CN102838593A - 2-(4-methyl-1,2,3-thiadiazole)-5-(substituent)-1,3,4-oxa(thia)diazole derivative and application thereof - Google Patents

2-(4-methyl-1,2,3-thiadiazole)-5-(substituent)-1,3,4-oxa(thia)diazole derivative and application thereof Download PDF

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CN102838593A
CN102838593A CN2012103771401A CN201210377140A CN102838593A CN 102838593 A CN102838593 A CN 102838593A CN 2012103771401 A CN2012103771401 A CN 2012103771401A CN 201210377140 A CN201210377140 A CN 201210377140A CN 102838593 A CN102838593 A CN 102838593A
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thiadiazoles
isophthalic acid
methyl isophthalic
benzyl
methyl
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CN102838593B (en
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徐维明
杨松
薛伟
金林红
陈卓
贺鸣
黎世泽
陈妍
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Guizhou University
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Abstract

The invention provides a 2-(4-methyl-1,2,3-thiadiazole)-5-(substituent)-1,3,4-oxa(thia)diazole derivative with better crop virus disease resistant activity. A target compound has a novel structure; and a commercial 2-(4-methyl-1,2,3-thiadiazole)-5-(substituent)-1,3,4-oxa(thia)diazole derivative is not available on a pesticide market; therefore, cross resistance cannot be generated between the 2-(4-methyl-1,2,3-thiadiazole)-5-(substituent)-1,3,4-oxa(thia)diazole derivative and the traditional antiviral agent; and better application prospects are obtained.

Description

2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative and application thereof
Technical field
The present invention relates to chemical industry and agricultural chemicals, concrete technology is 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3, and 4-dislikes (thiophene) diazoles derivative and application thereof.
Background technology
Tobacco mosaic virus(TMV) (Tobacco mosaic virus; Abbreviation: TMV) be the pathogenic agent of tobacco mosaic disease etc.; Belong to Tobamovirus crowd; Its host range is very wide, can infect 36 sections, 350 kind of plant such as Cruciferae, Solanaceae, composite family, Chenopodiaceae and Amaranthaceae, comprises tobacco, tomato, eggplant, capsicum, spinach etc.Virus as finding at first in the world and confirming has had the history in more than 100 year, and each cigarette district generally takes place in the world by its tobacco mosaic disease that causes.After tobacco plant is caught an illness, young leaflet tablet lateral vein and the offshoot tissue shape that is translucent, promptly bright arteries and veins, vein both sides mesophyll tissue gradually is light green.Virus propagation in a large number in leaf tissue increases the part mesophyll cell or increases, and it is irregular the blade thin and thick to occur, and color is yellowish green alternate, is the floral leaf shape.The mottled degree of back floral leaf strengthens, and existing big area Vandyke brown necrotic plaque, middle and lower part Lao Ye more so, leaf-shrinkage, deformity, distortion that morbidity is heavy.The plant internode of early stage morbidity shortens, the serious dwarfing, and poor growth can not normally be blossomed and beared fruit, and is prone to come off.Little and the shrinkage of developable shady fruit, seed dose is few and little, how can not germinate.Characteristics such as tobacco mosaic virus(TMV) has that host range is wide, strong stress resistance and the harm that on producing, causes are big; In China north and south cigarette district generation is arranged all; Especially southern cigarette district morbidity is heavier, and field strain sickness rate is general 5% ~ 20%, and indivedual fields piece can be up to 90% ~ 100%; The loss of early stage morbidity can reach 50% ~ 70%, even loses and receive.In addition, sick leaf is at the roasting back irregular colour that shines, and smoke is poor, and quality greatly reduces.The financial loss that whole world every year causes because of TMV is just above 100,000,000 dollars.Because virus is in case invade the host, its propagation just combines together with host's metabolism, suppresses that the medicament of virus multiplication is very difficult not to injure the host, and therefore, the control of this virus disease is the difficult point of control of plant disease all the time.(Li Caihua, Ling Shouheng, Shen Li, circumferentially flat, Huangshi is prosperous. several kinds of medicament screenings that prevent and treat tobacco mosaic disease, Anhui agricultural sciences, 2009,37 (34): 16909-16910), press for the antiviral agent of some novel structures of exploitation.
Sulfone compound has in fields such as agricultural chemicals widely to be used, like the biological activity of desinsection, sterilization, weeding, tuberculosis, anti-inflammatory, anti-hyperplasia, anti-HIV-1, anti-infective, anticancer, anti-consumptive disease, wide spectrum such as antitumor.In the early-stage Study, this seminar design is synthetic a series of new to contain 1,3, and 4-dislikes (thiophene) di azoly sulfone (sulfoxide) derivative, adopts growth rate method, with the former bacterium of tuber of pinellia damping-off ( R. solani), fusarium graminearum ( G. zeae), the former bacterium of gray mold of cucumber ( B. cinerea), Sclerotinia sclerotiorum ( S. sclerotiorum) etc. soil-borne disease and migrating property plant disease be tested object, the part target compound has been carried out bacteriostatic activity research, find the part target compound have good bacteriostatic activity [ Bioorg. Med. Chem. 2007, 15, 3981; Bioorg. & Med. Chem. 2008, 16,3632].At present, further find that the part target compound shows anti-preferably crop virus activity after the composition optimizes.
