WO2021147521A1 - Triazole derivative, preparation method therefor, and use thereof - Google Patents

Abstract

A triazole derivative, a preparation method therefor, and a use thereof, relating to the technical field of organic synthetic drugs. The structure of the triazole derivative is shown in formula I, wherein R1 and R2 in formula I are H, Cl, Br, —CF₃, —CH(CH₃)₂, or —OCH₃, and R1 and R2 are not H at the same time; R3 is —CH₂— or —COCH₂—; X and Y are N or C, and X and Y are not C at the same time, and X and Y are not N at the same time. The triazole derivative has a certain inhibitory effect on the pathogens of various crop diseases, and fewer toxic side effects for plants. The preparation method for the triazole derivative is simple.

Description

Triazole derivative and its preparation method and use

Cross-references to related applications

This application claims the rights and priority of the Chinese patent application CN2020100690036 filed on January 21, 2020, and this application is hereby cited in its entirety for reference and all other purposes.

Technical field

The invention relates to a triazole derivative, a preparation method and application thereof, and belongs to the technical field of organic synthetic drugs.

Background technique

With the development of modern agriculture, pesticides have become a powerful weapon to ensure the prevention and control of pests and the production of cash crops. However, the excessive use of pesticides leads to stronger insect resistance. At the same time, as the food chain passes, it causes various harms to human health. In order to reduce the pollution of pesticides to the environment and improve our inherently fragile environmental problems, finding pesticides that are safe, non-toxic, high-efficiency, and low-residue to humans and animals has become an important issue that chemists need to solve urgently.

In addition, long-term use of the same antibacterial drugs makes the germs easy to be resistant. Therefore, the development of new compounds that have good bactericidal effects and small side effects on crop growth, and even can promote crop growth, is of great significance.

Summary of the invention

The first technical problem to be solved by the present invention is to provide a new triazole derivative.

To solve the first technical problem of the present invention, the structure of the triazole derivative is shown in formula I:

Wherein, R1 and R2 in the formula I are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R1 and R2 are not H at the same time; R3 is —CH ₂ — or —COCH ₂ —; The X and Y are N or C, and X and Y are not C at the same time, and X and Y are not N at the same time.

Preferably, the R3 is —CH ₂ —.

Preferably, the R1 and R2 are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R ₁ and R _{2 are not —OCH 3} at the same time.

Preferably, the X is C and Y is N.

Preferably, said R1 and R2 are H, Cl, Br, -CF ₃ or -CH(CH ₃ ) ₂ ; preferably said R1 and R2 are H, Cl, Br or -CF ₃ ; more preferably said R1 and R2 is H, -CF ₃ .

Preferably, the triazole derivative is at least one of the following structural formulas:

The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned triazole derivative. When R3 is —CH ₂ —, the method includes:

The a is NaBH ₄ , MeOH or MeCN, 0°C; b is SOCl ₂ , 0°C; c is NaH, K ₂ CO ₃ or CsCO ₃ , DMF;

When the R3 is —COCH ₂ —, the method includes:

The third technical problem to be solved by the present invention is to provide the use of the above-mentioned triazole derivative or the triazole derivative prepared by the above-mentioned method in the preparation of medicines for preventing or treating crop diseases or regulating plant growth.

Preferably, the crop disease is kiwi brown spot, strawberry anthracnose, potato late blight, strawberry gray mold or grape downy mildew.

Preferably, the triazole derivative that regulates plant growth is:

The use concentration of the XZY-3-S34 is preferably 0.01-0.1 ppm, and the plant is preferably rice.

Beneficial effects:

1. The triazole derivatives of the present invention have a certain inhibitory effect on the pathogens of various crop diseases.

2. The triazole derivatives of the present invention have little toxic and side effects on plants.

3. The triazole derivative XZY-3-S34 of the present invention also has a certain promoting effect on the growth of plants.

4. The preparation method of the present invention is simple.

Description of the drawings

Figure 1 is a diagram of XZY-3-S34 plant growth promotion;

Figure 2 is an experimental photo of grape downy mildew with 3% XZY-3-S10, clear water, and chemical control group.

