CN102391193A - 1,2,4-triazole derivative and preparation method and use thereof - Google Patents
1,2,4-triazole derivative and preparation method and use thereof Download PDFInfo
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- CN102391193A CN102391193A CN2011102606718A CN201110260671A CN102391193A CN 102391193 A CN102391193 A CN 102391193A CN 2011102606718 A CN2011102606718 A CN 2011102606718A CN 201110260671 A CN201110260671 A CN 201110260671A CN 102391193 A CN102391193 A CN 102391193A
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Abstract
The invention discloses a 1,2,4-triazole derivative shown as a formula (I). In the formula (I), R is a phenyl or a substituted phenyl, a substituent that substitutes the phenyl is methoxy, tert-butyl, cyano, isopropyl or halogen, the substitution is monosubstitution or polysubstitution. The preparation method of the 1,2,4-triazole derivative comprises the following steps of: enabling 4-cyclopropyl-5-methyl-4H-1,2,4-triazole-3-thiol shown as a formula (II) and substituting benzyl chloride shown as a formula (III) to carry out coupling reaction for 1-20 hours in an organic solvent at the temperature of 0-20 DEG C under the action of a catalyst; and carrying out an aftertreatment on a reacted solution to prepare the 1,2,4-triazole derivative shown as the formula (I). The 1,2,4-triazole derivative has weeding and sterilizing activity and has a special effect on cucumber downy mildew.
Description
(1) technical field
The present invention relates to a kind of preparation and application of heterogeneous ring compound, particularly a kind of 1,2,4-triazole derivative and preparation method thereof and application.
(2) background technology
Heterogeneous ring compound has been the main flow of novel pesticide development, and in heterogeneous ring compound, is main with nitrogen heterocyclic ring again.Triazole class compounds is one type more rapidly of a development in recent years, and many commercial sterilant belong to such.The DOW Chemical scientific research personnel passes through composition optimizes again after having found sterilant triarimol, find active better triazole bactericidal agent.The scientific research personnel of Bayer AG has found clotrimazole a series of high-activity compounds such as (medicine) earlier on this basis afterwards.Up to now, many commercial sterilant such as triadimenol, cyproconazole, tebuconazole, sterilant such as flutriafol.
Yet Shang Weijian is relevant of the present invention 1,2, the bibliographical information of 4-triazole derivative and synthetic and bioactivity research.
(3) summary of the invention
It is a kind of 1,2 that the object of the invention provides, 4-triazole derivative and preparation method thereof and application, and this compound has weeding and fungicidal activity.
The technical scheme that the present invention adopts is:
Shown in a kind of formula (I) 1,2, the 4-triazole derivative,
R is phenyl, substituted-phenyl in the formula (I), and the substituting group of said substituted-phenyl is: methoxyl group, the tertiary butyl, cyanic acid, sec.-propyl or halogen describedly are substituted by single replace or polysubstituted.
Further; Described 1; 2, the 4-triazole derivative, in the shown formula (I) R be phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, 2; 4-dichlorophenyl, 3,4-dichlorophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, p-methoxyphenyl, a cyano-phenyl or isopropyl phenyl.
Described 1,2,4-triazole derivative, described verivate are one of following:
A kind of of the present invention 1,2, the preparation method of 4-triazole derivative; Described method is: with the 4-cyclopropyl-5-methyl-4H-1 shown in the formula (II), and 2, the replacement benzyl chlorine shown in 4-triazole-3-mercaptan and the formula (III) is under catalyst action; 0～20 ℃ is carried out linked reaction 1～20h in organic solvent, and the reaction solution aftertreatment makes 1,2 shown in the formula (I); The 4-triazole derivative; Said catalyzer is an inorganic base substance, and said organic solvent is N, N N, acetonitrile, toluene or THF;
R is phenyl, substituted-phenyl in the formula (III), and the substituting group of said substituted-phenyl is: methoxyl group, the tertiary butyl, cyanic acid, sec.-propyl or halogen.
Described catalyzer is salt of wormwood, sodium hydrogencarbonate or sodium hydroxide.
Described organic solvent is N, the N N.
4-cyclopropyl-5-methyl-4H-1 shown in the described formula (II); 2; The feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and the formula (III) is 1: 1.0～1.5: 1～3, and said volume of organic solvent consumption is counted 20～50mL/g with compound quality shown in the formula (II).
Further, of the present invention 1,2; Reaction solution post-treating method described in the preparation method of 4-triazole derivative is: reaction finishes, and reaction solution is poured in the frozen water, suction filtration; Filtrating column chromatography or use the recrystallization solvent recrystallization, further separation and purification obtains described 1,2; The 4-triazole derivative, described column chromatography eluent or recrystallization solvent are the mixing of following one or more arbitrary proportions: sherwood oil, ETHYLE ACETATE, normal hexane or ethanol.
