CN107602547A - Heterocycle triazole derivative and its production and use - Google Patents
Heterocycle triazole derivative and its production and use Download PDFInfo
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Abstract
The invention provides heterocycle triazole derivative and its production and use, and the present invention relates to 3,4 two chloroisothiazole triazole derivatives and 1,2,3 thiadiazoles triazole derivatives, they have the chemical structure of general formula as shown in IV.
Description
Technical field
Technical scheme is related to containing heterocycle triazole class compounds of the N containing S, and in particular to 3,4- bis- chloroisothiazoles three
Azole compounds, 1,2,3- thiadiazoles triazole class compounds, the i.e. chloroisothiazoles of 3,4- bis- and 1,2,3- thiadiazoles triazole types derive
Thing.
Background technology
Heterocyclic compound have potential broad-spectrum biological activity (N.P.Belskaya, et al,
Chem.Heterocycl.Compd.2016,52,627-636), the heterocycle of this structure or a kind of Development of Novel agricultural chemicals include killing
Critical policies (the and Thiazole of Chen L, et al.Synthesis of 1,2,3-Thiadizole including microbial inoculum
Based Strobilurins as Potent Fungicide Candidates.J.Agric.Food Chem.2017,65,
745-751).In the drug molecule of patent literature 70%, at least containing a heterocyclic fragments；Wherein, thiazole is largely to report
Road and the five-ring heterocycles of research, and isothiazole and thiadiazoles are relative as the research of five yuan of important nitrogenous sulfur heterocyclic compounds
Rareness, discovered in recent years, 3,4- bis- chloroisothiazoles, 1,2,3- thiadiazoles heterocycle have activating plants agent, bactericide, plant growth
The activity of conditioning agent and insecticide (Chen L., Guo, X.F., Fan, Z.J., et al.Synthesis and fungicidal
Activity of 3,4-dichloroisothiazole based strobilurins as potent fungicide
Candidates.RSC Advances, 2017,7,3145-3151), such as the different thiophene bacterium of environment friendly agricultural activating plants agent of commercialization
Amine and tiadinil are exactly the derivative of isothiazole and thiadiazoles.
Triazole bactericidal agent has the bactericidal activity of wide spectrum, is widely used in by Ascomycetes, Basidiomycetes, Fungi Imperfecti
Prevented and treated Deng multiple diseases caused by fungus disease；Belong to sterol biosynthesis C-14 demethylations enzyme inhibitor (DMI), pass through
Inhibitory action is played to ergosterol synthesis in plant.Such medicament possesses efficient, wide spectrum, low toxicity, lasting period length, absorbability
A variety of advantages such as strong (Zhou Ziyan, wait the progress Agriculture of Anhui science of triazole bactericidal agents, 2008,36 (27)：11842-
11844), in addition, triazole type makees compound is also received much concern as plant growth regulator.Triazole class compounds are global dosages
Maximum disinfectant use in agriculture；The triazole bactericidal agent kind of viable commercial product is more, such as Difenoconazole, prothioconazoles, alkene
Azoles alcohol, Tebuconazole, Flutriafol etc..It is long-term largely using the resistance problem brought because triazole bactericidal agent action site is single
It is very prominent；And activating plants agent has the system resume of broad spectrum durable, it is not directly placed on pathogen but passes through
Plant is acted in itself to reach disease-resistant effect, it is extremely urgent without drug-fast risk, its innovative research.
For find and find more efficiently, wide spectrum, low toxicity, low ecological risk and with the agriculture of existing bactericide no interactions resistance
Medicine lead compound, the present invention will contain N, S isothiazole and thiadiazoles pharmacophore 3, the chloroisothiazole rings of 4- bis- and 4- methyl isophthalic acids, and 2,
3- Thiadiazoles are incorporated into the guide structure of triazole type, design synthesis heterocycle triazole derivative, while carry out system
Bioactivity screening and evaluation, to provide the candidate chemical combination of the low resistance risk of more high activities for New pesticides discovery research
Thing.
The content of the invention
The technical problems to be solved by the invention are：There is provided a kind of new heterocycle triazole derivative and preparation method thereof and its
Regulate and control agricultural, gardening, health and forestry plant insect, the bioactivity of the phytopathy original and its assay method, while this is provided
A little applications of the compound in agriculture field, horticultural field, field of forestry and health field.The present invention solves the technical problem
Used technical scheme is：With agriculture field, horticultural field, field of forestry desinsection, acaricidal activity, bactericidal activity, anti-plant
The chemical structure of general formula for the heterocycle triazole class compounds that thing virus activity, induction plant produce anti-disease activity is shown in Formula IV：
Wherein：
R1It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkenyl, C2-
C6Haloalkenyl group, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6It is cycloalkyl, substituted piperidin-1-yl, substituted
Morpholine -1- bases, substituted nafoxidine -1- bases, phenyl or C1-C6Alkyl-substituted phenyl or C1-C6Haloalkyl substitution
Phenyl or C3-C6The phenyl of cycloalkyl substitution or phenyl, pyridine radicals or the C of nitro substitution1-C6Alkyl-substituted pyridine radicals or C1-
C6The pyridine radicals or C of haloalkyl substitution3-C6The pyridine radicals of cycloalkyl substitution or the pyridine radicals of nitro substitution, substituted contain 1
Individual or 2 N atoms five yuan or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl, containing 1
Individual or 2 O atoms substituted five yuan or six membered heteroaryl, substituted five yuan or six containing 1 N atom and 1 S atom
Unit's heteroaryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, containing 2 N atoms and 1 S atom
Substituted five yuan or six membered heteroaryl, substituted five yuan containing 2 N atoms and 1 O atom or six membered heteroaryl；On
State five yuan or six membered heteroaryl is selected from：Substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, different thiophene
Oxazolyl, oxazolyl, isoxazolyl, oxadiazolyls, thiadiazolyl group, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, four
Piperazine base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, BTA base, benzothiazolyl, benzene
And thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazoline
Base, cinnolines base or naphthyridines base；
R2It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkenyl,
C2-C6Haloalkenyl group, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Cycloalkyl, substituted piperidin-1-yl, it is substituted
Morpholine -1- bases, substituted nafoxidine -1- bases, phenyl or C1-C6Alkyl-substituted phenyl or C1-C6Haloalkyl substitutes
Phenyl or C3-C6The phenyl of cycloalkyl substitution or phenyl, pyridine radicals or the C of nitro substitution1-C6Alkyl-substituted pyridine radicals or
C1-C6The pyridine radicals or C of haloalkyl substitution3-C6The pyridine radicals of cycloalkyl substitution or the pyridine radicals, substituted of nitro substitution
Five yuan containing 1 or 2 N atom or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl,
Substituted five yuan or six membered heteroaryl, substituted five yuan containing 1 N atom and 1 S atom containing 1 or 2 O atom
Or six membered heteroaryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, containing 2 N atoms and 1 S
Substituted five yuan of atom or six membered heteroaryl, substituted five yuan containing 2 N atoms and 1 O atom or hexa-atomic heteroaryl
Base；Above-mentioned five yuan or six membered heteroaryl are selected from：Substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazole
Base, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyls, thiadiazolyl group, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, three
Piperazine base, tetrazine base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, BTA base, benzo thiophene
Oxazolyl, diazosulfide base, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl,
Quinazolyl, cinnolines base or naphthyridines base；
Halogen is fluorine, chlorine, bromine or iodine in the definition of above-mentioned Formula IV；
The alkyl, alkenyl or alkynyl are straight chain or side chain alkyl；Alkyl is in itself or the portion as other substituents
Methyl, ethyl, propyl group, butyl, amyl group, hexyl and its isomers are selected from, its isomers is selected from isopropyl, isobutyl group, Zhong Ding
Base, the tert-butyl group, isopentyl or tertiary pentyl；
Halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, the haloalkyl choosing
From CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl in itself or as the part of other substituents；
Alkenyl is selected from vinyl, pi-allyl, 1- acrylic, butene-2-base, fourth in itself or as the part of other substituents
Alkene -3- bases, amylene -1- bases, amylene -3- bases, hexene -1- bases or 4- methyl-3-pentenyls；
Alkynyl is selected from acetenyl, propine -1- bases, propine -2- bases, butine -1- in itself or as the part of other substituents
Base, crotonylene-base, 1- methyl -2- butynyls, hexin -1- bases or 1- ethyl -2- butynyls；
The enantiomeric form and its mixture of Formula IV heterocycle triazole derivative, the optical isomer is enantiomerism
Body；
The geometric isomer of Formula IV heterocycle triazole derivative, i.e. (R)-(S) isomery and its mixture；
The atropisomer and its mixture of Formula IV heterocycle triazole derivative.