Summary of the invention
The objective of the invention is initiative the crop virosis evil is had efficient, eco-friendly novel antiviral agent; 2-(the 4-methyl isophthalic acid that a synthetic class formation is novel, agricultural chemicals does not have on the market, can not produce cross resistance with existing agricultural chemicals; 2; The 3-thiadiazoles)-and 5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative.
2-of the present invention (4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, has following general formula:
Figure 282177DEST_PATH_IMAGE001
Formula (I) formula II
In the formula:
X is O (oxygen) or S (sulphur), ， Wei oxadiazole compounds when X is O (oxygen); When X is S (sulphur), be thiadiazole compound;
R is selected from ester group, benzyl or the substituted benzyl of hydrogen, C1-C5 alkyl, C1-C2 haloalkyl, C1-C3 alkoxyl group, C2-C5 thiazolinyl, C2-C5.
Said halogen atom is fluorine, chlorine, bromine or iodine,
Said C1-C5 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or neo-pentyl,
Said C1-C2 haloalkyl is fluoroform alkyl, methyl chlorofluoride base, trichloromethane base, methylene fluoride base, methylene chloride-based, a fluoromethane base, 1,2-C2H4F2 C2H4F2 base, 1, and 2-Tetrafluoroethane base, 1,2-ethylene dichloride base or 1,2-tetrachloroethane base,
Said C1-C3 alkoxyl group is a methoxyl group, oxyethyl group or positive propoxy,
The thiazolinyl of said C2-C5 is vinyl, propenyl, allyl group, crotonyl, isobutenyl, pentenyl, isopentene group or new pentenyl,
The ester group of said C2-C5 is methyl-formiate base, group-4 ethyl formate, propyl formate base, methyl acetate base, ethyl acetate base or propyl acetate base,
Said substituted benzyl is 4-methyl-benzyl, 3-methyl-benzyl, 2-methyl-benzyl, 3,4-dimethyl benzyl, 2,4-dimethyl benzyl, 2; 6-dimethyl benzyl, 4-luorobenzyl, 3-luorobenzyl, 2-luorobenzyl, 3,4-difluorobenzyl, 2,4-difluorobenzyl, 2; 6-difluorobenzyl, 4-benzyl chloride base, 3-benzyl chloride base, 2-benzyl chloride base, 3,4-dichloro benzyl, 2,4-dichloro benzyl, 2; 6-dichloro benzyl, 4-methoxy-benzyl, 3-methoxy-benzyl, 2-methoxy-benzyl, 3; 4-dimethoxy-benzyl, 2,4-dimethoxy-benzyl, 2,6-dimethoxy-benzyl.
Part of compounds is:
I 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3, the 4-oxadiazole;
I 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3, the 4-oxadiazole;
I 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-chloro benzyl sulfur ether)-1,3, the 4-oxadiazole;
I 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3, the 4-oxadiazole;
I 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(4-nitrobenzyl thioether group)-1,3, the 4-oxadiazole;
I 6 :2-(ethoxycarbonyl methylene radical thioether)-5-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,3, the 4-oxadiazole;
II 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-oxadiazole;
II 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-oxadiazole;
II 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-benzyl chloride base sulfuryl)-1,3, the 4-oxadiazole;
II 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-oxadiazole;
III 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3, the 4-thiadiazoles;
III 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3, the 4-thiadiazoles;
III 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl thioether group)-1,3, the 4-thiadiazoles;
III 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl sulfide ether)-1,3, the 4-thiadiazoles;
III 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3, the 4-thiadiazoles;
IV 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-thiadiazoles;
IV 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-thiadiazoles;
IV 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl sulfuryl)-1,3, the 4-thiadiazoles;
IV 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl group sulfuryl)-1,3, the 4-thiadiazoles;
IV 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-thiadiazoles.
Described 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, is used for control or suppresses the crop virosis evil.
Described 2-(4-methyl isophthalic acid; 2; The 3-thiadiazoles)-5-(substituting group)-1; 3,4-dislikes (thiophene) diazoles derivative and is used for control or suppresses tobacco mosaic virus disease evil, cucumber mosaic virus virus disease, oryza virus 3 disease, rice dwarf virus disease virus disease, MRDV virus disease, rice black-streaked dwarf virus disease, tomato virus disease virus disease.
Described 2-(4-methyl isophthalic acid; 2; The 3-thiadiazoles)-5-(substituting group)-1; 3, the formulation that 4-dislikes (thiophene) diazoles derivative is missible oil, micro emulsion, water and milk, suspending agent, the agent of kind clothing, seed dressing, wettable powder, sustained-release granular formulation, controlled release granule, water dispersible granules, dry suspending agent or granule.
In the formulation of said preparation, active ingredient 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative and accounts for 1% ~ 90% of total formulation weight amount, and content is 10% ~ 85% more specifically.
Described 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislike (thiophene) diazoles derivative and are used to handle the purposes that virus, viral habitat maybe need prevent and treat material, crop, zone, soil, seed or the space of virus attack.
