CN111574466A - A novel triazole-containing allyl benzoate compound and its preparation method and application - Google Patents

Abstract

The invention discloses a novel allyl benzoate compound containing triazole and a preparation method and application thereof, wherein the structural formula of the novel allyl benzoate compound containing triazole is shown as a formula (I):

in formula (I): substituent R¹Is phenyl or substituted phenyl, the number of the substituent groups on the benzene ring of the substituted phenyl is one or more, and each substituent group is independently selected from H, halogen, C1-C4 alkyl, methoxy or nitro; substituent R²Is hydrogen or trifluoromethyl. The novel allyl benzoate compound containing triazole disclosed by the invention is a novel compound with bactericidal activity, and can kill rape bacteria at a concentration of 50ppmThe sclerotinia sclerotiorum has better inhibition rate, and provides a foundation for the research and development of new pesticides.

Description

A novel triazole-containing allyl benzoate compound and preparation method thereof application

technical field

The invention relates to a novel triazole-containing allyl benzoate compound and a preparation method and application thereof.

Background technique

Nitrogen-containing heterocyclic compounds have a wide range of biological activities and are therefore of great significance in the creation of pesticides. Triazole fungicides belong to organic heterocyclic nitrogen compounds, are ergosterol synthesis inhibitors, and have good control effects on most fungal diseases that harm crop growth. In recent decades, triazole fungicides have occupied a huge market with their advantages of high efficiency, broad spectrum and low toxicity. Because most triazole fungicides also have plant growth regulation functions, so triazole fungicides are antifungal. Research on drug types has received much attention. So far, tens of thousands of triazole compounds have been synthesized and discovered, of which 1,2,4-triazole compounds occupy most of them, of which more than 40 species have been commercialized, such as triadimefon (triadimefon). ), triadimenol, propiconazole, Paclobutrazol and the like. With the frequent use of triazole fungicides in agriculture, some disadvantages have also been exposed. Their single active site, due to frequent use, makes fungi more and more resistant to drugs and thus loses its high efficiency.

The design and synthesis of new triazole fungicides is of great significance for us to develop new pesticides with high efficiency, low toxicity and low residues.

SUMMARY OF THE INVENTION

In view of the above-mentioned technical problems existing in the prior art, the purpose of the present invention is to provide a novel triazole-containing allyl benzoate compound and its preparation method and application. The present invention is based on the uniconazole structure as the parent body, keeps the benzene ring, the triazole ring and the carbon-carbon double bond of the uniconazole unchanged, replaces the chlorine on the benzene ring with hydrogen and trifluoromethyl, and replaces the olefin effect with the benzene ring The tert-butyl group of azoles, ester groups and aromatic rings were introduced into the hydroxyl groups to synthesize ester compounds to investigate the influence on the biological activity of the compounds, and a series of triazole compounds were designed and synthesized.

Described a kind of novel allyl benzoate compound containing triazole is characterized in that its structural formula is shown in formula (I):

In formula (I): the substituent R ¹ is a phenyl group or a substituted phenyl group, the number of substituent groups on the benzene ring of the substituted phenyl group is one or more, and each substituent group is independently selected from H, halogen, C1 -C4 alkyl, methoxy or nitro; substituent R ² is hydrogen or trifluoromethyl.

Said novel triazole-containing allyl benzoate compound is characterized in that R in formula (I) is ^one of the following: phenyl, 2-methylphenyl, 2-chlorophenyl, 2,4-Dichlorophenyl, 3-methoxyphenyl, 2,6-dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-methylphenyl, 2,3-dichlorophenyl Chlorophenyl, 4-tert-butylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 3-methylphenyl, 4-fluorophenyl, 3-nitrophenyl, 3- Chlorophenyl.

Described a kind of preparation method of novel triazole-containing allyl benzoate compound is characterized in that comprising the following steps:

1) ɑ-Bromoacetophenone and 1,2,4-triazole are mixed in organic solvent A, the temperature is controlled to below 0°C, after triethylamine is added dropwise, the reaction is stirred at room temperature, and the reaction progress is tracked by TLC After the reaction is finished, suction filtration removes the triethylamine hydrochloride that the reaction generates, and after the filtrate is desolubilized, the 1-phenyl-2-(1H-1 shown in the formula (II) is obtained by recrystallization with the organic solvent B. ,2,4-triazol-1-yl)ethan-1-one;

2) 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one, benzaldehyde or p-trifluoromethyl represented by formula (II) obtained in step 1) Benzaldehyde and piperidine are heated and refluxed in organic reagent C, and the reaction process is tracked by TLC; after the reaction is completed, cooled to room temperature, the reaction solution is transferred to a separatory funnel, washed with water and layered, and the organic phase is then saturated brine. After washing 1-3 times, it is dried over anhydrous sodium sulfate, filtered, the filtrate is concentrated to remove the solvent, and the concentrate is separated and purified by column chromatography to obtain (E)-1,3-diphenyl shown in formula (III). base-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one compounds;

3) (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-ene-1 represented by formula (III) obtained in step 2) -The ketone compound is dispersed in the organic reagent D, PEG 600 and sodium borohydride are added, the reaction is stirred under the condition of ice bath at 0°C, and the reaction progress is tracked by TLC; 0.5-2N hydrochloric acid solution was added dropwise, extracted with organic reagent E, and the organic phases were combined, then dried over anhydrous sodium sulfate, filtered, and spin-dried for solvent treatment to obtain (E)-1,3- as shown in formula (IV). Diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol compounds;

4) (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-ene represented by formula (IV) obtained in step 3) The -1-alcohol compounds were dispersed in the organic reagent F, and DMAP, EDC and substituted benzoic acid were added, the reaction was stirred at room temperature, and the reaction progress was tracked by TLC; Sodium drying, filtration, separation and purification by column chromatography to obtain a novel triazole-containing allyl benzoate compound as shown in formula (I);

Wherein, the R ¹ is phenyl or substituted phenyl, the number of substituents on the benzene ring of the substituted phenyl is one or more, and each substituent is independently selected from H, halogen, C1-C4 alkyl , methoxy or nitro; substituent R ² is hydrogen or trifluoromethyl.