In said structure, target compound is preferred：
R1It is selected from：3,4- bis- chloroisothiazole -5- bases, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases；R2It is selected from：Phenyl, to tertiary fourth
Base phenyl, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, an aminomethyl phenyl, o-methyl-phenyl, 2,4- dichlorophenyls；
The chloroisothiazole triazole derivative VI of 3,4- bis- of present invention synthetic method is as follows：
Wherein, substituent is defined as described above, preferably：
R1It is selected from：3,4- bis- chloroisothiazole -5- bases, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases；R2It is selected from：Phenyl, to tertiary fourth
Base phenyl, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, an aminomethyl phenyl, o-methyl-phenyl, 2,4- dichlorophenyls.
The synthesis of heterocycle triazole derivative and the specific method of biological activity determination of the present invention is divided into following steps：
A. compound II preparation method：
9.00 mMs of compound I are added in 100 milliliters of twoport round-bottomed flasks, it is molten with 30 milliliters of anhydrous tetrahydro furans
Solution, and 9.00 mMs of phenyl class bromination magnesium compounds, the phenyl class bromination is added dropwise again under ice salt bath, nitrogen protective condition
Magnesium compound is selected from：Phenyl, to tert-butyl-phenyl, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, an aminomethyl phenyl,
O-methyl-phenyl, 2,4- dichlorophenyl magnesium bromides；Ice salt bath stirs half an hour, and half an hour is stirred at room temperature, and is added after reacting completely
The ammonium chloride solution of 40 milliliters of saturations, extracted with 30 milliliters of ethyl acetate, separate organic layer, organic layer saturated sodium bicarbonate
Respectively wash one time, anhydrous sodium sulfate drying, filter, removal of solvent under reduced pressure, residue is through 100~200 mesh silica gel with saturated sodium-chloride
Column chromatography purifies to obtain compound II, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, body
Product is than being 20: 1-10: 1, yield 15-90%；Compound II prepare amount and reaction vessel volume by corresponding proportion expand or
Reduce.
B. compound III preparation method：
2.94 mMs of compound II are added in 100 milliliters of single necked round bottom flask, it is molten with 25 milliliters of anhydrous tetrahydro furans
Solve, and 3mol/L 1.18 milliliters of methyl-magnesium-bromide is added dropwise again under ice salt bath, nitrogen protective condition, then ice salt bath stirring 30
Minute, room temperature continues stirring 2 hours, the ammonium chloride solution of 40 milliliters of saturations is added after reacting completely, with 30 milliliters of acetic acid second
Ester is extracted, and separates organic layer, and organic layer is washed one time with saturated sodium-chloride, anhydrous sodium sulfate drying, is filtered, removal of solvent under reduced pressure,
Residue purifies to obtain compound III through 100~200 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: acetic acid
Ethyl ester, according to the difference of product, volume ratio 10: 1-5: 1, yield 37-96%；Amount and reaction vessel prepared by compound II
Volume is expanded or shunk by corresponding proportion.
C. compound IV preparation method：
2.19 mMs of compound III are added in 50 milliliters of single necked round bottom flask, are dissolved with 25 milliliters of dry toluene,
0.21 gram is added into reaction, be i.e. 1.09 mMs of p-methyl benzenesulfonic acid hydrates, is heated to reflux 2 hours after adding, reaction knot
Shu Hou, organic layer are respectively washed one time with saturated sodium bicarbonate and saturated sodium-chloride, anhydrous sodium sulfate drying, are filtered, are removed under reduced pressure molten
Agent, residue purify to obtain compound IV through 100~200 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: second
Acetoacetic ester, volume ratio 20: 1-10: 1, yield 82-100%；Amount and the volume of reaction vessel prepared by compound IV is by corresponding
Ratio is expanded or shunk.
C. compound V preparation method：
2.07 mMs of compound IV are added in 50 milliliters of single necked round bottom flask, are dissolved with 25 milliliters of dichloromethane, to
0.72 gram 85% of metachloroperbenzoic acid is added in reaction, i.e., 4.14 mMs, reaction is stirred overnight at room temperature, and reaction terminates
Afterwards, the complete metachloroperbenzoic acid of the saturated solution quenching unreacted of sodium peroxydisulfate is added in reaction solution, separates organic layer, it is organic
Layer is washed one time with saturated sodium-chloride, anhydrous sodium sulfate drying, is filtered, removal of solvent under reduced pressure, and residue direct plunges into next step
D. compound VI preparation method：
0.84 mM of 1,2,4- 1-Sodium-1,2,4-Triazoles are added in 50 milliliters of single necked round bottom flask, add 10 milliliters of N, N- bis-
NMF, is stirred at room temperature down, and 0.7 mM of compound V tetrahydrofuran is added into reaction solution, is then stirred at room temperature
Finished to reaction, reaction solution adds 20 milliliters of ethyl acetate, and mixed liquor is washed with water three times, organic layer is separated, with saturation chlorine
Change sodium to wash one time, anhydrous sodium sulfate drying filters, and removal of solvent under reduced pressure, residue purifies through 100~200 mesh silica gel column chromatographies
Compound VI is obtained, eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 5: 1-1: 1, yield 9-45%；
Amount and the volume of reaction vessel prepared by compound VI is expanded or shunk by corresponding proportion.
