CN102633744B - 3-(4-methyl-1, 2, 3-thiadiazole-5-yl)-1, 5-diketone derivatives as well as preparation method and application thereof - Google Patents
3-(4-methyl-1, 2, 3-thiadiazole-5-yl)-1, 5-diketone derivatives as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN102633744B CN102633744B CN201210096833.3A CN201210096833A CN102633744B CN 102633744 B CN102633744 B CN 102633744B CN 201210096833 A CN201210096833 A CN 201210096833A CN 102633744 B CN102633744 B CN 102633744B
- Authority
- CN
- China
- Prior art keywords
- thiadiazoles
- methyl isophthalic
- isophthalic acid
- preparation
- add
- 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.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides 3-(4-methyl-1, 2, 3-thiadiazol-5-yl)-1, 5-diketone derivatives as well as a preparation method and application thereof and relates to heterocyclic compounds containing 1, 2, 3-thiadiazole. The compounds have a chemical structure general formula as shown in V. The invention discloses the structure general formula and the synthetic method of the compounds, the application of the compounds as bactericides and a processing technology for preparing the bactericides, plant virtues resisting agents and 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, 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 and virus diseases and the preparation method of the compounds.
Description
Technical field
Technical scheme of the present invention relates to containing 1,2-diazole compound, is specifically related to 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives.
Background technology
Michael reaction is the important reaction that generates C-C and increase carbochain, the wide range of its reaction substrate, generally application in organic synthesis.Robinson is carrying out when steroidal compounds is synthetic utilizing Michael reaction to synthesize 6,6-condensed ring system, be Michael reaction one of the most successful application case (Rapson, W.S., etc., J.Chem.Soc.1935,1285).In (+)-Dihydromevinolin complete synthesis, the introducing Michael such as Hanessian have reacted the synthetic (Hanessian of precursor structure, S., Deng .J.Org.Chem.1990, 55:5755), other drug is synthetic as thymoleptic Paxil effective constituent (-)-Paroxetin and (+)-Femoxetin (Brandau, S., Deng .Angew.Chem.2006, (Okino 45:4305) and in (-)-Baclofen complete synthesis, T., Deng .J.Am.Chem.Soc.2005, 127:1 19) all introduce Michael reaction.
Three conditions of Michael reaction needed: reaction give body, acceptor and catalyzer; React a lot of to the compound of body, as contain reactive hydrogen, can generate the compound (Oare, D.A. wait .J.Org.Chem.1990,55,157) of stabilized carbanions; If without reactive hydrogen, can utilize metal reagent or catalyzer to be converted into carbanion and participate in again reaction (Hallnemo, G wait .Tetrahedron.1983,39:1621); Heteroatoms nucleophilic reagent (the Southwick such as N, S, O, P, Si, Se and Sn in addition, P.L., J.Am.Chem.Soc.1 959,8 1:5435) and (Mitch such as enamine and enol ether, C.H.Tetrahedron Lett.1988,29:6831) also can be used as reaction give body.The structure of Michael reaction acceptor comprises two parts: drawing electron group and undersaturated system are as α, alpha, beta-unsaturated ketone, α, beta-unsaturated esters, α, beta-unsaturated aldehyde, α, beta-unsaturated acyl amine, α, beta-unsaturated carboxylic acid derivative, α, β-unsaturated lactan, α, β-unsaturated lactone (Wang, N.Y., Deng .Tetrahedron Lett.1979,20:1121; Cartier, D., waits .Tetrahedron Lett.1982,23:1897; Krafft, M.E., Deng .Tetrahedron Lett.1986,27:2087), (Corey, E.J. wait .J.Am.Chem.Soc.1978 for prussiate, sulfoxide compound, nitroethylene derivative, (the Ono such as the ethene derivatives that 100:6294), sulphur and phosphorus replace, N., wait .Tetrahedron Lett.1982,23:2957).The catalyzer of Michael reaction mainly comprises 4 large classes: basic catalyst is as the metal alkoxide of highly basic, metal hydride and lithium ammoniate; Weak base comprises triethylamine, sodium-acetate, PPh
3, DBU and TMG, a lot of phase-transfer catalysts are also used to the catalyzer of Michael reaction, as quaternary alkylammonium halides; Lewis acid is as TiCl
4deng; Metal catalyst can prevent the side reaction that highly basic causes, as transistion metal compound FeCl
36H
2o and lanthanide metal compound Yb (OTf)
3;
acid catalyst is as TSOH and Tf
2nH etc.The asymmetric Michael reaction of catalysis becomes study hotspot, catalyzer comprises proline(Pro) and analogue, chirality (sulphur) urea, chirality guanidine, polypeptide, chiral imidazole quinoline and derivative, golden pheasant soda and the (Li Ning such as derivative and chiral catalysts of transition metal complexes thereof, Deng. organic chemistry .2009,29 (7): 1018-1038).
In product in Michael reaction, having a compounds is 1,5-dicarbonyl compound, the people such as Hua have reported the chiral phosphine acyl compounds and the α that get with ephedrine derivatives, alpha, beta-unsaturated ketone has obtained 1,5-dicarbapentaborane ketone compounds (Hua., Deng .J.Am.Chem.Soc.1987,109:5026-5029), contain 1, the compound of 5-dicarbapentaborane group is very important organic synthesis intermediate: 6,7-dihydro-5H-pentamethylene also [b] pyridine is the important source material of synthetic cefpirome, has antiulcer agent and anticancer isoreactivity; 1,5-dicarbonyl compound be exactly important source material in its cyclization step (Duan Xuemin, etc. fine-chemical intermediate .2004,4:8-11); 3; 7-dimethyl-2; 7-octadiene-1-alcohol propionic ester is the main component of San Jose scale sex pheromone; if synthetic taking methyl aceto acetate and ethyl propenoate as raw material; route is very long, and with 1,5-dicarbonyl compound carries out synthetic easy many (Wang Shimin of skeleton structure; Deng. SCI .1990,4:428-430).
