichlorophenyl, 3; The 5-dinitrophenyl, to chlorophenylmethyl, 2; 4-dichlorobenzene methyl, 1-naphthyl, 2-chloropyridine-3-base ,-chloropyridine-5-base, 2; 5-dichloropyridine-6-base, furans-2-base, thiophene-2-base, 2-methyl ethylene, cyclopropyl, cyclohexyl, 1-cyclopentyl ethyl, 5-ethyl-1-methylpyrazole-3-base, 5-methyl isophthalic acid, 2, the group of 3-thiadiazoles-4-base.
Table 2 synthetic 5-of the present invention methyl isophthalic acid, 2, the stripped fungicidal activity of 3-thiadiazoles bishydrazide derivative I
(concentration: 50 mcg/ml, average inhibiting rate/%)
| Compound number | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| WH-5-34 | 0 | 4.17 | 27.50 | 19.05 | 45.83 | 24.32 | 49.23 | 22.62 | 34.62 |
| WH-5-38 | 15.15 | 11.54 | 29.41 | 42.03 | 31.48 | 34.15 | 40.54 | 20.24 | 26.19 |
| WH-5-42 | 7.14 | 8.33 | 40.00 | 9.52 | 50.00 | 27.03 | 41.54 | 47.62 | 26.92 |
| WH-5-47 | 12.12 | 0 | 39.22 | 42.03 | 33.33 | 31.71 | 27.03 | 20.24 | 11.90 |
| WH-5-50 | 7.14 | 0 | 25.00 | 11.90 | 41.67 | 24.32 | 32.31 | 21.43 | 23.08 |
| WH-5-45-3 | 7.14 | 8.33 | 22.50 | 19.05 | 43.75 | 78.38 | 44.62 | 16.67 | 23.08 |
| WH-6-8-A | 0 | 8.33 | 25.00 | 11.90 | 43.75 | 64.86 | 44.62 | 41.67 | 23.08 |
| WH-6-15 | 6.45 | 3.85 | 20.83 | 18.75 | 22.73 | 24.14 | 56.34 | 15.48 | 9.76 |
| WH-6-17 | 3.57 | 4.17 | 12.50 | 23.81 | 37.50 | 37.84 | 58.46 | 48.81 | 34.62 |
| WH-6-20-2 | 6.45 | 7.69 | 33.33 | 18.75 | 20.45 | 68.97 | 40.85 | 22.62 | 2.44 |
| WH-6-19-1 | 9.09 | 0 | 41.18 | 40.58 | 37.04 | 82.93 | 40.54 | 22.62 | 19.05 |
| WH-6-22-2 | 3.57 | 0 | 20.00 | 16.67 | 52.08 | 24.32 | 49.23 | 48.81 | 23.08 |
| WH-6-25-2 | 9.68 | 11.54 | 22.92 | 25.00 | 36.36 | 72.41 | 53.52 | 33.33 | 14.63 |
| WH-6-24-2 | 12.12 | 0 | 27.45 | 43.48 | 48.15 | 34.15 | 37.84 | 19.05 | 14.29 |
| WH-6-28-2 | 6.45 | 3.85 | 33.33 | 79.17 | 25.00 | 68.97 | 52.11 | 53.57 | 14.63 |
| WH-6-29-2 | 15.15 | 7.69 | 29.41 | 52.17 | 46.30 | 17.07 | 40.54 | 25.00 | 26.19 |
| WH-6-30-2 | 6.45 | 15.38 | 29.17 | 28.13 | 43.18 | 10.34 | 42.25 | 20.24 | 7.32 |
| WH-6-31-2 | 12.90 | 15.38 | 6.25 | 21.88 | 27.27 | 34.48 | 40.85 | 23.81 | 17.07 |
| WH-6-48-2 | 7.14 | 4.17 | 15.00 | 28.57 | 52.08 | 24.32 | 56.92 | 39.29 | 26.92 |
| WH-7-10-1-(2) | 0 | 4.35 | 15.15 | 33.33 | 31.58 | 76.67 | 40.00 | 39.29 | 14.29 |
| WH-6-35-2 | 0 | 0 | 27.50 | 11.90 | 45.83 | 24.32 | 50.77 | 44.05 | 19.23 |
| WH-6-4-(2) | 16.13 | 7.69 | 20.83 | 43.75 | 29.55 | 68.97 | 60.56 | 39.29 | 17.07 |
| WH-6-33-2 | 3.23 | 7.69 | 27.08 | 18.75 | 25.00 | 3.45 | 47.89 | 7.14 | 7.32 |
| WH-6-34-2-(1) | 26.67 | 0 | 6.06 | 41.03 | 23.68 | 76.67 | 16.36 | 20.24 | 17.14 |
| WH-6-48-1 | 9.68 | 11.54 | 29.17 | 40.63 | 40.91 | 24.14 | 46.48 | 29.76 | 9.76 |
| WH-6-39-2-(2) | 27.27 | 23.08 | 27.45 | 49.28 | 53.70 | 39.02 | 66.22 | 22.62 | 21.43 |
| WH-6-40-2 | 9.68 | 11.54 | 10.42 | 34.38 | 25.00 | 44.83 | 54.93 | 22.62 | 14.63 |
| WH-6-46-2 | 9.68 | 7.69 | 35.42 | 28.13 | 36.36 | 10.34 | 49.30 | 41.67 | 12.20 |
| WH-7-6-2 | 10.00 | 21.74 | 0 | 23.08 | 23.68 | 70.00 | 27.27 | 17.86 | 14.29 |
| WH-7-7-1-(1) | 10.00 | 4.35 | 12.12 | 33.33 | 34.21 | 73.33 | 41.82 | 14.29 | 0 |
| WH-6-44-2 | 6.45 | 3.85 | 25.00 | 18.75 | 29.55 | 27.59 | 42.25 | 20.24 | 7.32 |
| WH-6-45-2-(2) | 12.90 | 3.85 | 18.75 | 3.13 | 27.27 | 79.31 | 32.39 | 36.90 | 4.88 |
| WH-6-47-1-(2) | 12.90 | 3.85 | 14.58 | 6.25 | 50.00 | 51.72 | 45.07 | 26.19 | 12.20 |
| WH-7-7-2-(1) | 10.00 | 8.70 | 18.18 | 46.15 | 28.95 | 70.00 | 69.09 | 23.81 | 14.29 |
| WH-7-8-1 | 3.33 | 13.04 | 0 | 33.33 | 15.79 | 56.67 | 41.82 | 2.38 | 8.57 |
| WH-7-8-2 | 13.33 | 0 | 9.09 | 35.90 | 13.16 | 70.00 | 50.91 | 0 | 25.71 |
| WH-7-10-2-(2) | 10.00 | 13.04 | 0 | 20.51 | 28.95 | 76.67 | 38.18 | 16.67 | 8.57 |
| WH-6-43-2-(1) | 21.21 | 3.85 | 9.80 | 56.52 | 40.74 | 29.27 | 51.35 | 17.86 | 11.90 |
| WH-5-40 | 12.12 | 3.85 | 29.41 | 39.13 | 29.63 | 82.93 | 39.19 | 13.10 | 16.67 |
Table 3 synthetic 5-of the present invention methyl isophthalic acid, 2, the activity of 3-thiadiazoles bishydrazide derivative I resisting tobacco mosaic virus
(concentration: 50 mcg/ml, average inhibiting rate/%)
| Compound | Treatment | Passivation | Protection | Induce | Half leaf |