Embodiment: target compound synthetic
2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-oxadiazole analog derivative synthetic
Synthesizing of midbody carbazic acid ethyl ester
Figure 137001DEST_PATH_IMAGE003
(11.8g 0.1mol) throws in 100 mL there-necked flasks with 80% Hydrazine Hydrate 80 (5.9g, 0.095 mol), and room temperature (23 ℃) stirs 4h, and TCL follows the tracks of reaction (iodine colour developing, V sherwood oil: V ETHYLE ACETATE=3:1) with diethyl carbonate.The second alcohol and water is taken off in decompression, separates out clear crystal, and the rate of taking out obtains product 9g, 44 ~ 45 ℃ of fusing points (45 ~ 46 ℃, Fan, Z. J., et al, 2009), yield 87%.
Synthesizing of condensation midbody
Methyl aceto acetate (6.5g, 0.05 mol) and methylene dichloride (35 mL) are thrown in 100 mL there-necked flasks, carbazic acid ethyl ester (5.2g, 0.05 mol) is dissolved in methylene dichloride (17 mL) back slowly drips in the there-necked flask, dropwised in about 30 minutes.TCL follows the tracks of reaction, and (the iodine colour developing, the V sherwood oil: V ETHYLE ACETATE=3:1), reaction in 6 hours finishes.The decompression desolventizing obtains the white powder solid, and recrystallization gets product 5.5g (ethanol: water=3:1), 64 ~ 67 ℃ of fusing points (65-66 ℃, Fan, Z. J., et al., 2009), yield 85%.
Midbody 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate synthetic
Sulfur oxychloride 25 mL are thrown in 50 mL there-necked flasks, and ice bath keeps temperature to be lower than 10 ℃ down; Condensation product (6 g, 46 mmol) is dissolved in methylene dichloride (20 mL) back slowly drips in the reaction flask, keep temperature to be lower than 10 ℃; Dropwised in 1 hour, continuation is stirred under being lower than 10 ℃ and is moved to room temperature (being lower than 20 ℃) reaction 20 hours after 2 hours.Change water distilling apparatus into after reaction finishes and steam methylene dichloride and water, underpressure distillation then (collecting 136 ~ 140 ℃ of cuts) obtains slightly yellowy liquid, quality 5.2 g (Fan, Z. J., et al., 2009), yield 64%.
Midbody 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine synthetic
Figure 2012103771401100002DEST_PATH_IMAGE006
With the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate (5g, 29 mmol) and absolute ethyl alcohol (40 mL) are thrown in 100 mL there-necked flasks, are warming up to backflow behind dropping 80% Hydrazine Hydrate 80 (2 g, 32 mmol) under the room temperature, and TCL follows the tracks of reaction, and reaction in 5 hours finishes.The decompression desolventizing obtains yellow solid, and the absolute ethyl alcohol recrystallization gets yellow solid.Quality 3.7 g, 113 ~ 115 ℃ of fusing points, (Yang Zhiguang etc., 2001), yield 81%.
Midbody 2-sulfydryl-5-(4-methyl isophthalic acid, 2,3-thiadiazoles)-1,3,4-oxadiazole synthetic
Figure 498898DEST_PATH_IMAGE007
With the 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formyl hydrazine (3 g, 19 mmol), Pottasium Hydroxide (1.3 g, 19 mmol) and ethanol (30 mL) are thrown in l00 mL there-necked flask, the stirring at room dissolving.Be warming up to the end in 6 hours of 77 ~ 78 ℃ of back flow reaction after slowly adding dithiocarbonic anhydride (2.1 g, 28 mmol).Decompression is sloughed ethanol and is got yellow solid, and (100 mL) washes out with water, transfers pH=6 with 3% Hydrogen chloride, leaves standstill and obtains white cotton-shaped solid after 1 hour; Suction filtration, 95% ethyl alcohol recrystallization get 2-sulfydryl-5-(4-methyl isophthalic acid, 2,3-thiadiazoles)-1; 3,4-oxadiazole 2.4 g, white crystal; Fusing point: 144 ~ 148 ℃, yield 63% 1H NMR (500 MHz, CDCl 3) δ: 11.23 (s, 1H, SH), 3.27 (s, 3H, CH 3).