1,2,3-thiadiazole compound has biological activity widely equally, relevant patent and document are summed up and are seen Bakulev, et al.Newyork:John Wiley & Sons, Inc, 2004 monograph, about the research of thiadiazoles mainly concentrates on 1,3,4-thiadiazoles derivative, 1,2,5-thiadiazoles derivative and 1, on 2,4-thiadiazoles derivative, and for 1, the research report of 2,3-thiadiazoles derivative activity is but relatively less.1,2,3-thiadiazoles derivative commercial kind in medicine and agricultural chemicals is few, what agriculture field was applied only has cotton defoliant--disleave spirit (N-phenyl-N '-1,2,3-thiadiazoles-5-urea, TDZ), activating plants agent--Acibenzolar (phendioxin, 2,3-thiadiazoles-7-thiocarboxylic acid methyl esters, BTH), rice field sterilant--tiadinil (3 '-chloro-4,4 '-dimethyl-1,2,3-thiadiazoles-5-formylaniline, TDL).Contriver's research and design is in earlier stage synthesized and has found that first thiophene lures the inducing anti-disease activity of amine, at present just in industrialization development process.
In order to find 1,2 of high biological activity more, 3-thiadiazole new compound, the present invention utilizes Michael reaction, by 1,2,3-Thiadiazole introduces 1, in 5 dicarbonyl compound molecules, class 3-(4-methyl isophthalic acid, 2 have been synthesized in design, 3-thiadiazoles-5-yl)-1,5-derovatives, and carried out the bioactive screening of system, to providing candidate compound for novel pesticide initiative research.
Summary of the invention
Technical problem to be solved by this invention is: new 3-(4-methyl isophthalic acid is provided, 2,3-thiadiazoles-5-yl)-1, the synthetic method of 5-derovatives, provide this compounds to suppress biological activity and the measuring method thereof of agricultural and gardening and forestry plant pathogen, the middle application of these compounds in agriculture field and gardening field and field of forestry is provided simultaneously.
The present invention solves this technical problem adopted technical scheme: 3-(the 4-methyl isophthalic acid with agriculture field, gardening field, field of forestry insecticidal activity, fungicidal activity, anti-phytoviral activity, inducing plant generation anti-disease activity, 2,3-thiadiazoles-5-yl)-1, the chemical structure of general formula of 5-derovatives is shown in formula V:
Wherein, R
1for being selected from the group of phenyl, 4-nitrophenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 2,4 dichloro benzene base; R
2for being selected from the group of hydrogen, ethyl, propyl group.
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic method of 5-derovatives V is as follows:
Wherein: R
1for being selected from the group of phenyl, 4-nitrophenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 2,4 dichloro benzene base, R
2for being selected from the group of hydrogen, ethyl, propyl group; R.t.: room temperature; Aq: the aqueous solution; PCC: pyridinium chloro-chromate; NaBH
4: sodium borohydride; EtOH: ethanol; CH
3oH: ethanol; CH
2c1
2: methylene dichloride.
Specifically be divided into following steps:
A. intermediate 4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-ethyl formate I:
Intermediate 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-ethyl formate utilizes Hurd-Mori method reference literature (Fan Zhijin, Shi Zugui, Liu Xiufeng, Fan Zhiyin, Ai Yingwei, [1, 2, 3] thiadiazoles derivative and preparation method and use thereof, China national patent of invention, accept the date: on February 20th, 2006, application number: 200610013185.5, publication number: CN1810808A, publication date: on August 2nd, 2006, the Granted publication date: on September 24th, 2008, the patent No.: ZL 200610013185.5, Granted publication number: CN 100420686C) method synthetic.
B.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-methyl alcohol II
In 500 milliliters of round-bottomed flasks, add 30 grams of 4-methyl isophthalic acids, 2, 3-thiadiazoles-5-ethyl formate I, the ethanol of 240 milliliters, under ice bath agitation condition, add 13.2 grams of sodium borohydrides in batches, add rear continuation stirs 1 hour under ice bath, remove ice bath stirred overnight at room temperature, after monitoring has been reacted, suction filtration, concentrating under reduced pressure is except desolventizing, be extracted with ethyl acetate, with anhydrous sodium sulfate drying, suction filtration, remove anhydrous sodium sulphate, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: ethyl acetate is the column chromatography separating purification Compound I I of 2: 1 eluents, obtain 17.50 grams of weak yellow liquids, yield is 77%, 4-methyl isophthalic acid, amount prepared by 2,3-thiadiazoles-5-methyl alcohol II expands or dwindles by corresponding proportion, and the volume of reaction vessel expands or dwindles by corresponding proportion, and commercially available Compound I has same effect.