E. heterocycle triazole derivative VI of the invention bactericidal activity measure：
The heterocycle triazole derivative VI of present invention sterilization or bacteriostatic activity use thalli growth rate determination method, specific steps
For：1.8 milligrams of samples are taken to be dissolved in 2 drop DMFs, then with the water containing a certain amount of polysorbas20 emulsifying agent
Solution is diluted to the medicament of 500 mcg/mls, reagent agent is aseptically respectively drawn to 1 milliliter in culture dish, then divide
Not Jia Ru 9 milliliters of PDA culture mediums, 50 mcg/ml drug containing flat boards are made after shaking up, with add 1 milliliter of aqua sterilisa flat board do
Blank control, bacterium disk is cut along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board, is put in equilateral triangle
Put, often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivated, and colony diameter to be compareed expands to
Each processing bacterium disk extension diameter is investigated after 2-3 centimetres, averages, relative bacteriostasis rate is calculated compared with blank control, for trying bacterium
Kind is the kind of most of typical plant pathogen that field actually occurs in China's agricultural production, and its code name and title are as follows：
AS：Tomato early blight bacterium, its Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：
Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、GZ：Wheat is red
Mildew bacterium, its Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, its Latin are entitled：Phyophthora
infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora piricola、PS：
Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：
Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia sclerotiorum.
F. heterocycle triazole derivative VI of the invention live body determination of activity：
The heterocycle triazole derivative VI of present invention live body Screening of Antibacterial Activities method is as follows：Weigh target compound
0.0111 gram is dissolved in 0.5 milliliter of DMF, is then diluted to 100 mcg/mls with water (containing 0.1% Tween 80), then
Plant leaf surface, two hour naturally dries are sprayed on, then after 24 hours, fungi is seeded on plant.Each test design
Blank control, blank control VAcetone∶VMethanol∶VWater=1: 1: 2 solution sprays plant, fungi is seeded to plant after 24 hours
On.Compared with blank control, Disease management percentage is calculated, 0 represents inactive, and 100 represent complete inhibition, the phytopathy of test
Bacterium has bacterium of downy mildew of cucumber, wheat powdery mildew, corn rust bacterium.
G. the measure of heterocycle triazole derivative VI of the invention inducing anti-disease activity：
Heterocycle triazole derivative VI method for screening active ingredients is as follows, and tobacco mosaic virus (TMV) is abbreviated as TMV：
(1) positive controls activating plants agent：It is positive control to select tiadinil of the quality purity purity more than 99.5%
Activating plants agent；Tiadinil is abbreviated as TDL；
(2) screening technique of the anti-TMV activity of heterocycles triazole derivative VI evoking tobacco：In vitro direct antiviral activity
Measure using half leaf method carry out；Live body induction is that 3 basins are one group, before inoculation before 7 days by the consistent common cigarette of seedling age
Treated tobacco seedlings, processing mode include：Spray test compounds solution 2 to 3 times, 10 milliliters every time, or soil treatment, every time
10 milliliters, measure concentration is 100 mcg/mls, in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings is placed in into its life within the 7th day
After being cultivated 3 days under long preference temperature and illumination, incidence is checked, test compound pair is calculated as follows out in comprehensive scab number
TMV induction antiviral effect, each processing set 3 repetitions, and blank control and standard agent control select water and TDL respectively：
Wherein, R be test compound TMV anti-to tobacco inducing effect, unit：%；CK is that clear water compares the flat of blade
Equal withered spot number, unit：It is individual；I is that the average withered spot number for handling rear blade is induced through test compound, unit：It is individual.
By way of example only, particular compound substituent is defined as described above for above description.
The present invention beneficial effect be：Guide's optimization has been carried out to heterocycle triazole derivative VI, and to heterocycle triazole derivative
The screening of bacteriostatic activity and inducing anti-disease activity is carried out.
The present invention illustrates heterocycle triazole derivative VI's by the way that specific preparation and biological activity determination embodiment are more specific
Synthesis and bioactivity and application, the embodiment, which is only used for illustrating the present invention, to be not intended to limit the present invention, especially biological
Activity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1：Compound II preparation method：
9.00 mMs of compound I are added in 100 milliliters of twoport round-bottomed flasks, it is molten with 30 milliliters of anhydrous tetrahydro furans
Solution, and 9.00 mMs of phenyl class bromination magnesium compounds, the phenyl class is added dropwise again in ice salt bath, under nitrogen protective condition
Bromination magnesium compound is selected from：Phenyl, to tert-butyl-phenyl, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, a methyl
Phenyl, o-methyl-phenyl, 2,4- dichlorophenyl magnesium bromides；Ice salt bath stirs half an hour, half an hour is stirred at room temperature, after reaction completely
The ammonium chloride solution of 40 milliliters of saturations is added, is extracted with 30 milliliters of ethyl acetate, separates organic layer, organic layer unsaturated carbonate
Hydrogen sodium and saturated sodium-chloride are respectively washed one time, anhydrous sodium sulfate drying, are filtered, removal of solvent under reduced pressure, residue is through 100~200 mesh
Silica gel column chromatography purifies to obtain compound II, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, according to product not
Together, volume ratio 20: 1-10: 1, yield 15-90%；Physical and chemical parameter is illustrated：Work as R1For the chloroisothiazole -5- bases of 3,4- bis-, R2To be right
During fluorophenyl, nuclear magnetic data is as follows：δ 7.99-7.90 (m, 2H), 7.24 (t, J=8.2Hz, 2H).Compound II prepare amount and
The volume of reaction vessel is expanded or shunk by corresponding proportion.
Embodiment 2：Compound III preparation method：
2.94 mMs of compound II are added in 100 milliliters of single necked round bottom flask, it is molten with 25 milliliters of anhydrous tetrahydro furans
Solve, and 3mol/L 1.18 milliliters of methyl-magnesium-bromide is added dropwise again under ice salt bath, nitrogen protective condition, then ice salt bath stirring 30
Minute, room temperature continues stirring 2 hours, the ammonium chloride solution of 40 milliliters of saturations is added after reacting completely, with 30 milliliters of acetic acid second
Ester is extracted, and separates organic layer, and organic layer is washed one time with saturated sodium-chloride, anhydrous sodium sulfate drying, is filtered, removal of solvent under reduced pressure,
Residue purifies to obtain compound III through 100~200 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: acetic acid
Ethyl ester, according to the difference of product, volume ratio 10: 1-5: 1, yield 37-96%；Physical and chemical parameter is illustrated：Work as R1For 3,4- dichloros
Isothiazole -5- bases, R2For aminomethyl phenyl when, nuclear magnetic data is as follows：δ 7.27 (dd, J=7.3,5.2Hz, 3H), 7.15 (dd, J
=5.7,2.0Hz, 1H), 2.97 (d, J=10.8Hz, 1H), 2.36 (s, 3H), 2.06 (s, 3H).Amount prepared by compound III
Expanded or shunk with the volume of reaction vessel by corresponding proportion.Compound III physical and chemical parameter and structural parameters is shown in Table 1.
