CN111574466B - A kind of allyl benzoate compound containing triazole and preparation method and application thereof - Google Patents

A kind of allyl benzoate compound containing triazole and preparation method and application thereof Download PDF

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CN111574466B
CN111574466B CN202010504490.4A CN202010504490A CN111574466B CN 111574466 B CN111574466 B CN 111574466B CN 202010504490 A CN202010504490 A CN 202010504490A CN 111574466 B CN111574466 B CN 111574466B
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刘幸海
余陈升
王翰
余玮
武宏科
翁建全
谭成侠
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Zhejiang University of Technology ZJUT
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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Abstract

本发明公开了一种新型含三唑的烯丙基苯甲酸酯类化合物及其制备方法和应用，新型含三唑的烯丙基苯甲酸酯类化合物的结构式如式(Ⅰ)所示：

Figure DDA0002526045180000011
式(Ⅰ)中：取代基R1为苯基或取代苯基，所述取代苯基的苯环上的取代基数量为一个或多个，各个取代基各自独立地选自H、卤素、C1‑C4烷基、甲氧基或硝基；取代基R2为氢或三氟甲基。本发明公开的新型含三唑的烯丙基苯甲酸酯类化合物为具有杀菌活性的新化合物，其在50ppm浓度下对油菜菌核病菌有较好的抑制率，为新农药的研发提供了基础。The invention discloses a novel triazole-containing allyl benzoate compound and a preparation method and application thereof. The structural formula of the novel triazole-containing allyl benzoate compound is shown in formula (I):
Figure DDA0002526045180000011
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. The novel triazole-containing allyl benzoate compound disclosed in the invention is a novel compound with bactericidal activity, which has a good inhibition rate against Sclerotinia sclerotiorum at a concentration of 50 ppm, and provides a basis for the research and development of new pesticides .

Description

Allyl benzoate compound containing triazole as well as preparation method and application thereof
Technical Field
The invention relates to an allyl benzoate compound containing triazole and a preparation method and application thereof.
Background
The nitrogen-containing heterocyclic compound has wide biological activity, and is therefore significant in the process of pesticide preparation. The triazole fungicide belongs to an organic heterocyclic nitrogen compound, is an ergosterol synthesis inhibitor and has good control effect on most fungal diseases harmful to the growth of crops. Over the last several decades, triazole bactericides occupy a huge market due to the advantages of high efficiency, broad spectrum, low toxicity and the like, and due to the fact that most triazole bactericides have the plant growth regulating function, research on triazole antifungal medicines is concerned. To date, several tens of thousands of triazole compounds have been synthesized one after another, and most of them are 1,2, 4-triazole compounds, and the varieties that have been commercialized are more than 40, such as triadimefon (triadimifon), triadimenol (triadiminol), propiconazole (propiconazole), Paclobutrazol (Paclobutrazol), and the like. With the frequent use of triazole fungicides in agriculture, some disadvantages are revealed, and the single active site of the triazole fungicides loses high efficiency due to the fact that the triazole fungicides are more and more resistant to the fungi due to the frequent use.
The design and synthesis of the novel triazole bactericide have important significance for developing novel pesticides with high efficiency, low toxicity and low residue.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to provide a triazole-containing allyl benzoate compound and a preparation method and application thereof. The invention designs and synthesizes triazole series compounds based on that an uniconazole structure is taken as a matrix, a benzene ring, a triazole ring and a carbon-carbon double bond of the uniconazole are kept unchanged, chlorine on the benzene ring is replaced by hydrogen and trifluoromethyl, a tert-butyl group of the uniconazole is replaced by the benzene ring, an ester group and an aromatic ring are introduced on a hydroxyl group to synthesize an ester compound so as to investigate the influence on the biological activity of the compound.
The allyl benzoate compound containing triazole is characterized in that the structural formula is shown as the formula (I):
Figure GDA0003030913650000021
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 allyl benzoate compound containing triazole is characterized in that R in the formula (I)1Is 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, 3-chlorophenyl.