C.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formaldehyde III
In 500 milliliters of round-bottomed flasks, add 10 grams of 4-methyl isophthalic acids, 2,3-thiadiazoles-5-methyl alcohol II, 300 milliliters of methylene dichloride add 26.48 grams of pyridinium chloro-chromates, stirred overnight at room temperature in batches, after monitoring has been reacted, suction filtration, concentrating under reduced pressure, except desolventizing, is used volume ratio sherwood oil: ethyl acetate is that 8: 1 eluents are through column chromatography separating purification intermediate III, obtain 6.40 grams of brown color liquid, yield is 65%.4-methyl isophthalic acid, amount prepared by 2,3-thiadiazoles-5-formaldehyde III expands or dwindles by corresponding proportion, and the volume of reaction vessel expands or dwindles by corresponding proportion, and commercially available Compound I I has same effect.
D.3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the preparation of 5-diketone V
3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the preparation of 5-diketone V utilizes Michael reaction preparation.
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid taking mol ratio as the ratio of 1: 2,2,3-thiadiazoles-5-formaldehyde III and ketone compounds IV and 20 ml methanol; Dropwise splash into again 50% potassium hydroxide solution, 4-methyl isophthalic acid, the mol ratio of 2,3-thiadiazoles-5-formaldehyde and potassium hydroxide amount is 1: 5; Stirring at room temperature 5 hours, after monitoring has been reacted, the potassium hydroxide that adds dilute hydrochloric acid solution to neutralize to add to pH be 7, concentrating under reduced pressure, except desolventizing, is used volume ratio sherwood oil: the column chromatography separating purification product V of the eluent that ethyl acetate is 8: 1, obtains solid, by gained sterling calculated yield, according to the ketone difference of reacting, yield scope from 42% to 60%, measure fusing point and
1h NMR, the amount of product V expands or dwindles by corresponding proportion, and the volume of reaction vessel expands or dwindles by corresponding proportion, and commercially available compound III has same effect; The chemical structure of product V and physico-chemical property are in table 1.
E.3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the mensuration to pathogenic fungi growth activity of 5-diketone V:
3-of the present invention (4-methyl isophthalic acid, 2, 3-thiadiazoles-5-yl)-1, the V sterilization of 5-diketone or bacteriostatic activity adopt thalli growth rate assay method, detailed process is: get 5 milligrams of sample dissolution in appropriate dimethyl formamide, then with the medicament that contains a certain amount of polysorbas20 emulsifier aqueous solution and be diluted to 500 ug/ml, by reagent agent each absorption in 1 milliliter of injection culture dish under aseptic condition, add respectively again 9 milliliters of substratum, after shaking up, make 50 ug/ml pastille flat boards, do blank with the flat board that adds 1 milliliter of aqua sterilisa, cut bacterium dish along mycelia outer rim with the punch tool of 4 millimeters of diameters, move on pastille flat board, being equilateral triangle puts, every processing repeats 3 times, culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and is cultivated, colony diameter to be contrasted expands to 2-3 centimetre of " Invest, Then Investigate " and respectively processes bacterium dish expansion diameter, average, relatively calculate relative bacteriostasis rate with blank, comprise frequently seen plants pathogenic bacteria in various agricultural for examination bacterial classification, its title and code name comprise AS: tomato early blight bacterium (Alternaria solani), BC: botrytis cinerea pers (Botrytis cinerea), CA: peanut Cercospora bacteria (Cercospora arachidicola), GZ: fusarium graminearum (Gibberella zeae), PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary), PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola), PS: Rhizoctonia solani Kuhn (Pellicularia sasakii), RC: Rhizoctonia cerealis (Rhizoctonia cerealis), SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum), these pathogenic fungies can represent the kind of most of pathogenic bacteria of the actual generation in field in China's agriculture production.
The invention has the beneficial effects as follows: the present invention is to 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V has carried out the optimization of guide structure, and synthetic new compound has been carried out the screening of bacteriostatic activity and mixed use research, this compounds can be for the control of the plant pest in control agriculture field and field of forestry and gardening field.
The present invention more specifically describes 3-(4-methyl isophthalic acid by specific preparation and biological activity determination embodiment, 2,3-thiadiazoles-5-yl)-1, synthetic and biological activity and the application thereof of 5-derovatives V, described embodiment is unrestricted the present invention for specific description the present invention only, especially its biological activity only illustrates, and unrestricted this patent, embodiment is as follows:
Embodiment 1
4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-methyl alcohol II
In 500 milliliters of round-bottomed flasks, add 30 grams of 4-methyl isophthalic acids, 2, 3-thiadiazoles-5-ethyl formate, the ethanol of 240 milliliters, under ice bath agitation condition, add 13.2 grams of sodium borohydrides in batches, add rear continuation stirs 1 hour under ice bath, remove ice bath stirred overnight at room temperature, after monitoring has been reacted, suction filtration concentrating under reduced pressure is except desolventizing, be extracted with ethyl acetate, with anhydrous sodium sulfate drying, suction filtration, remove anhydrous sodium sulphate, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: ethyl acetate is the column chromatography separating purification compound of 2: 1 eluents, obtain 17.50 grams of weak yellow liquids, yield is 77%.
Embodiment 2
4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formaldehyde III
In 500 milliliters of round-bottomed flasks, add 10 grams of 4-methyl isophthalic acids, 2,3-thiadiazoles-5-methyl alcohol, 300 milliliters of methylene dichloride add 26.48 grams of PCC, stirred overnight at room temperature in batches, after monitoring has been reacted, suction filtration, concentrating under reduced pressure, except desolventizing, is used volume ratio sherwood oil: ethyl acetate is the column chromatography separating purification compound of 8: 1 eluents, obtain 6.40 grams of brown color liquid, yield is 65%.