| WH-5-34 | 10.65 | 40.23 | 29.25 | 57.99 | 20.45 |
| WH-5-38 | ND | ND | ND | ND | ND |
| WH-5-42 | 47.69 | 37.93 | 56.46 | 45.67 | 28.94 |
| WH-5-47 | 52.91 | 27.78 | 15.59 | 47.13 | 19.92 |
| WH-5-50 | 62.50 | 68.97 | 40.14 | 79.45 | 24.83 |
| WH-5-45-3 | 17.99 | 29.63 | 21.51 | 24.71 | 12.27 |
| WH-6-8-A | 15.74 | 63.79 | 28.57 | 67.12 | 21.37 |
| WH-6-15 | 35.04 | 14.35 | 40.16 | 45.73 | ND |
| WH-6-17 | 51.71 | 43.05 | 25.30 | 41.03 | ND |
| WH-6-20-2 | 21.76 | 44.25 | 57.14 | 29.23 | 19.16 |
| WH-6-19-1 | 13.25 | 37.96 | 54.22 | 25.64 | ND |
| WH-6-22-2 | 49.54 | 58.04 | 12.24 | 59.36 | 13.59 |
| WH-6-25-2 | 22.65 | 46.76 | 32.13 | 50.43 | ND |
| WH-6-24-2 | 25.00 | 65.52 | 18.37 | 65.29 | 13.86 |
| WH-6-28-2 | 19.66 | 29.17 | 11.25 | 29.06 | ND |
| WH-6-29-2 | 18.06 | 50.58 | 19.05 | 6.39 | 19.44 |
| WH-6-30-2 | 59.72 | 26.43 | 52.38 | 62.55 | 26.56 |
| WH-6-31-2 | 70.83 | 43.11 | 22.45 | 11.87 | 26.87 |
| WH-6-48-2 | 40.74 | 68.52 | 30.65 | 20.12 | 13.41 |
| WH-7-10-1-(2) | 18.47 | 21.30 | 44.74 | 28.31 | 29.73 |
| WH-6-35-2 | 67.59 | 66.09 | 72.11 | 30.60 | 9.76 |
| WH-6-4-(2) | 50.80 | 37.04 | 27.96 | 60.34 | 27.89 |
| WH-6-33-2 | 62.96 | 62.07 | 5.44 | 25.57 | 19.56 |
| WH-6-34-2-(1) | 48.59 | 25.00 | 29.39 | 47.95 | 31.45 |
| WH-6-48-1 | 21.16 | 38.89 | 24.19 | 42.53 | 18.42 |
| WH-6-39-2-(2) | 38.62 | 62.96 | 30.11 | 29.31 | 26.49 |
| WH-6-40-2 | 53.44 | 55.09 | 26.34 | 42.53 | 12.63 |
| WH-6-46-2 | 42.33 | 12.04 | 6.45 | 56.32 | 29.52 |
| WH-7-6-2 | 17.67 | 12.04 | 8.77 | 42.47 | 14.06 |
| WH-7-7-1-(1) | 20.48 | 35.19 | 43.86 | 49.77 | 21.77 |
| WH-6-44-2 | 51.32 | 40.74 | 33.87 | 43.68 | 19.02 |
| WH-6-45-2-(2) | 48.68 | 30.55 | 31.72 | 30.46 | 18.84 |
| WH-6-47-1-(2) | 32.80 | 54.63 | 54.84 | 41.96 | 19.16 |
| WH-7-7-2-(1) | 22.89 | 14.35 | 12.72 | 46.12 | 19.86 |
| WH-7-8-1 | 32.93 | 6.48 | 39.47 | 8.22 | 13.41 |
| WH-7-8-2 | 29.72 | 6.48 | 12.72 | 36.53 | 17.86 |
| WH-7-10-2-(2) | 23.29 | 15.74 | 8.33 | 33.79 | 29.73 |
| WH-6-43-2-(1) | 44.98 | 50.92 | 16.13 | 20.69 | 14.29 |
| WH-5-40 | 5.09 | 61.50 | 10.20 | 57.99 | 20.17 |
ND: undetermined
Table 4 synthetic 5-of the present invention methyl isophthalic acid, 2,3-thiadiazoles bishydrazide derivative I is to the The selection result (96h) of small cabbage moth
(concentration: 400mg/L soaks leaf dish method)
Table 5 synthetic 5-of the present invention methyl isophthalic acid, 2, the working method that 3-thiadiazoles bishydrazide derivative I and commercially available agricultural chemical are used with
Claims (10)
1. one type of 5-methyl isophthalic acid, 2,3-thiadiazoles bishydrazide verivate is characterized in that having the chemical structure of general formula suc as formula shown in the I:
Wherein: R
2For be selected from o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, to cyano-phenyl, 3; 5-3,5-dimethylphenyl, 3-methoxyl group-2-aminomethyl phenyl, 3; 5-dichlorophenyl, 2; 6-one dichlorophenyl, 3; The 5-dinitrophenyl, to chlorophenylmethyl, 2; 4-dichlorobenzene methyl, 1-naphthyl, 2-chloropyridine-3-base, 2-chloropyridine-5-base, 2; 5-dichloropyridine-6-base, furans-2-base, thiophene-2-base, 2-methyl ethylene, cyclopropyl, cyclohexyl, 1-cyclopentyl ethyl, 5-ethyl-1-methylpyrazole-3-base, 5-methyl isophthalic acid, 2, the group of 3-thiadiazoles-4-base.
2. the described 5-methyl isophthalic acid of claim 1,2, the compound method of 3-thiadiazoles bishydrazide derivative I, concrete synthetic route is following:
Wherein: R
2For be selected from o-methyl-phenyl-, an aminomethyl phenyl, p-methylphenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethyl phenyl, m-trifluoromethylphenyl, p-trifluoromethyl phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, ortho-nitrophenyl base, m-nitro base, p-nitrophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, to cyano-phenyl, 3; 5-3,5-dimethylphenyl, 3-methoxyl group-2-aminomethyl phenyl, 3; 5-dichlorophenyl, 2; 6-dichlorophenyl, 3; The 5-dinitrophenyl, to chlorophenylmethyl, 2; 4-dichlorobenzene methyl, 1-naphthyl, 2-chloropyridine-3-base, 2-chloropyridine-5-base, 2; 5-dichloropyridine-6-base, furans-2-base, thiophene-2-base, 2-methyl ethylene, cyclopropyl, cyclohexyl, 1-cyclopentyl ethyl, 5-ethyl-1-methylpyrazole-3-base, 5-methyl isophthalic acid, 2, the group of 3-thiadiazoles-4-base;