2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-substituting group thioether group-1,3, synthetic (I) of 4-oxadiazole
Figure 2012103771401100002DEST_PATH_IMAGE008
With 2-sulfydryl-5-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,3,4-oxadiazole (5 mmol), sodium hydroxide (0.2 g, 5 mmol) and water (20 mL) are thrown in l00 mL there-necked flask, the stirring at room dissolving.Slowly add methyl-sulfate (0.82 g, 6.5 mmol), Benzyl Chloride or replace Benzyl Chloride (6.5 mmol) back room temperature (22 ℃) reaction and finished in 1 hour.Suction filtration gets faint yellow solid, 95% ethyl alcohol recrystallization.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3,4-oxadiazole (I 1 )
Clear crystal, 132 ~ 134 ℃ of m.p.; Yield 65.6%; 1H NMR (500 MHz, CDCl 3) δ: 3.12 (s, 3H, CH 3), 3.45 (s, 3H, SCH 3). 13C NMR (125 MHz, CDCl 3) δ: 159.99,157.75,153.42,131.58,29.57,14.32; Anal. Calcd for C 6H 6N 4OS 2: C 33.63, and H 2.82, and N 26.15; Found:C 33.51, and H 2.51, N 25.75.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3,4-oxadiazole (I 2 )
Clear crystal, 71 ~ 72 ℃ of m.p.; Yield 78.2%; 1H NMR (500 MHz, CDCl 3) δ: 7.47 ~ 7.31 (m, 5H, benzyl-H), 4.55 (s, 2H, CH 2S), 3.05 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 166.02,159.39,158.55,135.11,131.67,129.25,128.99,128.41,36.96,14.33; IR (KBr, cm -1) ν:3031,2917,1566,1506,1326,705; Anal. Calcd for C 12H 10N 4OS 2C 49.64, and H 3.47, and N 19.30; Found:C 49.66, and H 3.52, N 19.22.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-chloro benzyl sulfur ether)-1,3,4-oxadiazole (I 3 )
Clear crystal, m.p. 61 ~ 63 oC; Yield 80.8%; 1H NMR (500 MHz, CDCl 3) δ: 7.47 ~ 7.29 (m, 4H, benzyl-H), 4.51 (s, 2H, CH 2-S), 3.06 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 165.57,159.45,158.71,137.26,134.75,131.57,130.21,129.29,128.65,127.45,36.17,14.34; IR (KBr, cm -1) ν:3037,2927,1557,1456,1357,1172; Anal. Calcd for C 12H 9ClN 4OS 2: C 44.37, and H 2.79, and N 17.25; Found:C 44.18, and H 2.64, and N 17.04;
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3,4-oxadiazole (I 4 )
White crystal, 43 ~ 45 ℃ of m.p.; Yield 72.3%; 1H NMR (500 MHz, CDCl 3) δ:3.64 (q, J=7.45,2H, CH 2), 3.06 (s, 3H, CH 3), 1.53 (t, J=7.45,3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 159.81,158.24,152.24,151.43,132.73,23.43,6.94; IR (KBr, cm -1) ν:2916,1566,1506,1426,705; Anal. Calcd for C 7H 8N 4OS 2: C 36.83, and H 3.53, and N 24.54; Found:C 36.73, and H 3.54, N 24.77.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(4-nitrobenzyl thioether group)-1,3,4-oxadiazole (I 5 )
Colourless powdery solid, 92 ~ 94 ℃ of m.p.; Yield 72.5%; 1H NMR (500 MHz, CDCl 3) δ: 8.22 ~ 7.68 (m, 4H, benzyl-H), 4.61 (s, 2H, CH 2-S), 3.06 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 165.09,159.53,158.96,147.81,142.86,131.38,130.26,124.11,35.69,14.37; IR (KBr, cm -1) ν:3031,2909,1588,1537,1462,702; Anal. Calcd for C 12H 9N 5O 3S 2: C 42.98, and H 2.70, and N 20.88; Found:C 42.34, and H 2.67, N 20.31.
2-(ethoxycarbonyl methylene radical thioether)-5-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,3,4-oxadiazole (I 6 )
Clear crystal, m.p. 75 ~ 76 oC; Yield 80.8%; 1H NMR (500 MHz, CDCl 3) δ: 4.28 (q, J=6.9,2H, CH 2 CH 3), 4.14 (s, 2H, CH 2-S), 3.07 (s, 3H, CH 3), 1.31 (t, J=7.45,3H, CH 2 CH 3 ); 13C NMR (125 MHz, CDCl 3) δ: 167.09,159.52,158.84,165.07,131.55,62.77,34.48,14.34,14.19; IR (KBr, cm -1) ν:2985,2939,1534,1432,667; Anal. Calcd for C 9H 10N 4O 3S 2: C 37.75, and H 3.52, and N 19.57; Found:C 37.51, and H 3.77, N 19.27.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-substituting group sulfuryl-1,3, synthetic (II) of 4-oxadiazole
With 2-methyl thioether group-5-(4-methyl isophthalic acid, 2,3-thiadiazoles)-1,3,4-oxadiazole (0.70 g, 3.27 mmol) and glacial acetic acid (10 mL) are thrown in 50 mL there-necked flasks 22 ℃ of stirring and dissolving.It is the KMnO of 5% aqueous solution that slow adding is joined 4(0.62 g, 3.9 mmol).TCL follows the tracks of, and reaction finishes the back with saturated sodium sulfite anhy 96 decolouring, pours into and promptly separates out solid in the frozen water, and the absolute ethyl alcohol recrystallization gets target compound.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-oxadiazole (II 1 )