Embodiment 3
Compound D GD-1:1,5-phenylbenzene-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 0.94 gram of methyl phenyl ketone, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 0.70 gram of white solid, fusing point: 105-107 degree Celsius, yield 51%.Nuclear magnetic data (CDCl
3, chemical shift): 2.805 (s, 3H, CH
3), 3.464 (dd, J=7.2Hz, 18Hz, 2H, CH
2), 3.628 (dd, J=6.0Hz, 17.6Hz, 2H, CH
2), 4.493-4.558 (m, 1H, CH), 7.482 (t, J=8.0Hz, 7.6Hz, 4H, ph-H), 7.602 (t, J=7.2Hz, 7.6Hz, 2H, ph-H), 7.933 (d, J=7.2Hz, 4H, ph-H).
Embodiment 4
Compound D GD-2:1,5-(4,4 '-dinitrobenzene)-phenylbenzene-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 1.28 grams of 4-nitro-acetophenones, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 0.72 gram of yellow solid, fusing point: 100-102 degree Celsius, yield 42%.Nuclear magnetic data (CDCl
3, chemical shift): 2.804 (s, 3H, CH
3), 3.420 (dd, J=6.8Hz, 17.6Hz, 2H, CH
2), 3.585 (dd, J=6.4Hz, 18Hz, 2H, CH
2), 4.457-4.522 (m, 1H, CH), 7.461 (d, J=8.0Hz, 4H, ph-H), 7.871 (d, J=8.0Hz, 4H, ph-H).
Embodiment 5
Compound D GD-3:1,5-(4,4 '-dichloro)-phenylbenzene-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 1.20 grams of 4-chloro-acetophenones, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 0.98 gram of white solid, fusing point: 133-135 degree Celsius, yield 60%.Nuclear magnetic data (CDCl
3, chemical shift): 2.816 (s, 3H, CH
3), 3.418 (dd, J=6.8Hz, 17.6Hz, 2H, CH
2), 3.592 (dd, J=6.0Hz, 7.6Hz, 2H, CH
2), 4.463-4.528 (m, 1H, CH), 7.464 (d, J=8.4Hz, 4H, ph-H), 7.875 (d, J=8.8Hz, 4H, ph-H).
Embodiment 6
Compound D GD-4:1,5-(4,4 '-dimethoxy)-phenylbenzene-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 1.29 grams of 4-methoxyacetophenones, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 0.91 gram of white solid, fusing point: 119-121 degree Celsius, yield 57%.Nuclear magnetic data (CDCl
3, chemical shift): 2.769 (s, 3H, CH
3), 3.378 (dd, J=7.2Hz, 17.6Hz, 2H, CH
2), 3.581 (dd, J=6.0Hz, 17.2Hz, 2H, CH
2), 3.875 (s, 6H, ph-CH
3), 4.448-4.513 (m, 1H, CH), 6.933 (d, J=8.4Hz, 4H, ph-H), 7.906 (d, J=8.4Hz, 4H, ph-H).
Embodiment 7
Compound D GD-5:1,5-(2,2 ', 4,4 '-tetrachloro)-phenylbenzene-2,4-diethyl-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 2, 1.7 grams of 4-dichlorobenzene butanone, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 0.93 gram of white solid, fusing point: 134-136 degree Celsius, yield 44%.Nuclear magnetic data (CDCl
3, chemical shift): 0.947 (t, J=7.2Hz, 6H, ph-CH
3), 1.392-1.489 (m, 2H, ph-CH
2cH
2), 1.645-1.778 (m, 2H, ph-CH
2cH
2), 2.700 (t, J=15.2Hz, 2H, CH), 2.773 (s.3H, CH
3), 3.710-3.856 (m, 1H, CH), 7.334-7.360 (m, 2H, ph-H), 7.522 (s, 2H, ph-H) 7.980 (t, J=8.4Hz, 2H, ph-H).
Embodiment 8
Compound D GD-6:1,5-(2,2 ', 4,4 '-tetrachloro)-phenylbenzene-2,4-dipropyl-3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic and Structural Identification of 5-diacetylmethane
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid, 2, 0.5 gram, 3-thiadiazoles-5-formaldehyde, 2, 1.8 grams of 4-dichlorobenzene pentanones, 20 milliliters of methyl alcohol, dropwise splash into again 50% potassium hydroxide solution containing 1.1 grams of potassium hydroxide and the preparation of 1.1 ml waters, stirring at room temperature 5 hours, after monitoring has been reacted, add in dilute hydrochloric acid solution and excessive potassium hydroxide, to pH be 7, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: the column chromatography separating purification compound of the eluent that ethyl acetate is 8: 1, obtain 1.01 grams of white solids, fusing point: 134-136 degree Celsius, yield 46%.Nuclear magnetic data (CDCl
3, chemical shift): 0.941 (t, J=7.2Hz, 7.6Hz, 6H, ph-CH
3), 1.333-1.439 (m, 4H, ph-CH
2cH
2), 1.650-1.725 (m, 4H, ph-CH
2cH
2), 2.835 (s.3H, CH
3), 2.930 (t, J=7.2Hz, 7.6Hz, 2H, CH), 3.979-4.171 (m, 1H, CH), 7.302-7.328 (m, 2H, ph-H), 7.414 (s, 2H, ph-H) 7.441 (t, J=2.0Hz, 2.4Hz, 2H, ph-H).
