CN102391193B - 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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- CN102391193B CN102391193B CN201110260671.8A CN201110260671A CN102391193B CN 102391193 B CN102391193 B CN 102391193B CN 201110260671 A CN201110260671 A CN 201110260671A CN 102391193 B CN102391193 B CN 102391193B
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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, take again nitrogen heterocyclic ring as main.Triazole class compounds is a development in recent years class more rapidly, and many commercial sterilant belong to such.DOW Chemical scientific research personnel, after having found sterilant triarimol, passes through again composition optimizes, finds active better triazole bactericidal agent.The scientific research personnel of Bayer AG on this basis, has first found a series of high-activity compounds such as clotrimazole (medicine) afterwards.Up to now, many commercial sterilant are as triadimenol, cyproconazole, tebuconazole, the sterilant such as flutriafol.
Yet, there is not yet 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 is to provide, 4-triazole derivative and preparation method thereof and application, and this compound has weeding and fungicidal activity.
The technical solution used in the present invention is:
Shown in a kind of formula (I) 1,2,4-triazole derivative,
In formula (I), R is phenyl, substituted-phenyl, and the substituting group of described substituted-phenyl is: methoxyl group, the tertiary butyl, cyano group, sec.-propyl or halogen, described being substituted by is monosubstituted or polysubstituted.
Further, described 1,2,4-triazole derivative, in 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 derivative is one of following:
A kind of of the present invention 1,2, the preparation method of 4-triazole derivative, described method is: by the 4-cyclopropyl-5-methyl-4H-1 shown in formula (II), 2, replacement benzyl chlorine shown in 4-triazole-3-mercaptan and formula (III) is under catalyst action, in organic solvent, 0～20 ℃ is carried out linked reaction 1～20h, reaction solution aftertreatment makes 1 shown in formula (I), 2,4-triazole derivative, described catalyzer is inorganic base substance, described organic solvent is DMF, acetonitrile, toluene or tetrahydrofuran (THF);
In formula (III), R is phenyl, substituted-phenyl, and the substituting group of described substituted-phenyl is: methoxyl group, the tertiary butyl, cyano group, sec.-propyl or halogen.
Described catalyzer is salt of wormwood, sodium bicarbonate or sodium hydroxide.
Described organic solvent is DMF.
4-cyclopropyl-5-methyl-4H-1 shown in described formula (II), 2, the feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and formula (III) is 1: 1.0～1.5: 1～3, and the volumetric usage of described organic solvent is counted 20～50mL/g with compound quality shown in formula (II).
Further, of the present invention 1, reaction solution post-treating method described in the preparation method of 2,4-triazole derivative is: reaction finishes, and reaction solution is poured in frozen water, suction filtration, filtrate column chromatography or use recrystallization solvent recrystallization, further separation and purification obtains described 1,2,4-triazole derivative, the mixing that described column chromatography eluent or recrystallization solvent are following one or more arbitrary proportions: sherwood oil, ethyl acetate, normal hexane or ethanol.
Further, of the present invention 1, 2, the preparation method of 4-triazole derivative is recommended as: by the 4-cyclopropyl-5-methyl-4H-1 shown in formula (II), 2, replacement benzyl chlorine shown in 4-triazole-3-mercaptan and formula (III) is under catalyst action, in organic solvent, 0～20 ℃ is carried out linked reaction 1～20h, reaction solution adds in frozen water and filters, filtrate take the ethyl acetate of volume ratio 1: 1～100 and sherwood oil mixed solution carries out column chromatography as eluent, make 1 shown in formula (I), 2, 4-triazole derivative, described catalyzer is salt of wormwood, sodium bicarbonate or sodium hydroxide, described organic solvent is N, N dimethyl formamide, 4-cyclopropyl-5-methyl-4H-1 shown in described formula (II), 2, the feed intake ratio of amount of substance of replacement benzyl chlorine, catalyzer shown in 4-triazole-3-mercaptan and formula (III) is 1: 1.0: 2, and the volumetric usage of described organic solvent be take compound quality shown in 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 1,2,4-triazole derivative adopts 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 to test: described rape Plating for placing filter paper in culture dish, add of the present invention 1,2,4-triazole derivative and pretreated Semen Brassicae campestris, measure radicel length after dark culturing 72h at 28 ℃, by compound under dark condition, the growth-inhibiting of rape radicle carried out the weeding activity of detection compound; The little agar diffusion method of described barnyard grass for adding granulated glass sphere and filter paper in small beaker, the barnyard grass seed that adds compound of the present invention and just showed money or valuables one carries unintentionally, at 28 ℃, after illumination cultivation 72h, measure seedling height, by compound under illumination condition, the growth-inhibiting of barnyard grass Seedling Height is carried out the weeding activity of detection compound.
Of the present invention 1, 2, 4-triazole derivative fungicidal activity be take cucumber as tested object, test scab of cucumber (Cladosporium cucumerinum) spore suspended substance, Cucumber Target Leaf Spot (Corynespora cassiicola) spore suspended substance, cucumber timberrot (Sclerotinia sclerotiorum (Lib.) de Bary) is containing 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, add of the present invention 1, 2, 4-triazole derivative, after 2h, inoculate pathogenic bacteria, 18～30 ℃, relative humidity 80%, moisturizing is cultivated, disease index and prevention effect are calculated according to following formula:
Compared with prior art, beneficial effect of the present invention is mainly reflected in: of the present invention 1,2,4-triazole derivative has weeding and fungicidal activity, and cucumber downy mildew is had to 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 25mL round-bottomed flask, add 0.31g (2mmol) 4-cyclopropyl-5-methyl-4H-1, the K of 2,4-triazole-3-mercaptan, the adjacent fluorobenzyl chloride of 2mmol, 8mL DMF (DMF) and 2.4mmol
2cO
3, room temperature (25 ℃) stirring reaction 24h, TLC follows the tracks of reaction, after completion of the reaction, in reaction solution impouring 30mL frozen water, separate out solid, filter, filtrate is crossed silica gel column chromatography, take the volume ratio ethyl acetate of 1: 4: sherwood oil mixed solution is eluent, collect target liquid, concentrate drying obtains solid product 1,2,4-triazole derivative (I-1) 0.44g, productive rate 85% is (with 4-cyclopropyl-5-methyl-4H-1,2,4-triazole-3-mercaptan meter), as shown in Table 1 and Table 2.