In Figure 2, 4--1-a is 1# leaf before medication, 4--1-b is 1# leaf is treated with 3% XZY-3-S10 diluted 200 times with the agent for 14 days, 4-4-a is 4# Before the leaves are treated with medicine, 4-4-b is 4#, and the leaves are treated with 3% XZY-3-S10 diluted 200-fold medicament for 14 days, 4-5-a is 5# before the leaves are treated with medicine, 4-5-b is 5# The leaves were treated with 3% XZY-3-S10 diluted 200 times with the agent for 14 days, 4-6-a was CK-10 leaves before treatment with water, 4-6-b was CK-10 leaves after treatment with water for 14 days , 4-7-a is for CK-8 leaves before being treated with clean water, 4-7-b is for CK-7 leaves after being treated with clean water for 14 days, and 4-8-a is for leaves 1-2 with Zengweiying Green Before treatment, 4-8-b was No. 1-2 leaves after 14 days after treatment with Zengwei Yinglu.

Detailed ways

To solve the first technical problem of the present invention, the structure of the triazole derivative is shown in formula I:

Wherein, R1 and R2 in the formula I are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R1 and R2 are not H at the same time; R3 is —CH ₂ — or —COCH ₂ —; The X and Y are N or C, and X and Y are not C at the same time, and X and Y are not N at the same time.

Preferably, the R3 is —CH ₂ —.

Preferably, the R1 and R2 are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R ₁ and R _{2 are not —OCH 3} at the same time.

Preferably, the X is C and Y is N.

Preferably, said R1 and R2 are H, Cl, Br, -CF ₃ or -CH(CH ₃ ) ₂ ; preferably said R1 and R2 are H, Cl, Br or -CF ₃ ; more preferably said R1 and R2 is H, -CF ₃ .

Preferably, the triazole derivative is at least one of the following structural formulas:

The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned triazole derivative. When R3 is —CH ₂ —, the method includes:

The a is NaBH ₄ , MeOH or MeCN, 0°C; b is SOCl ₂ , 0°C; c is NaH, K ₂ CO ₃ or CsCO ₃ , DMF;

When the R3 is —COCH ₂ —, the method includes:

The third technical problem to be solved by the present invention is to provide the use of the above-mentioned triazole derivative or the triazole derivative prepared by the above-mentioned method in the preparation of medicines for preventing or treating crop diseases or regulating plant growth.

Preferably, the crop disease is kiwi brown spot, strawberry anthracnose, potato late blight, strawberry gray mold or grape downy mildew.

Preferably, the triazole derivative that regulates plant growth is:

The use concentration of the XZY-3-S34 is preferably 0.01-0.1 ppm, and the plant is preferably rice.

The specific implementation of the present invention will be further described below in conjunction with the examples, which does not limit the present invention to the scope of the described examples.

The raw materials and equipment used in the specific embodiments of the present invention are all known products and are obtained by purchasing commercially available products. Synthesis of XZY-3-S5

Compound 7 (100 mg, 1.44 mmol) was dissolved in 3 mL DMF, NaH (87 mg, 1.74 mmol) was added under stirring at room temperature, activated at room temperature for 1 h, compound 3 (364 mg, 2.16 mmol) was added, and the temperature was raised to 60°C for 5 h. Quench with water, add water, and extract 3 times with ethyl acetate. The organic layer is washed with saturated brine, dried with anhydrous MgSO ₄ and concentrated to obtain a crude product, which is purified by column chromatography to obtain 185 mg, 64%, which is a colorless transparent liquid. ¹ H NMR (400MHz, DMSO, ppm) δ 8.06 (s, 1H), 7.98 (s, 1H), 7.29-7.21 (m, 4H), 5.33 (s, 2H), 2.97-2.90 (m, 1H) ,1.26(d,J=8.0Hz,6H).