The method for preparing a novel triazole-containing allyl benzoate compound is characterized in that the organic solvent A in step 1) is a ketone solvent, preferably acetone; the organic solvent B is an alcohol solvent, It is preferably isopropanol; the organic solvent C in the step 2) is a benzene solvent, preferably toluene; the organic reagent D in the step 3) is an alcohol solvent, preferably methanol; the organic reagent E in the step 3) and the step The organic solvent F in 4) is all methylene chloride.

The preparation method of described a kind of novel triazole-containing allyl benzoate compound is characterized in that in step 1), described ɑ-bromoacetophenone and 1,2,4-triazole are prepared. The feeding molar ratio is 1:1.1-1.5; in step 2), 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one represented by formula (II) and the molar ratio of (p-trifluoromethyl)benzaldehyde is 1:1.1～1.5; in step 3), (E)-1,3-diphenyl-2-(1H- The molar ratio of 1,2,4-triazol-1-yl)prop-2-en-1-one compound and sodium borohydride is 1:1.1～1.5; in step 4), shown in formula (IV) The molar ratio of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl) prop-2-en-1-ol compound and substituted benzoic acid It is 1:1.1～1.5.

The preparation method of described a kind of novel allyl benzoate compound containing triazole is characterized in that in step 1), the volumetric consumption of organic solvent A is counted as 1 with the amount of substance of ɑ-bromoacetophenone. ～2mL/mmol, the volume dosage of organic solvent C in step 2) is 1-phenyl-2-(1H-1,2,4-triazol-1-yl)b-1- The amount of the ketone substance is calculated as 1～1.5mL/mmol, and the volume dosage of the organic solvent D in step 3) is the (E)-1,3-diphenyl-2-(1H-1 represented by the formula (III) , 2,4-triazol-1-yl) prop-2-en-1-one compound substance is calculated as 2～3mL/mmol, and the volumetric amount of organic solvent F in step 4) is calculated as formula (IV) The amount of the (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol compound shown is calculated as 6～8mL/mmol.

The method for preparing a novel triazole-containing allyl benzoate compound is characterized in that the eluents in step 2) and step 4) are separated by column chromatography in a volume ratio of 1:0.5 to 2 ethyl acetate and petroleum ether mixture.

The application of the novel triazole-containing allyl benzoate compound in the preparation of fungicides.

Further, the novel triazole-containing allyl benzoate compound is used to prepare a bactericide for inhibiting Sclerotinia sclerotiorum.

The synthetic route of the novel allyl benzoate compound containing triazole of the present invention is as follows:

Compared with the prior art, the beneficial effects of the present invention are mainly reflected in: the present invention provides a novel triazole-containing allyl benzoate compound and its preparation method and its application in the preparation of fungicides, and its preparation method Simple and convenient to operate, the obtained compound has the best inhibitory activity against Sclerotinia sclerotiorum under the effective concentration of 50 ppm, and the inhibition rate reaches 71.4%. Base.

Detailed ways

The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.

Example 1 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl benzoate

1) Synthesis of 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one (II):

Add ɑ-bromoacetophenone (19.90g, 0.10mol) and 1,2,4-triazole (7.60g, 0.11mol) to a 500mL three-necked flask in turn, add 150mL of acetone as a solvent, and control with an ice-salt bath. When the temperature was below 0°C, triethylamine (11.13 g, 0.11 mol) was slowly added dropwise through a constant pressure dropping funnel. After the dropwise addition, the reaction was continued for 1 h, the ice bath was removed, and the stirring was continued for 1 h at room temperature, and the reaction progress was followed by TLC ( _VE A /V _PE =1/1, v/v). After the reaction, the triethylamine hydrochloride generated by the reaction was removed by suction filtration, and the triethylamine hydrochloride was rinsed with acetone. After combining the eluent and the filtrate, a red oil was obtained by precipitation, which was cooled and solidified. 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one represented by formula (II) was obtained by recrystallization from isopropanol;

2) Synthesis of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one (III-1):

1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethyl- 1-ketone (5.62g, 30.00mmol), benzaldehyde (3.50g, 33.00mmol), add 30mL of toluene as a solvent, dropwise add piperidine (0.20g, 2.35mmol) as a catalyst, heat under reflux for 6h, TLC (V _EA /V _PE = 1/1, v/v) to track the progress of the reaction. After the reaction was completed, it was cooled to room temperature, and the reaction solution was transferred to a separatory funnel. After washing, the layers were separated. The organic phase was washed twice with saturated brine (the volume of saturated brine used for each washing was 20 mL), and anhydrous sulfuric acid Dry over sodium, filter, concentrate the filtrate to remove the solvent, and separate and purify the concentrated residue by column chromatography (eluent is 1:1 petroleum ether and ethyl acetate by volume) to obtain (E) represented by formula (III-1) -1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one;

3) Synthesis of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol (IV-1):

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one ( 1.93g, 7.00mmol) was added to a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, the temperature was controlled at 0°C in an ice bath, PEG600 (0.50g, 0.83mmol) was added, and sodium borohydride (0.42 mmol) was added in batches under stirring. g, 11.00 mmol), reacted at 0°C under ice bath for 4 h, TLC (V _EA /V _PE =1/2, v/v) followed the reaction progress. After the reaction was completed, the reaction solution was desolubilized, 1N hydrochloric acid solution was added dropwise to the precipitation concentrate, extracted three times with dichloromethane (15 mL of dichloromethane was used for each extraction), the organic phases were combined, and then dried over anhydrous sodium sulfate. , filtered, and spin-dried to obtain (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)propan-2 represented by formula (IV-1) -en-1-ol;

4) Synthesis of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allylbenzoate (C1):

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol ( 0.20g, 0.72mmol), benzoic acid (0.10g, 0.80mmol), DMAP (0.09g, 0.72mmol), EDC (0.28g, 1.44mmol) were added to 5mL of dichloromethane, and reacted at room temperature for 4h, then the reaction The liquid was transferred to a separatory funnel, washed with water (3×5 mL), washed with saturated brine (2×5 mL), dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated to remove the solvent, and the concentrated residue was separated and purified by column chromatography (The eluent is 1:1 petroleum ether and ethyl acetate by volume) to prepare compound (C1).