Clear crystal, m.p. 132-134 ℃; Yield 70.5%; 1H NMR (500 MHz, CDCl 3) δ: 3.12 (s, 3H, CH 3), 3.45 (s, 3H, SO 2CH 3). 13C NMR (125 MHz, CDCl 3) δ: 159.99,157.75,153.42,131.58,29.57,14.32; IR (KBr, cm -1) ν:2909,1546,1423,676; Anal. Calcd for C 6H 6N 4O 3S 2: C 29.26, and H 2.46, and N 22.75; Found:C 29.16, and H 2.73, N 22.44.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-oxadiazole (II 2 )
Clear crystal, 131 ~ 132 ℃ of m.p.; Yield 82.6%; 1H NMR (500 MHz, CDCl 3) δ: 7.40 ~ 7.35 (m, 5H, benzyl-H), 4.83 (s, 2H, CH 2-SO 2), 3.01 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 162.12,161.12,159.52,131.34,130.16,130.03,129.42,124.58,62.39,14.40; IR (KBr, cm -1) ν:3033,2937,1575,1458,1355,1155; Anal. Calcd for C 12H 10N 4O 3S 2: C 44.71, and H 3.13, and N 17.38; Found:C 44.91, and H 3.04, N 17.29.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-benzyl chloride base sulfuryl)-1,3, the 4-oxadiazole (II 3 )
Clear crystal, 143 ~ 144 ℃ of m.p.; Yield 82.6%; 1H NMR (500 MHz, CDCl 3) δ: 7.44 ~ 7.32 (m, 4H, benzyl-H), 5.01 (s, 2H, CH 2-SO 2), 3.06 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 165.71,159.12,157.03,138.45,135.66,131.34,131.02,130.47,129.67,128.74,51.65,14.31; IR (KBr, cm -1) ν:3034,2937,1575,1429,1357,1157; Anal. Calcd for C 12H 9ClN 4O 3S 2: C 40.39, and H 2.54, and N 15.70; Found:C 40.79, and H 2.54, N 15.11.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-oxadiazole (II 4 )
Clear crystal, 108 ~ 110 ℃ of m.p.; Yield 82.6%; 1H NMR (500 MHz, CDCl 3) δ:3.71 (q, J=7.45,2H, CH 2), 3.04 (s, 3H, CH 3), 1.55 (t, J=7.45,3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 162.27,159.43,151.32,151.77,133.38,52.17,6.94; IR (KBr, cm -1) ν:3032,2902,1575,1506,1344,1155; Anal. Calcd for C 7H 8N 4O 3S 2: C 32.30, and H 3.10, and N 21.52; Found:C 32.54, and H 3.03, N 21.79.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-mercaptan-1,3,4-thiadiazoles synthetic
With the 4-methyl isophthalic acid, 2,3-thiadiazoles-5 formyl hydrazine (1.9 g, 0.012 mol) is thrown in 50 mL, three neck round-bottomed flasks, adds absolute ethyl alcohol (20 mL), Pottasium Hydroxide (0.92g, 0.013 mol), stirring and dissolving.Controlled temperature is room temperature (21 ℃), drips (1.1 g, 0.014 mol) dithiocarbonic anhydride, stirs 5 h fast.Suction filtration is used absolute ethanol washing, gets white solid.After the infrared drying sylvite (2 g, 7.3 mmol) is added in the 10 mL sulfuric acid, reaction under agitation is violent, a large amount of heat releases, < 3 ℃ of temperature controls.After adding, treat all solids dissolving, restir 90 minutes is slowly poured into reactant in the frozen water of 200 mL then with the thread shape; The product deposition is separated out, and suction filtration washs with suitable quantity of water; Solid dissolves with 10% sodium hydroxide solution, and the elimination insolubles is used 5% hcl acidifying again, gets white solid.Ethyl alcohol recrystallization gets colourless acicular crystal 1.1g.Fusing point 191 ~ 192 С, yield 70%. 1H?NMR(500?MHz,?CDCl 3)? δ:?11.24?(s,?1H,?SH),?3.13(s,?3H,?CH 3)。
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-substituting group thioether-1,3, synthetic (III) of 4-thiadiazoles
With 2-sulfydryl-5-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,3, the 4-thiadiazoles (0.6g, 2.79mmol), sodium hydroxide (0.11 g, 2.79mmol) and water (20mL) throw in the l00mL there-necked flask stirring at room dissolving.Slowly add methyl-sulfate (0.52g, 4.18mmol), ethyl sulfate (0.52g, 4.18mmol) or halohydrocarbon (2.79mmol) back room temperature (22 ℃) reaction finished in 4 hours.Suction filtration gets faint yellow solid, and 95% ethyl alcohol recrystallization gets target compound.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3, the 4-thiadiazoles (III 1 )
Clear crystal, 114 ~ 116 ℃ of m.p.; Yield 91.6%; 1H NMR (500 MHz, CDCl 3) δ: 7.46 ~ 7.29 (m, 5H, benzyl-H), 4.64 (s, 2H, CH 2), 2.94 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 167.91,157.02,155.63,139.35,135.38,129.36,128.96,128.28,38.42,14.44; IR (KBr, cm -1) ν:3033,2974,1571,1352,1047,698; Anal. Calcd for C 12H 10N 4S 3: C 47.03, and H 3.29, and N 18.28; Found:C 46.71, and H 3.14, N 18.04.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3, the 4-thiadiazoles (III 2 )