Synthesis of XZY-3-S10

Under N ₂ protection, use 2L DMF to dissolve 1,2,4-triazole (142.0g, 2.0mol, 1.1eq), and slowly add NaH (112.0g, 2.8mol, 1.5eq) in batches to detect the reaction The temperature was stabilized at about 0°C. After 1h, 4-trifluoromethylbenzyl bromide (450.0g, 1.9mol, 1.0eq) was added in DMF solution, 2.5h was detected by TLC, the reaction was completed, ethanol quenched, extracted, 697.0 g of light yellow oily liquid was obtained. ¹ H NMR(400MHz,DMSO,ppm) δ8.23(s,1H),8.01(s,1H),7.70(d,J=8.0Hz,2H), 7.38(d,J=8.0Hz,2H), 5.48(s,2H).Synthesis of XZY-3-S24:

Dissolve the raw material 4-trifluoromethylbenzaldehyde (320.0mg, 1.8mmol, 1.0eq) with 10mL of anhydrous methanol, slowly add NaBH ₄ (207.4mg, 5.5mmol, 3.0eq) at 0°C, and stir for 30min. Stop stirring and add acetone to quench the reaction. Add diatomaceous earth to filter in a hole-shaped funnel, and remove the solvent under reduced pressure to obtain 302.7 mg of p-trifluoromethyl benzyl alcohol with a yield of 94.6%.

_{SOCl 2} (5mL) was added dropwise to p-trifluoromethylbenzyl alcohol (288.6mg, 1.64mmol, 1.0eq) at 0℃. After reacting for 5min, it was moved to 70℃ and refluxed. After stirring for 1h, TLC thin layer chromatography The reaction was monitored to be complete, and the stirring was stopped. Distill under reduced pressure, add water and ethyl acetate to extract, and _{adjust the pH to weak alkaline with solid NaHCO 3} , wash the organic layer with saturated aqueous NaCl, dry with anhydrous MgSO ₄ , filter, distill the organic layer under reduced pressure, and column chromatography on the crude product , 277.3 mg of p-trifluoromethylbenzyl chloride was obtained, and the yield was 86.7%.

At room temperature, cesium carbonate (2052.7mg, 6.3mmol, 3.0eq) was added to the dry acetonitrile solution of 1,2,3-triazole (174.0mg, 2.5mmol, 1.2eq), stirred for 20min, and the above intermediate was added dropwise (500.0 mg, 2.1 mmol, 1.0 eq) of acetonitrile solution, after stirring for 30 min, the reaction was completed as monitored by TLC thin layer chromatography, and the stirring was stopped. Add diatomaceous earth to filter in a hole-shaped funnel, distill under reduced pressure, and column chromatography to obtain 293.6 mg of white solid, with a yield of 61.6%. ¹ H NMR(400MHz,DMSO,ppm)δ8.72(s,1H),8.03(s,1H),7.74(d,J=8.0Hz,2H),7.48(d,J=8.0Hz,2H), 5.56(s,2H).

Synthesis of XZY-3-S27:

Dissolve the raw material p-isopropylbenzaldehyde (300.0mg, 2.0mmol, 1.0eq) with anhydrous methanol (12.0mL), slowly add sodium borohydride (229.7mg, 6.1mmol, 3.0eq) at 0℃, and stir for 30min Afterwards, 1.0 mL of acetone was added to quench the sodium borohydride, diatomaceous earth was added to filter in a pore-shaped funnel, and 291.9 mg of oily liquid was obtained by spin-drying. The yield was 97.3%.

Then use DCM (12.0mL) to dissolve p-isopropylbenzyl alcohol (286.7mg, 1.9mmol, 1.0eq), add thionyl chloride (565.0mg, 4.8mmol, 2.5eq, 345ul) at 0℃ and stir, react After 50 minutes, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. Distill under reduced pressure, extract, adjust the pH to neutral, dry with saturated brine, and anhydrous magnesium sulfate to obtain 272.3 mg (yield 95.0%) of aromatic oily liquid p-isopropylbenzyl chloride.

Dissolve 1,2,3-triazole (93.0mg, 1.4mmol, 2.0eq) in DMF (3.0ml), slowly add sodium hydride (40.8mg, 1.7mmol, 2.5eq) at 0°C, stir for 20min, add to Isopropylbenzyl chloride (114.0 mg, 0.7 mmol, 1.0 eq), after 40 minutes of reaction, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. Extraction with EA, washing with saturated brine, drying with anhydrous magnesium sulfate, distillation under reduced pressure, and column chromatography to obtain 87.0 mg of white solid with a yield of 63.7%. ¹ H NMR (400MHz, DMSO, ppm) δ 8.17 (s, 1H), 7.73 (s, 1H), 7.23 (s, 4H), 5.57 (s, 2H), 2.90-2.83 (m, 1H), 1.18 (s, 3H), 1.16 (s, 3H). ¹³ C NMR (100MHz, DMSO, ppm) δ 148.8, 134.1, 134.0, 128.4, 127.1, 125.3, 52.9, 33.6, 24.3 ppm.