Further, of the present invention 1,2; The preparation method of 4-triazole derivative is recommended as: with the 4-cyclopropyl-5-methyl-4H-1 shown in the formula (II), and 2, the replacement benzyl chlorine shown in 4-triazole-3-mercaptan and the formula (III) is under catalyst action; 0～20 ℃ is carried out linked reaction 1～20h in organic solvent, filters in the reaction solution adding frozen water, and filtrating is that eluent carries out column chromatography with the ETHYLE ACETATE and the sherwood oil mixed solution of volume ratio 1: 1～100; Make 1,2 shown in the formula (I), the 4-triazole derivative; Said catalyzer is salt of wormwood, sodium hydrogencarbonate or sodium hydroxide, and said organic solvent is N, the N N; 4-cyclopropyl-5-methyl-4H-1 shown in the described formula (II); 2; The feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and the formula (III) is 1: 1.0: 2, said volume of organic solvent consumption with compound quality shown in the formula (II) than being 30mL/g.
Of the present invention 1,2, the application of 4-triazole derivative in weeding and fungicidal activity.
Of the present invention 1,2, the 4-triazole derivative adopts the pesticide bioactivity standard method of test to carry out biological activity test.
Of the present invention 1; 2,4-triazole derivative weeding activity adopts rape Plating and the little agar diffusion method of barnyard grass grass to test: described rape Plating adds of the present invention 1 in petridish, to place filter paper; 2; 4-triazole derivative and pretreated Semen Brassicae campestris are measured radicel length behind 28 ℃ of following dark culturing 72h, the growth-inhibiting of rape radicle are come the weeding activity of detection compound through compound under the dark condition; The little agar diffusion method of described barnyard grass grass is in small beaker, to add granulated glass sphere and filter paper; The barnyard grass grass seed that adds compound of the present invention and just showed money or valuables one carries unintentionally; Measure the seedling height behind 28 ℃ of following illumination cultivation 72h, the growth-inhibiting of barnyard grass grass seedling plant height is come the weeding activity of detection compound through compound under the illumination condition.
Of the present invention 1,2,4-triazole derivative fungicidal activity is tested object with the cucumber; Test scab of cucumber (Cladosporium cucumerinum) spore suspended substance, cucumber brown spot (Corynespora cassiicola) spore suspended substance, cucumber timberrot (Sclerotinia sclerotiorum (Lib.) de Bary) contain toxic medium method, powdery mildew of cucumber (Erysiphe cichoracearum) spore suspended substance, cucumber anthracnose (Colletotrichum orbiculare (Berk aLMont) Arx.); Select two cotyledon period cucumber seedlings for use, add of the present invention 1,2; The 4-triazole derivative; Inoculate pathogenic bacteria behind the 2h, 18～30 ℃, relative humidity 80%; The cultivation of preserving moisture, disease index and control effect are according to computes:
Compared with prior art, beneficial effect of the present invention is mainly reflected in: of the present invention 1,2, the 4-triazole derivative has weeding and fungicidal activity, and cucumber downy mildew is had special efficacy.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 11,2,4-triazole derivative (I-1)
In the 25mL round-bottomed flask, add 0.31g (2mmol) 4-cyclopropyl-5-methyl-4H-1,2,4-triazole-3-mercaptan, the adjacent fluorobenzyl chloride of 2mmol, 8mL N, the K of N N (DMF) and 2.4mmol
2CO
3, room temperature (25 ℃) stirring reaction 24h, TLC follows the tracks of reaction, after reaction finishes, in the reaction solution impouring 30mL frozen water; Separate out solid, filter, the silica gel column chromatography of filtrating, with 1: 4 ETHYLE ACETATE of volume ratio: the sherwood oil mixed solution is an eluent; Collect target liquid, concentrate drying obtains solid product 1,2,4-triazole derivative (I-1) 0.44g; Productive rate 85% (with 4-cyclopropyl-5-methyl-4H-1,2,4-triazole-3-mercaptan meter), shown in table 1 and table 2.
Embodiment 2-111,2,4-triazole derivative (I-2)～(I-11)
Change replacement benzyl chlorine, other are operated with embodiment 1, and the result is shown in table 1 and table 2.
Table 11,2,4-triazole derivative (I-1)～(I-11)
Table 21,2,4-triazole derivative 1H NMR and ESI-MS data
The test of embodiment 13 weeding activity
1) sample liquid preparation
With of the present invention 1,2,4-triazole derivative (I-1)～(I-3) is mixed with 10 μ g/mL and 100 μ g/mL sample liquid respectively with DMF, and is for use.
2) rape Plating
In the petridish of two groups of diameter 6cm, complete the filter paper of a diameter 5.6cm respectively; Add 2 milliliter of 10 μ g/mL and the described sample liquid of 100 μ g/mL respectively; Add 10 of 4 hours Semen Brassicae campestriss of seed soaking, under 28 ± 1 ℃, dark culturing was measured radicle length after 72 hours; Through compound under the dark condition growth-inhibiting of rape radicle is come the weeding activity of detection compound, each handles twice of repetition.Activity index: radicle grew inhibiting rate (%), the result sees table 3.
3) the little agar diffusion method of barnyard grass grass
After in two groups 50 milliliters small beaker, completing granulated glass sphere and filter paper respectively; Add 6 milliliter of 10 μ g/mL and the described sample liquid of 100 μ g/mL respectively; Add 10 of the barnyard grass grass seeds just showed money or valuables one carries unintentionally respectively, under 28 ± 1 ℃, illumination cultivation is measured the height of seedling after 72 hours; Through compound under the illumination condition growth-inhibiting of barnyard grass grass seedling plant height is come the weeding activity of detection compound, each handles twice of repetition.Activity index: plant height growth inhibition ratio (%), the result sees table 3.
Table 31,2,4-triazole derivative weeding activity
The test of embodiment 14 fungicidal activities
1) crop and strains tested
Crop: the cucumber seedling of 2 cotyledon periods (Cucumis sativus L.), kind is: the close thorn in Xintai City.
Strains tested:
| Controlling object | The Latin formal name used at school |
| The cucumber brown spot | Corynespora?cassiicola |
| Cucumber bacterial angular leaf spot | Pseudomonas?syringae?pv.lachrymans |
| Cucumber fusarium axysporum | Fusarium?oxysporum |
| Cucumber downy mildew | Pseudoperonospora?cubensis |
| Powdery mildew of cucumber | Sphaerotheca?fuligenea |
| Bacterial spot of tomato | Xanthomonas?axonopodis |
| Rice sheath blight disease | Rhizoctonia?solanii |
[0052]2) supply reagent agent and contrast medicament
Supply the reagent agent: will be of the present invention 1,2,4-triazole derivative (I-1) (I-4)～(I-11) is mixed with 500mg/L confession reagent agent with DMF respectively.
The contrast medicament: the DMF solution with middle living rhzomorph (commercially available) is the contrast medicament, and concentration is 500mg/L.
3) dispenser, vaccination ways
Select 2 cotyledon period cucumber seedlings for use; Cucumber brown spot, Powdery Mildew, oidium adopt the spore suspension spray inoculation; Cucumber bacterial angular leaf spot, bacterial spot of tomato adopt the bacteria suspension spray inoculation; The sick radicle seed soaking inoculation method that adopts of cucumber fusarium axysporum, rice sheath blight disease adopts mycelia spray inoculation method.Cucumber cotyledons is divided into test group and control group, in the greenhouse, will supplies reagent agent and contrast medicament evenly to spray on cucumber cotyledons respectively, inoculate pathogenic bacteria after 2 hours, 24C, relative humidity 80%, the cultivation of preserving moisture the fine morning.The cucumber cotyledons soil for growth is that the peat composed of rotten mosses, vermiculite, chicken manure mass ratio are 25: 12: 1; Treat that control group fully falls ill the back according to grade scale, the investigation state of an illness is according to formula (1) and formula (2) calculating disease index and preventive effect.3 repetitions are established in all processing respectively, repeat 10 young plants at every turn, adopt random alignment in the greenhouse, and the result sees table 4.
Table 41,2, the 4-triazole derivative is to the control effect of various diseases
Table 4 can find out, 1,2, and the 4-triazole derivative has excellent preventive effect to cucumber downy mildew.
Claims (10)
1. 1,2 shown in the formula (I), the 4-triazole derivative,
R is phenyl, substituted-phenyl in the formula (I), and the substituting group of said substituted-phenyl is: methoxyl group, the tertiary butyl, cyanic acid, sec.-propyl or halogen describedly are substituted by single replace or polysubstituted.
2. as claimed in claim 11; 2; The 4-triazole derivative; It is characterized in that in the described formula (I) R be phenyl, adjacent fluorophenyl, a fluorophenyl, to fluorophenyl, 2,4 dichloro benzene base, 3,4-dichlorophenyl, Chloro-O-Phenyl, a chloro-phenyl-, rubigan, to tert-butyl-phenyl, p-methoxyphenyl, a cyano-phenyl or isopropyl phenyl.
3. as claimed in claim 11,2, the 4-triazole derivative is characterized in that described verivate is one of following:
One kind as claimed in claim 11,2, the preparation method of 4-triazole derivative; It is characterized in that described method is: with the 4-cyclopropyl-5-methyl-4H-1 shown in the formula (II), 2, the replacement benzyl chlorine shown in 4-triazole-3-mercaptan and the formula (III) is under catalyst action; 0～20 ℃ is carried out linked reaction 1～20h in organic solvent, and the reaction solution aftertreatment makes 1,2 shown in the formula (I); The 4-triazole derivative; Said catalyzer is an inorganic base substance, and said organic solvent is N, N N, acetonitrile, toluene or THF;
R is phenyl, substituted-phenyl in the formula (III), and the substituting group of said substituted-phenyl is: methoxyl group, the tertiary butyl, cyanic acid, sec.-propyl or halogen describedly are substituted by single replace or polysubstituted.
5. as claimed in claim 41,2, the preparation method of 4-triazole derivative is characterized in that described catalyzer is salt of wormwood, sodium hydrogencarbonate or sodium hydroxide.
6. as claimed in claim 41,2, the preparation method of 4-triazole derivative is characterized in that described organic solvent is N, the N N.
7. as claimed in claim 41; 2; The preparation method of 4-triazole derivative is characterized in that the 4-cyclopropyl-5-methyl-4H-1 shown in the described formula (II), 2; The feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and the formula (III) is 1: 1.0～1.5: 1～3, and said volume of organic solvent consumption is counted 20～50mL/g with compound quality shown in the formula (II).
8. as claimed in claim 41,2, the preparation method of 4-triazole derivative; It is characterized in that described reaction solution post-treating method is: reaction finishes, and reaction solution is poured in the frozen water, suction filtration; Filtrating column chromatography or use the recrystallization solvent recrystallization, further separation and purification obtains described 1,2; The 4-triazole derivative, described column chromatography eluent or recrystallization solvent are the mixing of following one or more arbitrary proportions: sherwood oil, ETHYLE ACETATE, normal hexane or ethanol.
9. as claimed in claim 41,2, the preparation method of 4-triazole derivative; It is characterized in that described preparation method is: with the 4-cyclopropyl-5-methyl-4H-1 shown in the formula (II), 2, the replacement benzyl chlorine shown in 4-triazole-3-mercaptan and the formula (III) is under catalyst action; 0～20 ℃ is carried out linked reaction 1～20h in organic solvent, filters in the reaction solution adding frozen water, and filtrating is that eluent carries out column chromatography with the ETHYLE ACETATE and the sherwood oil mixed solution of volume ratio 1: 1～100; Make 1,2 shown in the formula (I), the 4-triazole derivative; Said catalyzer is salt of wormwood, sodium hydrogencarbonate or sodium hydroxide, and said organic solvent is N, the N N; 4-cyclopropyl-5-methyl-4H-1 shown in the described formula (II); 2; The feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and the formula (III) is 1: 1.0: 2, said volume of organic solvent consumption with compound quality shown in the formula (II) than being 30mL/g.
10. as claimed in claim 11,2, the application of 4-triazole derivative in weeding and fungicidal activity.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130917A (en) * | 2015-09-18 | 2015-12-09 | 浙江工业大学 | 1,2,4-triazolothio-ether derivative as well as preparation and application thereof |
| EP3210469A1 (en) | 2016-02-23 | 2017-08-30 | Bayer Cropscience AG | Use of substituted thio-1,2,4-triazoles for increasing stress tolerance in plants |
| CN110878087A (en) * | 2019-11-18 | 2020-03-13 | 长江大学 | Shenqinmycin triazole derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1288540A (en) * | 1968-09-04 | 1972-09-13 | ||
| US3701784A (en) * | 1968-09-04 | 1972-10-31 | Rohm & Haas | 1,2,4-4h-triazole derivatives |
-
2011
- 2011-09-05 CN CN201110260671.8A patent/CN102391193B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1288540A (en) * | 1968-09-04 | 1972-09-13 | ||
| US3701784A (en) * | 1968-09-04 | 1972-10-31 | Rohm & Haas | 1,2,4-4h-triazole derivatives |
Non-Patent Citations (1)
| Title |
|---|
| STN COLUMBUS: "cas rn：941171-51-3，941102-75-6，940840-42-6，923779-68-4，878268-22-5，878232-94-1", 《REGISTRY》, 4 July 2007 (2007-07-04) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130917A (en) * | 2015-09-18 | 2015-12-09 | 浙江工业大学 | 1,2,4-triazolothio-ether derivative as well as preparation and application thereof |
| CN105130917B (en) * | 2015-09-18 | 2018-05-08 | 浙江工业大学 | A kind of 1,2,4- triazoles sulfide derivative and its preparation and application |
| EP3210469A1 (en) | 2016-02-23 | 2017-08-30 | Bayer Cropscience AG | Use of substituted thio-1,2,4-triazoles for increasing stress tolerance in plants |
| CN110878087A (en) * | 2019-11-18 | 2020-03-13 | 长江大学 | Shenqinmycin triazole derivative and preparation method and application thereof |
| CN110878087B (en) * | 2019-11-18 | 2021-04-09 | 长江大学 | Shenqinmycin triazole derivative and preparation method and application thereof |
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