Embodiment 3：The IV of compound preparation method：
2.19 mMs of compound III are added in 50 milliliters of single necked round bottom flask, are dissolved with 25 milliliters of dry toluene,
0.21 gram is added into reaction, be i.e. 1.09 mMs of p-methyl benzenesulfonic acid hydrates, is heated to reflux 2 hours after adding, reaction knot
Shu Hou, organic layer are respectively washed one time with saturated sodium bicarbonate and saturated sodium-chloride, anhydrous sodium sulfate drying, are filtered, are removed under reduced pressure molten
Agent, residue purify to obtain compound IV through 100~200 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius of petroleum ether: second
Acetoacetic ester, volume ratio 20: 1-10: 1, yield 82-100%；Physical and chemical parameter is illustrated：Work as R1For the chloroisothiazole -5- bases of 3,4- bis-,
R2For aminomethyl phenyl when, nuclear magnetic data is as follows：δ 7.30 (t, J=7.4Hz, 1H), 7.23 (d, J=7.4Hz, 1H), 7.16
(d, J=11.6Hz, 2H), 5.87 (s, 1H), 5.78 (s, 1H), 2.40 (s, 3H).Amount and reaction vessel prepared by compound IV
Volume expanded or shunk by corresponding proportion.Compound IV physical and chemical parameter and structural parameters is shown in Table 1
Embodiment 4：Compound V preparation method：
2.07 mMs of compound IV are added in 50 milliliters of single necked round bottom flask, are dissolved with 25 milliliters of dichloromethane, to
0.72 gram 85% of metachloroperbenzoic acid is added in reaction, i.e., 4.14 mMs, reaction is stirred overnight at room temperature, and reaction terminates
Afterwards, the complete metachloroperbenzoic acid of the saturated solution quenching unreacted of sodium peroxydisulfate is added in reaction solution, separates organic layer, it is organic
Layer is washed one time with saturated sodium-chloride, anhydrous sodium sulfate drying, is filtered, removal of solvent under reduced pressure, and residue direct plunges into next step；Reason
Change parameter citing：Work as R1For the chloroisothiazole -5- bases of 3,4- bis-, R2For p-methylphenyl when, the nuclear magnetic data of the compound is as follows：1HNMR(CDCl3) δ 7.13 (dd, J=20.0,8.2Hz, 4H), 3.38 (d, J=5.1Hz, 1H), 3.31 (d, J=5.2Hz,
1H), 2.28 (s, 3H).Amount and the volume of reaction vessel prepared by compound V is expanded or shunk by corresponding proportion.
Embodiment 5：Compound VI preparation method：
0.84 mM of 1,2,4- 1-Sodium-1,2,4-Triazoles are added in 50 milliliters of single necked round bottom flask, add 10 milliliters of N, N- bis-
NMF, is stirred at room temperature down, and 0.7 mM of compound V tetrahydrofuran is added into reaction solution, is then stirred at room temperature
Finished to reaction, reaction solution adds 20 milliliters of ethyl acetate, and mixed liquor is washed with water three times, organic layer is separated, with saturation chlorine
Change sodium to wash one time, anhydrous sodium sulfate drying filters, and removal of solvent under reduced pressure, residue purifies through 100~200 mesh silica gel column chromatographies
Compound VI is obtained, eluant, eluent is 60~90 degrees Celsius of petroleum ether: ethyl acetate, volume ratio 5: 1-1: 1, yield 9-45%；
Physical and chemical parameter is illustrated：Work as R1For the chloroisothiazole -5- bases of 3,4- bis-, R2For p-methylphenyl when, the nuclear magnetic data of the compound is such as
Under：δ 8.03 (s, 1H), 7.72 (s, 1H), 7.36 (d, J=7.1Hz, 2H), 7.14 (d, J=7.5Hz, 2H), 5.26 (d, J=
14.3Hz, 1H), 4.80 (d, J=14.2Hz, 1H), 2.29 (s, 3H).Amount and the volume of reaction vessel prepared by compound VI is pressed
Corresponding proportion is expanded or shunk.Compound VI physical and chemical parameter and structural parameters is shown in Table 1.
Embodiment 6：The heterocycle triazole derivative VI of present invention Antibacterial Activity result：
The code name and title for the frequently seen plants disease fungus that the present invention tests are as follows：AS：Tomato early blight bacterium, its latin name
For：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：Botrytis cinerea、RC：Cereal silk core
Bacterium, its Latin are entitled：Rhizoctonia cerealis、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora
arachidicola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、GZ：Fusarium graminearum,
Its Latin is entitled：Gibberella zeae、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia
sclerotiorum、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora piricola、PI：The late blight of potato
Bacterium, its Latin are entitled：Phytophthora infestans (Mont.) de Bary, these strains have representativeness well,
The kind of most of pathogen that field occurs in agricultural production can be represented.
Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, in 50 mcg/ml, the heterocycle three of the invention synthesized
All compounds of azole have different degrees of bactericidal activity.For tomato early blight bacterium, compound CL06-64, CL06-85
Inhibiting rate more than 70%, and be higher by the bactericidal activity more than 10% of commercialization bactericide Fluoxastrobin；To cucumber grey mold
The active testing of germ shows that compound CL06-64, CL06-85, CL06-80, CL06-99, CL06-86-2 inhibiting rate are equal
More than 95%, above-claimed cpd is being higher by document report with the immediate compound of target compound chemical constitution of the present invention
The bactericidal activity more than 10% of Flutriafol, especially compound CL06-64, CL06-80, CL06-99, bactericidal activity highest,
Up to 100%；For Rhizoctonia cerealis, compound CL06-71, CL06-84-2, CL06-64, CL06-85, CL06-80,
CL06-99, CL06-86-2, Ljw01-04 inhibiting rate more than 90%, wherein compound CL06-64, CL06-85,
CL06-80, CL06-99, CL06-86-2 inhibiting rate are follow-up to carry out more scientific and reasonable EC up to 100%50Measurement result
Comparison；Compound is for peanut Cercospora asparagagas, and the inhibiting rate of compound CL06-64, CL06-99 is more than 90%；To water
For Rhizoctonia solani Kuhn, compound CL06-64 inhibiting rate is 76%；For fusarium graminearum, compound CL06-64,
CL06-86-2 bacteriostatic activity is more than 60%；For Sclerotinia sclerotiorum, compound CL06-71, CL06-84-2,
CL06-64, CL06-85, CL06-80, CL06-99, CL06-98, CL06-86-2 inhibiting rate are more than 90%, wherein changing
Compound CL06-85, CL06-80, CL06-99, CL06-86-2 inhibiting rate are higher by 100% than control medicine Flutriafol
More than 7%；For Botryosphaeria berengeriana f. sp, the bacteriostatic activity of compound CL06-64, CL06-86-2 is high more than 90%
Go out comparison medicine Fluoxastrobin more than 6%, and compound CL06-86-2 bactericidal activity highests, up to 98%；For phytophthora infestans
Activity show that compound CL06-64, CL06-85, CL06-99 inhibiting rate are more than 70%；As fully visible, compound
CL06-64 and compound CL06-86-2 has the bactericidal activity of wide spectrum.