Synthesis of XZY-3-S28:

Dissolve the raw material 4-bromo-2-chlorobenzaldehyde (100mg, 0.5mmol, 1.0eq) in anhydrous methanol (3mL), slowly add sodium borohydride (68.9mg, 61.8mmol, 4.0eq) at 0℃, and stir for 35min Afterwards, TLC thin layer chromatography monitored the reaction to be complete, stop stirring, add 500uL of acetone to quench the sodium borohydride, add diatomaceous earth to filter in a pore-shaped funnel, spin dry to obtain 94.3mg (yield 94.3%) of oily liquid 4-bromo-2. ????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????? -Chlorobenzyl alcohol.

_{Add SOCl 2} (164.2mg, 1.4mmol, 3.0eq) in 4-bromo-2-chlorobenzyl alcohol (94.3mg, 0.4mmol, 1.0eq) dropwise at 0°C. After reacting for 5min, move to 70°C and reflux. After stirring for 1 h, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. After extraction with ethyl acetate, the _{pH of the solid NaHCO 3 was} adjusted to neutral, and then it was dried with saturated NaCl aqueous solution and anhydrous MgSO ₄ to obtain 81.1 mg of 4-bromo-2-chlorobenzyl chloride with a yield of 74.4%.

Dissolve 1,2,4-triazole (189.2mg, 2.7mmol, 1.2eq) in acetone (10mL), slowly add potassium carbonate (945.4mg, 6.8mmol, 3.0eq) at 0℃, stir for 40min, add 4- Bromo-2-chlorobenzyl chloride (548.0 mg, 2.3 mmol, 1.0 eq), after 60 minutes of reaction, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. EA was extracted three times, washed with saturated brine, dried over anhydrous magnesium sulfate, distilled under reduced pressure, and thin-layer chromatography yielded 281.5 mg of white solid, with a yield of 45.0%. ¹ H NMR(400MHz,DMSO,ppm)δ8.68(s,1H), 8.02(s,1H), 7.80-7.78(m,1H), 7.60-7.58(m,1H), 7.16(d,J= 8Hz, 1H), 5.51 (s, 2H) ppm.

Synthesis of XZY-3-S31:

MeCN (3mL) dissolve 1,2,4-triazole (84.8mg, 1.2mmol, 1.2eq) and CsCO ₃ (997.0mg, 3.1mmol, 3.0eq) at room temperature, stir for 40min, add raw material 1,3 -Dichloro-5-chlorotoluene (200.0mg, 1.0mmol, 1.0eq), react for 1.5h, the reaction is complete. The MeCN was distilled off under reduced pressure, the reaction solution was dissolved in ethyl acetate, filtered, and column chromatography was performed to obtain 140.0 mg of white solid, with a yield of 60.3%. ¹ H NMR(400MHz,CDCl ₃ )δ8.16(s,1H),8.00(s,1H),7.33(s,1H),7.13(d,J=1.3Hz,2H),5.31(s,2H) . ¹³ C NMR (100MHz, DMSO) δ 152.6, 145.1, 140.8, 134.7, 128.1, 127.2, 51.2

Synthesis of XZY-3-S34:

Dissolve 1,2,4-triazole (78.1mg, 1.1mmol, 1.1eq) and K ₂ CO ₃ (427.1mg, 3.1mmol, 3.0eq) with DMF (3mL) at room temperature, stir for 40min, add 2 -Trifluoromethylbenzyl chloride (200.0mg, 1.0mmol, 1.0eq), reacted for 1.5h, the reaction is complete; extracted with ethyl acetate 3 times, washed with saturated sodium chloride, dried with anhydrous magnesium sulfate, filtered, and obtained by column chromatography 103.0mg pale yellow oily liquid, yield 44.0%. ¹ H NMR (400MHz, CDCl ₃ ) δ 8.09 (s, 1H), 7.94 (s, 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.56-7.37 (m, 2H), 7.23-7.21 ( m, 1H), 5.61 (d, J = 69.9 Hz, 2H).