Specifically be divided into following steps:
A. midbody 5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles-4-formyl chloride
With the 5-methyl isophthalic acid of 67 mmoles, 2,3-thiadiazoles-4-formic acid and 30 milliliters of thionyl chlorides join in 100 milliliters of three mouthfuls of round-bottomed flasks; 80 degrees centigrade of following reflux 6 hours remove excessive thionyl chloride under reduced pressure, and underpressure distillation is collected 94-96 degree centigrade cut and got faint yellow product 9.25 grams under 2000Pa; Yield 85%, midbody 5-methyl isophthalic acid, 2; The 3-thiadiazoles-sealing of 4-formyl chloride is kept in the moisture eliminator subsequent use; The 5-methyl isophthalic acid, 2, the amount of 3-thiadiazoles-4-formyl chloride preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles;
B. the preparation of intermediate N (5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine
In 250 milliliters two-mouth bottle, add 31 mmole tertiary butyl hydrazonium salt hydrochlorates, add 60 milliliters of methylene dichloride again and make solvent, under condition of ice bath, add 10 ml water solution of 31 mmole sodium hydroxide; Stir after 20 minutes the 5-methyl isophthalic acid that is dissolved in 26 mmoles in 30 milliliters of dichloromethane solutions, 2,3-thiadiazoles-4-formyl chloride slowly is added drop-wise in the reaction flask; Remove ice bath, room temperature reaction 5 hours closes organic layer after the reaction solution washing and spends the night with anhydrous sodium sulfate drying; Suction filtration is removed SODIUM SULPHATE ANHYDROUS 99PCT, and rotary evaporation removes and desolvates, and obtains faint yellow blocks of solid 4.05g; Yield 72%; Be intermediate N (5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine; The amount of synthetic compound enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles, commercially available 5-methyl isophthalic acid, and 2,3-thiadiazoles-4-formyl chloride has same effect;
C. the preparation of substituted formyl chlorine
The replacing acid that in 50 milliliters of round-bottomed flasks, adds 0.2 mmole adds the sulfur oxychloride of 1.2 mmoles again, and with reaction mixture oil bath reflux 3-4 hour, air distillation obtained substituted formyl chlorine after going out unreacted sulfur oxychloride, and sealing is preserved subsequent use; The amount of substituted formyl chlorine preparation enlarges by corresponding proportion or dwindles; The volume of respective reaction container enlarges in proportion or dwindles, and commercially available substituted formyl chlorine has same effect;
D.5-methyl isophthalic acid, 2, the preparation of 3-thiadiazoles bishydrazide verivate: N-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-the formyl radical)-N '-tertiary butyl-N '-substituted formyl hydrazine compound I
Get 0.1 mmole N-(5-methyl isophthalic acid; 2; 3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine is dissolved in 20 milliliters of methylene dichloride; Join in 50 milliliters of round-bottomed flasks, add 0.12 mmole acid binding agent triethylamine then, the ice bath cooling slowly drips 5 milliliters of dichloromethane solutions of 0.1 mmole substituted formyl chlorine down; At room temperature continued stirring reaction after dripping 4 hours, after reaction finished, reaction mixture was with washing 3 times; Anhydrous sodium sulfate drying spends the night, and filters back decompression precipitation, and crude product is with the ethyl acetate petroleum ether recrystallization or with 200-300 order purification by silica gel column chromatography; Eluent is 60-90 degree centigrade a sherwood oil: ETHYLE ACETATE volume ratio 3: 1 gets N-(5-methyl isophthalic acid, 2; 3-thiadiazoles-4-formyl radical)-the N '-tertiary butyl-N '-pure article of substituted formyl hydrazine class compound I, carry out fusing point,