Embodiment 9
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the antibacterial or fungicidal activity of 5-diketone V:
Title and the code name of the frequently seen plants pathogenic fungi of the present invention's test comprise AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), these bacterial classifications have good representativeness, can represent the kind of most of pathogenic bacteria that in agriculture production, field occurs.Thalli growth rate method measurement result is in table 2, and table 2 shows, in the time of 50 ug/ml, all compounds that the present invention synthesizes all have fungicidal activity in various degree, especially outstanding the is synthetic Compound D GD-6 of the present invention to the fungicidal activity of AS higher than 70%; DGD-6 to the fungicidal activity of GZ all higher than 60%; DGD-1, DGD-6 to the fungicidal activity of PP all higher than 60%; DGD-1, DGD-6 to the fungicidal activity of BC all higher than 60%; DGD-1, DGD-2, DGD-3, DGD-4, DGD-5, DGD-6 to the fungicidal activity of RC all higher than 60%; DGD-3, DGD-6 to the fungicidal activity of PS all higher than 70%; DGD-6 is to the fungicidal activity of PI all higher than 80%, and therefore, this compounds has shown good fungicidal activity.
Embodiment 10
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the application in 5-derovatives V and insecticide composition control agricultural and forestry and gardening plant insect pest
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the total quality percentage composition of 5-derovatives V in composition is 1%-90%, 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the ratio of 5-derovatives V and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%, can directly be watered rear spraying, comprise the upper acceptable solvent of agricultural and emulsifying agent and solubility promoter and synergistic agent etc. in its preparation, the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, granule, microemulsion, oil-suspending agent, finish, with the seed of 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, CG/Encapsulated granule, capsule suspension, dispersible dense dose, pulvis, Waterless Seed Dressing 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, large granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, any one in wet-mixing kind water-dispersible powder, 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, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, Nezara viridula smaragdula Fabricius., green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, cnidocampa flavescens walker, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, small cabbage moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, Pyrausta nubilalis (Hubern)., yellow rice borer, Oeobia undalis, Cnaphalocrocis medinali(rice leaf roller), bar snout moth's larva, the wild snout moth's larva of lap leaf, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point diamond drill, black cutworm, large cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, 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, gold edge buprestid beetle, tenebrio molitor, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, large daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, Phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm is hanged cocoon ichneumon wasp, bollworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melon trypetid, the latent fly of wheat leaf ash, Americal rice leaf miner, the black latent fly of beans stalk, frit fly, plant fly, onion fly, radish fly, full skirt chases after posts fly, Pyrausta nubilalis (Hubern). is strict posts fly, armyworm lacks must post the Agricultural pests such as fly, forestry pest, gardening pest insect and sanitary insect pest, controlling mode also comprises double controlling simultaneously, 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V can mix use with one or more in the sterilant of lower group: Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, efficient fenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, young urea goes out, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron is noviflumuron, and it is for No. CAS 121451-02-3, flucycloxuron, Novaluron is Rimon, fluorine pyridine urea, i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea } of Bay sir 6874, Bay SIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron is bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, desinsection list, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, the young ketone of rattling away, Nylar, emaricins etc., the prevention effect of composition is good, and drug effect is played stably.The applicable crop of these compositions comprises paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, potted landscape.Composition has improved the defence capability of plant in desinsection, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 11
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the application in 5-derovatives V and sterilant combination control agricultural and forestry and gardening plant disease
All 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V and existing sterilant are as diazosulfide, tiadinil, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil (isotianil), virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, Whitfield's ointment, flumorph, dimethomorph, efficient metaxanin, efficient M 9834, two chlorine zarilamids, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, alkene azoles alcohol, efficient alkene azoles alcohol, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, the third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc manganese ethylenebisdithiocarbamate, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, other known any any one or two kinds that can be used as in sterilant such as allyl isothiazole are used in combination, 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the total quality percentage composition of 5-derovatives V in composition is 1%-90%, 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the ratio of 5-derovatives V and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%, the prevention effect of medicament is good, and these compositions have certain synergism and summation action, does not find to have the composition of antagonistic action, above-mentioned composition can be for the control of agricultural plants disease and gardening plant disease, controlling object comprises that more than 20 of the Achylas, Aphanomyces, pythium, phytophthora, Sclerospora, Plasmopara, Pseudoperonospora, Peronospora of Oomycete etc. belong to the diseases that produce, as other diseases of plurality of cereals crop, cash crop, gardening plant and the forestry plants such as seedling blight of rice, tomato root maize ear rot, the late blight of potato, black shank, millet Powdery Mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose etc., the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, granule, microemulsion, oil-suspending agent, finish, with the seed of 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, CG/Encapsulated granule, capsule suspension, dispersible dense dose, pulvis, Waterless Seed Dressing 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, large granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, any one in wet-mixing kind water-dispersible powder.The applicable crop of these compositions comprises that cereal (comprises paddy, wheat, barley, oat, corn, millet, Chinese