Embodiment 7：The heterocycle triazole derivative VI of present invention bacteriostatic activity EC50Measurement result：
EC50It is the parameter and index that can most illustrate chemical combination microbic activity, compound of the invention is in 50 mcg/mls
When, thalli growth rate method measure inhibiting rate is more than 90% all compounds of the invention, concentration EC during it suppresses50It is shown in Table 3, it is right
For bacterium of downy mildew of cucumber (BC), compound CL06-64, CL06-99 and CL06-86-2 EC50Less than comparison medicine Flutriafol
19.14 mcg/mls, i.e. their activity is 5.08,4.10 and 1.85 times of the similar compound Flutriafol of structure respectively；
For Rhizoctonia cerealis；Compound CL06-71, CL06-64, CL06-85, CL06-80, CL06-99 and CL06- of the present invention
86-2 is both less than the EC of comparison medicine Flutriafol506.20 mcg/mls, i.e., their activity is the similar compound of structure respectively
7.75,2.27,1.74,1.32,4.84 and 1.89 times of Flutriafol；For compound Sclerotinia sclerotiorum, compound CL06-
85, CL06-80 and CL06-99 EC50Less than the mcg/ml of comparison medicine Flutriafol 4.63, i.e., their activity is structure respectively
1.39,1.25 and 1.25 times of similar compound Flutriafol；For Botryosphaeria berengeriana f. sp, compound CL06-64 and CL06-
86-2 EC50Respectively 3.07 and 4.74 mcg/mls, less than 45.75 mcg/mls of comparison medicine Flutriafol, i.e., they
Activity is 14.90 and 9.65 times of the similar compound Flutriafol of structure respectively；It is visible in summary, compound CL06-64 and
Compound CL06-86-2 is to bacterium of downy mildew of cucumber, the EC of Rhizoctonia cerealis and Botryosphaeria berengeriana f. sp50All significantly less than positive control
Flutriafol.Therefore, isothiazole is introduced into triazole type target molecule, the bactericidal activity of target compound has obtained unexpected pole
It is big to improve.
Embodiment 8：The heterocycle triazole derivative VI of present invention live body Antibacterial Activity result：
The frequently seen plants name of disease that the present invention tests claims as follows：Wheat powdery mildew, corn rust, gray mold of cucumber and rice rice
Seasonal febrile diseases；Measurement result is shown in Table 4, and table 4 shows, suppression of the compound CL06-64 to wheat powdery mildew reaches 40%, less than comparison medicine
The 100% of agent Flutriafol；Suppression of the compound CL06-64 to gray mold of cucumber reaches 40%, and comparison medicine Flutriafol does not have
Inhibitory action, its inhibiting rate are 0.It can be seen that isothiazole is introduced into triazole type target molecule, the fungicidal spectrum of target compound also occurs
It is unexpected greatly to change, achieve unexpected effect.
Embodiment 9：The heterocycle triazole derivative VI of present invention resisting tobacco mosaic virus (abbreviation TMV) activity：
The measurement result of TMV activity is shown in Table 5, and table 5 shows, under passivating conditions, compound CL06-64, CL06-80,
Ljw01-04 activity of resisting tobacco mosaic virus is substantially suitable with positive control drug virazole more than 70%, but its passivation is lived
Property is significantly higher by with the immediate azoles alcohol of target compound chemical constitution up to more than 50%；In the therapeutic mode, compound CL06-
80 and CL06-98 activity of resisting tobacco mosaic virus is higher by closest with target compound chemical constitution more than 40%
Compound Flutriafol up to more than 10%；In protected mode, compound CL06-71 and CL06-80 resisting tobacco mosaic virus are lived
Property is higher by with the immediate compound Flutriafol of target compound chemical constitution up to more than 10% more than 25%；Luring
Under waveguide mode, compound CL06-71, CL06-64, CL06-99, CL06-86-24 activity of resisting tobacco mosaic virus 50% with
On, it is higher by with the immediate compound Flutriafol of target compound chemical constitution up to more than 35%.It can be seen that compound CL06-64
Under passivation pattern and under induction pattern, fabulous activity of resisting tobacco mosaic virus is illustrated.Therefore, isothiazole is introduced three
Azole target molecule, the antiviral activity of target compound obtained it is unexpected be greatly improved, reached design originally and closed
Into the purpose of the design synthesis of the biocide molecule with inducing anti-disease activity.
The target compound of the present invention has good bioactivity, and therefore, any one in these compounds can be with
Composition pesticide is formed, it includes the heterocycle triazole derivative VI of the present invention as active component, and the content of active component is 0.1
To 99% weight, the solid or liquid adjuvants of 99.9 to 1% weight, and the surfactant of optional 0 to 25% weight.
The target compound of the present invention can also form pesticide complex composition, and these pesticide complex compositions, it is included
Any one heterocycle triazole derivative VI of the present invention and other insecticides, acaricide, bactericide or antivirotic compounding conduct
Active component, heterocycle triazole derivative VI and other insecticides, acaricide, bactericide or antivirotic ratio are quality percentage
Than 1%: 99% to 99%: 1%, the content of active component is 0.1 to 99% weight, the solid or liquid of 99.9 to 1% weight
Auxiliary agent, and the surfactant of optional 0 to 25% weight.These pesticide complex compositions are used in agricultural, forestry and garden
The harm of pest control, evil mite, pathogen, plant virus in skill.Specific embodiment is as follows：
Embodiment 10：The heterocycle triazole derivative VI of the present invention is with insecticide composition in preventing and treating agricultural and forestry and gardening
Application in insect pest of the plant：
All heterocycle triazole derivative VI of the present invention combine formation with any one in commodity insecticide or two kinds and killed
Worm composition is used to prevent and treat agricultural and forestry and gardening plant insect pest, and the commodity insecticide is selected from：Chlopyrifos, sub- Nong,
Acetamiprid, emamectin benzoate, milbemectin, AVM, pleocidin, fenvalerate, esfenvalerate, chlorine cyanogen chrysanthemum
Ester, effective cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylates, Lambda- trifluoro chlorine
Cyano chrysanthemate, Permanone, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, chlorine fluorine
Amine fenvalerate, imidacloprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan,
Diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron,
Noviflumuron is noviflumuron, its No. CAS be 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron,
Bay sir 6874 are that { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 are
[1- (4- Trifluoromethoxyphen-ls) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron are bistrifluron, furans worm acyl
Hydrazine, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, triazole
Phosphorus, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf
Disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine,
Propargite, diafenthiuron, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos,
Ethiprole, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrrole
Piperazine ketone, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The heterocycle triazole derivative VI of the present invention is in the desinsection
Weight/mass percentage composition in composition is 1%-90%, heterocycle triazole derivative VI of the invention and foregoing commodity insecticide ratio
Example is mass percent 1%: 99% to 99%: 1%；The formulation of the Pesticidal combination processing is selected from：Seed treatment emulsion, water
It is emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block poison bait, granular
Poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, smoke cartridge, smog
Rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, the agent of solid-liquid mixing dress, liquid liquid mixing dress
Solid agent, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, sprinkle and pour agent, plant clothing
Agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The insect pest of the plant of the Pesticidal combination preventing and treating is selected from：
Red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses, onion thrips,
Greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing
The flat angle plant hopper of plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane, 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, green rice bug, green plant bug, alfalfa plant bug, in it is black blind
Stinkbug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, pink bollworm, sweet potato wheat
Moth, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roller, plan little Huang
It is leaf roller, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, bar snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, glutinous
Worm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, black cutworm, the earth are old
Tiger, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, Papilio xuthus, jade belt
Swallowtail butterfly, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus,
It is the small buprestid beetle of Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, miscellaneous
Intend ostomatid, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck day
Ox, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, wheat
Sawfly, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp,
Mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melonfly, the latent fly of wheat leaf ash, America spot are dived
Fly, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm；The desinsection group
The plant of Researches On Hydrate Prevention is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, Holland
Beans, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, people
Ginseng, fritillaria, 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, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, perfume (or spice)
Any of several broadleaf plants, papaya, orchid, potted landscape.