1The mensuration of HNMR is confirmed its chemical structure, and the amount of compound I preparation enlarges by corresponding proportion or dwindles, and commercially available N-(5-methyl isophthalic acid, 2,3-thiadiazoles-4-formyl radical)-N '-tertiary butyl hydrazine and substituted formyl chlorine have same effect.
3. sterilant is characterized in that: by the described 5-methyl isophthalic acid of claim 1, and 2,3-thiadiazoles bishydrazide verivate is gone up acceptable assistant with agricultural and is formed.
4. sterilant is characterized in that: by the described 5-methyl isophthalic acid of claim 1, and 2,3-thiadiazoles bishydrazide verivate is gone up acceptable assistant with agricultural and is formed.
5. anti-plant virus agent is characterized in that: contain 5-methyl isophthalic acid as claimed in claim 1 in the said composition, and 2,3-thiadiazoles bishydrazide verivate is gone up acceptable assistant with agricultural.
6. a kind of plant activator is characterized in that: contain 5-methyl isophthalic acid as claimed in claim 1 in the said composition, and 2,3-thiadiazoles bishydrazide verivate is gone up acceptable assistant with agricultural.
7. the described 5-methyl isophthalic acid of claim 1; 2; 3-thiadiazoles bishydrazide derivative I and agricultural go up acceptable assistant and be selected from Chlorpyrifos 94, inferior Nong, acetamiprid, Affirm (Merck Co.), more visit that rhzomorph, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, PP-383, beta_cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-FCR-1272, FCR-1272, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, WL 43479, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiophene worm quinoline, thiophene worm piperazine, thiophene worm amine, MTI-446, clothianadin, Da Tenan, diflubenzuron, the young urea that goes out, Teflubenzuron, deinsectization are grand, fluorine bell urea, WL 115110, pyridine worm are grand, Acarus tritici urea, poisonous insect urea, penfluron, Noviflumuron are noviflumuron, its CAS number for 121451-02-3, flucycloxuron, Novaluron be Rimon, fluorine pyridine urea, Bay sir 6874 promptly { 1-[(3.5-two chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, Bay SIR-8514 promptly [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, promptly two three WL 115110s of Bistrifluron, furans worm hydrazides, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, PP-062, MTMC, isoprocarb, cartap, fenobucarb, leaf disperse, one or more medicaments in the carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, azoles mite ester, pyridaben, four mite piperazines, alkynes mite Te, butyl ether urea, benfuracarb, pyrrole aphid ketone, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, PP618, ethoprophos, fluorine worm nitrile, desinsection list, disosultap, chlorine insect amide, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, azoles insect amide, tebufenpyrad, bromothalonil, pyrazine ketone, second mite azoles, tebufenpyrad, the young ketone of rattling away, pyrrole propyl ether, emaricin mix the purposes of using in preparing sterilant; The described 5-methyl isophthalic acid of claim 1; 2; The total quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%; The described 5-methyl isophthalic acid of claim 1,2, the ratio of 3-thiadiazoles bishydrazide derivative I and said medicament is mass percent 1%: 99% to 99%: 1%; The formulation of compsn is selected from sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Microemulsion; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Dry mixing kind pulvis; Missible oil; The electrostatic spray agent; Water-in-oil emulsion; Oil-in-water emulsion; Smoke candle; Granula subtilis; Smoke candle; Smoke cartridge; The smog rod; The seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; The drift pulvis; 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; Microgranules; Oil suspending agent; 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 emulsion; The film forming finish; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; In the wet-mixing kind water-dispersible powder any one; The plant that compsn is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, 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, tea, bamboo shoots, hops, pepper.