sorghum etc.), tuber crops (comprise sweet potato, potato, cassava etc.), beans (comprises 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 (ginseng, the bulb of fritillary etc.), the torrid zone (rubber, coconut, oil palm, sisal hemp etc.) etc. food crop and fruit, flowers, oil plant, sugar material and cotton, fiber crops, tea, tobacco, the cash crop such as Chinese medicinal materials and plantation melon, really, tea, silkworm and mulberry, vegetables (containing various wild vegetable etc.), bamboo shoots, flowers and ornamental plant, hops, medicinal material, pepper, the garden crops such as seedling and other garden crops are as tobacco (flue-cured tobacco, air-curing of tobacco leaves, suncured tabacco), vegetables, (tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic etc.), melon (watermelon, muskmelon, hami melon, pawpaw etc.), beans (soybean, broad bean, pea-pods etc.), potato, wheat, corn, paddy rice, peanut, fruit tree, (apple, banana, citrus, peach, papaya), flowers (as orchid), potted landscape etc.Composition has improved the defence capability of plant in sterilization, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 12
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V and antiviral agent are combined in the application in control agricultural and forestry and gardening plant virus disease
3-(4-methyl isophthalic acid, 2, 3-thiadiazoles-5-yl)-1, 5-derovatives V and existing Antiphytoviral medicament diazosulfide, tiadinil (TDL), isotianil (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 lures amine or Whitfield's ointment, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, any 1 or 2 compound combinations in jingganmycin, be used for preventing and treating agricultural plants virus disease, these virus diseases are selected from tobacco mosaic virus disease, various melon virus diseases, various solanaceous vegetables virus diseases, beans virus disease, Cruciferae virus disease, grain and oil crop virus disease, any in cotton virus disease and various fruit tree virus disease, wherein endanger serious being selected from: tobacco virus, peppery pimento virus disease, tomato virus disease, Chinese cabbage virus disease, Virus Diseases of Rice comprises rice dwarf virus disease, yellow dwart, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease and tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, oranges and tangerines virus disease, cymbidium mosaic virus, any in cybidium ring spot virus.The applicable crop of these compositions is selected from paddy, wheat, barley, oat, corn, Chinese sorghum, sweet potato, potato, cassava, soybean, pea-pods, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, Sunflower Receptacle, beet, sugarcane, coffee, cocoa, ginseng, the bulb of fritillary, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, hami melon, pawpaw, really, tea, wild vegetable, bamboo shoots, hops, potato, paddy rice, pepper, apple, banana, citrus, peach, papaya, orchid, the agriculturals such as potted landscape, gardening, economical, the plants such as forestry, the use of these compositions is improved the immunizing power of crop self, in 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 prevention effect of virus disease, therefore, these compositions can be for preparation and the purposes of Antiphytoviral medicament and inducing plant Antiphytoviral medicament.3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the total quality percentage composition of 5-derovatives V in composition is 1%-90%, 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the ratio of 5-derovatives V and commercially available agricultural chemical is mass percent 1%: 99% to 99%: 1%, the formulation of composition processing is selected from wettable powder, sustained release dosage, pulvis, micro-capsule suspension, dispersible body preparation, dispersible solid preparation, seed treatment emulsion, aqueous emulsion, large granula, granule, microemulsion, oil-suspending agent, finish, with the seed of 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, CG/Encapsulated granule, capsule suspension, dispersible dense dose, pulvis, Waterless Seed Dressing 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, large granula, drift pulvis, granula, ointment, thermal fog, solid-liquid mixes dress agent, liquid/liquid mixes dress agent, cold mist agent, Gu Gu/mix filling agent, medicine paint, seed treatment liquor, microgranules, oil suspending agent, finish, oil-dispersing property pulvis, paste, sheet poison bait, dense jelly, sprinkle and water agent, stylus, seed coat agent, poison bait, basting agent, fritter poison bait, suspension agent, suspension emulsion, water-soluble granule, soluble thick agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspension agent, tablet, follow the trail of pulvis, ultra low volume liquids, steam releasing agent, water-dispersible granules, wettable powder, any one in wet-mixing kind water-dispersible powder, between these compositions, all show and be added or synergism, in keeping insecticidal activity, its antiviral activity is all greater than the effect that any one compound uses separately, find no the composition of antagonistic action, the drug effect lasting period of composition is long.
From the basic principles of chemistry, 3-(4-methyl isophthalic acid, 2, 3-thiadiazoles-5-yl)-1, thereby 5-derovatives V can produce 4-methyl isophthalic acid from carbonyl fracture in plant with after water molecules effect, 2, 3-thiadiazoles-5-formic acid, also confirm that by relevant software prediction and test compound of the present invention can produce 4-methyl isophthalic acid in the degraded of plant materials intracellular metabolite, 2, 3-thiadiazoles-5-formic acid, bibliographical information confirms 4-methyl isophthalic acid, 2, 3-thiadiazoles-5-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 compositions can be used in and prepare Antiphytoviral medicament and inducing plant Antiphytoviral medicament.Composition has improved the defence capability of plant in Antiphytoviral, makes plant produce the defence capability to pathogenic fungi, bacterium and virus infection.
Embodiment 13
3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, complete processing and the stability of 5-derovatives V and commercially available agricultural chemical compound preparation
3-of the present invention (4-methyl isophthalic acid, 2, 3-thiadiazoles-5-yl)-1, the mixed preparation complete processing of 5-derovatives V and commercially available agricultural chemical is in table 3, from table 3, most medicament all can be processed according to the method for statement, the main component of liquid preparation is effective constituent and solubility promoter and tensio-active agent, synergistic agent, antifreezing agent, stablizer, other the component etc. such as thickening material or permeate agent, the composition of solid preparation mainly includes effect composition, the upper acceptable adjuvant component of other agriculturals such as tensio-active agent and filler, the cold storage test of process preparation, liquid preparation is placed 1 week without Precipitation at 0 ± 2 degree Celsius, solid preparation is placed 2 weeks at 54 ± 2 degrees Celsius, there is not caking phenomenon in medicament, all preparations store the medicament drug effect of placing front and back without significant difference, the rate of decomposition of composition effective constituent is in 5%, composite preparation qualified stability.