Comparative example 1

Synthesis of XZY-3-S25:

Dissolve 1,2,4-triazole (107.1mg, 1.5mmol, 1.2eq) in acetone _{(5.0mL), add K 2} CO ₃ (534.9mg, 3.9mmol, 3.0eq), stir at room temperature for 1 h; The raw material 2-bromo-2'-chloroacetophenone (300.0 mg, 1.3 mmol, 1.0 eq) was added at 0°C, and after 30 minutes of reaction, TLC thin-layer chromatography monitored the reaction to be complete, and the stirring was stopped. The solvent was removed under reduced pressure, and the crude product was column chromatographed (PE:EA=1:2) to obtain 274.0 mg of yellow solid with a yield of 84.0%. ¹ H NMR(300MHz,DMSO,ppm)δ8.55(s,1H), 8.03(s,1H), 7.90(d,J=7.8Hz,1H), 7.64–7.58(m,2H), 7.56–7.48 (m, 1H), 5.85 (s, 2H). ¹³ C NMR (100MHz, DMSO, ppm) δ 194.8, 152.0, 146.0, 135.4, 133.9, 131.4, 131.0, 130.4, 128.0, 57.7.

Synthesis of XZY-3-S26:

Dissolve 1,2,4-triazole (133.6mg, 1.9mmol, 1.5eq) in acetone (6mL), add K ₂ CO ₃ (534.9mg, 3.9mmol, 3.0eq), stir at room temperature for 40 min, then at 0 Add the raw material 2-bromo-4'-chloroacetophenone (300.0mg, 1.3mmol, 1.0eq), (PE:EA=1:1) at ℃, after 30min reaction, TLC thin layer chromatography monitors the reaction to be complete, stop stirring . The solvent was removed under reduced pressure, and the crude product was separated by column chromatography (PE:EA=1:2) to obtain 281.8 mg of a brown-yellow solid with a yield of 93.0%. ¹ H NMR (400MHz, DMSO, ppm) δ 8.51 (s, 1H), 8.08-8.03 (m, 3H), 7.71-7.64 (m, 2H), 6.00 (s, 2H). ¹³ C NMR (100MHz, DMSO, ppm) δ 192.2, 151.8, 146.1, 139.6, 133.4, 130.5, 129.6, 55.7 ppm.

Synthesis of XZY-3-S29:

The raw material veratraldehyde (400.0mg, 2.4mmol, 1.0eq) was dissolved in anhydrous methanol (8.0mL), and sodium borohydride (273.4mg, 7.2mmol, 3.0eq) was slowly added at 0℃. After stirring for 30min, the TLC was thin. Layer chromatography monitors that the reaction is complete, the stirring is stopped, 1 mL of acetone is added to quench the sodium borohydride, diatomaceous earth is added to the pore-shaped funnel and filtered, and 381.7 mg of oily liquid veratrol is obtained by distillation under reduced pressure. The yield is 95.4%.

_{SOCl 2} (1714.2 mg, 14.4 mmol, 6.0 eq) was added dropwise to veratrol (381.7 mg, 2.3 mmol, 1.0 eq) at 0°C, and after stirring for 1 h, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. Extraction with ethyl acetate, _{adjust the pH to neutral with solid NaHCO 3} , dry treatment with saturated NaCl aqueous solution and anhydrous MgSO ₄ to obtain 256.6 mg of white oily liquid 4-chloromethyl-1,2-dimethoxybenzene, the yield is 57.5% .

DMF (5.0mL) dissolve 1,2,4-triazole (114.3mg, 1.7mmol, 1.2eq), slowly add potassium carbonate (572.2mg, 4.1mmol, 3.0eq) at 0℃, stir for 40min, add 4 -Chloromethyl-1,2-dimethoxybenzene (256.6 mg, 1.4 mmol, 1.0 eq), after 60 minutes of reaction, TLC thin layer chromatography monitored the reaction to be complete, and the stirring was stopped. EA was extracted three times, dried with saturated brine and anhydrous magnesium sulfate, rotary evaporated, and column chromatography yielded 224.3 mg of yellow oily liquid with a yield of 74.2%. ¹ H NMR(400MHz,DMSO,ppm)δ8.63(s,1H),7.97(s,1H), 6.98(d,J=2.0Hz,1H), 6.93(d,J=8.2Hz,1H), 6.83(dd,J=8.2,1.8Hz,1H), 5.33(s, 2H), 2.90(s, 3H), 2.74(s, 3H).