The process of claim 1, wherein the 5 - methyl-1, 2,3 - thiadiazole derivatives Diacylhydrazine I and agriculturally acceptable additives selected from benzothiazole and thiadiazole, thiazole amine acid bacteria , induced a thiophene amine 4 - methyl-1, 2,3 - thiadiazole-5 - carboxylic acid 4 - methyl-1, 2,3 - thiadiazole-5 - Sodium 4 - methyl- , 2,3 - thiadiazol-5 - Ethyl 4 - (bromomethyl) -1,2,3 - thiadiazole-5 - Ethyl 4 - iodo-methyl-1, 2,3 - thiadiazole oxadiazol-5 - Ethyl 4 - bromo-5 - methyl-1, 2,3 - thiadiazole-4 - iodo-5 - methyl-1, 2,3 - thiadiazole , 4,4 - dibromo-1 ,2,3 - thiadiazole-5 - carboxylic acid ethyl ester, DL-β-aminobutyric acid, ribavirin, An Tuofen, Ningnanmycin or salicylic acid, Cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, Isotianil, Cymoxanil, thiram, ziram, mancozeb, fosetyl, thiophanate-methyl, chlorothalonil, the enemy can be loose, procymidone, Fenpropidine, thiophanate, thiophanate, metalaxyl, salicylic acid, flumorph, Dimethomorph, efficient metalaxyl, efficient Benalaxyl, diclofenac cyano bacteria amine, flusulfamide, flusulfamide methyl, thiophene amine fluoride bacteria, flutolanil, leaf blight phthalate, cyclopropane amino acid bacteria, cyflufenamid, cycloalkyl amine acid bacteria, cyano bacteria amine, amine silica thiabendazole, topiramate furosemide bacteria amines, penthiopyrad, diacetylene amine acid bacteria, zoxamide, ofurace, carboxin, B strains Lee, iprodione, azoxystrobin, Kresoxim amines, fluoxastrobin, kresoxim-methyl, phenoxy bacteria amine, oxime ether amines bacteria, picoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, alkenyl amines trifloxystrobin, oxygen Propiconazole, bromuconazole, cyproconazole , difenoconazole azole, Diniconazole, efficient diniconazole, Epoxiconazole, fenbuconazole, fluorine quinazoline, Flusilazole, Flutriafol, Hexaconazole, imines azole, Ipconazole, leaf fungus azole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, PTFE ether, triazole alcohol, sterilization azole, Bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, triflumizole, Cyazofamid, imidazole cycloheximide, evil imidazole, pefurazoate, Famoxadone, pyridine bacteria oxazole, hymexazol oxadixyl, thiazole pyraclostrobin, earth benomyl, octyl thiophene ketones, benzene thiophene thiocyanate, dodecyl tridemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, piperidine spot oxime, amine fungus piperidine ring, boscalid, fluorine boscalid, piperidine amine bacteria, cyprodinil, mepanipyrim fluorine, ferimzone, mepanipyrim, pyrimethanil, fenarimol, nuarimol, Chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, quinoline propoxy, phenoxy quinoline, diethofencarb, isopropyl bacteria amine, benzyl amine thiabendazole, propamocarb , sulfur bacteria Granville, edifenphos, iprobenfos, topiramate bacteria phosphorus, tolclofos, blasticidin, kasugamycin, polymyxin, Polyoxin, validamycin, Jinggangmycin streptomycin, metalaxyl, furalaxyl, Benalaxyl, furosemide amide, mepronil, carbendazim, benomyl, thiophanate-methyl, triadimefon, ethirimol sulfonate, dimethyl ethyl phenol, ethirimol, captafol, captan, folpet, vinclozolin, chlorofluorocarbons sclerotia Lee, Dimetachlone, chlorothalonil, Isoprothiolane, kitazine, leaf blight, quintozene, mancozeb, propineb, fosetyl-aluminum, sulfur, Bordeaux mixture, copper sulfate, copper oxychloride, cuprous oxide, cupric hydroxide, benzene, cycloheximide, pencycuron, da cycloheximide, tetrachlorophthalide, pyroquilon, Spiro bacteria amines, Tricyclazole, triforine, more fruit pyridine, Iminoctadine salt Iminoctadine amine, Dicloran, flusulfamide benzene, toluene sulfonamide bacteria amine, indole ester, Fenaminosulf, oxolinic acid, allyl benzene, thiazole, bronopol, methyl iodide, metham, enemy lines esters, dazomet dichloride, isopropyl ether, Fosthiazate, Cadusafos, fensulfothion, insects fenamiphos, fenamiphos, Ethoprophos, in addition to line phosphorus, chlorine triazophos, carbosulfan cyclophosphamide, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropene in any one or combination of the two agents for the preparation of fungicides and their use in the control of plant diseases; composition is suitable for a plant selected from rice, wheat, barley, oats, maize, sorghum, sweet potato, potato, tapioca, soy, beans, peas, green beans, red beans, cotton, sericulture, peanut, rapeseed, sesame, sunflower, sugar beet, sugar cane, coffee, cocoa, ginseng, Fritillaria, rubber, coconut, oil