Embodiment 11：The heterocycle triazole derivative VI of the present invention is with antimicrobial combination in preventing and treating agricultural and forestry and gardening
Application in plant disease：
All heterocycle triazole derivative VI of the present invention combine formation with any one in commodity bactericide or two kinds and killed
Bacteria composition is used to prevent and treat agricultural and forestry and gardening plant disease, and the commodity bactericide is selected from：Diazosulfide, thiophene acyl
Bacterium amine, it is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiophenes two
Azoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acids, isotianil, its English are general
It is entitled：Isotianil, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazoles of 3,4- bis- -
5- Ethyl formates, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb, second phosphorus
Aluminium, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, flumorph,
Dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil, leaf
Withered phthalein, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid
Amine, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, benzene oxygen
Bacterium amine, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, the azoles of ring third
Alcohol, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole, Asia
Amine azoles, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, triazole
Alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid, miaow
The white spirit of cycloheximide triazole, Evil imidazoles, pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, octhilinone,
Benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, pyridine
Acyl bacterium amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, Fenarimol, fluorine
Benzene ancymidol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, iprovalicarb,
It is benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, kasugarnycin, more anti-
It is mycin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, mebenil, more
Bacterium spirit, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, captan, sterilizing
It is pellet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloronitrobenzene, third gloomy
Zinc, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone, Pencycuron,
Diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, iminoctadine, chlorine nitre
Amine, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane, metham-sodium,
Oppose line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, dichlofenthion, chlorazol
Phosphorus, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；The present invention
Total weight/mass percentage compositions of the heterocycle triazole derivative VI in the bactericidal composition be 1%-90%, heterocycle of the invention
The ratio of triazole derivative VI and foregoing commodity bactericide is mass percent 1%: 99% to 99%: 1%；The Bactericidal composite
The formulation of thing processing is selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, particulate
Agent, soluble thick agent, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil-in-water
Emulsion, smoke candle, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol
Gu agent, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil
Property pulvis, dense jelly are dissipated, sprinkles and pours agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；It is described to kill
The plant disease of bacteria composition preventing and treating is selected from：Seedling blight of rice, tomato root rot, the late blight of potato, tobacco black shank, millet
Powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose；The applicable plant choosing of the bactericidal composition
From：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean,
Red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, 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, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 13：The heterocycle triazole derivative VI of the present invention combine with anti-plant virus agent prevent and treat agriculture and forestry with
And the application in gardening plant virus disease：
All heterocycle triazole derivative VI of the present invention combine shape with any one in commodity antiviral agent or two kinds
It is used to prevent and treat agricultural and forestry and gardening plant virus disease into antiviral composition, the commodity antiviral agent is selected from：
Diazosulfide, tiadinil, TDL, isotianil are abbreviated as, its English is general entitled：Isotianil, 4- methyl isophthalic acid, 2,3-
Thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, 3,
Chloroisothiazole -5- the formic acid of 4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-, DL- β-ammonia
Base butyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro-isonicotinic acid, alkene
Third isothiazole, well ridge azanol, jinggangmeisu；The heterocycle triazole derivative VI of the present invention is total in the antiviral composition
Weight/mass percentage composition is 1%-90%, and the ratio of heterocycle triazole derivative VI of the invention and foregoing commodity anti-plant virus agent is
Mass percent 1%: 99% to 99%: 1%；The formulation of the antiviral composition processing is selected from：Seed treatment emulsion, water and milk
Agent, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block poison bait, granular poison
Bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, smoke cartridge, smog rod,
Smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid mix and fill agent, liquid liquid mixing fills agent,
Gu Gu/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, sprinkle pour agent, seed coat agent,
Liniment, film forming finish, ultra low volume liquids, steam releasing agent；The virus disease of the antiviral composition preventing and treating is selected from：Water
Rice dwarf wilt, BYDV, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease, jade
Rice short mosaic disease, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, cybidium ring spot virus；The antiviral compound
The plant that thing is used to prevent and treat is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, Holland
Beans, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, people
Ginseng, fritillaria, 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, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, perfume (or spice)
Any of several broadleaf plants, papaya, orchid, potted landscape.
Embodiment 14：The heterocycle triazole derivative VI of the present invention is combined with acaricide in preventing and treating agricultural and forestry and gardening
Application in plant mites evil：
All heterocycle triazole derivative VI of the present invention combine formation with any one in commodity acaricide or two kinds and killed
Acaricidal composition is used to prevent and treat agricultural and forestry and gardening plant mite does harm to, and the commodity acaricide is selected from：Azacyclotin, plictran,
Fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos, DDVP, heptenophos, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate, poison
Dead tick, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Ethodan, malathion, methacrifos, Phosalone, pungent sulphur
Phosphorus, methylpyrimidine sulphur phosphorus, quinalphos, sulfotep, Hostathion, Kilval, isocarbophos, acephatemet, propetamphos, chlorimide sulphur
Phosphorus, phosmet, acrinathrin, Biphenthrin, lambda-cyhalothrin, smart gamma cyhalothrin, Fenpropathrin, the chrysanthemum of fluorine cyanogen penta
It is ester, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, Aldicarb, butocarboxim, oxamyl, pest-resistant