Wherein, the substituents R ² in the structural formulae of formula (III) and formula (IV) are all hydrogen, respectively forming the molecular structures of formula (III-1) and formula (IV-1).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allylbenzoate: yellow oil, yield 52.36%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.08(s,1H,triazole-H), 7.68(s,1H,triazole-H), 7.60-7.56(m,1H,ArH), 7.48-7.42(m,5H,ArH) ),7.38-7.33(m,4H,ArH),7.21-7.17(m,3H,ArH),7.03(s,1H,CH),6.95(s,1H,=CH),6.84-6.79(m,2H ,ArH).HRMS(ESI)for C ₂₄ H ₁₉ N ₃ O ₂ m/z:Calculated,382.1550,Found,382.1556[M+H] ⁺ .

Example 2 (E) Preparation of 1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-methylbenzoate (C2)

Substitute the benzoic acid in step 4) of Example 1 with 2-methylbenzoic acid in the same molar amount, and other operations are the same as in Example 1, to prepare compound (C2).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-methylbenzoate: yellow oil, yield 42.62% ; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.09(s, 1H, triazole-H), 7.98(d, J=7.8Hz, 1H, ArH), 7.66(s, 1H, triazole-H), 7.45- 7.42(m,2H,ArH),7.41-7.31(m,4H,ArH),7.27-7.21(m,2H,ArH),7.20-7.15(m,3H,ArH),7.02(s,1H,CH) ,6.93(s,1H,=CH),6.82-6.79(m,2H,ArH),2.56(s,3H,CH ₃ ).HRMS(ESI)for C ₂₅ H ₂₁ N ₃ O ₂ m/z:Calculated ,396.1707,Found,396.1712[M+H] ⁺ .

Example 3 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-chlorobenzoate (C3)

Substitute the benzoic acid in step 4) of Example 1 with 2-chlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 1 to prepare compound (C3).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-chlorobenzoate: yellow oil, yield 60.21%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.09(s,1H,triazole-H),7.87(dd,J=7.8,1.3Hz,1H,ArH),7.67(s,1H,triazole-H),7.48 -7.41(m,4H,ArH),7.38-7.31(m,4H,ArH),7.23-7.17(m,3H,ArH),7.03(s,1H,CH),6.98(s,1H,=CH) ,6.84-6.77(m,2H,ArH).HRMS(ESI)forC ₂₄ H ₁₈ ClN ₃ O ₂ m/z: Calculated,416.1160,Found,416.1166[M+H] ⁺ .

Example 4 (E) of 1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,4-dichlorobenzoate (C4) preparation

Substitute the benzoic acid in step 4) of Example 1 with 2,4-dichlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C4).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,4-dichlorobenzoate: white oil, yield 42.17%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.09(s,1H,triazole-H),7.85(d,J=8.5Hz,1H,ArH),7.64(s,1H,triazole-H), 7.48 (d, J=2.0Hz, 1H, ArH), 7.44-7.40 (m, 2H, ArH), 7.39-7.33 (m, 3H, ArH), 7.32 (dd, J=8.5, 2.0Hz, 1H, ArH) ),7.23-7.17(m,3H,ArH),7.02(s,1H,CH),6.96(s,1H,=CH),6.84-6.77(m,2H,ArH).HRMS(ESI)for C ₂₄ H ₁₇ Cl ₂ N ₃ O ₂ m/z: Calculated, 450.0771, Found, 450.0776[M+H] ⁺ .

Example 5 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-methoxybenzoate (C5)

Substitute the benzoic acid in step 4) of Example 1 with 3-methoxybenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C5).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-methoxybenzoate: white wax, yield 25.35%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.07 (s, 1H, triazole-H), 8.06-8.02 (m, 2H, ArH), 7.69 (s, 1H, triazole-H), 7.44-7.40 (m, 2H, ArH), 7.37-7.31 (m, 3H, ArH), 7.21-7.16 (m, 3H, ArH), 7.00 (s, 1H, CH), 6.95 (s, 1H, =CH), 6.94 -6.91(m,2H,ArH),6.83-6.79(m,2H,ArH),3.83(s, _3H , _OCH3 ) _.HRMS (ESI)for _{C25H21N3O3 m} /z:Calculated, 412.1656,Found,412.1661[M+H] ⁺ .

Example 6 (E) of 1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,6-dichlorobenzoate (C6) preparation

Substitute the benzoic acid in step 4) of Example 1 with 2,6-dichlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C6).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,6-dichlorobenzoate: yellow oil, yield 47.66%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.08(s,1H,triazole-H),7.78(s,1H,triazole-H),7.52-7.49(m,2H,ArH),7.46-7.41 (m,1H,ArH),7.39-7.35(m,3H,ArH),7.30-7.25(m,2H,ArH),7.21-7.17(m,3H,ArH),7.12(s,1H,CH), 6.87(s,1H,=CH),6.82-6.78(m,2H,ArH).HRMS(ESI)for C ₂₄ H ₁₇ Cl ₂ N ₃ O ₂ m/z: Calculated,450.0771,Found,450.0776[M+ H] ⁺ .

Example 7 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-fluorobenzoate (C7)

Substitute the benzoic acid in step 4) of Example 1 with 2-fluorobenzoic acid in an equivalent molar amount, and other operations are the same as those in Example 1, to prepare compound (C7).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2-fluorobenzoate: yellow oil, yield 56.35%; ¹ HNMR (500MHz, CDCl ₃ )δ: 8.07(s,1H,triazole-H),8.00-7.92(m,1H,ArH),7.72(s,1H,triazole-H),7.55-7.47(m,1H) ,ArH),7.46-7.40(m,2H,ArH),7.38-7.29(m,3H,ArH),7.22-7.10(m,5H,ArH),7.04(s,1H,CH),7.02(s, 1H,=CH),6.86-6.78(m,2H,ArH).HRMS(ESI)for C ₂₄ H ₁₈ FN ₃ O ₂ m/z:Calculated,400.1456,Found,400.1461[M+H] ⁺ .