Example 2

Antibacterial activity test

1) Experimental principle of antibacterial activity:

Use the test drug to diffuse in the culture medium to inhibit the growth of the surrounding bacteria to form a transparent circle, that is, the inhibition zone. The size of the inhibition zone is compared with the size of the colony without drug treatment to determine the antibacterial effect of the test drug .

2) Experimental method:

Firstly, the strain is inoculated and expanded and activated; secondly, make PDA medium, wash and peel the potatoes, cut into thin slices, add water and boil them through (it can be easily pierced with a glass rod), and then filter them with gauze and add 18g agar Mix 20g glucose with 20g glucose, stir evenly, dilute to 1000mL, dispense into Erlenmeyer flask, seal, autoclave (120℃) sterilize for 30min before use; weigh the drug solution, that is, weigh each drug 10mg+1mL ethanol +1mL of 1% Tween, add water to 10mL to make a concentration of 100ppm, and use clear water as a control; then add the medicine, pour the culture medium, that is, Strawberry Botrytis, potato late blight group, measure 1ml of the formulated liquid and 9ml of LPDA liquid Cultivation is based on the kiwi brown spots in a petri dish, respectively measure 1.5ml of the prepared liquid medicine and 13.5ml LPDA, cool them for use, and set up 3 repetitions for each agent; inoculate bacteria; and finally investigate. The potato late blight was cultured in an incubator for 2 days and then taken out, the diameter of the colony was measured and the data was recorded, and the antibacterial rate of the agent was calculated. Strawberry Botrytis cinerea was cultured in an incubator for 3 days and then taken out. The diameter of the colony was measured and the data was recorded to calculate the antibacterial rate of the agent. The kiwi fruit brown spots were cultured in the incubator for 5 days and then taken out, the diameter of the colony was measured and the data was recorded, and the antibacterial rate of the agent was calculated.

Inhibition rate calculation formula: I=【(D0-Dt)/D0】*100%

I: Inhibition rate

D0: blank colony diameter (the diameter of the bacterial cake has been subtracted)

Dt: the diameter of the colony treated by the agent (the diameter of the bacterial cake has been subtracted)

3) Experimental results:

Triazole compounds were tested for the bactericidal effect of kiwi brown spot, strawberry anthracnose, potato late blight, and strawberry gray mold. It can be seen from the data in Table 1 that the compound of the present invention has a certain antibacterial effect on kiwi brown spot, strawberry anthracnose, potato late blight, and strawberry gray mold, and has a broad antibacterial spectrum. Among them, the compound XZY-3-S10 has a broad antibacterial spectrum. , Potato late blight, Strawberry Botrytis cinerea, and kiwi brown spots showed the best antibacterial activities, and their antibacterial rates were all above 90%. In addition, the compound has good antibacterial durability, and its antibacterial activity is still excellent when the activity test is carried out on the fifth day.

Table 1. Experimental data of antibacterial activity of test compounds

Example 3

Rice germination and growth-promoting activity experiment

Principle: In the process of different medicaments on rice germination, measure the roots and shoots of rice seeds to obtain the growth length of the roots and shoots, and then enter the relevant formulas to obtain the vigor index of the roots and shoots; the germination potential is the seed’s vigor index. Germination rate.

Method: The sterilized seeds were soaked at room temperature according to the designed concentration, and the seeds were soaked for 24 hours. After soaking the seeds, rinse the seeds with distilled water 3 to 5 times, and blot them dry with filter paper for later use. Place two layers of qualitative filter paper in the petri dish and moisten the filter paper with distilled water. Arrange 30 seeds evenly on a moist petri dish, keeping a certain distance between the seeds. Move the placed culture apparatus into an artificial climate box, control the temperature at 25°C, and the humidity at about 70%. Add distilled water dropwise according to the situation to keep the filter paper moist. Regularly investigate and record the germination and growth status of seedlings. Three days later, the roots and shoots of the rice seeds were tested and treated.

Vigor index (root, shoot)=V _I ＝X ₁ /X ₀ *S*100

Wherein V _I - activity index, X ₁ - treated seeds germinated, X ₀ - Total seed treatment, S- germination seedlings per plant root length / shoot (cm).

Table 2. Experimental data of test compounds on rice germination and growth promotion

It can be seen from Table 2 that the compounds of the present invention have little toxic and side effects on crops, and some compounds even promote plant growth. Combining the comprehensive evaluation of the vigor index of rice bud length and root length with water and solvent, the concentration in the experiment is obtained as The XZY-3-S34 compound of 0.01 ppm has the strongest promoting effect, and the root vigor index is 886.2, which is significantly higher than the 803.0 of clear water, as shown in Figure 1.

Example 4

Field trial

Principle: Taking the medicine against grape downy mildew as an example, the synthetic compound XZY-3-S10 is formulated into a 3% preparation product, and diluted 200 times to prevent grape downy mildew, which has a good effect on grape downy mildew. The Zengwei Yinglu was set as a chemical control, and a blank control was set up. Each agent treated 3 to 4 grapes. According to the experimental design, the leaves were evenly sprayed on the front and back, and sprayed across the board. By observing the health of the grape leaves, the overall effect is evaluated.

Method: First set up a chemical control and a blank control; secondly, spray the liquid medicine once in 4 to 5 days, with a water consumption of 60L/mu; finally, record and investigate, that is, select 30 leaf numbers before the medicine, and record them separately, and finally The spread of leaf lesions was investigated and recorded statistically 6 days after the first treatment. The experimental photos of 3% XZY-3-S10 against grape downy mildew are shown in Figure 2.

Calculation method

Disease index = (∑(number of diseased leaves at all levels×relative grade value)/(total number of leaves in investigation×9))×100

Control effect (%)=(1-(treatment area disease index/CK disease index))×100.

Table 3. Field test disease index table

Claims (10)

1. The triazole derivative is characterized in that the structure of the triazole derivative is shown in formula I:

   

   R1 and R2 in the formula I are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R1 and R2 are not H at the same time; R3 is —CH ₂ — or —COCH ₂ —; The X and Y are N or C, and X and Y are not C at the same time, and X and Y are not N at the same time.
2. The triazole derivative of claim 1, wherein the R3 is —CH ₂ —.
3. The triazole derivative of claim 1 or 2, wherein the R1 and R2 are H, Cl, Br, —CF ₃ , —CH(CH ₃ ) ₂ or —OCH ₃ , and R _{1 It is not -OCH 3} at the same time as R ₂ .
4. The triazole derivative according to any one of claims 1 to 3, wherein the X is C and Y is N.
5. The triazole derivative according to any one of claims 1 to 4, wherein said R1 and R2 are H, Cl, Br, —CF ₃ or —CH(CH ₃ ) ₂ ; preferably, said R1 And R2 are H, Cl, Br or —CF ₃ ; more preferably, said R1 and R2 are H, —CF ₃ .
6. The triazole derivative of claim 1, wherein the triazole derivative is at least one of the following structural formulas:

   
7. The method for preparing triazole derivatives according to any one of claims 1 to 6, wherein when the R3 is —CH ₂ —, the method comprises:

   

   The a is NaBH ₄ , MeOH or MeCN, 0°C; b is SOCl ₂ , 0°C; c is NaH, K ₂ CO ₃ or CsCO ₃ , DMF;

   When the R3 is —COCH ₂ —, the method includes:

   
8. Use of the triazole derivative according to any one of claims 1 to 6 or the triazole derivative prepared by the method according to claim 7 in the preparation of a medicine for preventing or treating crop diseases or regulating plant growth.
9. The use of the triazole derivative according to claim 8 in the preparation of a medicament for preventing or treating crop diseases or regulating plant growth, wherein the crop diseases are kiwi brown spot, strawberry anthracnose, potato late blight , Strawberry Botrytis or Grape Downy Mold.
10. The use of the triazole derivative according to claim 8 in the preparation of a medicament for preventing or treating crop diseases or regulating plant growth, wherein the triazole derivative for regulating plant growth is:

    

    XZY-3-S34;

    The use concentration of the XZY-3-S34 is preferably 0.01-0.1 ppm, and the plant is preferably rice.

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