CN109053605A - The preparation method and purposes of heterocycle triazole derivative - Google Patents
The preparation method and purposes of heterocycle triazole derivative Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
Abstract
The present invention provides heterocycle triazole derivatives and its preparation method and application, and the present invention relates to heterocycle triazole class compounds, its its general formula of the chemical structure is shown in formula III:
Description
Technical field
Technical solution of the present invention is related to synthesis and the activity research of the heterocycle triazole class compounds containing N, and in particular to and 1,
2,4- triazole derivatives.
Background technique
Heterocyclic compound has potential broad-spectrum biological activity (Lai Chen, et al.Synthesis and
Fungicidal activity of 3,4-dichloroisothiazole based strobilurins as potent
Fungicide candidates.RSC Adv., 2017,7:3145-3151), the heterocycle of this structure or a kind of Development of Novel
Critical policies (Chen L, et al.Synthesis of 1,2,3-Thiadizole and of the pesticide including fungicide
Thiazole Based Strobilurins as Potent Fungicide Candidates.J.Agric.Food
Chem.2017,65,745-751).In the drug molecule of patent literature report 70%, at least contain a heterocyclic fragments；Wherein,
Thiazole is a large amount of five-ring heterocycles reported and study, and isothiazole and thiadiazoles are as five yuan of important nitrogenous sulfur heterocyclic ring chemical combination
The research relative rarity of object, discovered in recent years, 3,4- bis- chloroisothiazoles, 1,2,3- thiadiazoles heterocycle have activating plants agent, kill
Activity (Chen L, Guo, X.F., Fan, Z.J., the et al.Synthesis of microbial inoculum, plant growth regulator and insecticide
And fungicidal activity of 3,4-dichloroisothiazole based strobilurins as
Potent fungicide candidates. RSC Advances, 2017,7,3145-3151), such as green agriculture of commercialization
Medicine activating plants agent isotianil and tiadinil are exactly the derivative of isothiazole and thiadiazoles.Fluorine thiazole pyrrole ethyl ketone is containing thiophene
The plant disease prevention and control medicament that the Pseudoperonospora cubensis of the ultra high efficiency of azoles piperidines and phytophthora germ cause.Difluoromethyl pyrazole intermediate is
The important intermediate of succinate dehydrogenase inhibitors.
Triazole bactericidal agent has the bactericidal activity of wide spectrum, is widely used in by Ascomycetes, Basidiomycetes, Fungi Imperfecti
Multiple diseases caused by equal fungus diseases prevent and treat；Belong to sterol biosynthesis C-14 demethylation enzyme inhibitor (DMI), passes through
Inhibiting effect is played to ergosterol synthesis in plant.Such medicament has efficient, wide spectrum, low toxicity, lasting period length, absorbability
A variety of advantages (Chen, et al.Design, Synthesis and Biological Evaluation of such as strong
Isothiazole Based 1,2,4-Trizaole Derivatives.Chin.J.Chem.2018,36), in addition, triazole type
Make compound as plant growth regulator to be also concerned.Triazole class compounds are the maximum disinfectant use in agriculture of global dosage；
The triazole bactericidal agent kind being commercialized that succeeded is more, such as difenoconazole, Tebuconazole.Since triazole bactericidal agent acts on
Site is single, long-term largely very prominent using bring resistance problem；And there is the system of broad spectrum durable to obtain for activating plants agent
Disease resistance, be not directly placed on pathogen but achieved the effect that by acting on plant itself it is disease-resistant, no drug resistance
Risk, innovative research are extremely urgent.
To find and finding more efficient, wide spectrum, low toxicity, low ecological risk and the agriculture of without cross-resistance with existing fungicides
Medicine lead compound, the present invention will contain N, the isothiazole and thiadiazoles pharmacophore 3 of S, bis- chloroisothiazole ring of 4- and 4- methyl-1, and 2,
3- Thiadiazole and thiophene piperidines and fluorine-containing pyrazoles are introduced into the guide structure of triazole type, design synthesis heterocycle three
Zole derivatives, while bioactivity screening and the evaluation of system are carried out, it is more high living to be provided for New pesticides discovery research
The candidate compounds of the low resistance risk of property.
Summary of the invention
The technical problems to be solved by the present invention are: provide a new class of heterocycle triazole derivative and preparation method thereof and its
Regulate and control the bioactivity and its measuring method of agricultural, gardening, health and forestry plant pest, the phytopathy original, while this being provided
A little applications of the compound in agriculture field, horticultural field, field of forestry and health field.
The present invention solves technical solution used by the technical problem: having agriculture field, horticultural field, field of forestry
Desinsection, bactericidal activity the general formula of the chemical structures of heterocycle triazole class compounds see formula III:
Wherein, R24、R25It is selected from: hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy,
C2-C6Alkenyl, C2-C6Halogenated alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Naphthenic base, substituted piperidines -1-
The phenyl or C that base, substituted morpholine -1- base, substituted nafoxidine -1- base, phenyl or halogen replace1-C6Alkyl takes
The phenyl or C in generation1-C6The phenyl or C that halogenated alkyl replaces3-C6The phenyl or C that the phenyl or nitro that naphthenic base replaces replace2-
C6The phenyl or C that alkenyl replaces2-C6The phenyl or C that halogenated alkenyl replaces3-C6The phenyl or C that cycloalkenyl replaces2-C6Alkynyl
Substituted phenyl or C2-C6The phenyl or C that halo alkynyl replaces3-C6What phenyl, pyridyl group or the halogen that cycloalkynyl radical replaces replaced
Pyridyl group or C1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6What naphthenic base replaced
The pyridyl group or C that pyridyl group or nitro replace2-C6The pyridyl group or C that alkenyl replaces2-C6The pyridyl group of halogenated alkenyl substitution,
Or C3-C6The pyridyl group or C that cycloalkenyl replaces2-C6The pyridyl group or C of alkynyl substituted2-C6Halo alkynyl replace pyridyl group or
C3-C6The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that cycloalkynyl radical replaces replace1-C6Alkyl-substituted pyrimidine radicals or C1-
C6The pyrimidine radicals or C that halogenated alkyl replaces3-C6The pyrimidine radicals or C that the pyrimidine radicals or nitro that naphthenic base replaces replace2-C6Alkenyl
Substituted pyrimidine radicals or C2-C6The pyrimidine radicals or C that halogenated alkenyl replaces3-C6The pyrimidine radicals or C that cycloalkenyl replaces2-C6Alkynyl
Substituted pyrimidine radicals or C2-C6The pyrimidine radicals or C that halo alkynyl replaces3-C6Pyrimidine radicals that cycloalkynyl radical replaces substituted contains 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, contain 1
Or substituted five yuan or six membered heteroaryl, substituted five yuan or hexa-atomic containing 1 N atom and 1 S atom of 2 O atoms
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 or six membered heteroaryl containing 2 N atoms and 1 O atom；It is above-mentioned
Five yuan or six membered heteroaryl are selected from: substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazole
Base, oxazolyl, isoxazolyl, oxadiazoles base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine
Base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazole base, benzothiazolyl, benzo
Thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl,
The silicon substrate that cinnoline base or naphthyridines base, alkyl or alkenyl replace；
Halogen is fluorine, chlorine, bromine or iodine in above-mentioned definition；
The alkyl, alkenyl or alkynyl are straight chain or branch alkyl；Alkyl itself or portion as other substituent groups
It is selected from methyl, ethyl, propyl, butyl, amyl, hexyl and its isomers, isomers is selected from isopropyl, isobutyl group, Zhong Ding
Base, tert-butyl, isopentyl or tertiary pentyl；
The halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, the alkyl halide
Base is selected from CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Described naphthenic base itself or as other substituent groups part be selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
Described alkenyl itself or as other substituent groups part be selected from vinyl, allyl, 1- acrylic, butene-2-
Base, butylene -3- base, amylene -1- base, amylene -3- base, hexene -1- base or 4- methyl-3-pentenyl；
Described alkynyl itself or as other substituent groups part be selected from acetenyl, propine -1- base, propine -2- base, fourth
Alkynes -1- base, crotonylene-base, 1- methyl -2- butynyl, hexin -1- base or 1- ethyl -2- butynyl；
The enantiomeric form and its mixture of heterocycle triazole derivative III, the optical isomer are enantiomerism
Body or cis-trans-isomer；
The geometric isomer of heterocycle triazole derivative III, i.e. (R)-(S) isomery and its mixture；
The atropisomer and its mixture of heterocycle triazole derivative III.