Example 8 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-fluorobenzoate (C8)

Substitute the benzoic acid in step 4) of Example 1 with 3-fluorobenzoic acid in an equivalent molar amount, and other operations are the same as those in Example 1, to prepare compound (C8).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-fluorobenzoate: yellow oil, yield 58.34%; ¹ H NMR (500MHz, CDCl ₃ )δ:8.09(s,1H,triazole-H),7.90-7.85(m,1H,ArH),7.79-7.74(m,1H,ArH),7.65(s,1H, triazole-H),7.46-7.40(m,3H,ArH),7.39-7.33(m,3H,ArH),7.31-7.26(m,1H,ArH),7.23-7.17(m,3H,ArH),7.02 (s,1H,CH),6.94(s,1H,=CH),6.88-6.78(m,2H,ArH).HRMS(ESI) for C ₂₄ H ₁₈ FN ₃ O ₂ m/z: Calculated, 400.1456, Found,400.1461[M+H] ⁺ .

Example 9 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-methylbenzoate (C9)

Substitute the benzoic acid in step 4) of Example 1 with 4-methylbenzoic acid in the same molar amount, and other operations are the same as in Example 1, to prepare compound (C9).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-methylbenzoate: white oil, yield 44.72% ; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.07(s,1H,triazole-H),7.97(d,J=8.2Hz,2H,ArH),7.69(s,1H,triazole-H),7.45- 7.40(m,3H,ArH),7.36-7.32(m,4H,ArH),7.22-7.16(m,3H,ArH),7.01(s,1H,CH),6.95(s,1H,=CH), 6.84-6.78(m, 2H, ArH), 2.40(s, 3H, CH ₃ ).HRMS(ESI) for C ₂₅ H ₂₁ N ₃ O ₂ m/z: Calculated, 396.1707, Found, 396.1712[M+H] ⁺ .

Example 10 (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,3-dichlorobenzoate (C10) preparation

Substitute the benzoic acid in step 4) of Example 1 with 2,3-dichlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C10).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 2,3-dichlorobenzoate: yellow oil, yield 30.33%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.08(s,1H,triazole-H),8.03(d,J=8.3Hz,2H,ArH),7.71(s,1H,triazole-H), 7.50-7.45(m, 3H, ArH), 7.35-7.31(m, 3H, ArH), 7.21-7.15(m, 3H, ArH), 7.02(s, 1H, CH), 6.95(s, 1H, =CH) ),6.84-6.78(m,2H,ArH).HRMS(ESI)forC ₂₄ H ₁₇ Cl ₂ N ₃ O ₂ m/z:Calculated,450.0771,Found,450.0776[M+H] ⁺ .

Example 11 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-tert-butylbenzoate (C11)

Substitute the benzoic acid in step 4) of Example 1 with 4-tert-butylbenzoic acid in the same molar amount, and other operations are the same as those in Example 1 to prepare compound (C11).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-tert-butylbenzoate: white wax, yield 44.20%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.10 (s, 1H, triazole-H), 7.67 (dd, J=7.8, 1.5 Hz, 1H, ArH), 7.64 (s, 1H, triazole-H) ),7.62(dd,J=8.0,1.5Hz,1H,ArH),7.44-7.41(m,2H,ArH),7.41-7.32(m,4H,ArH),7.29(d,J=7.9Hz,1H ,ArH),7.24-7.20(m,3H,ArH),7.02(s,1H,CH),6.94(s,1H,=CH),6.83-6.80(m,2H,ArH),1.56(s,9H ,t-Bu).HRMS(ESI)forC ₂₈ H ₂₇ N ₃ O ₂ m/z: Calculated,438.2176,Found,438.2182[M+H] ⁺ .

Example 12 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-n-propylbenzoate (C12)

Substitute the benzoic acid in step 4) of Example 1 with 4-n-propylbenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C12).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-n-propylbenzoate: white wax, yield 48.96%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.07(s,1H,triazole-H),8.00(d,J=8.2Hz,2H,ArH),7.69(s,1H,triazole-H), 7.45-7.41(m,2H,ArH),7.36-7.31(m,3H,ArH),7.26(d,J=8.4Hz,2H,ArH),7.22-7.17(m,3H,ArH),7.01(s ,1H,CH),6.95(s,1H,=CH),6.81(dd,J=7.8,1.4Hz,2H,ArH),2.65(t,J=7.5Hz,2H,CH ₂ ),1.71-1.59 (m, 2H, CH ₂ ), 0.94 (t, J=7.3 Hz, 3H, CH ₃ ). HRMS (ESI) for C ₂₇ H ₂₅ N ₃ O ₂ m/z: Calculated, 424.2020, Found, 424.2025 [M +H] ⁺ .

Example 13 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-methoxybenzoate (C13)

Substitute the benzoic acid in step 4) of Example 1 with 4-methoxybenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C13).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-methoxybenzoate: white wax, yield 27.43%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.07(s,1H,triazole-H),8.06-8.02(m,2H,ArH),7.69(s,1H,triazole-H),7.42(d ,J=7.0Hz,2H,ArH),7.36-7.29(m,3H,ArH),7.20-7.15(m,3H,ArH),7.00(s,1H,CH),6.95(s,1H,=CH ), 6.92(d, J=8.9Hz, 2H, ArH), 6.83-6.79(m, 2H, ArH), 3.82(s, 3H, OCH ₃ ). HRMS(ESI) for C ₂₅ H ₂₁ N ₃ O ₃ m/z: Calculated,412.1656,Found,412.1661[M+H] ⁺ .

Example 14 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-methylbenzoate (C14)

Substitute the benzoic acid in step 4) of Example 1 with 3-methylbenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C14).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-methylbenzoate: white oil, yield 55.64% ; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.07(s, 1H, triazole-H), 7.89(d, J=7.6Hz, 2H, ArH), 7.70(s, 1H, triazole-H), 7.46- 7.41(m, 2H, ArH), 7.36-7.30(m, 5H, ArH), 7.20-7.15(m, 3H, ArH), 7.03(s, 1H, CH), 6.95(s, 1H, =CH), 6.83-6.78(m, 2H, ArH), 2.38(s, 3H, CH ₃ ).HRMS(ESI) for C ₂₅ H ₂₁ N ₃ O ₂ m/z: Calculated, 396.1707, Found, 396.1712[M+H] ⁺ .

Example 15 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-fluorobenzoate (C15)

Substitute the benzoic acid in step 4) of Example 1 with 4-fluorobenzoic acid in the same molar amount, and other operations are the same as those in Example 1, to prepare compound (C15).

(E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 4-fluorobenzoate: yellow oil, yield 47.25%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.08(s,1H,triazole-H),7.66(s,1H,triazole-H),7.44-7.39(m,3H,ArH),7.38-7.31(m, 4H, ArH), 7.21-7.15(m, 3H, ArH), 7.13-7.09(m, 2H, ArH), 7.02(s, 1H, CH), 6.95(s, 1H, =CH), 6.83-6.79( m,2H,ArH).HRMS(ESI)for C ₂₄ H ₁₈ FN ₃ O ₂ m/z: Calculated,400.1456,Found,400.1461[M+H] ⁺ .

Example 16 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-nitrobenzoate (C16)

Substitute benzoic acid in step 4) of Example 1 with 3-nitrobenzoic acid in an equivalent molar amount, and other operations are the same as those in Example 1, to prepare compound (C16).

(E)-1,3-Diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-nitrobenzoate: yellow wax, yield 15.16 %; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.95-8.89 (m, 1H, ArH), 8.47-8.43 (m, 1H, ArH), 8.41-8.38 (m, 1H, ArH), 8.11 (s, 1H, triazole-H), 7.68(t, J=8.0Hz, 1H, ArH), 7.63(s, 1H, triazole-H), 7.44-7.37(m, 5H, ArH), 7.25-7.20(m, 3H ,ArH),7.07(s,1H,CH),6.94(s,1H,=CH),6.84-6.81(m,2H,ArH).HRMS(ESI) for C ₂₄ H ₁₈ N ₄ O ₄ m/z :Calculated,427.1401,Found,427.1406[M+H] ⁺ .

Example 17 Preparation of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)allyl 3-nitrobenzoate

1) Synthesis of 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one (II):

Add ɑ-bromoacetophenone (19.90g, 0.10mol) and 1,2,4-triazole (7.60g, 0.11mol) to a 500mL three-necked flask in turn, add 150mL of acetone as a solvent, and control with an ice-salt bath. When the temperature was below 0°C, triethylamine (11.1 g, 0.11 mol) was slowly added dropwise through a constant pressure dropping funnel. After the dropwise addition, the reaction was continued for 1 h, the ice bath was removed, and the stirring was continued for 1 h at room temperature, and the reaction progress was followed by TLC ( _VE A /V _PE =1/1, v/v). After the reaction, the triethylamine hydrochloride generated by the reaction was removed by suction filtration, and the triethylamine hydrochloride was rinsed with acetone. After combining the eluent and the filtrate, a red oil was obtained by precipitation, which was cooled and solidified. 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one represented by formula (II) was obtained by recrystallization from isopropanol;

2) (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)prop-2-ene- Synthesis of 1-keto (Ⅲ-2):

1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethyl- 1-ketone (5.62g, 30.00mol), p-trifluoromethylbenzaldehyde (5.75g, 33.00mmol), add 30mL of toluene as a solvent, dropwise add piperidine (0.20g, 2.35mmol) as a catalyst, heat under reflux for 7h , TLC ( _VE A /V _PE =1/1, v/v) followed the progress of the reaction. After the reaction was completed, it was cooled to room temperature, and the reaction solution was transferred to a separatory funnel. After washing, the layers were separated. The organic phase was washed twice with saturated brine (volume of saturated brine used in each washing was 20 mL), and anhydrous sulfuric acid Dry over sodium, filter, concentrate the filtrate to remove the solvent, and separate and purify the concentrated residue by column chromatography (eluent is 1:1 petroleum ether and ethyl acetate by volume) to obtain (E) represented by formula (III-2) -1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)prop-2-en-1-one;

3) (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)prop-2-ene- Synthesis of 1-ol (IV-2):

(E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)benzene represented by formula (III-2) base) prop-2-en-1-one (2.40g, 7.00mmol) was added to a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, the temperature was controlled at 0°C in an ice bath, and PEG 600 (0.50g, 0.83mmol) was added Then, sodium borohydride (0.42 g, 11.0 mmol) was added in batches with stirring, and the reaction was carried out under ice bath at 0 °C for 4 h, and the reaction progress was followed by TLC ( _VE A /V _PE =1/2, v/v). After the reaction was completed, the reaction solution was desolubilized, 1N hydrochloric acid solution was added dropwise to the precipitation concentrate, extracted three times with dichloromethane (15 mL of dichloromethane was used for each extraction), the organic phases were combined and dried over anhydrous sodium sulfate, Filter, spin dry the solvent to obtain (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-( trifluoromethyl)phenyl)prop-2-en-1-ol;

4) (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allylbenzoic acid Synthesis of Ester (B1):

(E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)benzene represented by formula (IV-2) yl)prop-2-en-1-ol (0.25 g, 0.72 mmol), benzoic acid (0.10 g, 0.80 mmol), DMAP (0.09 g, 0.72 mmol), EDC (0.28 g, 1.44 mmol) were added to 5 mL of dilute In methyl chloride, react at room temperature for 4 h, then transfer the reaction solution to a separatory funnel, wash with water (3×5 mL), then with saturated brine (2×5 mL), dry over anhydrous sodium sulfate, filter, and concentrate the filtrate The solvent is removed, and the concentrated residue is separated and purified by column chromatography (eluent is petroleum ether and ethyl acetate in a volume ratio of 1:1) to obtain the compound of formula (B1).