Clear crystal, 74 ~ 76 ℃ of m.p.; Yield 81.9%; 1H NMR (500 MHz, CDCl 3) δ:3.46 (q, J=6.85,2H, CH 2), 2.97 (s, 3H, CH 3), 1.52 (t, J=6.9,3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 168.81,156.98,155.10,139.23,28.88,14.55,14.43; IR (KBr, cm -1) ν:2932,1558,1354,694; Anal. Calcd for C 7H 8N 4S 3: C 34.41, and H 3.30, and N 22.93; Found:C 34.21, and H 3.15, N 22.71.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl thioether group)-1,3, the 4-thiadiazoles (III 3 )
Clear crystal, 125 ~ 127 ℃ of m.p.; Yield 80.1%; 1H NMR (500 MHz, CDCl 3) δ: 7.54 ~ 7.07 (m, 4H, benzyl-H), 4.68 (s, 2H, CH 2), 2.95 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 167.55,156.98,155.64,139.21,131.57,130.29,130.22,124.48,115.87,115.70,31.59,14.43; IR (KBr, cm -1) ν:2927,1583,1487,1446,1350,692; Anal. Calcd for C 12H 9FN 4S 3: C 44.43, and H 2.80, and N 17.27; Found:C 44.26, and H 2.55, N17.11.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl sulfide ether)-1,3, the 4-thiadiazoles (III 4 )
Clear crystal, 104 ~ 106 ℃ of m.p.; Yield 78.3%; 1H NMR (500 MHz, CDCl 3) δ: 6.04 ~ 5.97 (m, 1H, CH=CH 2), 5.29 (m, 2H, CH=CH 2), 4.05 (d, J=6.9 Hz, 2H, CH 2-S), 2.97 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 167.74,159.28,155.36,139.33,131.49,120.32,36.94,14.46; IR (KBr, cm -1) ν:2909,1543,1423,677; Anal. Calcd for C 8H 8N 4S 3: C 37.48, and H 3.15, and N 21.85; Found:C 36.77, and H 2.93, N 21.75.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3, the 4-thiadiazoles (III 5 )
Clear crystal, 108 ~ 110 ℃ of m.p.; Yield 83.7%; 1H NMR (500 MHz, CDCl 3) δ: 2.97 (s, 3H, CH 3), 2.88 (s, 3H, SCH 3). 13C NMR (125 MHz, CDCl 3) δ: 169.63,156.99,155.22,139.36,16.60,14.43; IR (KBr, cm -1) ν:2931,1519,1350,657; Anal. Calcd for C 6H 6N 4S 3: C 31.29, and H 2.63, and N 24.32; Found:C 30.88, and H 2.67, N 24.31.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-substituting group sulfuryl-1,3, synthetic (IV) of 4-thiadiazoles
Figure 2012103771401100002DEST_PATH_IMAGE012
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-thiadiazoles (IV 1 )
Clear crystal, 147 ~ 149 ℃ of m.p.; Yield 89.6%; 1H NMR (500 MHz, CDCl 3) δ: 7.46 ~ 7.29 (m, 5H, benzyl-H), 4.85 (s, 2H, CH 2), 2.94 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 168.66,161.11,158.41,137.93,131.36,129.78,128.95,125.68,62.06,14.63; IR (KBr, cm -1) ν:3030,2923,1558,1456,1373,1149; Anal. Calcd for C 12H 10N 4O 2S 3: C 42.59, and H 2.98, and N 16.55; Found:C 42.75, and H 2.81, N 17.10.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-thiadiazoles (IV 2 )
Clear crystal, 84 ~ 86 ℃ of m.p.; Yield 79.2%; 1H NMR (500 MHz, CDCl 3) δ: 3.67 (q, J=6.85,2H, CH 2 CH 3), 3.04 (s, 3H, CH 3), 1.52 (t, J=7.45,3H, CH 2 CH 3 ); 13C NMR (125 MHz, CDCl 3) δ: 169.13,160.78,158.45,137.97,50.36,14.72,7.19; IR (KBr, cm -1) ν:3027,2918,1558,1508,1456,1328,1143; Anal. Calcd for C 7H 8N 4O 2S 3: C 30.42, and H 2.92, and N 20.27; Found:C 29.71, and H 2.69, N 19.80.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl sulfuryl)-1,3, the 4-thiadiazoles (IV 3 )
Clear crystal, 153 ~ 155 ℃ of m.p.; Yield 86.5%; 1H NMR (500 MHz, CDCl 3) δ: 7.41 ~ 7.07 (m, 4H, benzyl-H), 4.93 (s, 2H, CH 2), 2.97 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 168.31,161.25,158.35,137.70,133.02,132.21,125.00,116.23,55.51,14.68; IR (KBr, cm -1) ν:3032,2917,1583,1492,1454,1332,1155; Anal. Calcd for C 12H 9FN 4O 2S 3: C 40.44, and H 2.55, and N 15.72; Found:C 40.27, and H 2.54, N 15.50.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl group sulfuryl)-1,3, the 4-thiadiazoles (IV 4 )
Clear crystal, 125 ~ 127 ℃ of m.p.; Yield 88.4%; 1H NMR (500 MHz, CDCl 3) δ: 8.21 ~ 7.66 (m, 2H, CH 2), 4.71 (s, 1H, CH), 2.95 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 166.46,156.96,143.39,130.27,124.07,36.88,14.45; IR (KBr, cm -1) ν:2923,1565,1433,1357,1143; Anal. Calcd for C 8H 8N 4O 2S 3: C, 33.32, H, 2.80, N, 19.43; Found:C 33.98, and H 2.41, N 19.11.
2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-thiadiazoles (IV 5 )
Clear crystal, 99 ~ 101 ℃ of m.p.; Yield 76.7%; 1H NMR (500 MHz, CDCl 3) δ: 3.54 (s, 3H, SCH 2), 3.04 (s, 3H, CH 3); 13C NMR (125 MHz, CDCl 3) δ: 169.87,160.70,158.47,137.79,126.54,118.67,43.27,14.71; IR (KBr, cm -1) ν:3005,2918,1573,1411,1328,1143; Anal. Calcd for C 6H 6N 4O 2S 3: C 27.47, and H 2.31, and N 21.36; Found:C 27.38, and H 2.23, N 21.28.