palm, sisal, tobacco, tea, bamboo shoots, hops pepper; compositions for diseases selected from Alternaria solani, Botrytis cinerea fungus, peanut leaf spot fungus, Fusarium graminearum, Phytophthora infestans, apple ring rot fungus, Rhizoctonia solani, Sclerotinia sclerotiorum , Rhizoctonia cerealis plant diseases caused; claimed in claim 1, wherein the 5 - methyl-1, 2,3 - thiadiazole dihydrazide derivative (I) in the composition in a proportion of 1% -90 mass% %, selected from a sustained release dosage form of the composition, powder, microcapsule suspensions, dispersible liquid formulations, dispersible solid preparation, seed treatment, emulsions, aqueous emulsion, large granules, micro-emulsion, suspension emulsion, water soluble granules, soluble concentrate agent, water dispersible granules, poison Valley, aerosols, block bait, release block, concentrated bait, capsules granules, capsules, suspensions, dry dressing powders, emulsifiable concentrates, electrostatic sprays, oil-in-water emulsions, oil in water emulsions, aerosol cans, fine granules, smoke candle, smoke cartridges, smoke stick, suspension for seed treatment, smoke tablet, aerosol, smoke pellet, granular bait, gas evolution agents, drift powders, ointments, hot fogging agent, a solid / liquid mixing device agent, a liquid / liquid mixing device agents, fog agent, a solid / solid mixing device agent, drug paint, fine granules, oil suspension agents, oil dispersible powders, ointments, sheet bait, thick glue, sprinkling agents, stick agents, seed coating, bait, liniment, small baits, suspended emulsion, film oil, soluble powders, water soluble powder for seed treatment, ultra-low volume suspensions, tablets, tracking powder, ultra low volume liquid, vapor release agents, water-dispersible powder wet dressing of any one.
9. the described 5-methyl isophthalic acid of claim 1; 2,3-thiadiazoles bishydrazide derivative I 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, SD-9129, RE-4355, Chlorpyrifos 94, Pyrimithate, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Nialate, Malathion, methacrifos, RP-11974, Volaton, methylpyrimidine sulphur phosphorus, Resitox, sulfotep, triazophos, vamidothion, isocarbophos, SRA-5172, 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, MTMC, promacyl, formetanate, single carbonamidine, medimeform, amitraz, chlordimeform, peruscabin, bromopropylate, fourth fluorine mite ester, the mite quinone that goes out, Nissol, WL 115110, macro tetrolide, piericidin, thuringiensin, tetranactin, macro tetrolide, Avrmectin, doractin, Ai Pulinuo rhzomorph, ivermectin, match and draw any one or two kinds of medicament combined preparation in rhzomorph, CL-301423, pyrethrin, nicotine, matrine, nimbin, tubatoxin, tebufenpyrad, pyridaben, azoles mite ester, four mite piperazines, alkynes mite spy, hexythiazox, spiral shell mite ester, Fluacrypyrim, Ovotran, propargite, the pyridaben to become miticide and preventing and treating the purposes of plant mites in doing harm to; The described 5-methyl isophthalic acid of claim 1; 2; The total quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%; The described 5-methyl isophthalic acid of claim 1,2, the ratio of 3-thiadiazoles bishydrazide derivative I and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; The formulation of compsn is selected from sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Microemulsion; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Dry mixing kind pulvis; Missible oil; The electrostatic spray agent; Water-in-oil emulsion; Oil-in-water emulsion; Smoke candle; Granula subtilis; Smoke candle; Smoke cartridge; The smog rod; The seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; The drift pulvis; 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; Microgranules; Oil suspending agent; 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 emulsion; The film forming finish; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; In the wet-mixing kind water-dispersible powder any one; The plant that compsn is suitable for be selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, 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, yam, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape; 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, gardening evil mite and the harmful mite of health that the phytophagy evil mite that compsn is suitable for is selected from tetranychid.