Wherein, R24、R25It preferably is selected from: alkyl, alkoxy, hydrogen, halogen, alkenyl, alkynyl, cyclopropyl, 3,4-, bis- chloroisothiazole
Base, 4- methyl-1,2,3- thiadiazolyl groups, replace difluoro pyrazolyl at substituted thiazole piperidyl.
The synthetic method of heterocycle triazole derivative III of the invention is as follows:
Wherein, substituent R24、R25It is defined as described above, preferably as follows:
R25=-H.-F.-CH3.-OCH3.-Br
The synthesis of heterocycle triazole derivative III and the specific method of biological activity determination of the invention is divided into following step
It is rapid:
A. the synthesis of intermediate 10
Intermediate 10 reacts preparation with 1-Sodium-1,2,4-Triazole as raw material for melilotal using α-Br.
B. the synthesis of intermediate 11
Intermediate 11 is that raw material reacts preparation with hydroxylamine hydrochloride with intermediate 10.
C. the synthesis of heterocycle triazole derivative III
Heterocycle triazole derivative III is prepared by raw material and carboxylic acid dehydration with intermediate 11.
D. the bactericidal activity measurement of heterocycle triazole derivative III of the invention:
The sterilization of heterocycle triazole derivative of the invention or bacteriostatic activity use thalli growth rate measuring method, specific steps
Are as follows: take 1.8 milligrams of samples to be dissolved in 2 drop n,N-Dimethylformamide, then with the water for containing a certain amount of polysorbas20 emulsifier
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 tablets are made after shaking up, with add 1 milliliter of aqua sterilisa plate do
Blank control cuts bacterium disk along mycelia outer rim with 4 millimeters of diameter of punch, moves in drug containing tablet, pendulum in equilateral triangle
It puts, every processing is repeated 3 times, and culture dish is placed on culture, colony diameter to be compareed in 24 ± 1 degrees Celsius of constant incubators and is expanded to
Each processing bacterium disk extension diameter is investigated after 2-3 centimetres, is averaged, and opposite bacteriostasis rate is calculated compared with blank control, for trying bacterium
Kind is the kind for most of typical plant pathogen that field actually occurs in China's agricultural production, and code name and title are as follows:
AS: tomato early blight bacterium, latin name are as follows: Alternaria solani, BC: botrytis cinerea pers, latin name are as follows:
Botrytis cinerea, CA: peanut Cercospora bacteria, latin name are as follows: Cercospora arachidicola, GZ: wheat is red
Mildew bacterium, latin name are as follows: Gibberella zeae, PI: phytophthora infestans, latin name are as follows: Phytophthora
Infestans (Mont.) de Bary, PP: Botryosphaeria berengeriana f. sp, latin name are as follows: Physalospora piricola, PS:
Rhizoctonia solani Kuhn, latin name are as follows: Pellicularia sasakii, RC: Rhizoctonia cerealis, latin name are as follows:
Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, latin name are as follows: Sclerotinia sclerotiorum.
E. the insecticidal activity assay of heterocycle triazole derivative III of the invention:
Standard practice instructions of the insecticidal activity screening technique of heterocycle triazole derivative III of the invention referring to Nankai University
It carries out, is respectively mythimna separata, corn borer for examination insect.
Beneficial effect of the invention is: having carried out guide's optimization to heterocycle triazole derivative, and to heterocycle triazole derivative III
And the screening for having carried out bacteriostatic activity and insecticidal activity of intermediate.
The present invention by it is specific preparation and biological activity determination embodiment it is more specific illustrate heterocycle triazole derivative III and
The synthesis of intermediate 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
It is that bioactivity is merely illustrative of, rather than limits this patent, and specific embodiment is as follows:
Embodiment 1: the synthesis of intermediate 10
By taking 1- (1,2,4- triazol-1-yl) -2- (p-methylphenyl) -1- ketoxime as an example:
α-Br is added in the round-bottomed flask of 100mL for melilotal (5.00g, 23.47mmol, 1equiv.), 1,
2,4- triazole hydrochlorides (6.41g, 70.41mmol, 3equiv.).Amide is as solvent, room between the N of 20mL, N- dimethyl
Temperature stirring is for 24 hours.Since this reaction is difficult to fully reacting, when TLC shows that there are also handle reaction when a little raw material.Add
After entering a large amount of water stirring 1-2min, 100mL ethyl acetate is added, layering takes organic layer.Water layer uses 50mL ethyl acetate respectively
Back extraction 3 times merges organic layer.Saturated sodium-chloride water solution washs organic layer, and aqueous layer with ethyl acetate (20mL × 3) back extraction is closed
And organic layer.After the dry 3h of anhydrous sodium sulfate, concentration, a little oily dark matter of this solid dopant is washed with 20mL ethyl acetate
Solid after washing concentration, obtains product.Yield is 4.60g, yield 86%.
Embodiment 2: the synthesis of intermediate 11
By taking intermediate III-C as an example: structure is shown in appendix C.