The test of target compound resisting tobacco mosaic virus
Virus is purified
Adopt Gooding method (Gooding; Et al., 1967), choose more than 3 weeks of inoculation; TMV systemic infection host Nicotiana glutinosa (Nicotiana glutinosa L.) plant upper blade, homogenate in phosphoric acid buffer, double gauze filters; 1000 rpm are centrifugal, handle through 2 polyoxyethylene glycol, and are centrifugal again; Deposition suspends with phosphoric acid buffer, promptly obtains the crude extract of TMV.Whole test is carried out under 4 ° of C.Measure the absorbance of 260 nm wavelength with ultraviolet spectrophotometer, calculate virus concentration according to formula.
Virus concentration (mg ∕ mL)=(A 260* extension rate) ∕ E 0.1% 1 cm 260 nm
Wherein E representes optical extinction coefficient, and promptly during wavelength 260 nm, concentration is the suspension-s of 0.1% (1 mg ∕ mL), the photoabsorption when light path is l cm (optical density(OD)) value.The E of TMV 0.1% 1 cm 260 nmBe 3.1.
The live body therapeutic action that medicament infects TMV
Select the consistent Nicotiana glutinosa of growing way, dip in writing brush earlier and get viral juice, full leaf virus inoculation is used flushing with clean water after the inoculation.After treating that blade is done, spread medicament at Zuo Banye, the solvent that right half leaf spreads matched doses compares.The cultivation of in illumination box, preserving moisture subsequently, 23 ± 1 ° of C of controlled temperature, illumination 10000 Lux observe behind the 3-4 d and record produces the number of withered spot.Every chemicals treatment is established 3 strains, every strain 3 ~4 leaves.Every as stated above medicament carries out 3 times to be repeated.
Each is handled all is to use second half as contrast, and reference is done in the processing that one group of Ningnanmycin is set again.On half leaf of blank, present obvious withered spot, at experiment 3-4 d " Invest, Then Investigate ", write down respectively every leaf about the withered spot number of half leaf, press column count and go out the inhibiting rate of test compound, be i.e. effect relatively tobacco mosaic virus(TMV).
Method for expressing: Y=(C-A)/C * 100%
Wherein: Y is the inhibiting rate of compound to tobacco mosaic virus(TMV); C is the withered spot number of control group (right half leaf), and A is the withered spot number of control group (Zuo Banye).
Adopt the withered spot method of half leaf that part of compounds has been carried out the therapeutic activity test of resisting tobacco mosaic virus (TMV), test result is seen Table 1
Figure 340449DEST_PATH_IMAGE013
From Table 1Giving birth to survey active testing result can find out, when concentration is 500 μDuring g/mL, between 31 ~ 55%, it is active to have certain inhibition, wherein chemical compounds I to the treatment inhibiting rate of tobacco mosaic virus (TMV) (TMV) for institute's test compounds 3,I 4 And II 1 The treatment inhibiting rate be respectively 48%, 47% and 47%, chemical compounds I 1The treatment inhibiting rate be 55%, with contrast medicine Ningnanmycin effect basically quite (56%), because the target compound novel structure; Agricultural chemicals does not have commercial 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1 on the market; 3,4-dislikes (thiophene) diazoles derivative, therefore; Can not produce cross resistance, have application promise in clinical practice with existing antivirotic.
The embodiment of the invention is aided with technical scheme of the present invention, but the content of embodiment is not limited thereto.
Conclusion, effect
1,2-(4-methyl isophthalic acid, 2,3-the thiadiazoles)-5-(substituting group)-1,3 of control crop virosis evil, 4-dislikes (thiophene) diazoles derivative, and is effective, and the most widely used on the market at present antiviral agent of fundamental sum (Ningnanmycin) is suitable.
2,? 2 - (4 - methyl-1, 2,3 - thiadiazole) -5 - (substituted) -1,3,4 - evil (thiazole) oxadiazole derivatives used to control tobacco plants flower leaf diseases, novel structure, no pesticides on the market 2 - (4 - methyl-1 ,2,3 - thiadiazole) -5 - (substituted) -1,3,4 - evil (thiophene) two azole derivative matter, therefore, does not produce cross-resistance with existing pesticides.
3,2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislike (thiophene) diazoles derivative control crop bacteriosis, can be prepared into several formulations, are easy to be converted into practical application.

Claims (8)

  1. (1.2-4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, it is characterized in that having following general formula:
    Figure 2012103771401100001DEST_PATH_IMAGE001
    Formula (I) formula II
    In the formula:
    X is O (oxygen) or S (sulphur), ， Wei oxadiazole compounds when X is O (oxygen); When X is S (sulphur), be thiadiazole compound;
    R is selected from ester group, benzyl or the substituted benzyl of hydrogen, C1-C5 alkyl, C1-C2 haloalkyl, C1-C3 alkoxyl group, C2-C5 thiazolinyl, C2-C5.
  2. 2. 2-according to claim 1 (4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, it is characterized in that:
    Said halogen atom is fluorine, chlorine, bromine or iodine,
    Said C1-C5 alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or neo-pentyl,
    Said C1-C2 haloalkyl is fluoroform alkyl, methyl chlorofluoride base, trichloromethane base, methylene fluoride base, methylene chloride-based, a fluoromethane base, 1,2-C2H4F2 C2H4F2 base, 1, and 2-Tetrafluoroethane base, 1,2-ethylene dichloride base or 1,2-tetrachloroethane base,
    Said C1-C3 alkoxyl group is a methoxyl group, oxyethyl group or positive propoxy,
    The thiazolinyl of said C2-C5 is vinyl, propenyl, allyl group, crotonyl, isobutenyl, pentenyl, isopentene group or new pentenyl,
    The ester group of said C2-C5 is methyl-formiate base, group-4 ethyl formate, propyl formate base, methyl acetate base, ethyl acetate base or propyl acetate base,
    Said substituted benzyl is 4-methyl-benzyl, 3-methyl-benzyl, 2-methyl-benzyl, 3,4-dimethyl benzyl, 2,4-dimethyl benzyl, 2; 6-dimethyl benzyl, 4-luorobenzyl, 3-luorobenzyl, 2-luorobenzyl, 3,4-difluorobenzyl, 2,4-difluorobenzyl, 2; 6-difluorobenzyl, 4-benzyl chloride base, 3-benzyl chloride base, 2-benzyl chloride base, 3,4-dichloro benzyl, 2,4-dichloro benzyl, 2; 6-dichloro benzyl, 4-methoxy-benzyl, 3-methoxy-benzyl, 2-methoxy-benzyl, 3; 4-dimethoxy-benzyl, 2,4-dimethoxy-benzyl, 2,6-dimethoxy-benzyl.
  3. 3. 2-according to claim 1 (4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, it is characterized in that part of compounds is:
    I 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3, the 4-oxadiazole;
    I 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3, the 4-oxadiazole;
    I 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-chloro benzyl sulfur ether)-1,3, the 4-oxadiazole;
    I 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3, the 4-oxadiazole;
    I 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(4-nitrobenzyl thioether group)-1,3, the 4-oxadiazole;
    I 6 :2-(ethoxycarbonyl methylene radical thioether)-5-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-1,3, the 4-oxadiazole;
    II 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-oxadiazole;
    II 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-oxadiazole;
    II 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(3-benzyl chloride base sulfuryl)-1,3, the 4-oxadiazole;
    II 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-oxadiazole;
    III 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(dibenzylsulfide ether)-1,3, the 4-thiadiazoles;
    III 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl thioether base)-1,3, the 4-thiadiazoles;
    III 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl thioether group)-1,3, the 4-thiadiazoles;
    III 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl sulfide ether)-1,3, the 4-thiadiazoles;
    III 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl thioether group)-1,3, the 4-thiadiazoles;
    IV 1 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(benzyl sulfuryl)-1,3, the 4-thiadiazoles;
    IV 2 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(ethyl sulfuryl)-1,3, the 4-thiadiazoles;
    IV 3 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(adjacent luorobenzyl sulfuryl)-1,3, the 4-thiadiazoles;
    IV 4 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(allyl group sulfuryl)-1,3, the 4-thiadiazoles;
    IV 5 :2-(4-methyl isophthalic acid, 2,3-thiadiazoles-5-yl)-5-(methyl sulfuryl)-1,3, the 4-thiadiazoles.
  4. 4. according to claim 1 or 2 or 3 described 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative, is used for control or suppresses the crop virosis evil.
  5. 5. purposes according to claim 4; Wherein, Described 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1; 3,4-dislikes (thiophene) diazoles derivative and is used for control or suppresses tobacco mosaic virus disease evil, cucumber mosaic virus virus disease, oryza virus 3 disease, rice dwarf virus disease virus disease, MRDV virus disease, rice black-streaked dwarf virus disease, tomato virus disease virus disease.
  6. 6. according to claim 4 or 5 described purposes; The preparation that is used to prevent and treat the crop virosis evil or suppresses the crop virosis evil is characterized in that described 2-(4-methyl isophthalic acid; 2; The 3-thiadiazoles)-and 5-(substituting group)-1,3, the formulation that 4-dislikes (thiophene) diazoles derivative is missible oil, micro emulsion, water and milk, suspending agent, the agent of kind clothing, seed dressing, wettable powder, sustained-release granular formulation, controlled release granule, water dispersible granules, dry suspending agent or granule.
  7. 7. preparation according to claim 6 is characterized in that, in the formulation of said preparation; Active ingredient 2-(4-methyl isophthalic acid, 2,3-thiadiazoles)-5-(substituting group)-1; 3,4-dislikes (thiophene) diazoles derivative and accounts for 1% ~ 90% of total formulation weight amount, and content is 10% ~ 85% more specifically.
  8. 8. the described 2-of one of claim 1 to 3 (4-methyl isophthalic acid; 2; The 3-thiadiazoles)-and 5-(substituting group)-1,3,4-dislikes (thiophene) diazoles derivative and is used to handle the purposes that virus, viral habitat maybe need prevent and treat material, crop, zone, soil, seed or the space of virus attack.
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CN104672162A (en) * 2015-02-13 2015-06-03 贵州大学 Preparation method and use of pentadiene ketone compound containing 1,3,4-oxadiazole sulfo-ethyoxyl
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