Wherein, the substituents R ² in the structural formulae of formula (III) and formula (IV) are all trifluoromethyl groups, respectively forming the molecular structures of formula (III-2) and formula (IV-2).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allylbenzoate: Yellow oil, yield 46.37%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.10(s,1H,triazole-H),8.09-8.07(m,2H,ArH),7.67(s,1H,triazole-H) H), 7.59(t, J=7.5Hz, 1H, ArH), 7.49-7.42(m, 6H, ArH), 7.40-7.33(m, 3H, ArH), 7.04(s, 1H, CH), 6.99( s,1H,=CH),6.96(d,J=8.3Hz,2H,ArH).HRMS(ESI)for C ₂₅ H ₁₈ F ₃ N ₃ O ₂ m/z: Calculated,450.1424,Found,450.1423[M +H] ⁺ .

Example 18(E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2- Preparation of methyl benzoate (B2)

Substitute the benzoic acid in step 4) of Example 17 with 2-methylbenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B2).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2-methylbenzene Formate: yellow oil, yield 58.38%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.10(s, 1H, triazole-H), 8.01-7.94(m, 1H, ArH), 7.65(s, 1H, triazole-H), 7.48-7.42(m, 5H, ArH), 7.39-7.33(m, 3H, ArH), 7.26(t, J=7.4Hz, 2H, ArH), 7.03(s, 1H, CH) ), 6.96(s, 2H, ArH), 6.94(s, 1H, =CH), 2.57(s, 3H, CH ₃ ). HRMS(ESI) for C ₂₆ H ₂₀ F ₃ N ₃ O ₂ m/z: Calculated,464.1580,Found,464.1577[M+H] ⁺ .

Example 19 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2- Preparation of Fluorobenzoate (B3)

Substitute the benzoic acid in step 4) of Example 17 with 2-fluorobenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B3).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2-fluorobenzyl Ester: yellow oil, yield 72.35%; ¹ H NMR (500MHz, CDCl ₃ )δ: 8.08(s,1H,triazole-H),8.01-7.94(m,1H,ArH),7.69(s,1H) ,triazole-H),7.61-7.52(m,1H,ArH),7.48-7.42(m,4H,ArH),7.38-7.32(m,3H,ArH),7.23(t,J=7.6Hz,1H, ArH),7.20-7.14(m,1H,ArH),7.07(s,1H,CH),7.04(s,1H,=CH),6.96(d,J=8.2Hz,2H,ArH).HRMS(ESI ) for C ₂₅ H ₁₇ F ₄ N ₃ O ₂ m/z: Calculated,468.1330,Found,468.1327[M+H] ⁺ .

Example 20(E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4- Preparation of tert-butyl benzoate (B4)

Substitute the benzoic acid in step 4) of Example 17 with 4-tert-butylbenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B4).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4-tert-butyl Benzoate: white wax, yield 55.16%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.08 (s, 1H, triazole-H), 8.05-8.01 (m, 2H, ArH), 7.68 ( s,1H,triazole-H),7.50-7.48(m,2H,ArH),7.47-7.42(m,4H,ArH),7.38-7.32(m,3H,ArH),7.03(s,1H,CH) ,6.98(s,1H,=CH),6.95(d,J=8.3Hz,2H,ArH),1.34(s,9H,t-Bu).HRMS(ESI)for C ₂₉ H ₂₆ F ₃ N ₃ O ₂ m/z: Calculated,506.2050,Found,506.2061[M+H] ⁺ .

Example 21 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 3- Preparation of Chlorobenzoate (B5)

Substitute the benzoic acid in step 4) of Example 17 with 3-chlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B5).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 3-chlorobenzyl Ester: yellow oil, yield 48.75%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.10 (s, 1H, triazole-H), 8.04 (t, J=1.8 Hz, 1H, ArH), 7.98- 7.94(m,1H,ArH),7.64(s,1H,triazole-H),7.59-7.55(m,1H,ArH),7.46(d,J=8.3Hz,2H,ArH),7.43-7.36(m ,6H,ArH),7.04(s,1H,CH),6.97(s,2H,ArH),6.95(s,1H,=CH).HRMS(ESI) for C ₂₅ H ₁₇ ClF ₃ N ₃ O ₂ m /z:Calculated,484.1034,Found,484.1028[M+H] ⁺ .

Example 22(E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4- Preparation of n-propyl benzoate (B6)

Substitute the benzoic acid in step 4) of Example 17 with 4-n-propylbenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B6).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4-n-propyl Benzoate: white wax, yield 55.32%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.10 (s, 1H, triazole-H), 8.00 (d, J=8.2 Hz, 2H, ArH) ,7.72(s,1H,triazole-H),7.58(t,J＝7.4Hz,2H,ArH),7.45-7.41(m,3H,ArH),7.40-7.32(m,4H,ArH),7.02( s, 1H, CH), 6.99(s, 1H, =CH), 6.96(d, J=8.2Hz, 2H, ArH), 2.65(t, J=7.5Hz, 2H, CH ₂ ), 1.70-1.61( m, 2H, CH ₂ ), 0.94 (t, J=7.3 Hz, 3H, CH ₃ ). HRMS(ESI) for C ₂₈ H ₂₄ F ₃ N ₃ O ₂ m/z: Calculated, 492.1893, Found, 492.1861[ M+H] ⁺ .

Example 23 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4- Preparation of Methoxybenzoate (B7)

Substitute the benzoic acid in step 4) of Example 17 with 4-methoxybenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B7).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 4-methoxy Benzoate: white wax, yield 44.10%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.08 (s, 1H, triazole-H), 8.06-8.03 (m, 2H, ArH), 7.67 ( s,1H,triazole-H),7.46(d,J=8.3Hz,2H,ArH),7.43-7.40(m,2H,ArH),7.38-7.33(m,3H,ArH),7.00(s,1H ,CH),6.98(s,1H, ₌ CH),6.97-6.94( _m ,4H,ArH),3.86(s, _3H , _OCH3 ) _.HRMS (ESI)for _C26H20F3N3O3 m/z: Calculated,480.1530,Found,480.1530[M+H] ⁺ .

Example 24 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2, Preparation of 4-dichlorobenzoate (B8)

Substitute the benzoic acid in step 4) of Example 17 with 2,4-dichlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B8).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2,4-di Chlorobenzoate: yellow oil, yield 66.16%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.10 (s, 1H, triazole-H), 7.85 (d, J=8.5 Hz, 1H, ArH) ,7.63(s,1H,triazole-H),7.49-7.45(m,3H,ArH),7.39-7.35(m,4H,ArH),7.34-7.31(m,2H,ArH),7.04(s,1H ,CH),7.01(s,1H,=CH),6.95(d,J=8.2Hz,2H,ArH).

Example 25 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 3- Preparation of nitrobenzoate (B9)

Substitute the benzoic acid in step 4) of Example 17 with 3-nitrobenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to obtain compound (B9).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 3-nitrobenzene Formate: white wax, yield 23.17%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.93-8.89 (m, 1H, ArH), 8.48-8.43 (m, 1H, ArH), 8.40 (d ,J=7.9Hz,1H,ArH),8.13(s,1H,triazole-H),7.70(t,J=8.0Hz,1H,ArH),7.67(s,1H,triazole-H),7.49-7.39 (m, 7H, ArH), 7.09 (s, 1H, CH), 6.99 (s, 1H, =CH), 6.98 (d, J = 8.3 Hz, 2H, ArH). HRMS (ESI) for C ₂₅ H ₁₇ F ₃ N ₄ O ₄ m/z: Calculated, 495.1275, Found, 495.1271[M+H] ⁺ .

Example 26 (E)-1-phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2, Preparation of 3-dichlorobenzoate (B10)

Substitute benzoic acid in step 4) of Example 17 with 2,3-dichlorobenzoic acid in the same molar amount, and other operations are the same as those in Example 17, to prepare compound (B10).

(E)-1-Phenyl-2-(1H-1,2,4-triazol-1-yl)-3-(4-(trifluoromethyl)phenyl)allyl 2,3-di Chlorobenzoate: yellow oil, yield 33.25%; ¹ H NMR (500 MHz, CDCl ₃ ) δ: 8.11 (s, 1H, triazole-H), 7.67 (dd, J=7.8, 1.6 Hz, 1H, ArH), 7.64(s, 1H, triazole-H), 7.47(d, J=8.3Hz, 2H, ArH), 7.45-7.42(m, 2H, ArH), 7.41-7.36(m, 3H, ArH), 7.31-7.27(m,2H,ArH),7.04(s,1H,CH),6.99(s,1H,=CH),6.95(d,J=8.3Hz,2H,ArH).HRMS(ESI)for C ₂₅ H ₁₆ Cl ₂ F ₃ N ₃ O ₂ m/z: Calculated, 518.0644, Found, 518.0644[M+H] ⁺ .

Example 27 Bactericidal activity test

Test objects: Alternari assolani, Gibberellazeae, Phytophthora infestans, Phytophthoracapsici, Sclerotinia sclerotiorum, Botrytis cucumber (Phytophthora infestans) Botrytis cinerea), Rhizoctonia solani, Fusarium oxysporum, Cercospora arachidicola, Physalosporapiricola.

The compounds represented by formulas (C1) to (C16) prepared in Examples 1 to 16 and the compounds represented by formulas (B1) to (B10) prepared in Examples 17 to 26 were respectively marked as compounds to be tested, and the The bactericidal activity test was performed in the following ways:

Experimental treatment: each compound to be tested was dissolved in DMSO into a 1% EC stock solution for later use. The inhibition zone method was used to evaluate the indoor bactericidal activity of the tested compounds against the test target at a dose of 50 ppm. A solvent clear water control (QCK) and a fluoxamid control (YCK) with an effective content of 50 ppm were also set up.

Test method: suck 150 microliters of the EC mother solution prepared above with a pipette, dissolve it in 2.85 mL of Tween water, and prepare a medicinal solution with an effective concentration of 500 ppm of the compound to be tested. Pipette 1mL of liquid medicine into a sterilized petri dish, then put 9mL of PDA medium, shake well, and cool. Use a hole punch to punch out the circular bacterial cake and pick it to the center of the petri dish with an inoculating needle, then place the petri dish in an incubator at 27°C for cultivation, and measure the colony diameter after 48 to 72 hours. The pure growth of the colony is the difference between the average diameter of the colony and the diameter of the bacterial cake, and the calculation method of the bacteriostatic rate (%) is calculated by referring to the following formula.

The pure growth of the control colony in the above calculation formula refers to the pure growth of the colony under the clear water control (QCK) test.

The bactericidal activity test results are shown in Table 1.

Table 1 Bactericidal activity (% control effect) of each compound at 50 ppm

It can be seen from the table that the C series compounds showed a good inhibitory rate on rape sclerotium, and most of the compounds had an inhibitory rate of more than 60%. Among them, C1, C7, and C14 had an inhibitory rate of more than 70% on rape sclerotium. The antibacterial rate of C8 and C13 to rice sheath blight also exceeded 60%, and the antibacterial rate of C7, C11, C13, and C16 to apple ring striae reached 58.3%, but they were not as good as the control agent fluoxamid.

It can be seen from the table that the compounds in the B series all showed a certain activity, among which the compounds B1, B2, B3, B5, B6, B7, B8, and B9 all had more than 50% inhibition rates on rape sclerotia, and B7 had an inhibitory effect on the sclerotium of wheat. The inhibition rate of B1, B3, B6, and B7 for rice sheath blight exceeded 50%. Overall, the bactericidal activity of the B series is not very ideal. The control rate of Phytophthora capsicum was higher than that of Fluconazole, and the control rate of some compounds was also higher than that of Fluconazole.

The content described in this specification is only an enumeration of the realization forms of the inventive concept, and the protection scope of the present invention should not be regarded as being limited to the specific forms stated in the embodiments.

Claims (9)

1. a novel allyl benzoate compound containing triazole is characterized in that its structural formula is as shown in formula (I):

In formula (I): the substituent R ¹ is a phenyl group or a substituted phenyl group, the number of substituent groups on the benzene ring of the substituted phenyl group is one or more, and each substituent group is independently selected from H, halogen, C1 -C4 alkyl, methoxy or nitro; substituent R ² is hydrogen or trifluoromethyl. 2. a kind of novel allyl benzoate compound containing triazole as claimed in claim 1 is characterized in that in formula (I) R ¹ is one of the following: phenyl, 2-methylphenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 3-methoxyphenyl, 2,6-dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-methylphenyl , 2,3-dichlorophenyl, 4-tert-butylphenyl, 4-n-propylphenyl, 4-methoxyphenyl, 3-methylphenyl, 4-fluorophenyl, 3-nitrophenyl phenyl, 3-chlorophenyl. 3. the preparation method of a kind of novel allyl benzoate compound containing triazole as claimed in claim 1 or 2, is characterized in that comprising the following steps: 1) ɑ-Bromoacetophenone and 1,2,4-triazole are mixed in organic solvent A, the temperature is controlled to below 0°C, after triethylamine is added dropwise, the reaction is stirred at room temperature, and the reaction progress is tracked by TLC After the reaction is finished, suction filtration removes the triethylamine hydrochloride that the reaction generates, and after the filtrate is desolubilized, the 1-phenyl-2-(1H-1 shown in the formula (II) is obtained by recrystallization with the organic solvent B. ,2,4-triazol-1-yl)ethan-1-one;

2) 1-phenyl-2-(1H-1,2,4-triazol-1-yl)ethan-1-one, benzaldehyde or p-trifluoromethyl represented by formula (II) obtained in step 1) Benzaldehyde and piperidine are heated and refluxed in organic reagent C, and the reaction process is tracked by TLC; after the reaction is completed, cooled to room temperature, the reaction solution is transferred to a separatory funnel, washed with water and layered, and the organic phase is then saturated brine. After washing 1-3 times, it is dried over anhydrous sodium sulfate, filtered, the filtrate is concentrated to remove the solvent, and the concentrate is separated and purified by column chromatography to obtain (E)-1,3-diphenyl shown in formula (III). base-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one compounds;

3) (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-ene-1 represented by formula (III) obtained in step 2) -The ketone compound is dispersed in the organic reagent D, PEG 600 and sodium borohydride are added, the reaction is stirred under the condition of ice bath at 0°C, and the reaction progress is tracked by TLC; 0.5-2N hydrochloric acid solution was added dropwise, extracted with organic reagent E, and the organic phases were combined, then dried over anhydrous sodium sulfate, filtered, and spin-dried for solvent treatment to obtain (E)-1,3- as shown in formula (IV). Diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol compounds;

4) (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-ene represented by formula (IV) obtained in step 3) The -1-alcohol compounds were dispersed in the organic reagent F, and DMAP, EDC and substituted benzoic acid were added, the reaction was stirred at room temperature, and the reaction progress was tracked by TLC; Sodium drying, filtration, separation and purification by column chromatography to obtain a novel triazole-containing allyl benzoate compound as shown in formula (I); Wherein, the R ¹ is phenyl or substituted phenyl, the number of substituents on the benzene ring of the substituted phenyl is one or more, and each substituent is independently selected from H, halogen, C1-C4 alkyl , methoxy or nitro; substituent R ² is hydrogen or trifluoromethyl. 4. the preparation method of a kind of novel allyl benzoate compound containing triazole as claimed in claim 3, it is characterized in that the organic solvent A in step 1) is a ketone solvent, preferably acetone; organic solvent; B is an alcohol solvent, preferably isopropanol; the organic solvent C in step 2) is a benzene solvent, preferably toluene; the organic reagent D in step 3) is an alcohol solvent, preferably methanol; in step 3) The organic reagent E and the organic solvent F in step 4) are both dichloromethane. 5. the preparation method of a kind of novel allyl benzoate compound containing triazole as claimed in claim 3, is characterized in that in step 1), described ɑ-bromoacetophenone and 1,2, The molar ratio of 4-triazole is 1:1.1-1.5; in step 2), 1-phenyl-2-(1H-1,2,4-triazol-1-yl represented by formula (II) ) The molar ratio of ethan-1-one and (p-trifluoromethyl)benzaldehyde is 1:1.1 to 1.5; in step 3), (E)-1,3-diphenyl shown in formula (III) The molar ratio of -2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one compound and sodium borohydride is 1:1.1～1.5; in step 4), (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol compounds represented by formula (IV) and substituted The molar ratio of benzoic acid is 1:1.1～1.5. 6. the preparation method of a kind of novel allyl benzoate compound containing triazole as claimed in claim 3, it is characterized in that in step 1), the volumetric consumption of organic solvent A is with the amount of ɑ-bromoacetophenone. The amount of the substance is calculated as 1～2mL/mmol, and the volume dosage of the organic solvent C in step 2) is 1-phenyl-2-(1H-1,2,4-triazole-1- (E)-1,3-diphenyl-(E)-1,3-diphenyl- The amount of 2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-one compounds is calculated as 2～3mL/mmol, the volume of organic solvent F in step 4) The amount of (E)-1,3-diphenyl-2-(1H-1,2,4-triazol-1-yl)prop-2-en-1-ol compound represented by formula (IV) The amount of the substance was calculated to be 6 to 8 mL/mmol. 7. the preparation method of a kind of novel allyl benzoate compound containing triazole as claimed in claim 3, it is characterized in that the eluent of step 2) and step 4) middle column chromatography separation all adopts volume Mixture of ethyl acetate and petroleum ether in a ratio of 1:0.5 to 2. 8. The application of a novel triazole-containing allyl benzoate compound in the preparation of fungicides as claimed in claim 1 or 2. 9 . The application according to claim 8 , wherein the novel triazole-containing allyl benzoate compound is used to prepare a bactericide for inhibiting Sclerotinia sclerotiorum. 10 .