1- (1,2,4- triazol-1-yl) -2- (p-methylphenyl) -1- ketoxime is sequentially added in the single port bottle of 100mL
(4.6g, 22.86mmol, 1equiv.), the dehydrated alcohol of 50mL, hydroxylamine hydrochloride (3.16g, 91.44mmol, 4equiv.),
Triethylamine (9.25g, 91.44mmol, 3equiv.) is added dropwise after mixing evenly, 48h is stirred at room temperature.TCL detection reaction terminates
The solid being concentrated afterwards, the water that 1000mL is added are stirred overnight, and suction filtration obtains solid.
11 structural parameters of intermediate are as follows:
III-A:1H NMR (400MHz, DMSO) δ 11.98 (s, 1H), 8.56 (s, 1H), 7.90 (s, 1H), 7.71 (d, J
=4.2Hz, 2H), 7.37 (s, 3H), 5.53 (s, 2H)13C NMR (101MHz, DMSO) δ 151.22,151.10,145.04,
134.31,128.99,128.37,126.22,42.41.
III-B:1H NMR (400MHz, DMSO) δ 12.13-11.95 (m, 1H), 8.55 (s, 1H), 7.89 (s, 1H),
7.74 (dd, J=8.8,5.5Hz, 2H), 7.21 (td, J=8.8,3.2Hz, 2H), 5.52 (d, J=6.5Hz, 2H)13C NMR
(101 MHz, DMSO) δ 163.74,161.29,151.27,150.34,130.84,130.81,128.50,128.42,11542,
115.20,42.42.
III-C:1H NMR (400MHz, DMSO) δ 11.88 (s, 1H), 8.55 (s, 1H), 7.90 (s, 1H), 7.60 (d, J
=8.2Hz, 2H), 7.18 (d, J=8.0Hz, 2H), 5.50 (s, 2H), 2.29 (s, 3H)13C NMR (101MHz, DMSO) δ
151.19,150.98,144.98,138.56,131.49,128.95,126.13,42.34,20.74.
III-E:1H NMR (400MHz, DMSO) δ 11.77 (d, J=15.2Hz, 1H), 8.53 (s, 1H), 7.90 (s,
1H), 7.65 (d, J=8.8Hz, 2H), 6.94 (d, J=8.8Hz, 2H), 5.48 (s, 2H), 3.76 (s, 3H)13C NMR
(101MHz, DMSO) δ 159.89,151.16,150.62,144.95,127.61,126.67,113.80,55.12,42.30.
III-F:H NMR (400MHz, DMSO) δ 12.09 (d, J=7.1Hz, 1H), 8.57 (s, 1H), 7.90 (s, 1H),
7.65 (dd, J=8.6,2.6Hz, 2H), 7.62-7.55 (m, 2H), 5.51 (s, 2H)13C NMR (101MHz, DMSO) δ
151.80,150.92,145.59,134.08,131.85,128.77,122.97,42.70.
Embodiment 3: the synthesis of heterocycle triazole derivative III
By taking compound III-12 as an example:
III-C (500mg, 2.31mmol, 1equiv.) and 3 is added in the bottle with two necks of 100mL, the chloro- 2- methoxyl group of 6- bis-
Benzoic acid (1.53g, 6.93mmol, 3equiv.), 20mL methylene chloride is as solvent.Inert gas N2It protects, under the conditions of 0 DEG C
The mixing two of DCC (1.43g, 6.93mmol.3equiv.) and DMAP (135mg, 1.11mmol, 0.48equiv.) is added dropwise
Chloromethanes ((15mL) solution.TCL is detected after reaction, and suction filtration takes filtrate.Filtrate use respectively 1mol/L hydrochloric acid (10mL ×
2) and the sodium chloride (10mL × 2) of saturation washs.Water layer uses methylene chloride (20mL × 3) to be stripped respectively, merges organic layer.It is anhydrous
Sodium sulphate is dry.Solvent is removed under reduced pressure, obtains solid.With the obtained solid of a large amount of water washing, crude product is obtained.Again with few
Ethyl acetate (3-5ml) the washing solid of amount obtains alcohol product.The structural parameters of target compound III-1-III-20 are as follows:
III-1: white crystal；Fusing point: 157-158 DEG C；Yield: 300mg；Yield: 43%；1H NMR (400MHz,
CDCl3) δ 8.21 (s, 1H), 7.93 (d, J=3.9Hz, 1H), 7.79-7.74 (m, 2H), 7.54-7.48 (m, 1H), 743 (t, J
=7.5Hz, 2H), 5.68 (s, 2H)13C NMR (101MHz, CDCl3) δ 160.90,155.12,152.22,150.66,
147.40,143.87,132.10,130.58,129.19,128.72,127.80,126.96,126.30,45.51.HRMS (m/
z) calcd for C14H9Cl2N5O2S(M+H)+: 381.9932, found:381.9924.
III-2: white crystal；Fusing point: 123-124 DEG C；Yield: 428mg；Yield: 43%；1H NMR (400MHz,
DMSO) δ 8.71 (s, 1H), 7.93 (s, 1H), 7.79 (d, J=7.5Hz, 2H), 7.57-7.45 (m, 3H), 5.86 (s, 2H),
2.95 (s, 3H)13C NMR (101MHz, DMSO) δ 163.01,162.35,156.76,151.88,145.21,136.82,
131.37,131.14,128.79,127.71,44.85,13.83.HRMS (m/z) calcd for C14H12N6O2S(M+Na)+:
351.0640, found:351.0639.
III-3: colorless oil；Yield: 604mg；Yield: 43%；1H NMR (400MHz, DMSO) δ 8.59 (s, 1H),
7.91 (s, 1H), 7.74 (t, J=8.0Hz, 3H), 7.45 (d, J=8.6Hz, 4H), 5.80 (s, 2H), 3.90 (s, 3H)13C
NMR (101MHz, DMSO) δ 162.48,161.88,153.94,152.31,145.75,133.68,131.70,129.48,
129.18,128.35,128.14,126.81,126.57,62.78,45.05.HRMS (m/z) calcd for C18H14Cl2N5O3
(M+H)+: 405.0521, found:405.0517.
III-4: white crystal；Fusing point: 147-148 DEG C；Yield: 712mg；Yield: 43%；1H NMR (400MHz,
DMSO) δ 8.80 (s, 1H), 8.70 (s, 1H), 7.92 (s, 1H), 7.78-7.72 (m, 2H), 7.46 (ddd, J=13.4,6.8,
3.8Hz, 3H), 7.21 (d, J=53.4Hz, 1H), 5.91 (s, 2H), 3.99 (s, 3H)13C NMR (101MHz, DMSO) δ
161.26,158.43,152.33,145.65,137.46,132.17,131.40,129.11,128.05,112.53,110.19,
109.51,107.85,44.97.HRMS (m/z) calcd for C16H14Cl2N6O2S(M+H)+: 361.1224, found:
361.1218.
III-5: white crystal；Fusing point: 142-144 DEG C；Yield: 212mg；Yield: 45%；1H NMR (400MHz,
CDCl3) δ 8.29 (s, 1H), 8.04 (s, 1H), 7.92 (dd, J=8.7,5.2Hz, 2H), 7.24 (t, J=8.5Hz, 2H),
5.74 (s, 2H)13C NMR (101MHz, CDCl3) δ 166.30,163.77,159.84,154.98,152.31,150.81,
147.43,143.76,130.25,130.16,116.64,116.42,45.40.
III-6: white crystal；Fusing point: 160-161 DEG C；Yield: 214mg；Yield: 36%；1H NMR (400MHz,
CDCl3) δ 8.24 (s, 1H), 7.96 (s, 1H), 7.85 (s, 2H), 7.17 (s, 2H), 5.62 (s, 2H), 3.06 (d, J=
3.3Hz, 3H)13C NMR (101MHz, CDCl3) δ 164.83,159.31,156.80,152.29,143.80,135.07,
126.99,116.65,116.53,116.42,45.27,14.41.HRMS (m/z) calcd for C14H11FN6O4S(M+H)+:
347.0726, found:347.0716.
III-7: white powder；Fusing point: 123-124 DEG C；Yield: 598mg；Yield: 70%；1H NMR (400MHz,
DMSO) δ 8.80 (s, 1H), 8.71 (s, 1H), 7.94 (s, 1H), 7.86-7.79 (m, 2H), 7.29 (dd, J=14.0,4.9Hz,
3H), 5.91 (s, 2H), 3.99 (s, 3H)13C NMR (101MHz, DMSO) δ 161.26,158.43,152.33,146.34,
146.09,145.84,145.65,137.46,132.17,131.40,129.11,128.05,112.53,110.19,109.51,
107.85,44.97.HRMS (m/z) calcd for C16H13F3N6O2(M+H)+: 379.1130, found:379.1129.
III-8: white powder；Fusing point: 162-163 DEG C；Yield: 906mg；Yield: 74%；1H NMR (400MHz,
DMSO) δ 8.87 (s, 1H), 8.82 (s, 1H), 7.93 (dd, J=8.4,5.1Hz, 3H), 7.34 (t, J=8.8Hz, 2H), 5.85
(s, 2H), 4.04 (d, J=10.5Hz, 2H), 3.32 (ddd, J=11.5,8.1,3.6Hz, 1H), 2.92 (s, 2H), 2.11 (d,
J=11.3Hz, 2H), 1.63 (dd, J=11.9,3.3Hz, 2H), 1.41 (s, 9H)13C NMR (101MHz, DMSO) δ
176.09,165.47,162.99,160.88,157.68,154.32,152.26,146.03,143.55,130.78,
130.69,128.90,116.45,116.23,79.22,45.11,33.82,32.21,28.51.HRMS (m/z) calcd for
C24H27F6N4OS(M+H)+: 515.1877, found:515.1873.
III-9: white crystal；Fusing point: 128-129 DEG C；Yield: 865mg；Yield: 88%；1H NMR (400MHz,
DMSO) δ 8.61 (s, 1H), 7.93 (s, 1H), 7.84 (dd, J=8.6,5.4Hz, 2H), 7.70 (d, J=8.7Hz, 1H), 7.43
(d, J=8.7Hz, 1H), 7.29 (t, J=8.8Hz, 2H), 5.81 (s, 2H), 3.90 (s, 3H)13C NMR (101MHz, DMSO)
δ 165.51,163.03,161.63,153.96,152.35,145.75,133.66,130.77,130.68,129.50,
128.26,126.77,116.43,116.21,62.75,45.04HRMS (m/z) calcd for C18H13Cl2FN4O3(M+Na
)+: 445.0247, found:445.0245；C18H13Cl2FN4O3(M+Na+2)+: 447.0213.
III-10: white needle-like crystals；Fusing point: 142-143 DEG C；Yield: 653mg；Yield: 93%；1H NMR(400
MHz, DMSO) δ 8.71 (s, 1H), 7.93 (s, 1H), 7.70 (d, J=8.2Hz, 2H), 7.29 (d, J=8.0Hz, 2H), 5.83
(s, 2H), 2.95 (s, 3H)13C NMR (101MHz, DMSO) δ 163.48,162.55,157.31,152.36,145.67,
142.03,137.35,129.90,128.74,128.15,45.13,21.42,14.34.HRMS (m/z) calcd for
C15H14N6O2S (M+H)+: 343.0977, found:343.0973.C15H14N6O2S(M+Na)+: 365.0797, found:
365.0795.
III-11: pale yellowish oil；Yield: 372mg；Yield: 96%；1H NMR (400MHz, DMSO) δ 8.86 (s,
1H), 8.81 (s, 1H), 7.93 (s, 1H), 7.77 (d, J=8.2Hz, 2H), 7.30 (d, J=8.1Hz, 2H), 5.83 (s, 2H),
4.04 (dd, J=8.9,5.1Hz, 2H), 3.32 (ddd, J=15.0,7.6,3.7Hz, 1H), 2.92 (s, 2H), 2.35 (s,
3H), 2.11 (d, J=10.9Hz, 2H), 1.63 (qd, J=12.5,4.1Hz, 2H), 1.41 (s, 9H)13C NMR (101MHz,
DMSO) 175.55 δ, 160.98,157.28,153.82,151.67,145.47,143.19,141.16,130.13,129.31,
128.97,127.59,78.72,44.45,31.71,28.02,20.92.HRMS (m/z) calcd for C25H30N6O4S(M+
H)+: 511.2127, found:511.2122.
III-12: pale yellowish oil；Yield: 912mg；Yield: 94%；1H NMR (400MHz, CDCl3) δ 8.04 (s,
1H), 7.71 (s, 1H), 7.56 (d, J=8.1Hz, 2H), 7.27 (d, J=8.7Hz, 1H), 7.02 (d, J=8.6Hz, 3H),
5.42 (s, 2H), 3.76 (s, 3H)13C NMR (101MHz, CDCl3C) 161.43 δ, 160.35,154.05,151.77,
144.14,142.11,132.76,129.64,129.55,128.23,128.14,127.57,126.76,125.94,62.39,
44.71,21.33. HRMS (m/z) calcd for C19H16Cl2N4O3(M+Na)+: 441.0497, found:
441.0495.C19H16Cl2N4O3 (M+Na+1)+: 443.0464.
III-13: white powder；Fusing point: 138-139 DEG C；Yield: 1.10g；Yield: 82%；1H NMR (400MHz,
DMSO) δ 8.71 (s, 1H), 7.95 (s, 1H), 7.79 (d, J=8.7Hz, 2H), 7.04 (d, J=8.7Hz, 2H), 5.84 (s,
2H), 3.81 (s, 3H)13C NMR (101MHz, DMSO) δ 162.36,160.39,159.39,155.51,152.31,
151.63,151.09,130.06,128.10,114.82,114.29,55.89,45.01.HRMS (m/z) calcd for
C15H11Cl2N5O3S(M+H)+: 412.0038, found:412.0032.
III-14: white crystal；Fusing point: 116-118 DEG C；Yield: 806mg；Yield: 93%；1H NMR (400MHz,
DMSO) δ 8.72 (d, J=3.4Hz, 1H), 7.95 (d, J=1.7Hz, 1H), 7.80 (d, J=8.8Hz, 2H), 7.04 (d, J=
8.8Hz, 2H), 5.81 (s, 2H), 3.81 (s, 3H), 2.94 (s, 3H)13C NMR (101MHz, DMSO) δ 163.46,
162.30,161.89,157.38,152.32,145.60,137.34,129.99,123.63,114.80,55.87,44.93,
14.33. HRMS(m/z)calcd for C15H14N6O3S(M+H)+: 359.0562, found:359.0921.
III-15: white crystal；Fusing point: 98-99 DEG C；Yield: 987mg；Yield: 83%；1H NMR (400MHz, DMSO)
δ 8.87 (s, 1H), 8.79 (s, 1H), 7.94 (s, 1H), 7.85 (d, J=8.8Hz, 2H), 7.05 (d, J=8.8Hz, 2H),
5.80 (s, 2H), 4.04 (d, J=10.5Hz, 2H), 3.82 (s, 3H), 2.92 (s, 2H), 2.11 (d, J=11.9Hz, 2H),
1.63 (dd, J=11.9,3.2Hz, 3H), 1.41 (s, 9H)13C NMR (101MHz, DMSO) δ 176.04,162.09,
160.97,157.85,154.33,152.14,145.95,143.77,130.53,129.88,124.40,114.70,99.99,
79.23,55.86,44.79,33.82,32.22,28.53.HRMS (m/z) calcd for C25H30N6O5S(M+H)+:
327.2076., found:327.2072.
III-16: white crystal；Fusing point: 113-115 DEG C；Yield: 242mg；Yield: 64%；1H NMR (400MHz,
CDCl3) δ 8.13 (s, 1H), 7.89 (s, 1H), 7.83 (d, J=8.9Hz, 2H), 7.45 (d, J=8.7Hz, 1H), 7.19 (d, J
=8.7Hz, 1H), 6.92 (d, J=8.9Hz, 2H), 5.53 (s, 2H), 3.93 (s, 3H), 3.83 (s, 3H)13C NMR
(101MHz, CDCl3) δ 162.47,161.56,159.53,154.22,151.83,143.99,132.81,129.79,
129.52,128.33,126.94,126.00,123.25,114.42,62.58,55.43,44.66.HRMS (m/z) calcd
for C19H16Cl2N4O4(M+H)+: 435.0625, found:435.0622.
III-17: white crystal；Fusing point: 94-96 DEG C；Yield: 396mg；Yield: 78%；1H NMR (400MHz, DMSO)
δ 8.77 (s, 1H), 8.71 (s, 1H), 7.95 (s, 1H), 7.76 (d, J=8.8Hz, 2H), 7.29 (t, J=53.5Hz, 1H),
7.00 (d, J=8.9Hz, 2H), 5.88 (s, 2H), 3.99 (s, 3H), 3.79 (s, 3H)13C NMR (101MHz, DMSO)13C
NMR (101MHz, DMSO) δ 161.92,160.42,158.58,152.27,146.29,146.04,145.79,145.53,
137.31,129.71,124.21,114.59,112.53,110.20,109.67,107.86,55.75,44.59.HRMS (m/z)
calcd for C17H16CF2N6O3(M+H)+: 391.1330, found:391.1322.
III-18: yellow oily；Yield；419mg；Yield: 78%；1H NMR (400MHz, DMSO) δ 8.59 (s, 1H),
7.91 (s, 1H), 7.76 (d, J=8.9Hz, 1H), 7.68 (s, 4H), 7.48 (d, J=8.7Hz, 1H), 5.77 (s, 2H), 3.89
(s, 3H)13C NMR (101MHz, DMSO) δ 161.90,160.42,158.54,152.25,145.55,137.34,131.98,
129.72,129.26,129.13,124.21,114.61,110.18,109.65,55.80,44.57.HRMS (m/z) calcd
for C18H13BrCl2N4O3(M+Na)+: 504.9446, found:504.9407.
III-19: white crystal；Fusing point: 137-109 DEG C；Yield: 428mg；Yield: 74%；1H NMR (400MHz,
DMSO) δ 8.82 (s, 1H), 8.71 (s, 1H), 7.94 (s, 1H), 7.73-7.65 (m, 4H), 7.29 (dd, J=69.7,
37.1Hz, 1H), 5.91 (s, 2H), 3.99 (s, 3H)13C NMR (101MHz, DMSO) δ 160.02,157.79,151.90,
145.86,145.61,145.36,145.17,137.01,131.69,130.94,129.56,124.66,112.01,
109.67,108.85,107.33,44.33.HRMS (m/z) calcd for C16H13BrF2N6O2(M+H)+: 439.0329,
Found:439.0327.
III-20: white crystal；Fusing point: 107-108 DEG C；Yield: 542mg；Yield: 64%；1H NMR (400MHz,
CDCl3) δ 9.09 (s, 1H), 8.36 (s, 1H), 8.00-7.92 (m, 3H), 7.62 (d, J=8.6Hz, 2H), 5.59 (s, 2H),
4.29 (d, J=15.2Hz, 2H), 3.32-3.21 (m, 1H), 2.92 (s, 2H), 2.21 (d, J=11.6Hz, 2H), 1.88-
1.75 (m, 2H), 1.48 (s, 9H)13C NMR (101MHz, CDCl3) δ 176.28,159.24,157.60,154.66,
151.81,145.80,144.18,132.27,130.97,129.50,129.42,126.49,79.88,77.41,77.09,
76.78,44.97,40.88,32.33,28.43.HRMS (m/z) calcd for C24H27BrN6O4S(M+Na)+:
597.0896, found:597.0896.
Embodiment 4: the Antibacterial Activity result of heterocycle triazole derivative of the invention:
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, latin name
Are as follows: Alternaria solani, BC: botrytis cinerea pers, latin name are as follows: Botrytis cinerea, CA: peanut foxiness
Germ, latin name are as follows: Cercospora arachidicola, GZ: fusarium graminearum, latin name are as follows: Gibberella
Zeae, PI: phytophthora infestans, latin name are as follows: Phytophthora infestans (Mont.) de Bary, PP: apple
Fruit Target spot pathogen, latin name are as follows: Physalospora piricola, PS: Rhizoctonia solani Kuhn, latin name are as follows:
Pellicularia sasakii, RC: Rhizoctonia cerealis, latin name are as follows: Rhizoctonia cerealis, SS: Sclerotina Sclerotiorum in Winter Rape
Core germ, latin name are as follows: Sclerotinia sclerotiorum, these strains have representativeness well, can represent
The kind for most of pathogen that field occurs in agricultural production.
Heterocycle triazole derivative III inhibits the inhibiting rate of PI to be below positive control drug Fluoxastrobin and Flutriafol.Heterocycle three
Zole derivatives III inhibits the inhibiting rate of CA to be below positive control drug Fluoxastrobin and Flutriafol, and only there are two the inhibition of compound
Rate is more than 60%, respectively III-6 and III-13.Heterocycle triazole derivative III inhibits the inhibiting rate of AS to be below the phonetic bacterium of control
Ester and Flutriafol, only the inhibiting rate of compound III-13 has been more than 60%.The inhibiting rate of heterocycle triazole derivative III inhibition BC:
The bacteriostatic activity of compound III-5 is higher than 90%, is higher than control compound Fluoxastrobin and Flutriafol；Compound III-13 inhibiting rate
It is suitable with the activity of control compound Fluoxastrobin and Flutriafol 80% or more.The suppression of heterocycle triazole derivative III inhibition GZ
Rate processed: the inhibiting rate of compound III-13 and III-17 are higher than 90%, are above the work of control compound Fluoxastrobin and Flutriafol
Property, wherein the inhibiting rate of compound III-13 is up to 100%, and the inhibiting rate of compound III-17 is higher than 70%, with Fluoxastrobin phase
When slightly below Flutriafol.The inhibiting rate of compound III inhibition PP: the inhibiting rate of compound is below positive control drug Flutriafol.
For the activity of compound III-13 70% or more, activity is lower than Flutriafol, is higher than Fluoxastrobin.Heterocycle triazole derivative III inhibits
The inhibiting rate of SS is shown in: the inhibiting rate of compound III-2, III-5 and III-18 are in 80% or more, slightly below Fluoxastrobin and powder azoles
Alcohol.The inhibiting rate of heterocycle triazole derivative III inhibition RC: compound III-12's and III-18 is suppressed over 90%, and compares
Compound Fluoxastrobin and Flutriafol are suitable.The inhibiting rate of heterocycle triazole derivative III inhibition PS: the compound of synthesis is inhibiting this
Activity is not as good as control compound when pathogen.
Embodiment 5: the bacteriostatic activity EC of heterocycle triazole derivative of the invention50Measurement result:
Herein to the preferable compound of general sieve activity inhibited in concentration measurement, only compound III- as the result is shown
13 in the EC for inhibiting pathogen SS to be50For 0.65 μ g/mL, it can effectively inhibit SS bacterium, activity is higher than the phonetic bacterium of control compound
The 4.04 μ g/mL and 4.63 μ g/mL of ester and Flutriafol.Remaining compound activity on inhibiting pathogen is undesirable.
Embodiment 6: the insecticidal activity assay result of heterocycle triazole derivative of the invention:
The insecticidal activity assay of heterocycle triazole derivative the results are shown in Table 3, and test insect pest is armyworm and corn borer.Handle III
Series compound kills mythimna separata experimental data at this concentration, compound III-6, III-12, III-14, III-18, III-19 and
Lethality of the III-20 in mythimna separata is identical as control compound up to 100%.By compound III-6, III-12, III-14,
After the concentration of III-18, III-19 and III-20 are reduced to 50 μ g/mL, the desinsection lethality of compound III-12 and III-14
Still it can achieve 100%, it is identical as control compound metaflumizone and Diacloden.Corn borer is killed in III series compound
In experiment, at 100 μ g/mL, the lethality of compound III-6, III-12, III-14 when killing mythimna separata and is compareed up to 100%
Compound is identical, and lead compound of the invention does not have insecticidal activity.
Embodiment 7: heterocycle triazole derivative III and its intermediate of the invention is preparing the application in composition pesticide:
Heterocycle triazole derivative III of the invention and intermediate can prepare composition pesticide, and the composition includes this hair
Bright heterocycle triazole derivative III and its intermediate is 0.1 to 99.9% weight as active constituent, the content of active constituent,
The surfactant of the solid or liquid adjuvants of 99.9 to 0.1% weight and optional 0 to 25% weight.
Embodiment 8: heterocycle triazole derivative III of the invention and intermediate and antimicrobial combination are in controlling plant diseases
Using:
Heterocycle triazole derivative III and intermediate of the invention combines shape with any one or two kinds in commodity fungicide
It is selected from bactericidal composition for preventing and treating agricultural and forestry and gardening plant disease, the commodity fungicide: diazosulfide,
Tiadinil is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl-1,2,3- thiadiazoles -5- formic acid, 4- methyl-1,2,3- thiophenes
Diazole -5- sodium formate, 4- methyl-1,2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acid, isotianil, English are logical
With name are as follows: isotianil, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formate, the different thiophene of 3,4- dichloro
Azoles -5- Ethyl formate, 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, fluorine
Quinoline, dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil,
Tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, double alkynes acyls
Bacterium 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, cyclopropyl
Azoles alcohol, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, benzoxazole, Fluquinconazole, Flusilazole, Flutriafol, azoles alcohol,
Glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, three
Azoles alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid,
Fenamidone dislikes imidazoles, pefurazoate, Famoxate, oxazole, hymexazol, Wakil, Guardian, Grandox fumigant, pungent thiophene
Ketone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium
Amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, chlorobenzene pyrimidine
Alcohol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, isopropyl
Bacterium amine, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, spring thunder are mould
Element, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, goes out at polyoxin
Become rusty amine, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, gram bacterium
Pellet, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloro- nitro
Benzene, Propineb, 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, biguanides are pungent
Amine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane,
Metham-sodium, enemy line ester, dazomet, nemamort, lythidathion, fensulfothion, thionazin, dichlofenthion, fosthietan, oxamyl, sulphur
Acyl fluorides, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；Heterocycle triazole derivative III and intermediate of the invention is killed described
Total mass percentage in bacteria composition is 1%-90%, and heterocycle triazole derivative III of the invention and intermediate are with before
The ratio for stating commodity fungicide is mass percent 1%: 99% to 99%: 1%；The dosage form choosing of the bactericidal composition processing
From: seed treatment emulsion, aqueous emulsion, big granula, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain,
Aerosol, blocky poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray
Agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, cigarette
Mist piece, smog ball, granular poison bait, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly,
It sprinkles and pours agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume
Suspending agent, tracking pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder；The bactericidal composition is anti-
The plant disease controlled is selected from: seedling blight of rice, tomato root rot, the late blight of potato, tobacco black shank, millet powdery mildew, Portugal
Grape downy mildew, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose；The applicable plant of the bactericidal composition is selected from: paddy,
Wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton
Flower, silkworm and mulberry, peanut, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, cigarette
Grass, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple,
Citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 9: heterocycle triazole derivative III and pesticide combination of the invention is planted in protection agricultural and forestry and gardening
Application in object:
The invention further relates to the composition pesticides comprising heterocycle triazole derivative III as active constituent.Above-mentioned pesticide group
It closes object and generally includes the formula III compound of 0.1 to 99% weight, preferably 0.1 to 95% weight, 99.9 to 1% weight, preferably
The solid or liquid adjuvants of 99.8 to 5% weight and the surfactant of 0 to 25% weight, preferably 0.1 to 25% weight.
To above-mentioned comprising composition pesticide of the heterocycle triazole derivative III as active constituent, applicable dosage form is selected from seed treatment cream
Agent, aqueous emulsion, big granula, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison
Bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, the agent of wettable powder electrostatic spray,
Water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog
Piece, granular poison bait, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles smog ball
It is outstanding to pour agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume
Floating agent, tracking pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder.
Although it is preferred that being concentrate by commercial product preparation, terminal user is generally using dilution preparation.
Heterocycle triazole derivative III and commodity insecticide composition of the invention is in prevention and treatment agricultural and forestry and gardening plant
Application in insect pest:
Heterocycle triazole derivative III of the invention and agriculturally acceptable auxiliary agent and following one or more commodity desinsections
Agent combination is preparing the purposes in compounded pesticides；
The commodity insecticide is selected from: chlopyrifos, Asia Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM hereinafter
Rhzomorph, pleocidin, fenvalerate, esfenvalerate, cypermethrin, effective cypermethrin, Cyhalothrin, bromine cyanogen chrysanthemum
Ester, Fenpropathrin, cyfloxylate, permethrin, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox,
Flumethrin, fluvalinate, imidacloprid, Acetamiprid, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin,
Dinotefuran, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization be grand, flubenzuron, flufenoxuron, pyridine worm are grand, lufenuron,
Poisonous insect urea, penfluron, Noviflumuron, that is, noviflumuron, the i.e. double benzene of CAS 121451-02-3, flucycloxuron, Novaluron
Fluorine urea, chlorfluazuron, Bay sir 6874 are 1- [(3.5- bis- chloro- 4) 4- nitro-phenoxy phenyl 3-3- (2- chlorobenzene)-urea, Bay
SIR-8514, that is, 1- (4- Trifluoromethoxyphen-l) -3- (2- chlorobenzene)-urea, piperazine worm urea, Bistrifluron, that is, bistrifluron,
Furan tebufenozide, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, acetyl methylamine
It is phosphorus, Hostathion, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, secondary
Ding Wei, leaf disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben,
Clofentezine, propargite, diafenthiuron, Benfuracard micro, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, triazole
Tin, Buprofezin, phonamiphos, Fipronil, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide,
Tolfenpyrad, tebufenpyrad, chlorfenapyr, pyrazinones, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；
The total mass percentage of heterocycle triazole derivative III of the invention in gained compounded pesticides is 1%-
The ratio of 90%, heterocycle triazole derivative III of the invention and the commodity insecticide is that mass percent 1%: 99% arrives
99%: 1%；
The applicable dosage form of the compounded pesticides is selected from seed treatment emulsion, aqueous emulsion, big granula, microemulsion, water solubility
Granula, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro- glue
It is capsule suspending agent, Waterless Seed Dressing pulvis, missible oil, the agent of wettable powder electrostatic spray, water-in-oil emulsion, oil in water emulsion, smoke candle, thin
Granula, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, smog ball, granular poison bait, thermal fog, medicine paint,
Fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles and pours agent, seed coat agent, liniment, suspended emulsion, film forming oil suspending agent
Finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, wet-mixing
Plant any one in water-dispersible powder；
The applicable plant of the compounded pesticides is selected from paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
Potato, cassava, soybean, garden pea, semen viciae fabae, 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
Dish, hot pickled mustard tuber, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, Hu
Green pepper, banana, papaya, orchid, potted landscape；
The insect pest of the compounded pesticides prevention and treatment is selected from Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), list
Pierce mole cricket, Oriental burmeister, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipe thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci,
Rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, wheat
Schizaphis spp, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, red wax
A red-spotted lizard, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, rice are black
It is stinkbug, green rice bug, green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown
Slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple
Fruit Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice are vertical
Leaf roll snout moth's larva, snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer,
Bollworm, black cutworm, big cutworm, yellow cutworm, steals poison moth, is gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight ancient cooking vessel point spark
Line rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, gold
Star ground beetle, wrinkle sheath ground beetle, the steady first, pleonomus canaliculatus of wheat, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the small buprestid beetle of citrus, gold
Edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, North China gill gold black greatly
Tortoise, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, mung bean
As, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang a cocoon Ji
Bee, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, the big reality of citrus
Fly, melonfly, wheat leaf ash dive fly, Americal rice leaf miner, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis,
Corn borer is strict to post fly, armyworm.
The bacteriostatic activity (inhibiting rate/% of 50 mcg/mls) of the heterocycle triazole derivative III of the invention of table 1
| Compound | PI | CA | AS | BC | GZ | PP | SS | RC | PS |
| III-1 | 7 | 49 | 14 | 7 | 26 | 28 | 58 | 7 | 35 |
| III-2 | 10 | 21 | 13 | 60 | 23 | 20 | 83 | 5 | 35 |
| III-3 | 35 | 42 | 32 | 60 | 18 | 42 | 66 | 86 | 36 |
| III-4 | 24 | 33 | 48 | 33 | 29 | 35 | 45 | 16 | 17 |
| III-5 | 13 | 58 | 14 | 90 | 26 | 16 | 83 | 15 | 27 |
| III-6 | 14 | 68 | 10 | 67 | 16 | 18 | 15 | 3 | 27 |
| III-7 | 24 | 21 | 23 | 30 | 36 | 41 | 26 | 32 | 28 |
| III-8 | 21 | 25 | 16 | 37 | 29 | 38 | 5 | 26 | 31 |
| III-9 | 25 | 24 | 15 | 31 | 41 | 21 | 16 | 69 | 18 |
| III-10 | 18 | 29 | 16 | 10 | 18 | 51 | 13 | 26 | 25 |
| III-11 | 18 | 2 | 17 | 0 | 59 | 41 | 27 | 10 | 18 |
| III-12 | 18 | 19 | 19 | 22 | 35 | 29 | 32 | 92 | 24 |
| III-13 | 46 | 64 | 62 | 83 | 100 | 71 | 6 | 88 | 47 |
| III-14 | 29 | 13 | 13 | 13 | 21 | 46 | 26 | 45 | 6 |
| III-15 | 14 | 19 | 4 | 17 | 65 | 50 | 39 | 20 | 0 |
| III-16 | 14 | 19 | 8 | 44 | 0 | 29 | 0 | 61 | 16 |
| III-17 | 0 | 10 | 8 | 18 | 97 | 39 | 15 | 25 | 12 |
| III-18 | 18 | 43 | 27 | 51 | 76 | 57 | 81 | 95 | 24 |
| III-19 | 25 | 19 | 15 | 38 | 53 | 57 | 13 | 55 | 44 |
| III-20 | 39 | 14 | 27 | 36 | 68 | 39 | 0 | 25 | 29 |
| Fluoxastrobin | 84 | 94 | 73 | 77 | 75 | 69 | 100 | 95 | 88 |
| Flutriafol | 95 | 100 | 85 | 88 | 93 | 100 | 93 | 100 | 80 |
The EC of the heterocycle triazole derivative III of the invention of table 250Value
The insecticidal activity (death rate, %) of 3 series compound III of table
The chemical structure of 4 important intermediate of table
Claims (9)
1. heterocycle triazole derivative, it is characterised in that: have the general structure as shown in formula III:
Wherein: R24、R25It is selected from: hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6
Alkenyl, C2-C6Halogenated alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Naphthenic base, substituted piperidin-1-yl, quilt
The phenyl or C that substituted morpholine -1- base, substituted nafoxidine -1- base, phenyl or halogen replaces1-C6It is alkyl-substituted
Phenyl or C1-C6The phenyl or C that halogenated alkyl replaces3-C6The phenyl or C that the phenyl or nitro that naphthenic base replaces replace2-C6Alkene
The phenyl or C that base replaces2-C6The phenyl or C that halogenated alkenyl replaces3-C6The phenyl or C that cycloalkenyl replaces2-C6Alkynyl substituted
Phenyl or C2-C6The phenyl or C that halo alkynyl replaces3-C6The pyridine that phenyl, pyridyl group or the halogen that cycloalkynyl radical replaces replace
Base or C1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6The pyridine that naphthenic base replaces
The pyridyl group or C that base or nitro replace2-C6The pyridyl group or C that alkenyl replaces2-C6The pyridyl group or C that halogenated alkenyl replaces3-
C6The pyridyl group or C that cycloalkenyl replaces2-C6The pyridyl group or C of alkynyl substituted2-C6The pyridyl group or C that halo alkynyl replaces3-C6
The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that cycloalkynyl radical replaces replace1-C6Alkyl-substituted pyrimidine radicals or C1-C6Halogen
The pyrimidine radicals or C that substituted alkyl replaces3-C6The pyrimidine radicals or C that the pyrimidine radicals or nitro that naphthenic base replaces replace2-C6Alkenyl takes
The pyrimidine radicals or C in generation2-C6The pyrimidine radicals or C that halogenated alkenyl replaces3-C6The pyrimidine radicals or C that cycloalkenyl replaces2-C6Alkynyl takes
The pyrimidine radicals or C in generation2-C6The pyrimidine radicals or C that halo alkynyl replaces3-C6Cycloalkynyl radical replace pyrimidine radicals, it is substituted contain 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 contain 1 or 2
Substituted five yuan of a 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 or six membered heteroaryl, the quilt containing 2 N atoms and 1 S atom containing 1 N atom and 1 O atom
Five yuan or the six membered heteroaryl, substituted five yuan or six membered heteroaryl containing 2 N atoms and 1 O atom replaced；Above-mentioned five
Member or six membered heteroaryl are selected from: substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazole
Base, oxazolyl, isoxazolyl, oxadiazoles base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine
Base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazole base, benzothiazolyl, benzo
Thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl,
The silicon substrate that cinnoline base or naphthyridines base, alkyl or alkenyl replace；
Halogen is fluorine, chlorine, bromine or iodine in above-mentioned definition；
The alkyl, alkenyl or alkynyl are straight chain or branch alkyl；Alkyl itself or as other substituent groups part select
From methyl, ethyl, propyl, butyl, amyl, hexyl and its isomers, isomers is selected from isopropyl, isobutyl group, sec-butyl, uncle
Butyl, isopentyl or tertiary pentyl；
The halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, the halogenated alkyl choosing
From CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Described naphthenic base itself or as other substituent groups part be selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
Described alkenyl itself or as other substituent groups part be selected from vinyl, allyl, 1- acrylic, butene-2-base, fourth
Alkene -3- base, amylene -1- base, amylene -3- base, hexene -1- base or 4- methyl-3-pentenyl；
Described alkynyl itself or as other substituent groups part be selected from acetenyl, propine -1- base, propine -2- base, butine -1-
Base, crotonylene-base, 1- methyl -2- butynyl, hexin -1- base or 1- ethyl -2- butynyl；
The enantiomeric form of heterocycle triazole derivative III and its mixture, the optical isomer be enantiomter or
Cis-trans-isomer；
The geometric isomer of heterocycle triazole derivative III, i.e. (R)-(S) isomery and its mixture；
The atropisomer and its mixture of heterocycle triazole derivative III.
2. heterocycle triazole derivative III according to claim 1:
R24、R25It preferably is selected from:
R25=-H ,-F ,-CH3,-OCH3,-Br.
3. according to the heterocycle triazole derivative III of the claims 1 or 2, compound therein are as follows:
The specially compound of number III 1-20.
4. the synthetic method of any one of -3 heterocycle triazole derivative III, specific synthetic route are as follows according to claim 1:
The substituent R24、R25Definition it is as described in claim 1；Specific synthetic method is divided into following steps:
A. the synthesis of intermediate 10
Intermediate 10 reacts preparation with 1-Sodium-1,2,4-Triazole as raw material for melilotal using α-Br.
B. the synthesis of intermediate 11
Intermediate 11 is that raw material reacts preparation with hydroxylamine hydrochloride with intermediate 10.
C. the synthesis of heterocycle triazole derivative III
Heterocycle triazole derivative III is prepared by raw material and carboxylic acid dehydration with intermediate 11.
5. a kind of composition pesticide, it includes the described in any item heterocycle triazole derivative 7-1 of claim 1-3 and intermediate can
To prepare composition pesticide, the composition is comprising the described in any item heterocycle triazole derivative 7-1 of claim 1-3 and among it
Body is as active constituent, and the content of active constituent is 0.1 to 99.9% weight, and the solid or liquid of 99.9 to 0.1% weight help
The surfactant of agent and optional 0 to 25% weight.
6. heterocycle triazole derivative III and its intermediate described in claim 1-3 are preparing the purposes in fungicide.
7. heterocycle triazole derivative III and its intermediate described in claim 1-3 are preparing the purposes in insecticide.
8. a kind of pesticide complex composition, it includes the described in any item heterocycle triazole derivative 7-1 of claim 1-3 and wherein
Mesosome and other fungicide, herbicide, plant growth regulator compounding are used as active constituent, heterocycle triazole derivative 7-1 and its
Intermediate and other fungicide, herbicide, plant growth regulator ratio be mass percent 1%: 99% to 99%: 1%,
The content of active constituent is 1 to 99% weight, the solid or liquid adjuvants of 99 to 1% weight.
9. the purposes of pesticide complex composition according to claim 8 is cured the disease for preventing in agricultural, forestry and gardening
Opportunistic pathogen, the harm of weeds or the growth of adjusting plant.
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