Embodiment 2-111,2,4-triazole derivative (I-2)～(I-11)
Change and replace benzyl chlorine, other operate with embodiment 1, and result as 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
Embodiment 13 weeding activity tests
1) sample liquid preparation
By of the present invention 1,2,4-triazole derivative (I-1)～(I-3) be mixed with respectively 10 μ g/mL and 100 μ g/mL sample liquid with DMF, stand-by.
2) rape Plating
In the culture dish of two groups of diameter 6cm, complete respectively the filter paper of a diameter 5.6cm, add respectively the sample liquid described in 2 milliliter of 10 μ g/mL and 100 μ g/mL, add 10 of the seed soaking Semen Brassicae campestriss of 4 hours, at 28 ± 1 ℃, dark culturing was measured radicle length after 72 hours, by compound under dark condition, the growth-inhibiting of rape radicle is carried out the weeding activity of detection compound, each is processed and repeats twice.Activity index: radicle extends inhibiting rate (%), the results are shown in Table 3.
3) the little agar diffusion method of barnyard grass
In the small beaker of two groups 50 milliliters, complete respectively after granulated glass sphere and filter paper, add respectively the sample liquid described in 6 milliliter of 10 μ g/mL and 100 μ g/mL, add respectively 10, the barnyard grass seed that just showed money or valuables one carries unintentionally, at 28 ± 1 ℃, illumination cultivation is measured the height of seedling after 72 hours, by compound under illumination condition, the growth-inhibiting of barnyard grass Seedling Height is carried out the weeding activity of detection compound, each is processed and repeats twice.Activity index: height growth inhibiting rate (%), the results are shown in Table 3.
Table 31,2,4-triazole derivative weeding activity
Embodiment 14 fungicidal activity tests
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 | Latin formal name used at school |
| Cucumber Target Leaf 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 |
2) reagent agent and contrast medicament
Reagent agent: by of the present invention 1,2,4-triazole derivative (I-1), (I-4)～(I-11) with DMF, be mixed with 500mg/L reagent agent respectively.
Contrast medicament: take the DMF solution of Zhongshengmycin (commercially available) for contrasting medicament, concentration is 500mg/L.
3) dispenser, vaccination ways
Select 2 cotyledon period cucumber seedlings, Cucumber Target Leaf Spot, Powdery Mildew, oidium adopt spore suspension spray inoculation, cucumber bacterial angular leaf spot, bacterial spot of tomato adopt 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 greenhouse, in fine day, respectively reagent agent and contrast medicament is evenly sprayed in cucumber cotyledons the morning, after 2 hours, inoculate pathogenic bacteria, 24C, relative humidity 80%, moisturizing is cultivated.Cucumber cotyledons soil for growth is that the peat composed of rotten mosses, vermiculite, chicken manure mass ratio are 25: 12: 1; After control group is fully fallen ill, according to grade scale, the investigation state of an illness, calculates disease index and preventive effect according to formula (1) and formula (2).3 repetitions are established in all processing respectively, repeat 10 young plants at every turn, adopt random alignment in greenhouse, the results are shown in Table 4.
formula (1)
formula (2)
Table 41,2, the prevention effect of 4-triazole derivative to various diseases
Table 4 can find out, 1,2,4-triazole derivative has excellent preventive effect to cucumber downy mildew.
Claims (1)
1. 1,2 shown in a formula I, 4-triazole derivative is the application in control cucumber downy mildew as sterilant, it is characterized in that describedly 1,2, and 4-triazole derivative is one of following:
In formula I R be 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 or p-methoxyphenyl.
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| 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 |
| CN110878087B (en) * | 2019-11-18 | 2021-04-09 | 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 |
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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》.2007,cas rn:941171-51-3,941102-75-6,940840-42-6,923779-68-4,878268-22-5,878232-94-1. * |
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Effective date of registration: 20200518 Address after: 215008 Room 202, No. 10-4, oil truck farm, Gusu District, Suzhou City, Jiangsu Province Patentee after: Guan Yan Address before: 314100 Room 601, building 9, No. 568, Jinyang East Road, Luoxing street, Jiashan County, Jiaxing City, Zhejiang Province Patentee before: Jiashan talent technology transformation service center Effective date of registration: 20200518 Address after: 314100 Room 601, building 9, No. 568, Jinyang East Road, Luoxing street, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: Jiashan talent technology transformation service center Address before: 310014 Hangzhou city in the lower reaches of the city of Zhejiang Wang Road, No. 18 Patentee before: ZHEJIANG UNIVERSITY OF TECHNOLOGY |
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Effective date of registration: 20200714 Address after: 314100 floor 1, C7, No. 555 Chuangye Road, Dayun Town, Jiashan County, Jiaxing City, Zhejiang Province Patentee after: Jiasheng biomedical (Jiaxing) Co.,Ltd. Address before: 215008 Room 202, No. 10-4, oil truck farm, Gusu District, Suzhou City, Jiangsu Province Patentee before: Guan Yan |