10. the described 5-methyl isophthalic acid of claim 1,2,3-thiadiazoles bishydrazide derivative I and agricultural go up acceptable assistant and be selected from diazosulfide, tiadinil, 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, 4-brooethyl-1; 2,3-thiadiazoles-5-ethyl formate, 4-iodomethyl-1,2; 3-thiadiazoles-5-ethyl formate, 4-brooethyl-5-methyl isophthalic acid, 2,3-thiadiazoles, 4-iodomethyl-5-methyl isophthalic acid; 2,3-thiadiazoles, 4,4-dibromo methyl isophthalic acid; 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, virazole, antofine, Ningnanmycin, first thiophene lure any one or the two kinds of medicament combined preparation in amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, the different metsulfovax to become anti-plant virus agent or plant activator and prevent and treat the purposes of phytopathy in poisoning at Antiphytoviral disease or inducing plant; The described 5-methyl isophthalic acid of claim 1; 2; The total quality percentage composition of 3-thiadiazoles bishydrazide derivative I in compsn is 1%-90%; The described 5-methyl isophthalic acid of claim 1,2, the ratio of 3-thiadiazoles bishydrazide derivative I and above-mentioned medicament is mass percent 1%: 99% to 99%: 1%; The formulation of compsn is selected from sustained release dosage; Pulvis; Micro-capsule suspension; The dispersible body preparation; The dispersible solid preparation; Seed treatment emulsion; Aqueous emulsion; Big granula; Microemulsion; Suspended emulsion agent; Water-soluble granule; Soluble thick agent; Water-dispersible granules; Poison grain; Aerosol; Block poison bait; Sustained-release block; Dense poison bait; The capsule granula; Capsule suspension; Dry mixing kind pulvis; Missible oil; The electrostatic spray agent; Water-in-oil emulsion; Oil-in-water emulsion; Smoke candle; Granula subtilis; Smoke candle; Smoke cartridge; The smog rod; The seed treatment suspension agent; The smog sheet; Smoke substance; The smog ball; Granular poison bait; Foaming agent; The drift pulvis; 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; Microgranules; Oil suspending agent; 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 emulsion; The film forming finish; Soluble powder; The seed treatment water solube powder; The ultra-low volume suspension agent; Tablet; Follow the trail of pulvis; Ultra low volume liquids; The steam releasing agent; In the wet-mixing kind water-dispersible powder any one; The plant that compsn is suitable for is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, yam, cassava, soybean, 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, tea, bamboo shoots, hops, pepper; The phytopathy that compsn is suitable for is poisoned and is selected from tobacco mosaic virus disease and chilli pepper mosaic virus disease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100970780A CN102633747A (en) | 2012-04-05 | 2012-04-05 | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100970780A CN102633747A (en) | 2012-04-05 | 2012-04-05 | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102633747A true CN102633747A (en) | 2012-08-15 |
Family
ID=46618342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100970780A Pending CN102633747A (en) | 2012-04-05 | 2012-04-05 | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633747A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483288A (en) * | 2013-10-12 | 2014-01-01 | 南开大学 | 3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof |
| CN105837517A (en) * | 2016-04-07 | 2016-08-10 | 浙江工业大学 | Novel hydroxypyrimidine-containing acethydrazide derivatives and preparing method and applications thereof |
| CN111635399A (en) * | 2020-07-01 | 2020-09-08 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| CN113717070A (en) * | 2020-05-25 | 2021-11-30 | 南京正大天晴制药有限公司 | Preparation method of intermediate of vasopressin V2 receptor antagonist |
| WO2022002193A1 (en) * | 2020-07-01 | 2022-01-06 | 南通大学 | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020840A1 (en) * | 1995-12-07 | 1997-06-12 | Bayer Aktiengesellschaft | 1,2,3-thiadiazole carboxylic acid (thio)esters and the use thereof as a pest control agent or as a microbicide |
| CN101020687A (en) * | 2007-01-12 | 2007-08-22 | 南开大学 | New thiobizole formanide derivative and its synthesis process and bioactivity |
| CN101066972A (en) * | 2006-02-20 | 2007-11-07 | 南开大学 | [1,2,3]-thiobizole derivative and its synthesis process and use |
| CN101591308A (en) * | 2009-06-26 | 2009-12-02 | 南开大学 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
-
2012
- 2012-04-05 CN CN2012100970780A patent/CN102633747A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997020840A1 (en) * | 1995-12-07 | 1997-06-12 | Bayer Aktiengesellschaft | 1,2,3-thiadiazole carboxylic acid (thio)esters and the use thereof as a pest control agent or as a microbicide |
| CN101066972A (en) * | 2006-02-20 | 2007-11-07 | 南开大学 | [1,2,3]-thiobizole derivative and its synthesis process and use |
| CN101020687A (en) * | 2007-01-12 | 2007-08-22 | 南开大学 | New thiobizole formanide derivative and its synthesis process and bioactivity |
| CN101591308A (en) * | 2009-06-26 | 2009-12-02 | 南开大学 | A kind ofly contain 1,2, bishydrazide derivative of 3-thiadiazoles active group and its production and use |
| CN101891708A (en) * | 2009-06-26 | 2010-11-24 | 南开大学 | Diacylhydrazine compounds containing 4-methyl-1,2,3-thiadiazole groups, preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| EDWARD W. THOMAS，等: "Synthesis and Platelet Aggregation Inhibitory Activity of 4,5-Bis( substituted)-l,2,3-thiadiazoles", 《J. MED. CHEM.》 * |
| 王守信 等: "4-甲基-1,2,3-噻二唑-5-甲酸芳酯的合成及生物活性", 《农药学学报》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483288A (en) * | 2013-10-12 | 2014-01-01 | 南开大学 | 3,4-dichloroisothiazole containing bishydrazide compounds as well as preparation method and application thereof |
| CN103483288B (en) * | 2013-10-12 | 2016-03-30 | 南开大学 | One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use |
| CN105837517A (en) * | 2016-04-07 | 2016-08-10 | 浙江工业大学 | Novel hydroxypyrimidine-containing acethydrazide derivatives and preparing method and applications thereof |
| CN105837517B (en) * | 2016-04-07 | 2019-08-06 | 浙江工业大学 | A kind of hydrazide derivatives and the preparation method and application thereof of hydroxyl pyrimidine |
| CN113717070A (en) * | 2020-05-25 | 2021-11-30 | 南京正大天晴制药有限公司 | Preparation method of intermediate of vasopressin V2 receptor antagonist |
| CN111635399A (en) * | 2020-07-01 | 2020-09-08 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| WO2022002193A1 (en) * | 2020-07-01 | 2022-01-06 | 南通大学 | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
| CN111635399B (en) * | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| GB2610789A (en) * | 2020-07-01 | 2023-03-15 | Univ Nantong | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
| GB2610789B (en) * | 2020-07-01 | 2024-09-18 | Univ Nantong | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102174030B (en) | 5-methyl-1,2,3-thiadiazole-4-formoxyl urea compounds, and preparation method and application thereof | |
| CN101863856A (en) | Bi(4-methyl-1,2,3-thiadiazole-5-phenurone) compounds and preparation method and application thereof | |
| CN104650064A (en) | Aminothiazole carboxylic acid derivatives as well as preparation method and application thereof | |
| CN105622422A (en) | Bromohexahydro indanone compound and preparation method and application thereof | |
| CN103483287B (en) | 3,4-dichloroisothiazole containing bisamide compounds as well as preparation method and application thereof | |
| CN102816134B (en) | 1,2,3-thiadiazole-containing sulfilimine (sulfonimine) compounds and their preparation method and use | |
| CN102603669B (en) | Derivatives of alpha-methoxyl imino-5-methyl-1,2,3-thiadiazole-4- carboxylic acid methyl ester and preparation methods and uses thereof | |
| CN104650061A (en) | Thiazole oxime ether compounds as well as preparation method and use thereof | |
| CN101891710B (en) | 4-halogenated methyl-1,2,3-thiadiazole compounds and preparation method and application thereof | |
| CN102633747A (en) | 5-methyl-1, 2, 3-thiadiazole bishydrazide derivatives as well as preparation method and application thereof | |
| CN102417505A (en) | Tetrazole compounds containing methyl-1,2,3-thiadiazole as well as preparation methods and application thereof | |
| CN102382108A (en) | Tetrazole compounds containing 1,2,3-bismuththiol methylene, preparation methods for same and application thereof | |
| CN104649996A (en) | Isothiazole oxime ether derivatives as well as preparation method and application thereof | |
| CN101899042A (en) | 4-substituted-1,2,3-thiadiazole formoxyl ureide compound, preparation method and application thereof | |
| CN102816135B (en) | 5-methyl-1,2,3-thiadiazole-containing 1,3,4-thiadiazole derivatives and their preparation method and use | |
| CN102816158B (en) | 5-methyl-1,2,3-thiadiazole-1,3,4-oxadiazole derivatives, and preparation method and application thereof | |
| CN101921244B (en) | Derivative of 4-methyl-1,2,3-thiadiazole containing 4-(1,1,2,2-tetrafluoroethoxy)-3,5-dichlorobenzene amino and synthesis method and application thereof | |
| CN103193769A (en) | 4-methyl-1,2,3-thiadiazole-5-triazole compound as well as preparation method and use thereof | |
| CN103641795B (en) | One class contains acetophenone derivs of 1,2,3-thiadiazoles and its production and use | |
| CN103483288B (en) | One class 3,4-bis-chloroisothiazole bishydrazide compounds and its production and use | |
| CN102633746A (en) | Di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole and preparation method and application of di-hydrazide derivatives containing 5-methyl-1, 2, 3-thiadizole | |
| CN102633745B (en) | Alpha-methoxy imino group-4-methyl-1, 2, 3-thiadiazole-5-methyl carboxylic ester derivatives and preparation method and application thereof | |
| CN103012392B (en) | Pyridine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof | |
| CN104496980A (en) | Novel thiazole heterocyclic compound as well as preparation method and application thereof | |
| CN101591307B (en) | Di(1,2,3-thiadiazole-5-formic acid) and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |