CN105859645B - A kind of triazole compounds substituted containing phenyl ring and halogen and its production and use - Google Patents
A kind of triazole compounds substituted containing phenyl ring and halogen and its production and use Download PDFInfo
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- CN105859645B CN105859645B CN201610298825.5A CN201610298825A CN105859645B CN 105859645 B CN105859645 B CN 105859645B CN 201610298825 A CN201610298825 A CN 201610298825A CN 105859645 B CN105859645 B CN 105859645B
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- 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
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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- 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
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Abstract
Triazole compounds substituted the invention discloses one kind containing phenyl ring and halogen and its production and use.This has the structure of the expression of below formula I containing the triazole compounds that phenyl ring and halogen substitute：
Description
Technical field
The present invention relates to field of pharmaceutical chemistry technology, the triazole compounds that substitute more particularly to one kind containing phenyl ring and halogen and
Preparation method and use.
Background technology
Triazole compounds have extensive bioactivity in terms of agricultural chemicals and medicine, wherein the change containing triazole and substituted benzene ring
Structure is learned to be widely studied in bactericide field, developed so far oxygen ring azoles (The Pesticide Manual, 2003,13,
43), bromuconazole (EP 258161), Cyproconazole (US 4664696), olefin conversion (US 4203995), epoxiconazole (US
4464381), Flutriafol (US 4623654) etc. has good preventing and treating to multiple diseases such as crop powdery mildew, scab, banded sclerotial blights
The bactericide kind of effect.Chemically from the point of view of structure, above bactericide kind is all through 1,2,4- triazole ring by 2-3 carbon bridge
1 nitrogen-atoms docked with substituted benzene ring, and the change directly docked with phenyl ring or substituted benzene ring by 5 carbon atoms of triazole ring
The bacteriostatic activity correlative study of compound has no report.
The content of the invention
The present invention is intended to provide a kind of triazole compounds substituted containing phenyl ring and halogen and preparation method thereof, comprising it to crop
The application thereof to killing of germ, there is the triazole type substituted containing substituted benzene ring and halogen of bactericidal activity to crop germ to provide one kind
Compound.
To achieve these goals, specific technical scheme is as follows：
The first aspect of the present invention, there is provided a kind of triazole compounds substituted containing phenyl ring and halogen, this contains phenyl ring and halogen takes
The triazole compounds in generation have the structure that below formula I represents：
In formula I, R is hydrogen, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino；X be bromine atoms or
Chlorine atom.
Further, the above-mentioned triazole compounds substituted containing phenyl ring and halogen, selected from following compound：
The second aspect of the present invention, there is provided the preparation method of the above-mentioned triazole compounds substituted containing phenyl ring and halogen, pass through
The first compound represented by formula II obtains with the second compound reaction represented by general formula III to be substituted containing phenyl ring and halogen
Triazole compounds, the formula II and the general formula III are as follows：
In described II, R H, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino；
In described III, X is Br or Cl.
Further, the preparation method of the above-mentioned triazole compounds substituted containing phenyl ring and halogen is：
When second compound is N-bromosuccinimide, specific preparation method is：Using isopropyl acetate as solvent,
By the ratio of the amount of material be 1 ︰ 1.2~1.5 by first compound and N-bromosuccinimide, under counterflow condition, react 5
~12 hours, produce the triazole compounds containing phenyl ring and bromine substitution；
When second compound is N-chlorosuccinimide, specific preparation method is：With N,N-dimethylformamide
By the ratio of the amount of material it is 1 ︰ 1.2~1.5 by first compound and N-chlorosuccinimide for solvent, reaction temperature
For 45~50 DEG C, react 5~12 hours, produce the triazole compounds containing phenyl ring and chlorine substitution.
Further, the preparation method of the above-mentioned triazole compounds substituted containing phenyl ring and halogen is：When second compound is N-
During NBS, specific preparation method is：Using isopropyl acetate as solvent, by first compound and N- bromos
Succinimide be 1 ︰ 1.5 by the ratio of the amount of material, under counterflow condition, is reacted 5~12 hours, produces what is substituted containing phenyl ring and bromine
Triazole compounds；
When second compound is N-chlorosuccinimide, using DMF as solvent, by described first
Compound is 1 ︰ 1.5 by the ratio of the amount of material with N-chlorosuccinimide, and reaction temperature is 45~50 DEG C, and reaction 5~12 is small
When, produce the triazole compounds containing phenyl ring and chlorine substitution.
The third aspect of the present invention a, there is provided series bactericidal agent, the main active of the bactericide contain benzene comprising above-mentioned
Ring and the triazole compounds of halogen substitution.
The fourth aspect of the present invention, there is provided a kind of above-mentioned triazole compounds substituted containing phenyl ring and halogen or above-mentioned bactericide
There is the purposes of suppression and killing effect to caused germ in process of crop growth.
Further, germ is fusarium graminearum, P. capsici, tobacco brown spot pathogen, cucumber in such use
Ash arrhizus bacteria, Rhizoctonia solani Kuhn or Sclerotinia sclerotiorum.
Further, in such use, when germ is fusarium graminearum, the triazole compounds containing phenyl ring and halogen substitution
Structure it is as follows：
When germ is P. capsici, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When germ is tobacco brown spot pathogen, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When germ is botrytis cinerea pers, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When germ is Rhizoctonia solani Kuhn, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When germ is Sclerotinia sclerotiorum, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
The principle and advantage of the present invention is as follows：Technical scheme, based on triazole ring skeleton, draw at its 4
Enter halogen atom, and phenyl ring or substituted benzene ring are introduced at its 5, to obtain the triazole compounds substituted containing phenyl ring and halogen.It is this to contain
Phenyl ring and the triazole compounds of halogen substitution have preferable bactericidal activity to crop germ, can be used as in process of crop growth and produce
Germ bactericide.
Embodiment
To enable objects, features and advantages of the present invention more obvious understandable, with reference to specific embodiment to this hair
Bright embodiment is described in detail.Many details are elaborated in the following description in order to fully understand this
Invention, but the present invention can be implemented with being much different from other modes described here, those skilled in the art can be
Without prejudice to doing similar improvement in the case of intension of the present invention, therefore the present invention is not limited by following public specific embodiment.
The invention provides a kind of triazole compounds substituted containing phenyl ring and halogen, this triazole substituted containing phenyl ring and halogen
Compound has the structure that below formula I represents：
In above-mentioned formula I, R is hydrogen, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino, X Br
Or Cl.
This triazole compounds substituted containing phenyl ring and halogen provided by the present invention, pass through 4 introducing halogen in triazole ring
Atom, phenyl ring or substituted benzene ring are introduced at its 5, and the resulting triazole compounds substituted containing phenyl ring and halogen have to crop germ
There is preferable bactericidal activity.
The triazole compounds of the present invention substituted containing phenyl ring and halogen, its chemical constitution are as follows：
The above-mentioned 17 kinds different triazole compounds substituted containing phenyl ring and halogen have good bactericidal activity to crop germ,
Can be as the bactericide of caused germ in process of crop growth.
As a kind of preferably synthetic scheme of the present invention, by the first compound represented by formula II and by general formula III
Represented second compound reaction obtains the triazole compounds substituted containing phenyl ring and halogen represented by above-mentioned formula I, described logical
Formula II and general formula III are as follows：
In above-mentioned formula II, R H, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino；Above-mentioned formula
In III, X is Br or Cl.
In above-mentioned preparation method, a kind of preferential embodiment is：In the preparation of the triazole compounds of bromine substitution, with second
Isopropyl propionate (Isopropyl acetate) is solvent, by first compound represented by formula II and by general formula III
Represented N-bromosuccinimide (NBS) is 1 ︰ 1.2~1.5 by the ratio of the amount of material, is preferably in a proportion of 1 ︰ 1.5, is flowed back
Under the conditions of, react 5~12 hours, the described triazole compounds substituted containing phenyl ring and bromine can be obtained；In the triazole of chlorine substitution
In the preparation of compound, with DMF (DMF) for solvent, by first compound represented by formula II with
The ratio for the amount that N-chlorosuccinimide (NCS) represented by general formula III presses material is 1 ︰ 1.2~1.5, is preferably in a proportion of
1 ︰ 1.5, reaction temperature are 45~50 DEG C, are reacted 5~12 hours, can obtain the described triazole chemical combination substituted containing phenyl ring and chlorine
Thing.Under this process conditions, the triazole compounds containing phenyl ring and halogen substitution can be made, and have the yield more than medium.It is above-mentioned
The reaction equation of reaction is as follows：
The triazole compounds substituted containing phenyl ring and halogen obtained through above-mentioned preparation method are usually to substitute containing phenyl ring and halogen
Triazole compounds crude product, purification step includes, the triazole compounds substituted containing phenyl ring and bromine in isopropyl acetate system
Crude product uses the mixed solution (V with petroleum ether and ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, through silica gel column chromatography
It can must contain the triazole compounds sterling of phenyl ring and bromine substitution；Substitute containing phenyl ring and chlorine three in N,N-dimethylformamide system
Azole compounds crude product is extracted using ethyl acetate (30mL × 3), merges organic phase, and anhydrous magnesium sulfate is dried, and is filtered, and decompression removes
The crude product gone after solvent, then with petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, through silicon
Plastic column chromatography can must contain the triazole compounds sterling of phenyl ring and chlorine substitution.
In above-mentioned preparation method, the first compound represented by formula II can be by the intermediate that general formulae IV represents with folding
Sodium nitride reaction in the dimethyl sulfoxide (DMSO) obtains, concrete operations can refer to document (Organic Letters, 2009,11
(23):Synthetic method 5490-5493).The preparation method of the first compound represented by formula II is as follows：
In above-mentioned reaction, R represents H, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino.
The preparation of intermediate represented by general formulae IV：Using benzaldehyde or substituted benzaldehyde and nitromethane as raw material, in first
Alcohol is in solvent, and after the NaOH solution that mass fraction is 20% is added dropwise at 0 DEG C, then reaction can obtain intermediate IV at normal temperatures.
Concrete operations can refer to document (Tetrahedron Letters, 2012,53 (24):Synthetic method 2980-2984).Prepare
The chemical equation of intermediate IV is as follows：
In above-mentioned reaction, R represents H, halogen atom, methoxyl group, ethyoxyl, benzyloxy, nitro or dimethylamino.
Meanwhile additionally provide a kind of bactericide in the present invention, the bactericide include it is above-mentioned substitute containing phenyl ring and halogen three
Azole compounds.The above-mentioned triazole compounds substituted containing phenyl ring and halogen have preferable bactericidal activity to crop germ, can be used as and make
The bactericide of caused germ in thing growth course.
The compound of the present invention is as bactericide in use, load that can be by the compound of the present invention with allowing in other plant protection
Body or diluent mixing, will be tuned into usually used various formulations whereby, as pulvis, wettable powder, granule, suspending agent,
Aqueous emulsion etc. uses, and can also be used in mixed way with other bactericide or is used in combination simultaneously.
A kind of above-mentioned triazole compounds substituted containing phenyl ring and halogen or above-mentioned sterilization composition are additionally provided in the present invention
Suppress and kill the purposes of germ in process of crop growth.Wherein signified germ include but is not limited to fusarium graminearum,
In P. capsici, tobacco brown spot pathogen, botrytis cinerea pers, Rhizoctonia solani Kuhn or Sclerotinia sclerotiorum.In the present invention
A kind of preferred embodiment in, the general sieve concentration of the above-mentioned triazole compounds substituted containing phenyl ring and halogen is 25mg/L.
In the above-mentioned triazole compounds substituted containing phenyl ring and halogen provided by the present invention or above-mentioned Phytotoxins composite
In process of crop growth in the suppression of caused germ or killing action, killing effect of the different compounds to different germs
Fruit has differences.Appropriate compound is targetedly selected to be advantageous to improve the killing effect of germ.In one kind of the present invention
In preferred embodiment, the preferred compound corresponding to different germs is as follows：
When germ is fusarium graminearum, the above-mentioned triazole compounds substituted containing phenyl ring and halogen, preferably triazole in formula I
4 of ring are chlorine atom, hydrogeneous, chlorine atom or nitro substituent on phenyl ring.The triazole substituted containing phenyl ring and halogen being more highly preferred to
The structure of compound is：
When germ is P. capsici, above-mentioned triazole compounds be preferably 4 of triazole ring in formula I for chlorine atom or
Bromine atoms, hydrogeneous, chlorine atom or nitro substituent on phenyl ring.The above-mentioned triazole compounds substituted containing phenyl ring and halogen being more highly preferred to
Structure be：
When germ is tobacco brown spot pathogen, above-mentioned triazole compounds be preferably triazole ring in formula I 4 are chlorine atom,
Hydrogeneous or nitro substituent on phenyl ring.The structure for the above-mentioned triazole compounds substituted containing phenyl ring and halogen being more highly preferred to is：
When germ is botrytis cinerea pers, above-mentioned triazole compounds be preferably 4 of triazole ring in formula I for chlorine atom or
Bromine atoms, hydrogeneous, chlorine atom, bromine atoms, fluorine atom or nitro substituent on phenyl ring.What is be more highly preferred to above-mentioned takes containing phenyl ring and halogen
The structure of the triazole compounds in generation is：
When germ is Rhizoctonia solani Kuhn, above-mentioned triazole compounds be preferably triazole ring in formula I 4 are chlorine atom,
Hydrogen atoms on phenyl ring.The structure for the above-mentioned triazole compounds substituted containing phenyl ring and halogen being more highly preferred to is：
When germ is Sclerotinia sclerotiorum, above-mentioned triazole compounds be preferably 4 of triazole ring in formula I for chlorine atom or
Bromine atoms, hydrogeneous, chlorine atom, bromine atoms or nitro substituent on phenyl ring.The preferred above-mentioned triazole substituted containing phenyl ring and halogen
The structure of compound is：
Below with reference to specific embodiment illustrate containing phenyl ring and halogen substitution triazole compounds 1 to 17 synthetic method and its
Beneficial effect.
The preparation method of the compound of the present invention is specifically described below by embodiment.
Embodiment 1
I -1 preparation：
4- (2- chlorphenyls) -2H-1,2,3- triazoles 0.3g (1.67mmol) and NBS is added in 50mL stand up reaction bottle
0.45g (2.5mmol), add isopropyl acetate 10mL, back flow reaction, TLC monitoring reaction process.After reacting 5h, it is removed under reduced pressure
Solvent afforded crude material, with petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, through silica gel column layer
Analysis purifies to obtain white solid 0.47g, fusing point：78~80 DEG C, yield 84%.
Elementary analysis：Calculated value C%37.17, H%1.95, N%16.26；Measured value C%37.08, H%1.92, N%
16.28。
The detection data of resulting white solid are1H NMR(400MHz,CDCl3)(δ/ppm)：7.35-7.54(m,
4H,PhH),12.63(s,1H,NH)；EI MS:M/z (%) 259 ([M+1]+,38),258(M+,3),257([M-1]+,29),
152(14),150(100),123(32),130(100),114(21),75(12).From above-mentioned analyze data, by this side
Compound obtained by method is the bromo- 5- of 4- (2- chlorphenyls) -2H-1,2,3- triazoles.It is that the present invention contains benzene by what formula I represented
One kind of ring and the triazole compounds of halogen substitution.
Embodiment 2
I -2 preparation：
4- (the bromo- 4- fluorophenyls of 2-) -2H-1,2,3- triazoles 0.2g (0.83mmol) is added in 50mL stand up reaction bottle
With NBS 0.22g (1.24mmol), isopropyl acetate 10mL, back flow reaction, TLC monitoring reaction process are added.After reacting 5h, subtract
Pressure removes solvent afforded crude material, with petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, through silicon
It is gel column chromatography eluting to obtain colorless oil 0.24g, yield 96%.
Elementary analysis：Calculated value C%29.94, H%1.26, N%13.09；Measured value C%29.88, H%1.22, N%
13.03。
The detection data of resulting colorless oil are1H NMR(400MHz,CDCl3)(δ/ppm)：7.13-7.48(m,
3H,PhH),12.49(s,1H,NH)；EI MS:M/z (%) 322.9 ([M+2]+,7),320.9(M+,15),318.9([M-1]+,
8),213.9(97),211.9(100),161(6),133(36),106(18).From above-mentioned analyze data, by this method
Obtained compound is the bromo- 5- of 4- (the bromo- 4- fluorophenyls of 2-) -2H-1,2,3- triazoles.It is that the present invention is represented by formula I
One kind of the triazole compounds substituted containing phenyl ring and halogen.
Embodiment 3
I -5 preparation：
4- (2- bromophenyls) -2H-1,2,3- triazoles 0.3g (1.34mmol) and NBS is added in 50mL stand up reaction bottle
0.35g (2.0mmol), add isopropyl acetate 10mL, back flow reaction, TLC monitoring reaction process.After reacting 6h, it is removed under reduced pressure
Solvent afforded crude material, with petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, through silica gel column layer
Analysis purifies to obtain white solid 0.38g, fusing point：80~81 DEG C, yield 95%.
Elementary analysis：Calculated value C%31.72, H%1.66, N%13.87；Measured value C%31.67, H%1.59, N%
13.83。
The detection data of resulting white solid are1H NMR(400MHz,CDCl3)(δ/ppm)：7.26-7.72(m,
4H,PhH),13.21(s,1H,NH)；EI MS:M/z (%) 304.9 ([M+2]+,23),302.9(M+,47),318.9([M-2
]+,23),224(9),207(8),197(20),196(100),194(98),143(26),116(71),88(41).By above-mentioned point
Analyse data to understand, be the bromo- 5- of 4- (2- bromophenyls) -2H-1 as the compound obtained by this method, 2,3- triazoles.It is this hair
One kind of the bright triazole compounds substituted containing phenyl ring and halogen represented by formula I.
Embodiment 4
I -11 preparation：
4- (3- nitrobenzophenones) -2H-1,2,3- triazoles 0.3g (1.58mmol) and NCS is added in 50mL stand up reaction bottle
0.27g (2.01mmol), DMF 8mL is added, temperature rises to 50 DEG C, TLC monitoring reaction process.React 12h,
System is cooled to after normal temperature and is transferred in 100mL water, ethyl acetate extraction (30mL × 3) merges organic phase, and anhydrous magnesium sulfate is done
It is dry, filter, removal of solvent under reduced pressure obtains crude product.With petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is to wash
De- agent, white solid 0.19g, fusing point are purified to obtain through silica gel column chromatography：161~162 DEG C, yield 54%.
Elementary analysis：Calculated value C%42.78, H%2.24, N%24.94；Measured value C%42.71, H%2.22, N%
24.98。
The detection data of resulting white solid are1H NMR(400MHz,CDCl3)(δ/ppm)：7.26-8.86(m,
4H,PhH),11.76(s,1H,NH)；EI MS:M/z (%) 225 ([M+1]+,10),224(M+,100),180(13),178
(42),166(16),123(40),114(16),88(11),75(10).It is made by this method from above-mentioned analyze data
The compound obtained is the chloro- 5- of 4- (3- nitrobenzophenones) -2H-1,2,3- triazoles.It is the present invention by formula I represent containing phenyl ring and
One kind of the triazole compounds of halogen substitution.
Embodiment 5
I -13 preparation：
4- phenyl -2H-1,2,3- triazoles 0.3g (2.1mmol) and NCS0.36g are added in 50mL stand up reaction bottle
(2.7mmol), DMF 8mL is added, temperature rises to 50 DEG C, TLC monitoring reaction process.10h is reacted, by system
It is transferred to after being cooled to normal temperature in 100mL water, ethyl acetate extraction (30mL × 3), merges organic phase, anhydrous magnesium sulfate is dried, taken out
Filter, removal of solvent under reduced pressure obtain crude product.With petroleum ether and the mixed solution (V of ethyl acetatePetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent,
White solid 0.21g, fusing point are purified to obtain through silica gel column chromatography：137~138 DEG C, yield 58%.
Elementary analysis：Calculated value C%53.50, H%3.37, N%23.40；Measured value C%53.42, H%3.28, N%
23.46。
The detection data of resulting white solid are1H NMR(400MHz,CDCl3)(δ/ppm)：7.26-7.93(m,
5H,PhH),11.72(s,1H,NH)；EI MS:M/z (%) 180 ([M+1]+,10),179(M+,100),150(7),124
(22),116(20),89(45),76(11).It is that 4- is chloro- as the compound obtained by this method from above-mentioned analyze data
5- phenyl -2H-1,2,3- triazoles.It is the one kind for the triazole compounds substituted containing phenyl ring and halogen that the present invention is represented by formula I.
Embodiment 6
I -16 preparation：
4- (3,4- Dimethoxyphenyls) -2H-1,2,3- triazoles 0.2g is added in 50mL stand up reaction bottle
(0.97mmol) and NCS 0.17g (1.27mmol), DMF 8mL is added, temperature rises to 50 DEG C, TLC monitorings
Reaction process.12h is reacted, system is cooled to after normal temperature and is transferred in 100mL water, ethyl acetate extraction (30mL × 3), is associated with
Machine phase, anhydrous magnesium sulfate are dried, and are filtered, and removal of solvent under reduced pressure obtains crude product.With petroleum ether and the mixed solution of ethyl acetate
(VPetroleum ether︰ VEthyl acetate=10 ︰ 1) it is eluant, eluent, purify to obtain light yellow solid 0.19g, fusing point through silica gel column chromatography：218~220 DEG C,
Yield 83%.
Elementary analysis：Calculated value C%50.12, H%4.21, N%17.53；Measured value C%50.08, H%4.16, N%
17.49。
The detection data of resulting light yellow solid are1HNMR(400MHz,CDCl3)(δ/ppm)：3.92(s,6H,2×
CH3),6.92-7.55(m,3H,PhH),11.87(s,1H,NH)；EI MS:M/z (%) 240 ([M+1]+,12),239(M+,
100),224(28),133(10).From above-mentioned analyze data, as the compound obtained by this method be the chloro- 5- of 4- (3,
4- Dimethoxyphenyls) -2H-1,2,3- triazoles.It is the triazole chemical combination substituted containing phenyl ring and halogen that the present invention is represented by formula I
One kind of thing.
The present invention can be prepared using the preparation method similar with above-described embodiment 1 to 6 and other contain benzene by what formula I represented
Ring and the triazole compounds of halogen substitution.Other 11 kinds of compounds can be made with the preparation method in embodiment 1 or 4, and will be by leading to
The structure for the triazole compounds I -1 to I -17 substituted containing phenyl ring and halogen that formula I represents,1H NMR datas, physical property and yield
It is included in table 1.
The structure for the triazole compounds that table 1 substitutes containing phenyl ring and halogen,1H NMR datas, physical property and yield
Test：
Bactericidal activity experiment (three-dimensional active method)
Test bacterium：Fusarium graminearum (Gibberella zeae), P. capsici (Phytophythora
Capsici), tobacco brown spot pathogen (Alternaria alternata), botrytis cinerea pers (Botrytis cinerea), water
Rhizoctonia solani Kuhn (Rhizoctonia solani) and Sclerotinia sclerotiorum (Sclerotonia sclerotiorum).
Method of testing, using pastille culture medium method, bactericidal activity experiment is carried out, is comprised the following steps that：
Each compound 0.05g in taking above-mentioned I -1 to I -17, is dissolved with 0.20mLDMF, is added and is emulsified containing 0.1%Tween80
The sterilized water 98.8mL of agent, stirs, and it is 500mg/L solution to be configured to concentration.Each 500mg/L compounds decoction 2mL is taken, is added
In the potato agar culture medium (PDA) for entering the 38mL for being cooled to 45 DEG C, the pastille culture medium that final concentration of 25mg/L is made is put down
Plate.6.0mm diameter mycelia blocks are taken from cultured experiment germ colony edge, are moved in pastille culture medium.After being disposed, put
Cultivated in 28 DEG C of constant temperature biochemical cultivation case, experiment sets blank control, and colony diameter is measured after 4 days, calculates growth inhibition ratio.
Measurement result：The Activity Rank criteria for classifying is represented between inhibiting rate 80~100% with " +++ ", 60~79%
Between with " ++ " represent, represented with "+" between 40~59%, represented below 40% with "-", specific test result such as table 2
It is shown.
The general sieve result of the test of bactericidal activity for the triazole compounds that table 2 substitutes containing phenyl ring and halogen
As can be seen from Table 2, chemical compounds I -10, I -11 and I -13 pair of fusarium graminearum, P. capsici, tobacco are red
The crop germ such as star germ, botrytis cinerea pers and Sclerotinia sclerotiorum has good inhibition.With reference to above-mentioned test side
Method, the concentration (being respectively 10mg/L, 5mg/L, 2.5mg/L) for reducing by three compounds is further advanced by, and with commodity
Change kind Difenoconazole as control, investigate three compounds under the conditions of low dosage to the inhibitory activity of crop germ.Ⅰ-
10th, the bactericidal activity Primary Screening Test result such as table 3 of I -11 and I -13 three compound.
The bactericidal activity Primary Screening Test result of the chemical compounds I -10 of table 3, I -11 and I -13
As can be seen from Table 3, chemical compounds I -10, I -11 and I -13 pair of fusarium graminearum, P. capsici, tobacco are red
The inhibitory activity of star germ and botrytis cinerea pers reduces with the reduction of dosage concentration, but three compounds are in 10mg/L use
There are outstanding fungistatic effect, particularly chemical compounds I -13 to Sclerotinia sclerotiorum in the low of 5mg/L and 2.5mg/L under amount concentration
Outstanding fungistatic effect is still shown under the conditions of dosage to Sclerotinia sclerotiorum.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention.For those skilled in the art
For member, the present invention can have various modifications and variations, within the spirit and principles of the invention, any modification for being made, etc.
With replacement, improvement etc., should be included in the scope of the protection.
Claims (5)
1. a kind of triazole compounds substituted containing phenyl ring and halogen, it is characterised in that selected from following compound：
A 2. series bactericidal agent, it is characterised in that the main active of the bactericide include described in claim 1 containing phenyl ring and
The triazole compounds of halogen substitution.
3. the bactericide pair described in the triazole compounds or claim 2 that substitute described in a kind of claim 1 containing phenyl ring and halogen
Caused germ has the purposes suppressed with killing effect in process of crop growth.
4. purposes according to claim 3, it is characterised in that the germ be fusarium graminearum, P. capsici,
Tobacco brown spot pathogen, botrytis cinerea pers, Rhizoctonia solani Kuhn or Sclerotinia sclerotiorum.
5. according to the purposes described in claim any one of 3-4, it is characterised in that：
When the germ is fusarium graminearum, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When the germ is P. capsici, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When the germ is tobacco brown spot pathogen, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When the germ is botrytis cinerea pers, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When the germ is Rhizoctonia solani Kuhn, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
When the germ is Sclerotinia sclerotiorum, the structure of the triazole compounds substituted containing phenyl ring and halogen is as follows：
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