Prestige, thiofanox, benomyl, sok, carbofuran, carbosulfan, MTMC, promacyl, Carzol, single carbonamidine, mite killing
Amidine, Amitraz, Spanon, Ergol, fenisobromolate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, worm
Mite mycin, thuringiensin, tetranactin, macro tetrolide, AVM, doractin, eprinomectin, ivermectin, Sai La
Rhzomorph, moxidectin, pyrethrin, nicotine, matrine, nimbin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine,
Propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite, pyridaben；The heterocycle triazole derivative VI of the present invention is in institute
The total weight/mass percentage composition stated in miticide composition is 1%-90%, heterocycle triazole derivative VI of the invention and the commodity
Acaricidal ratio is mass percent 1%: 99% to 99%: 1%；The formulation of the miticide composition processing is selected from：Seed
Handle emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block
Shape poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, cigarette
Mist cylinder, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid mixing dress agent, liquid/
Solid liquid mixing dress agent, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, bold and vigorous pour
Agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The mite evil choosing of the miticide composition preventing and treating
From：For mite evil selected from Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, the evil mite of Eriophyidae, these evil mites are the world
Property Agricultural Mites, forestry harmful mites, gardening evil mite and hygienic evil mite；The plant that the miticide composition is used to prevent and treat is selected from：Paddy,
Wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton
Flower, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sword
Fiber crops, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon,
Pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
The heterocycle triazole derivative VI of the present invention of table 1 chemical constitution and physical and chemical parameter
The heterocycle triazole derivative VI of the present invention of table 1 chemical constitution and physical and chemical parameter (Continued)
The heterocycle triazole derivative VI of the present invention of table 1 chemical constitution and physical and chemical parameter (Continued)
The heterocycle triazole derivative VI of the present invention of table 2 bacteriostatic activity (inhibiting rate/% of 50 mcg/mls)
| Sequence number | Numbering | AS | BC | RC | CA | PS | GZ | SS | PP | PI |
| 1 | CL06-71 | 39 | 81 | 98 | 65 | 64 | 41 | 93 | 62 | 59 |
| 2 | CL06-84-2 | 55 | 75 | 90 | 57 | 68 | 57 | 97 | 85 | 58 |
| 3 | CL06-64 | 76 | 100 | 100 | 91 | 76 | 63 | 98 | 90 | 73 |
| 4 | CL06-85 | 71 | 97 | 100 | 74 | 58 | 49 | 100 | 77 | 75 |
| 5 | CL06-80 | 61 | 100 | 100 | 68 | 53 | 46 | 100 | 67 | 61 |
| 6 | CL06-99 | 61 | 100 | 100 | 92 | 69 | 54 | 100 | 76 | 75 |
| 7 | CL06-98 | 12 | 48 | 73 | 28 | 31 | 23 | 96 | 29 | 25 |
| 8 | CL06-86-2 | 62 | 96 | 100 | 78 | 68 | 61 | 100 | 98 | 73 |
| 9 | Ljw01-04 | 27 | 44 | 97 | 45 | 27 | 0 | 79 | 27 | 35 |
| 10 | Flutriafol | 85 | 88 | 100 | 100 | 100 | 93 | 93 | 100 | 95 |
| 11 | Fluoxastrobin | 61 | 88 | 96 | 83 | 96 | 88 | 100 | 84 | 90 |
The heterocycle triazole derivative VI of the present invention of table 3 bacteriostatic activity EC50
| Sequence number | Numbering | BC | RC | CA | SS | PP |
| 1 | CL06-71 | - | 0.80 | - | 45.80 | - |
| 2 | CL06-84-2 | - | - | -- | 11.59 | - |
| 3 | CL06-64 | 6.98 | 2.73 | 11.24 | 20.59 | 3.07 |
| 4 | CL06-85 | 158.59 | 3.56 | - | 3.34 | |
| 5 | CL06-80 | 66.69 | 4.68 | - | 3.70 | - |
| 6 | CL06-99 | 8.65 | 1.28 | 17.77 | 3.70 | |
| 7 | CL06-98 | - | - | - | 8.79 | - |
| 8 | CL06-86-2 | 19.14 | 3.28 | - | 11.31 | 4.74 |
| 9 | Ljw01-04 | - | 42.17 | - | - | - |
| 10 | Flutriafol | 35.45 | 6.20 | 6.59 | 4.63 | 45.75 |
The heterocycle triazole derivative VI of the present invention of table 4 live body bacteriostatic activity (inhibiting rate/% of 50 mcg/mls)
| Sequence number | Numbering | Wheat powdery mildew | Corn rust | Gray mold of cucumber | Rice blast |
| 1 | CL06-71 | 0 | 0 | 0 | 0 |
| 2 | CL06-84-2 | 0 | 0 | 0 | 0 |
| 3 | CL06-64 | 40 | 0 | 40 | 0 |
| 4 | CL06-85 | 0 | 0 | 0 | 0 |
| 5 | CL06-80 | 0 | 0 | 0 | 0 |
| 6 | CL06-99 | 0 | 0 | 0 | 0 |
| 7 | CL06-98 | 0 | 0 | 0 | 0 |
| 8 | CL06-86-2 | 0 | 0 | 0 | 0 |
| 9 | Ljw01-04 | 0 | 0 | 0 | 0 |
| 10 | Flutriafol | 100 | 0 | 0 | 60 |
Activity (the suppression of 100 mcg/mls of the heterocycle triazole derivative VI of the present invention of table 5 resisting tobacco mosaic virus
Rate/%)
| Sequence number | Compound | Passivation pattern | Therapeutic mode | Protected mode | Induction pattern |
| 1 | CL06-71 | 50.00±2.02 | 16.13±2.56 | 25.43±1.42 | 50.45±2.46 |
| 2 | CL06-84-2 | 0 | 0 | 0 | 0 |
| 3 | CL06-64 | 80.45±1.03 | 0 | 0 | 60.93±1.04 |
| 4 | CL06-85 | 0 | 0 | 0 | 0 |
| 5 | CL06-80 | 75.23±3.07 | 40.58±3.34 | 30.22±3.11 | 20.06±2.59 |
| 6 | CL06-99 | 0 | 0 | 10.03±2.00 | 60.59±4.31 |
| 7 | CL06-98 | 42.00±1.05 | 42.46±1.67 | 9.22±1.21 | 20.78±3.12 |
| 8 | CL06-86-2 | 0 | 0 | 0 | 60.84±2.89 |
| 9 | Ljw01-04 | 75.45±3.12 | 25.43±2.68 | 21.76±2.34 | 0 |
| 10 | Flutriafol | 21.72±7.30 | 26.41±2.12 | 14.20±3.25 | 15.24±2.83 |
| 11 | Ningnanmycin | - | 78.10±2.04 | - | - |
| 12 | TDL | - | - | - | 65.00±2.00 |
| 13 | BTH | - | - | 78.10±0.54 | 78.00±1.34 |
| 14 | SZG-7 | - | - | - | 79.00±2.27 |
| 15 | Virazole | 78.00±1.00 | - | - | - |
| 16 | Isotianil | 20.77±7.30 | 27.31±2.12 | 24.80±5.85 | 76.45±5.18 |
Claims (10)
1. heterocycle triazole derivative, it is characterised in that：With the general structure as shown in Formula IV：
Wherein：
R1It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkenyl, C2-C6Halo
Alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Cycloalkyl, substituted piperidin-1-yl, substituted morpholine -1-
Base, substituted nafoxidine -1- bases, phenyl or C1-C6Alkyl-substituted phenyl or C1-C6Haloalkyl substitution phenyl or
C3-C6The phenyl of cycloalkyl substitution or phenyl, pyridine radicals or the C of nitro substitution1-C6Alkyl-substituted pyridine radicals or C1-C6Halo
Alkyl-substituted pyridine radicals or C3-C6The pyridine radicals of cycloalkyl substitution or the pyridine radicals of nitro substitution, substituted contain 1 or 2
Five yuan of individual N atoms or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl, containing 1 or 2
Substituted five yuan of individual O atom or six membered heteroaryl, substituted five yuan or hexa-atomic miscellaneous containing 1 N atom and 1 S atom
Aryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, the quilt containing 2 N atoms and 1 S atom
Five yuan of substitution or six membered heteroaryl, substituted five yuan containing 2 N atoms and 1 O atom or six membered heteroaryl；Above-mentioned five
Member or six membered heteroaryl are selected from：Substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazole
Ji, oxazolyl, isoxazolyl, oxadiazolyls, thiadiazolyl group, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine
Base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, BTA base, benzothiazolyl, benzo
Thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl,
Cinnolines base or naphthyridines base；
R2It is hydrogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkenyl, C2-C6Halogen
For alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Cycloalkyl, substituted piperidin-1-yl, substituted morpholine-
1- bases, substituted nafoxidine -1- bases, phenyl or C1-C6Alkyl-substituted phenyl or C1-C6The phenyl of haloalkyl substitution
Or C3-C6The phenyl of cycloalkyl substitution or phenyl, pyridine radicals or the C of nitro substitution1-C6Alkyl-substituted pyridine radicals or C1-C6Halogen
The pyridine radicals or C of substituted alkyl substitution3-C6The pyridine radicals of cycloalkyl substitution or the pyridine radicals of nitro substitution, it is substituted containing 1 or
Five yuan of 2 N atoms or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl, containing 1 or 2
Substituted five yuan of individual O atom or six membered heteroaryl, substituted five yuan or hexa-atomic miscellaneous containing 1 N atom and 1 S atom
Aryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, the quilt containing 2 N atoms and 1 S atom
Five yuan of substitution or six membered heteroaryl, substituted five yuan containing 2 N atoms and 1 O atom or six membered heteroaryl；Above-mentioned five
Member or six membered heteroaryl are selected from：Substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazole
Ji, oxazolyl, isoxazolyl, oxadiazolyls, thiadiazolyl group, pyridine radicals, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine
Base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, BTA base, benzothiazolyl, benzo
Thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl,
Cinnolines base or naphthyridines base；
Halogen is fluorine, chlorine, bromine or iodine in the definition of above-mentioned Formula IV；
The alkyl, alkenyl or alkynyl are straight chain or side chain alkyl；Alkyl selects in itself or as the part of other substituents
From methyl, ethyl, propyl group, butyl, amyl group, hexyl and its isomers, its isomers is selected from isopropyl, isobutyl group, sec-butyl, uncle
Butyl, isopentyl or tertiary pentyl；
Halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, and the haloalkyl is selected from
CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl in itself or as the part of other substituents；
Alkenyl in itself or as other substituents part be selected from vinyl, pi-allyl, 1- acrylic, butene-2-base, butylene-
3- bases, amylene -1- bases, amylene -3- bases, hexene -1- bases or 4- methyl-3-pentenyls；
Alkynyl is selected from acetenyl, propine -1- bases, propine -2- bases, butine -1- bases, fourth in itself or as the part of other substituents
Alkynes -2- bases, 1- methyl -2- butynyls, hexin -1- bases or 1- ethyl -2- butynyls；
The enantiomeric form and its mixture of Formula IV heterocycle triazole derivative, the optical isomer is enantiomter；
The geometric isomer of Formula IV heterocycle triazole derivative, i.e. (R)-(S) isomery and its mixture；
The atropisomer and its mixture of Formula IV heterocycle triazole derivative.
2. heterocycle triazole derivative VI according to claim 1：
Wherein：R1Selected from the chloroisothiazole -5- bases of 3,4- bis-, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases；
R2Selected from phenyl, to tert-butyl-phenyl, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, an aminomethyl phenyl, adjacent first
Base phenyl, 2,4- dichlorophenyls.
3. according to the heterocycle triazole derivative VI of the claims 1 or 2, wherein：
R1Selected from the chloroisothiazole -5- bases of 3,4- bis-, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases；R2Selected from phenyl, to tert-butyl benzene
Base, p-fluorophenyl, p-trifluoromethyl phenyl, p-methylphenyl, an aminomethyl phenyl, o-methyl-phenyl, 2,4- dichlorophenyls.
4. according to the heterocycle triazole derivative VI of the claims 2, compound therein is：
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -1- phenyl -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) -1- [4- tert-butyl-phenyls] -1- [3,4- bis- chloroisothiazole -5- bases] -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -1- [4- fluorophenyls] -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -2- [1H-1,2,4- triazol-1-yls] -1- [4- trifluoromethyls] second
Alcohol；
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -1- p-methylphenyls -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) aminomethyl phenyl -2- [1H-1,2,4- triazol-1-yls] ethanol between -1- [3,4- bis- chloroisothiazole -5- bases] -1-；
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -1- o-methyl-phenyls -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) -1- [3,4- bis- chloroisothiazole -5- bases] -1- [3,5- dichlorophenyl] -2- [1H-1,2,4- triazol-1-yls] ethanol；
(RS) -1- [4- fluorophenyls] -1- [4- methyl isophthalic acids, 2,3- thiadiazoles -5- bases] -2- [1H-1,2,4- triazol-1-yls] second
Alcohol.
5. the synthetic method of the heterocycle triazole derivative VI according to claim any one of 1-4, specific synthetic route are：
The substituent R1And R2Substituent definition it is as claimed in claim 1；
The synthesis specific method of heterocycle triazole derivative VI described in claim 1 is divided into following steps：
A. the preparation of intermediate compound I：
Intermediate compound I can be by corresponding sour R1It is prepared by COOH reactions；The substituent R1Definition it is as claimed in claim 1；
B. the preparation of intermediate II：
Intermediate II can be by corresponding R1COCl and R2MgBr is prepared by nucleophilic substitution；The substituent R1And R2Definition
As claimed in claim 1；
C. the preparation of intermediate III：
Intermediate III can be prepared by intermediate II and methyl-magnesium-bromide by nucleophilic addition, taking in the intermediate III
For base R1And R2Definition it is as claimed in claim 1；
D. the preparation of intermediate compound IV：
Intermediate compound IV is made by intermediate III through Catalyzed by p-Toluenesulfonic Acid dehydration, the substituent R in the intermediate compound IV1With
R2Definition it is as claimed in claim 1；
E. intermediate V preparation：
Intermediate V is made by intermediate compound IV through metachloroperbenzoic acid oxidation reaction, the substituent R in the intermediate V1And R2
Definition it is as claimed in claim 1；
F. heterocycle triazole derivative VI preparation：
Heterocycle triazole derivative VI is reacted by intermediate V and 1-Sodium-1,2,4-Triazole to be made, the substituent R in the heterocycle triazole derivative VI1
And R2Definition as described in claim 1-4.
6. a kind of composition pesticide, its include heterocycle triazole derivative VI described in claim any one of 1-4 as activity into
Point, the content of active component is 0.1 to 99% weight, the solid or liquid adjuvants of 99.9 to 1% weight, and optional 0 arrives
The surfactant of 25% weight.
7. heterocycle triazole derivative VI sterilizations or antiviral purposes described in claim 1-4.
8. purposes according to claim 7, virus therein is tobacco mosaic virus (TMV).
9. a kind of pesticide complex composition, it includes the heterocycle triazole derivative VI described in claim any one of 1-4 and other
Insecticide, acaricide, bactericide or antivirotic compounding be used as active component, heterocycle triazole derivative VI and other insecticides,
The ratio of acaricide, bactericide or antivirotic is mass percent 1%: 99% to 99%: 1%, and the content of active component is
0.1 to 99% weight, the solid or liquid adjuvants of 99.9 to 1% weight, and the surfactant of optional 0 to 25% weight.
10. the purposes of pesticide complex composition according to claim 9, for being prevented and treated in agricultural, forestry and gardening
Insect, the harm of evil mite, pathogen, plant virus.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191787A (en) * | 2018-02-02 | 2018-06-22 | 南开大学 | A kind of isothiazole imdazole derivatives and its preparation method and application |
| CN108752287A (en) * | 2018-05-21 | 2018-11-06 | 南开大学 | The preparation method and purposes of heterocycle tertiary alcohol derivative |
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