Table 1 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, chemical structure and the physical and chemical parameter of 5-derovatives V
The 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1 that table 2 the present invention is synthetic, the fungicidal activity (/ %) of 5-derovatives V
| Compound | AS | CA | GZ | PP | BC | SS | RC | PS | PI |
| DGD-1 | 23.33 | 21.74 | 42.86 | 61.29 | 61.67 | 42.31 | 60.00 | 39.44 | 25.93 |
| DGD-2 | 23.33 | 30.43 | 47.62 | 51.61 | 50.00 | 46.15 | 66.00 | 57.75 | 18.52 |
| DGD-3 | 40.00 | 34.78 | 52.38 | 46.77 | 46.67 | 42.31 | 66.00 | 70.42 | 25.93 |
| DGD-4 | 36.67 | 26.09 | 42.86 | 51.61 | 41.67 | 23.08 | 64.00 | 30.99 | 18.52 |
| DGD-5 | 37.50 | 29.63 | 36.73 | 49.37 | 42.59 | 36.54 | 73.17 | 48.33 | 30.77 |
| DGD-6 | 75.00 | 40.74 | 67.35 | 78.48 | 85.19 | 40.38 | 80.49 | 71.67 | 88.46 |
Data are the measurement result of 50 ug/ml; AS: tomato early blight bacterium (Alternaria solani); BC: botrytis cinerea pers (Botrytis cinerea); CA: peanut Cercospora bacteria (Cercospora arachidicola); GZ: fusarium graminearum (Gibberella zeae); PI: phytophthora infestans (Phytophthora infestans (Mont.) de Bary); PP: Botryosphaeria berengeriana f. sp (Physalospora piricola); PS: Rhizoctonia solani Kuhn (Pellicularia sasakii); RC: Rhizoctonia cerealis (Rhizoctonia cerealis); SS: Sclerotinia sclerotiorum (Sclerotinia sclerotiorum).
Table 3 3-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V working method mixed with commercially available agricultural chemical
Claims (3)
1. a class 3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives, is characterized in that having the chemical structure of general formula suc as formula shown in V:
Wherein: R
1for being selected from the group of phenyl, 4-nitrophenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 2,4 dichloro benzene base; R
2for being selected from the group of hydrogen, ethyl, propyl group.
2. 3-claimed in claim 1 (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the synthetic method of 5-derovatives V, concrete synthetic route is as follows:
Wherein: R
1for being selected from the group of phenyl, 4-nitrophenyl, 4-p-methoxy-phenyl, 4-chloro-phenyl-, 2,4 dichloro benzene base; R
2for being selected from the group of hydrogen, ethyl, propyl group; R.t.: room temperature; Aq: the aqueous solution; PCC: pyridinium chloro-chromate; NaBH
4: sodium borohydride; EtOH: ethanol; CH
3oH: ethanol; CH
2cl
2: methylene dichloride;
Specifically be divided into following steps:
A.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-methyl alcohol II:
In 500 milliliters of round-bottomed flasks, add 30 grams of 4-methyl isophthalic acids, 2, 3-thiadiazoles-5-ethyl formate I, the ethanol of 240 milliliters, under ice bath agitation condition, add 13.2 grams of sodium borohydrides in batches, add rear continuation stirs 1 hour under ice bath, remove ice bath stirred overnight at room temperature, after monitoring has been reacted, suction filtration, concentrating under reduced pressure is except desolventizing, be extracted with ethyl acetate, with anhydrous sodium sulfate drying, suction filtration, remove anhydrous sodium sulphate, concentrating under reduced pressure is except desolventizing, use volume ratio sherwood oil: ethyl acetate is the column chromatography separating purification Compound I I of 2: 1 eluents, obtain 17.50 grams of weak yellow liquids, yield is 77%,
B.4-methyl isophthalic acid, the preparation of 2,3-thiadiazoles-5-formaldehyde III
In 500 milliliters of round-bottomed flasks, add 10 grams of 4-methyl isophthalic acids, 2,3-thiadiazoles-5-methyl alcohol II, 300 milliliters of methylene dichloride add 26.48 grams of pyridinium chloro-chromates, stirred overnight at room temperature in batches, after monitoring has been reacted, suction filtration, concentrating under reduced pressure, except desolventizing, is used volume ratio sherwood oil: ethyl acetate is that 8: 1 eluents are through column chromatography separating purification intermediate III, obtain 6.40 grams of brown color liquid, yield is 65%;
C.3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the preparation of 5-derovatives V
3-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1, the preparation of 5-derovatives V utilizes Michael reaction preparation:
In 50 milliliters of round-bottomed flasks, add 4-methyl isophthalic acid taking mol ratio as the ratio of 1: 2,2,3-thiadiazoles-5-formaldehyde III and ketone compounds IV and 20 ml methanol; Dropwise splash into again 50% potassium hydroxide solution, 4-methyl isophthalic acid, the mol ratio of 2,3-thiadiazoles-5-formaldehyde and potassium hydroxide amount is 1: 5; Stirring at room temperature 5 hours, after monitoring has been reacted, the potassium hydroxide that adds dilute hydrochloric acid solution to neutralize to add to pH be 7, concentrating under reduced pressure, except desolventizing, is used volume ratio sherwood oil: the column chromatography separating purification product V of the eluent that ethyl acetate is 8: 1, obtains solid, by gained sterling calculated yield, according to the ketone difference of reacting, yield scope from 42% to 60%, measure fusing point and
1hNMR.