The preparation method of the allyl benzoate compound containing triazole is characterized by comprising the following steps:
1) alpha-bromoacetophenone and 1,2, 4-triazole are mixed in an organic solvent A, the temperature is controlled to be below 0 ℃, triethylamine is dropwise added, the mixture is stirred at room temperature for reaction, and the reaction process is tracked by TLC; after the reaction is finished, filtering to remove triethylamine hydrochloride generated in the reaction, and after desolventizing the filtrate, recrystallizing the filtrate by using an organic solvent B to prepare 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethane-1-ketone shown in a formula (II);
Figure GDA0003030913650000031
2) heating 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) obtained in the step 1), benzaldehyde or p-trifluoromethylbenzaldehyde and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; after the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, washing with water, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and carrying out column chromatography separation and purification treatment on the concentrate to obtain the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III);
Figure GDA0003030913650000032
3) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) obtained in the step 2) in an organic reagent D, adding PEG 600 and sodium borohydride, stirring and reacting under the ice bath condition of 0 ℃, and tracking the reaction process by TLC; after the reaction is finished, desolventizing the reaction solution, dropwise adding 0.5-2N hydrochloric acid solution into the desolventized concentrate, extracting by using an organic reagent E, combining organic phases, drying by using anhydrous sodium sulfate, filtering, and treating by using a spin-dried solvent to obtain a (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as a formula (IV);
Figure GDA0003030913650000041
4) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding DMAP, EDC and substituted benzoic acid, stirring at room temperature for reaction, and tracking the reaction process by TLC; after the reaction is finished, washing with water, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain the allyl benzoate compound containing triazole as shown in the formula (I);
wherein, R is1Is 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 preparation method of the allyl benzoate compound containing triazole is characterized in that the organic solvent A in the step 1) is a ketone solvent, preferably acetone; the organic solvent B is an alcohol solvent, 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 organic solvent F in the step 4) are both dichloromethane.
The preparation method of the allyl benzoate compound containing triazole is characterized in that in the step 1), the feeding molar ratio of the alpha-bromoacetophenone to the 1,2, 4-triazole is 1: 1.1-1.5; in the step 2), the feeding molar ratio of 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) to (p-trifluoromethyl) benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) to the sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as the formula (IV) to the substituted benzoic acid is 1: 1.1-1.5.
The preparation method of the allyl benzoate compound containing triazole is characterized in that the volume usage of the organic solvent A in the step 1) is 1-2 mL/mmol based on the mass of alpha-bromoacetophenone, the volume usage of the organic solvent C in the step 2) is 1-1.5 mL/mmol based on the mass of 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one shown in the formula (II), the volume usage of the organic solvent D in the step 3) is 2-3 mL/mmol based on the mass of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III), the volume usage amount of the organic solvent F in the step 4) is 6-8 mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol compound shown in the formula (IV).
The preparation method of the allyl benzoate compound containing triazole is characterized in that eluant for column chromatography separation in the steps 2) and 4) adopts a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 0.5-2.
The allyl benzoate compound containing triazole is applied to preparation of bactericides.
Furthermore, the allyl benzoate compound containing triazole is used for preparing a bactericide for inhibiting sclerotinia sclerotiorum.
The synthesis process route of the allyl benzoate compound containing triazole is as follows:
Figure GDA0003030913650000061
compared with the prior art, the invention has the following beneficial effects: the invention provides an allyl benzoate compound containing triazole, a preparation method thereof and application thereof in preparing a bactericide, wherein the preparation method is simple and convenient to operate, the obtained compound has the best inhibition activity on sclerotinia sclerotiorum under the effective concentration of 50ppm, and the inhibition rate reaches 71.4%.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
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):
alpha-bromoacetophenone (19.90g,0.10mol) and 1,2, 4-triazole (7.60g,0.11mol) are sequentially added into a 500mL three-neck flask, 150mL of acetone is added as a solvent, an ice salt bath is used for controlling the temperature below 0 ℃, and triethylamine (11.13g,0.11mol) is slowly dropped through a constant-pressure dropping funnel. After the addition, the reaction was continued for 1h, the ice bath was removed, stirring was continued for 1h at room temperature, TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, filtering to remove triethylamine hydrochloride generated by the reaction, leaching the triethylamine hydrochloride with acetone, combining leacheate and filtrate, desolventizing to obtain red oily matter, cooling and solidifying, and recrystallizing with 20mL of isopropanol to obtain 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II);
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) ethan-1-one (5.62g,30.00mmol) represented by the formula (II), benzaldehyde (3.50g,33.00mmol) were added in one portion to a 100mL three-necked flask equipped with a water separator, a thermometer and a condenser, 30mL of toluene was added as a solvent, piperidine (0.20g,2.35mmol) was added dropwise as a catalyst, and the mixture was heated under reflux for 6 hours and TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction, the reaction solution was cooled to room temperature, the reaction solution was transferred to a separatory funnel, washed with water and then separated into layers, the organic phase was washed twice with saturated brine (the volume of the saturated brine used in each washing was 20mL), dried over anhydrous sodium sulfate, filtered,concentrating the filtrate to remove solvent, and purifying the concentrated residue by column chromatography (eluent is petroleum ether and ethyl acetate at a volume ratio of 1: 1) to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one shown in formula (III-1);
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) represented by the formula (III-1) was added to a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, the temperature in ice bath was controlled at 0 ℃, PEG 600(0.50g,0.83mmol) was added, then sodium borohydride (0.42g,11.00mmol) was added in portions under stirring, and reaction was carried out for 4 hours in ice bath at 0 ℃ by TLC (V-1)EA/VPE1/2, v/v) followed the progress of the reaction. After the reaction is finished, desolventizing the reaction solution, dropwise adding 1N hydrochloric acid solution into the desolventized concentrate, extracting with dichloromethane for three times (15 mL of dichloromethane is used for each extraction), combining organic phases, drying by anhydrous sodium sulfate, filtering, and spin-drying the solvent to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol shown as a formula (IV-1);
4) synthesis of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl benzoate (C1):
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) propan-2-en-1-ol (0.20g, 0.72mmol) represented by the formula (IV-1), benzoic acid (0.10g, 0.80mmol), DMAP (0.09g, 0.72mmol), EDC (0.28g, 1.44mmol) were added to 5mL of dichloromethane, reacted at room temperature for 4 hours, and then the reaction solution was transferred to a separatory funnel, washed with water (3X 5mL), washed with saturated brine (2X 5mL), dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated to remove the solvent, and the concentrated residue was purified by separation with an eluent of petroleum ether and ethyl acetate at a volume ratio of 1:1 to obtain a compound (C1).
Wherein the substituent R in the structural formulas of the formula (III) and the formula (IV)2Are both hydrogen, and form the molecular structures of formula (III-1) and formula (IV-1), respectively.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl benzoate: yellow oil, yield 52.36%;1H NMR(500MHz,CDCl3)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 C24H19N3O2m/z:Calculated,382.1550,Found,382.1556[M+H]+.
example 2 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-methylbenzoate (C2)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 2-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C2).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-methylbenzoate: yellow oil, yield 42.62%;1H NMR(500MHz,CDCl3)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,CH3).HRMS(ESI)for C25H21N3O2 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)
The procedure of example 1 was otherwise the same as that of example 1 except that the benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 2-chlorobenzoic acid, to obtain a compound (C3).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-chlorobenzoate: yellow oil, yield 60.21%;1H NMR(500MHz,CDCl3)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)for C24H18ClN3O2m/z:Calculated,416.1160,Found,416.1166[M+H]+.
EXAMPLE 4 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 4-dichlorobenzoate (C4)
The compound (C4) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 4-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 4-dichlorobenzoate: white oil, yield 42.17%;1H NMR(500MHz,CDCl3)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 C24H17Cl2N3O2 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)
The compound (C5) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-methoxybenzoic acid and the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methoxybenzoate: white wax, yield 25.35%;1H NMR(500MHz,CDCl3)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 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 6-dichlorobenzoate (C6)
The compound (C6) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 6-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 6-dichlorobenzoate: yellow oil, yield 47.66%;1H NMR(500MHz,CDCl3)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 C24H17Cl2N3O2 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)
The compound (C7) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2-fluorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2-fluorobenzoate: yellow oil, yield 56.35%;1HNMR(500MHz,CDCl3)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 C24H18FN3O2 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)
The compound (C8) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-fluorobenzoic acid and performing the same procedures as in example 1.
(E) 1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-fluorobenzoate as a yellow oil in a yield of 58.34%;1H NMR(500MHz,CDCl3)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 C24H18FN3O2 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)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 4-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C9).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methylbenzoate as white oil, yield 44.72%;1H NMR(500MHz,CDCl3)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,CH3).HRMS(ESI)for C25H21N3O2 m/z:Calculated,396.1707,Found,396.1712[M+H]+.
EXAMPLE 10 preparation of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 3-dichlorobenzoate (C10)
The compound (C10) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 2, 3-dichlorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 2, 3-dichlorobenzoate: yellow oil, yield 30.33%;1H NMR(500MHz,CDCl3)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)for C24H17Cl2N3O2 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)
The same operation as in example 1 was carried out except that benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 4-tert-butylbenzoic acid, to obtain a compound (C11).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-tert-butylbenzoate: white wax, yield 44.20%;1H NMR(500MHz,CDCl3)δ:8.10(s,1H,triazole-H),7.67(dd,J＝7.8,1.5Hz,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)for C28H27N3O2 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)
The compound (C12) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-n-propylbenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-n-propylbenzoate: white wax, yield 48.96%;1H NMR(500MHz,CDCl3)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,CH2),1.71-1.59(m,2H,CH2),0.94(t,J＝7.3Hz,3H,CH3).HRMS(ESI)for C27H25N3O2 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)
The compound (C13) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-methoxybenzoic acid and the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-methoxybenzoate: white wax, yield 27.43%;1H NMR(500MHz,CDCl3)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,OCH3).HRMS(ESI)for C25H21N3O3 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)
The benzoic acid in step 4) of example 1 was replaced with an equimolar amount of 3-methylbenzoic acid, and the other operations were the same as in example 1 to obtain a compound (C14).
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-methylbenzoate: white oil, yield 55.64%;1H NMR(500MHz,CDCl3)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,CH3).HRMS(ESI)for C25H21N3O2 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)
The compound (C15) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 4-fluorobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 4-fluorobenzoate: yellow oil, yield 47.25%;1H NMR(500MHz,CDCl3)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 C24H18FN3O2m/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)
The compound (C16) was obtained by substituting benzoic acid in step 4) of example 1 with an equimolar amount of 3-nitrobenzoic acid and performing the same procedures as in example 1.
(E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl 3-nitrobenzoate: yellow wax, yield 15.16%;1H NMR(500MHz,CDCl3)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 C24H18N4O4 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):
alpha-bromoacetophenone (19.90g,0.10mol) and 1,2, 4-triazole (7.60g,0.11mol) are sequentially added into a 500mL three-neck flask, 150mL of acetone is added as a solvent, an ice salt bath is used for controlling the temperature below 0 ℃, and triethylamine (11.1g,0.11mol) is slowly dropped through a constant-pressure dropping funnel. After the addition, the reaction was continued for 1h, the ice bath was removed, stirring was continued for 1h at room temperature, TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, filtering to remove triethylamine hydrochloride generated by the reaction, leaching the triethylamine hydrochloride with acetone, combining leacheate and filtrate, desolventizing to obtain red oily matter, cooling and solidifying, and recrystallizing with 20mL of isopropanol to obtain 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II);
2) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one (III-2):
a100 mL three-necked flask equipped with a water separator, a thermometer and a condenser was charged with 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (5.62g,30.00mol) represented by the formula (II), p-trifluoromethylbenzaldehyde (5.75g,33.00mmol), 30mL toluene as a solvent, piperidine (0.20g,2.35mmol) as a catalyst, and the mixture was heated under reflux for 7 hours and TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. After the reaction is finished, cooling toTransferring the reaction solution into a separating funnel at room temperature, washing with water, then carrying out layering, washing an organic phase with saturated saline water twice (the volume of the saturated saline water adopted in each washing is 20mL), drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and carrying out column chromatography separation and purification on a concentrated residue (eluent is petroleum ether and ethyl acetate with the volume ratio of 1: 1) to obtain (E) -1-phenyl-2- (1H-1,2, 4-triazole-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-ene-1-one shown in formula (III-2);
3) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-ol (IV-2):
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-en-1-one (2.40g,7.00mmol) represented by the formula (III-2) was charged into a 50mL round-bottomed flask, 15mL of methanol was added as a solvent, temperature was controlled at 0 ℃ in ice bath, PEG 600(0.50g,0.83mmol) was added, then sodium borohydride (0.42g,11.0mmol) was added in portions under stirring, and reaction was carried out for 4 hours in ice bath at 0 ℃ by TLC (V-2)EA/VPE1/2, v/v) followed the progress of the reaction. After the reaction is finished, desolventizing the reaction solution, dropwise adding 1N hydrochloric acid solution into the desolventized concentrate, extracting with dichloromethane for three times (15 mL of dichloromethane is used for each extraction), combining organic phases, drying through anhydrous sodium sulfate, filtering, and spin-drying the solvent to obtain (E) -1-phenyl-2- (1H-1,2, 4-triazole-1-yl) -3- (4- (trifluoromethyl) phenyl) prop-2-ene-1-ol shown as a formula (IV-2);
4) synthesis of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl benzoate (B1):
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) propan-2-en-1-ol represented by the formula (IV-2) (0.25g, 0.72mmol), benzoic acid (0.10g, 0.80mmol), DMAP (0.09g, 0.72mmol), EDC (0.28g, 1.44mmol) were added to 5mL of dichloromethane, reacted at room temperature for 4 hours, and then the reaction mixture was transferred to a separatory funnel, washed with water (3X 5mL), washed with saturated brine (2X 5mL), dried over anhydrous sodium sulfate, filtered, the filtrate was concentrated to remove the solvent, and the concentrated residue was purified by column chromatography (eluent was petroleum ether and ethyl acetate in a volume ratio of 1: 1) to obtain a compound of the formula (B1).
Wherein formula (III) andsubstituent R in the structural formula of formula (IV)2Are trifluoromethyl groups, and respectively form the molecular structures of a formula (III-2) and a formula (IV-2).
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl benzoate: yellow oil, yield 46.37%;1H NMR(500MHz,CDCl3)δ:8.10(s,1H,triazole-H),8.09-8.07(m,2H,ArH),7.67(s,1H,triazole-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 C25H18F3N3O2 m/z:Calculated,450.1424,Found,450.1423[M+H]+.
example 18 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-methylbenzoate (B2)
The compound (B2) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2-methylbenzoic acid and the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-methylbenzoate: yellow oil, yield 58.38%;1H NMR(500MHz,CDCl3)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,CH3).HRMS(ESI)for C26H20F3N3O2 m/z:Calculated,464.1580,Found,464.1577[M+H]+.
example 19 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-fluorobenzoate (B3)
The compound (B3) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2-fluorobenzoic acid and the same procedures used in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2-fluorobenzoate: yellow oil, yield 72.35%;1H NMR(500MHz,CDCl3)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 C25H17F4N3O2 m/z:Calculated,468.1330,Found,468.1327[M+H]+.
example 20 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-tert-butylbenzoate (B4)
The compound (B4) was obtained in the same manner as in example 17 except that the benzoic acid in step 4) of example 17 was replaced with an equimolar amount of 4-tert-butylbenzoic acid.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-tert-butylbenzoate: white wax, yield 55.16%;1H NMR(500MHz,CDCl3)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 C29H26F3N3O2 m/z:Calculated,506.2050,Found,506.2061[M+H]+.
example 21 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-chlorobenzoate (B5)
The procedure of example 17 was otherwise the same as that of example 17 except that the benzoic acid in step 4) of example 17 was replaced with an equimolar amount of 3-chlorobenzoic acid, to obtain a compound (B5).
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-chlorobenzoate: yellow oil, yield 48.75%;1H NMR(500MHz,CDCl3)δ:8.10(s,1H,triazole-H),8.04(t,J＝1.8Hz,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 C25H17ClF3N3O2 m/z:Calculated,484.1034,Found,484.1028[M+H]+.
example 22 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-n-propylbenzoate (B6)
The compound (B6) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 4-n-propylbenzoic acid and conducting the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-n-propylbenzoate: white wax, yield 55.32%;1H NMR(500MHz,CDCl3)δ:8.10(s,1H,triazole-H),8.00(d,J＝8.2Hz,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,CH2),1.70-1.61(m,2H,CH2),0.94(t,J＝7.3Hz,3H,CH3).HRMS(ESI)for C28H24F3N3O2 m/z:Calculated,492.1893,Found,492.1861[M+H]+.
example 23 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-methoxybenzoate (B7)
The compound (B7) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 4-methoxybenzoic acid and the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 4-methoxybenzoate: white wax, yield 44.10%;1H NMR(500MHz,CDCl3)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 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 4-dichlorobenzoate (B8)
The compound (B8) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2, 4-dichlorobenzoic acid and carrying out the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 4-dichlorobenzoate as a yellow oil in 66.16% yield;1H NMR(500MHz,CDCl3)δ:8.10(s,1H,triazole-H),7.85(d,J＝8.5Hz,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 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-nitrobenzoate (B9)
The compound (B9) was obtained by substituting benzoic acid in step 4) of example 17 with the equimolar amount of 3-nitrobenzoic acid and performing the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 3-nitrobenzoate as white wax in 23.17% yield;1H NMR(500MHz,CDCl3)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＝8.3Hz,2H,ArH).HRMS(ESI)for C25H17F3N4O4 m/z:Calculated,495.1275,Found,495.1271[M+H]+.
example 26 preparation of (E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 3-dichlorobenzoate (B10)
The compound (B10) was obtained by substituting benzoic acid in step 4) of example 17 with an equimolar amount of 2, 3-dichlorobenzoic acid and carrying out the same procedures as in example 17.
(E) -1-phenyl-2- (1H-1,2, 4-triazol-1-yl) -3- (4- (trifluoromethyl) phenyl) allyl 2, 3-dichlorobenzoate: yellow oil, yield 33.25%;1H NMR(500MHz,CDCl3)δ:8.11(s,1H,triazole-H),7.67(dd,J＝7.8,1.6Hz,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 C25H16Cl2F3N3O2 m/z:Calculated,518.0644,Found,518.0644[M+H]+.
example 27 bactericidal Activity test
Test subjects: tomato early blight (Alternaria solani), wheat scab (Gibberella zeae), potato late blight (Phytophthora infestans), Phytophthora capsici (Phytophthora capsici), sclerotium napellum (Sclerotinia sclerotiorum), cucumber gray mold (Botrytis cinerea), Rhizoctonia solani (Rhizoctonia solani), cucumber Fusarium oxysporum (Fusarium oxysporum), peanut brown spot (Cercospora arachidicola), and apple ring rot (Phycospora piricola).
The compounds represented by the formulae (C1) to (C16) prepared in examples 1 to 16 were labeled as test compounds for bactericidal activity test in the following manner, and the compounds represented by the formulae (B1) to (B10) prepared in examples 17 to 26 were labeled as test compounds:
and (3) test treatment: each test compound was dissolved in DMSO to 1% EC stock solution for use. The indoor bactericidal activity of the compound to be tested to the test target under the dosage of 50ppm is evaluated by adopting a bacteriostatic ring method, and a solvent clean water control (QCK) and a fluxapyroxad control (YCK) with the effective content of 50ppm are additionally arranged.
The test method comprises the following steps: 150 microliter of the prepared EC mother liquor is absorbed by a pipette gun and dissolved in 2.85mL of Tween water to prepare a liquid medicine with the effective concentration of the compound to be detected being 500 ppm. Sucking 1mL of the liquid medicine by using a pipette, putting the liquid medicine into a sterilized culture dish, putting 9mL of PDA culture medium into the culture dish, shaking up, and cooling. And (3) beating the round bacterial cake by using a puncher, picking the round bacterial cake to the center of a culture dish by using an inoculating needle, then placing the culture dish in an incubator at 27 ℃ for culture, and measuring the diameter of a bacterial colony after 48-72 hours. The pure growth amount of the bacterial colony is the difference value between the average diameter of the bacterial colony and the diameter of the bacterial cake, and the bacteria inhibition rate (%) calculation method is calculated according to the following formula.
Figure GDA0003030913650000231
The pure growth amount of the control colony in the above calculation formula refers to the pure growth amount of the colony under the test of the clear water control (QCK).
The bactericidal activity test results are shown in table 1.
Table 150 ppm fungicidal Activity of Compounds (% control)
Figure GDA0003030913650000241
As can be seen from the table, the C series compounds show good inhibition rate on the sclerotium rolfsii, and most of the compounds have the inhibition rate of over 60 percent, wherein the inhibition rates of C1, C7 and C14 on the sclerotium rolfsii are over 70 percent, the inhibition rates of C8 and C13 on rice sheath blight are over 60 percent, and the inhibition rates of C7, C11, C13 and C16 on apple ring rot are 58.3 percent, but not as good as that of a control medicament fluxapyroxad.
As shown in the table, the compounds of the B series all show certain activity, wherein the inhibition rates of the compounds B1, B2, B3, B5, B6, B7, B8 and B9 on sclerotium of rape are all over 50 percent, the inhibition rate of the compounds B7 on gibberellic disease of wheat is over 50 percent, the prevention and control rates of the compounds B1, B3, B6 and B7 on rice sheath blight are over 50 percent, the bactericidal activity of the B series is not ideal overall, compared with a control medicament fluxapyroxad, the prevention and control rate on phytophthora capsici is higher than that of fluxad, and the prevention and control rate on gibberellic disease of wheat is higher than that of the fluxad for part of the compounds.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.

Claims (10)

1. The allyl benzoate compound containing triazole is characterized in that the structural formula is shown as the formula (I):
Figure FDA0003030913640000011
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.
2. The allyl benzoate compound containing triazole as claimed in claim 1, wherein R in the formula (I)1Is 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, 3-chlorophenyl.
3. The process for producing a triazole-containing allylbenzoate compound according to claim 1 or 2, comprising the steps of:
1) alpha-bromoacetophenone and 1,2, 4-triazole are mixed in an organic solvent A, the temperature is controlled to be below 0 ℃, triethylamine is dropwise added, the mixture is stirred at room temperature for reaction, and the reaction process is tracked by TLC; after the reaction is finished, filtering to remove triethylamine hydrochloride generated in the reaction, and after desolventizing the filtrate, recrystallizing the filtrate by using an organic solvent B to prepare 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethane-1-ketone shown in a formula (II);
Figure FDA0003030913640000021
2) heating 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) obtained in the step 1), benzaldehyde or p-trifluoromethylbenzaldehyde and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; after the reaction is finished, cooling to room temperature, transferring the reaction liquid into a separating funnel, washing with water, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and carrying out column chromatography separation and purification treatment on the concentrate to obtain the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound shown in the formula (III);
Figure FDA0003030913640000022
3) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) obtained in the step 2) in an organic reagent D, adding PEG 600 and sodium borohydride, stirring and reacting under the ice bath condition of 0 ℃, and tracking the reaction process by TLC; after the reaction is finished, desolventizing the reaction solution, dropwise adding 0.5-2N hydrochloric acid solution into the desolventized concentrate, extracting by using an organic reagent E, combining organic phases, drying by using anhydrous sodium sulfate, filtering, and treating by using a spin-dried solvent to obtain a (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as a formula (IV);
Figure FDA0003030913640000023
4) dispersing the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding DMAP, EDC and substituted benzoic acid, stirring at room temperature for reaction, and tracking the reaction process by TLC; after the reaction is finished, washing with water, washing with saturated saline solution, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain the allyl benzoate compound containing triazole as shown in the formula (I);
wherein, R is1Is 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.
4. The process for producing an allylbenzoic acid ester compound containing triazole as claimed in claim 3, wherein the organic solvent A in the step 1) is a ketone solvent; the organic solvent B is an alcohol solvent; the organic solvent C in the step 2) is a benzene solvent; the organic reagent D in the step 3) is an alcohol solvent; the organic reagent E in the step 3) and the organic solvent F in the step 4) are both dichloromethane.
5. The process for producing an allylbenzoic acid ester compound containing triazole as claimed in claim 4, wherein the organic solvent A in the step 1) is acetone; the organic solvent B is isopropanol; the organic solvent C in the step 2) is toluene; the organic reagent D in the step 3) is methanol.
6. The method of claim 3, wherein in step 1), the molar ratio of the alpha-bromoacetophenone to the 1,2, 4-triazole is 1: 1.1-1.5; in the step 2), the feeding molar ratio of 1-phenyl-2- (1H-1,2, 4-triazole-1-yl) ethyl-1-ketone shown in the formula (II) to (p-trifluoromethyl) benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one compound shown as the formula (III) to the sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol compound shown as the formula (IV) to the substituted benzoic acid is 1: 1.1-1.5.
7. The method according to claim 3, wherein the volume of the organic solvent A used in the step 1) is 1 to 2mL/mmol based on the amount of the alpha-bromoacetophenone, the volume of the organic solvent C used in the step 2) is 1 to 1.5mL/mmol based on the amount of the 1-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one represented by the formula (II), the volume of the organic solvent D used in the step 3) is 2 to 3mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one compound represented by the formula (III), the volume usage amount of the organic solvent F in the step 4) is 6-8 mL/mmol based on the amount of the (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-ene-1-ol compound shown in the formula (IV).
8. The method for preparing allyl benzoate compound containing triazole as claimed in claim 3, wherein the eluent for column chromatography separation in step 2) and step 4) is a mixture of ethyl acetate and petroleum ether at a volume ratio of 1: 0.5-2.
9. The use of the allyl benzoate compound containing triazole as claimed in claim 1 or 2 for the preparation of a bactericide.
10. The use according to claim 8, characterized in that the allyl benzoate compound containing triazole is used for the preparation of a fungicide for the inhibition of sclerotinia sclerotiorum.
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