3. 3-claimed in claim 1 (4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,5-derovatives V forms composition in the purposes of preparing in sterilant with the upper acceptable auxiliary agent of agricultural.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210096833.3A CN102633744B (en) | 2012-04-05 | 2012-04-05 | 3-(4-methyl-1, 2, 3-thiadiazole-5-yl)-1, 5-diketone derivatives as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210096833.3A CN102633744B (en) | 2012-04-05 | 2012-04-05 | 3-(4-methyl-1, 2, 3-thiadiazole-5-yl)-1, 5-diketone derivatives as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102633744A CN102633744A (en) | 2012-08-15 |
| CN102633744B true CN102633744B (en) | 2014-06-18 |
Family
ID=46618339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210096833.3A Expired - Fee Related CN102633744B (en) | 2012-04-05 | 2012-04-05 | 3-(4-methyl-1, 2, 3-thiadiazole-5-yl)-1, 5-diketone derivatives as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102633744B (en) |
Citations (3)
| 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 |
| CN1232458A (en) * | 1996-09-30 | 1999-10-20 | 日本农药株式会社 | 1,2,3-thiadiazole derivs. and salts thereof, disease agent for agricultural and horticultural use and method for use thereof |
| CN101891709A (en) * | 2010-07-27 | 2010-11-24 | 南开大学 | 5-halogenated methyl-1,2,3-thiadiazole compound and preparation method and use thereof |
-
2012
- 2012-04-05 CN CN201210096833.3A patent/CN102633744B/en not_active Expired - Fee Related
Patent Citations (3)
| 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 |
| CN1232458A (en) * | 1996-09-30 | 1999-10-20 | 日本农药株式会社 | 1,2,3-thiadiazole derivs. and salts thereof, disease agent for agricultural and horticultural use and method for use thereof |
| CN101891709A (en) * | 2010-07-27 | 2010-11-24 | 南开大学 | 5-halogenated methyl-1,2,3-thiadiazole compound and preparation method and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| 4-甲基-1,2,3-噻二唑-5-甲酸芳酯的合成及生物活性;王守信 等;《农药学学报》;20101231;第12卷(第3期);255-263 * |
| Edward W. Thomas,等.Synthesis and Platelet Aggregation Inhibitory Activity of 4,5-Bis(substituted)-1,2,3-thiadiazoles.《J. Med. Chem.》.1985,第28卷(第4期),442-446. * |
| 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》.2010,第12卷(第3期),255-263. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102633744A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172613B (en) | One class contains anthranilic diamides derivative of N-cyano group sulfone (sulphur) imines and its production and use | |
| CN103450154B (en) | Substituted pyrazolecarboxylic benzamide type bisamide derivatives of one class Sulfide-containing Hindered, N-cyano group sulphur (sulfone) imine structure and its production and use | |
| CN103497182B (en) | One class contains 3 of 4,5-thiazoline carboxylic ester, 4-dichloro Isothizole derivatives and its production and use | |
| CN103467463A (en) | Lignin derivatives as well as preparation method and use thereof | |
| CN103172614B (en) | One class contains anthranilic diamides derivative of sulfone (sulphur) imines and its production and use | |
| CN102816134B (en) | 1,2,3-thiadiazole-containing sulfilimine (sulfonimine) compounds and their preparation method and use | |
| CN103483287B (en) | 3,4-dichloroisothiazole containing bisamide compounds as well as preparation method and application thereof | |
| CN102382108B (en) | Tetrazole compounds containing 1,2,3-bismuththiol methylene, preparation methods for same and application thereof | |
| CN102417505B (en) | Tetrazole compounds containing methyl-1,2,3-thiadiazole as well as preparation methods and application thereof | |
| CN102603669B (en) | Derivatives of alpha-methoxyl imino-5-methyl-1,2,3-thiadiazole-4- carboxylic acid methyl ester and preparation methods and uses thereof | |
| CN101891710B (en) | 4-halogenated methyl-1,2,3-thiadiazole compounds and 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 | |
| CN101891709B (en) | 5-halogenated methyl-1,2,3-thiadiazole compound and preparation method and use thereof | |
| CN102816158B (en) | 5-methyl-1,2,3-thiadiazole-1,3,4-oxadiazole derivatives, and preparation method and application 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 | |
| CN103193769A (en) | 4-methyl-1,2,3-thiadiazole-5-triazole compound as well as preparation method and use thereof | |
| CN102633745B (en) | Alpha-methoxy imino group-4-methyl-1, 2, 3-thiadiazole-5-methyl carboxylic ester derivatives and preparation method and application thereof | |
| CN104974150A (en) | 3,4-dichloroisothiazolyl-5-formamidine derivatives, and preparation method and application thereof | |
| CN103012392B (en) | Pyridine derivatives containing 1.2,3-thiadiazole, and preparation method and application thereof | |
| CN101921244A (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 | |
| CN104496980A (en) | Novel thiazole heterocyclic compound as well as preparation method and application thereof | |
| CN103214474B (en) | One class contains the 5-methyl isophthalic acid of 4,5-thiazoline carboxylic ester, 2,3-thiadiazoles derivative and its production and use | |
| CN102816133B (en) | 5-chloro-1,2,3-thiadiazole-4-acrylic derivatives, and preparation method and application thereof | |
| CN103012391B (en) | Pyrimidine derivatives containing 1,2,3-thiadiazole, 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140618 Termination date: 20160405 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |