CN111620827A - Novel allyl ether compound containing triazole as well as preparation method and application thereof - Google Patents

Novel allyl ether compound containing triazole as well as preparation method and application thereof Download PDF

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CN111620827A
CN111620827A CN202010505059.1A CN202010505059A CN111620827A CN 111620827 A CN111620827 A CN 111620827A CN 202010505059 A CN202010505059 A CN 202010505059A CN 111620827 A CN111620827 A CN 111620827A
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triazole
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刘幸海
康胜杰
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
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract

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

Description

Novel allyl ether compound containing triazole as well as preparation method and application thereof
Technical Field
The invention relates to a novel allyl ether compound containing triazole and a preparation method and application thereof.
Background
Triazole bactericide belongs to organic heterocyclic compounds, is the largest bactericide, has a basic structure containing hydroxyl/ketone groups, substituted phenyl and 1,2, 4-triazole groups, occupies a great market in recent decades due to the advantages of high efficiency, low toxicity and broad spectrum, and is concerned about the research of triazole antifungal drug types because most triazole bactericides have plant growth regulating function. Up to now, there are systemic bactericides such as triazoles, benzimidazoles, imidazoles and morpholines, and the main systemic bactericides among them are triazole compounds. 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 novel triazole-containing allyl ether compound and a preparation method and application thereof. The invention is based on the uniconazole structure as a matrix, keeps the benzene ring, the triazole ring and the carbon-carbon double bond of the uniconazole unchanged, replaces chlorine on the benzene ring with hydrogen, replaces tert-butyl of the uniconazole with the benzene ring, introduces halide on hydroxyl to synthesize an ether compound so as to investigate the influence on the biological activity of the compound, and designs and synthesizes the triazole series compounds.
The novel allyl ether compound containing triazole is characterized in that the structural formula is shown as the formula (I):
Figure BDA0002526241940000021
in formula (I): r is phenyl, substituted phenyl, methyl acetate or cyclohexane;
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 halogen, cyano or C1-C4 alkyl.
The novel triazole-containing allyl ether compound is characterized in that R in the formula (I) is one of the following compounds: phenyl, 2-chlorophenyl, 2-fluorophenyl, 4-chlorophenyl, 2, 4-dichlorophenyl, 3-fluorophenyl, 4-tert-butylphenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-cyanophenyl, carbomethoxy acetate, 3, 4-dichlorophenyl or cyclohexyl.
The preparation method of the novel allyl ether 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 BDA0002526241940000031
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 and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; cooling to room temperature after the reaction is finished, transferring the reaction liquid into a separating funnel, layering after washing, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown in the formula (III);
Figure BDA0002526241940000032
3) dispersing (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown as a formula (III) obtained in the step 2) in an organic reagent D, adding PEG600 and sodium borohydride, stirring and reacting under the condition of ice bath at 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 with an organic reagent E, combining organic phases, drying with anhydrous sodium sulfate, filtering, and treating with a spin-dried solvent to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol shown in the formula (IV);
Figure BDA0002526241940000041
4) dispersing (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding NaH and halide, stirring for reaction at room temperature, and tracking the reaction process by TLC; after the reaction is finished, washing with water, extracting with an organic reagent G, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, and performing column chromatography separation and purification treatment to obtain the novel triazole-containing allyl ether compound shown in the formula (I);
wherein the halide is substituted benzyl halide, 2-bromoethyl acetate or halogenated methylcyclohexane, the number of the substituent groups on the benzene ring of the substituted benzyl halide is one or more, and each substituent group is independently selected from H, halogen, cyano or C1-C4 alkyl.
The preparation method of the novel allyl ether 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 solvent F in the step 4) is DMF, and the organic reagent E in the step 3) and the organic solvent G in the step 4) are dichloromethane.
The preparation method of the novel triazole-containing allyl ether compound 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 benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown in the formula (III) to sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol shown as the formula (IV) and halide is 1: 1.1-1.5.
The preparation method of the novel triazole-containing allyl ether compound is characterized in that the volume usage of the organic solvent A in the step 1) is 1-2 mL/mmol based on the amount of alpha-bromoacetophenone, the volume usage of the organic solvent C in the step 2) is 1-1.5 mL/mmol based on the amount 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 amount of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-one 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 substance of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol shown in the formula (IV).
The preparation method of the novel triazole-containing allyl ether compound is characterized in that in the step 2) and the step 4), the eluent for column chromatography separation and purification adopts a mixed solution of ethyl acetate and petroleum ether in a volume ratio of 1: 0.5-2.
The novel allyl ether compound containing triazole is applied to preparation of bactericides.
Further, the novel triazole-containing allyl ether compound is used for preparing a bactericide for inhibiting cucumber fusarium wilt.
The synthesis process route of the novel allyl ether compound containing triazole is as follows:
Figure BDA0002526241940000061
compared with the prior art, the invention has the following beneficial effects: the invention provides a novel allyl ether compound containing triazole, a preparation method thereof and application thereof in preparing bactericide, the preparation method is simple and convenient to operate, the obtained compound has the best inhibitory activity on cucumber fusarium wilt bacteria at an effective concentration of 50mg/mL, and the inhibition rate reaches 73.82%.
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- (benzyloxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
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-phenyl-2- (1H-1,2, 4-triazol-1-yl) ethan-1-one (5.62g,30.00mmol) represented by the formula (II), benzyl were sequentially added to a 100mL three-necked flask equipped with a water separator, a thermometer and a condenserAldehyde (3.50g,33.00mmol), 30mL of toluene as a solvent, piperidine (0.20g,2.35mmol) as a catalyst were added dropwise, and the mixture was heated under reflux for 6 hours, TLC (V)EA/VPE1/1, v/v) followed the progress of the reaction. Cooling to room temperature after the reaction is finished, transferring the reaction liquid into a separating funnel, carrying out water washing, layering, washing an organic phase twice with saturated saline solution (the volume of the saturated saline solution adopted in each washing is 20mL), drying with anhydrous sodium sulfate, filtering, concentrating the filtrate to remove a 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, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown in the formula (III);
3) synthesis of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol (IV):
(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) was added to a 50mL round-bottom flask, 15mL methanol was added as a solvent, the temperature in ice bath was controlled at 0 ℃, PEG600(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 4H in ice bath at 0 ℃, TLC (V)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-en-1-ol shown as a formula (IV);
4) synthesis of (E) -1- (3- (benzyloxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole (A1):
(E) -1, 3-Diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol of formula (IV) (0.20g,0.72mmol) was added to 5mL of DMF, NaH (0.02g, 0.83mmol) was added under ice bath, after stirring for 20min, the ice bath was removed, and benzyl bromide (0.18g, 1.05mmol) was added. Reacting at room temperature for 4H, then transferring the reaction liquid into a separating funnel, adding 10mL of water, adding dichloromethane for extraction (3X 15mL), combining organic phases, washing by saturated saline solution (3X 5mL), drying by anhydrous sodium sulfate, filtering, concentrating the filtrate to remove the solvent, and purifying the concentrated residue by column chromatography (eluent is petroleum ether and ethyl acetate with the volume ratio of 1: 1) to obtain (E) -1- (3- (benzyloxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole shown as the formula (A1).
Figure BDA0002526241940000081
(E) -1- (3- (benzyloxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: pale yellow oil, yield 50.14%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),7.59(s,1H,triazole-H),7.48-7.44(m,1H,ArH),7.40-7.31(m,6H,ArH),7.30-7.23(m,3H,ArH),7.24-7.16(m,3H,ArH),6.90(s,1H,＝CH),6.85-6.78(m,2H,ArH),5.48(s,1H,CH),4.72(s,2H,CH2).HRMS(ESI)for C24H21N3O m/z:Calculated,368.1757,Found,368.1763[M+H]+.
example 2 preparation of (E) -1- (3- ((2-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 2-chlorobenzyl bromide and the other procedures were the same as in example 1 to obtain (E) -1- (3- ((2-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 2);
Figure BDA0002526241940000091
(E) -1- (3- ((2-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: light yellow oil, yield 47.35%;1H NMR(500MHz,CDCl3):8.04(s,1H,triazole-H),7.57(s,1H,triazole-H),7.44(dd,J＝7.4,1.8Hz,1H,ArH),7.37-7.33(m,6H,ArH),7.27-7.24(m,2H,ArH),7.21-7.17(m,3H,ArH),6.88(s,1H,＝CH),6.82-6.78(m,2H,ArH),5.46(s,1H,CH),4.71(s,2H,CH2).HRMS(ESI)for C24H20ClN3O m/z:Calculated,402.1368,Found,402.1373[M+H]+.
EXAMPLE 3 preparation of (E) -1- (3- ((2-Fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 2-fluorobenzyl bromide, and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((2-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 3);
Figure BDA0002526241940000101
(E) -1- (3- ((2-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: light yellow oil, yield 33.46%;1H NMR(500MHz,CDCl3):8.04(s,1H,triazole-H),7.56(s,1H,triazole-H),7.43-7.41(m,1H,ArH),7.37-7.34(m,5H,ArH),7.19-7.17(m,2H,ArH),7.14-7.11(m,4H,ArH),6.86(s,1H,＝CH),6.81-6.79(m,2H,ArH),5.42(s,1H,CH),4.69(s,1H,CH2),4.67(s,1H,CH2).HRMS(ESI)for C24H20FN3O m/z:Calculated,386.1663,Found,386.1669[M+H]+.
EXAMPLE 4 preparation of (E) -1- (3- ((4-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 4-chlorobenzyl bromide and the other procedures were the same as in example 1 to obtain (E) -1- (3- ((4-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 4);
Figure BDA0002526241940000111
(E) -1- (3- ((4-chlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: light yellow oil, yield 29.25%;1H NMR(500MHz,CDCl3):8.05(s,1H,triazole-H),7.52(s,1H,triazole-H),7.33-7.29(m,6H,ArH),7.22-7.17(m,5H,ArH),7.17-7.14(m,1H,ArH),6.85(s,1H,＝CH),6.80-6.77(m,2H,ArH),5.38(s,1H,CH),4.58(s,1H,CH2),4.55(s,1H,CH2).HRMS(ESI)for C24H20ClN3O m/z:Calculated,402.1368,Found,402.1373[M+H]+.
EXAMPLE 5 preparation of (E) -1- (3- ((2, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 2, 4-dichlorobenzyl bromide, and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((2, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 5);
Figure BDA0002526241940000112
Figure BDA0002526241940000121
(E) -1- (3- ((2, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: yellow oil, yield 25.12%;1HNMR(500MHz,CDCl3):8.05(s,1H,triazole-H),7.58(s,1H,triazole-H),7.43(dd,J＝7.4,1.8Hz,1H,ArH),7.37-7.32(m,6H,ArH),7.28-7.24(m,2H,ArH),7.20-7.17(m,2H,ArH),6.88(s,1H,＝CH),6.82-6.78(m,2H,ArH),5.46(s,1H,CH),4.71(s,2H,CH2).HRMS(ESI)for C24H19Cl2N3O m/z:Calculated,436.0978,Found,436.0983[M+H]+.
EXAMPLE 6 preparation of (E) -1- (3- ((3-Fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 3-fluorobenzyl bromide, and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((3-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 6);
Figure BDA0002526241940000122
(E) -1- (3- ((3-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: light yellow oil, yield 33.84%;1H NMR(500MHz,CDCl3):8.06(s,1H,triazole-H),7.53(s,1H,triazole-H),7.40-7.34(m,6H,ArH),7.24-7.21(m,2H,ArH),7.15-7.11(m,4H,ArH),6.88(s,1H,＝CH),6.81-6.79(m,2H,ArH),5.40(s,1H,CH),4.61(s,1H,CH2),4.59(s,1H,CH2).HRMS(ESI)for C24H20FN3O m/z:Calculated,386.1663,Found,386.1669[M+H]+.
example 7 preparation of (E) -1- (3- ((4- (tert-butyl) benzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 4-tert-butylbenzyl bromide and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((4- (tert-butyl) benzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 7);
Figure BDA0002526241940000131
(E) -1- (3- ((4- (tert-butyl) benzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: white oil, yield 42.10%;1H NMR(500MHz,CDCl3):7.96(s,1H,triazole-H),7.50(s,1H,triazole-H),7.44-7.38(m,6H,ArH),7.36-7.31(m,4H,ArH),7.17-7.13(m,2H,ArH),6.93(s,1H,＝CH),6.82-6.78(m,2H,ArH),5.24(s,1H,CH),4.66(s,2H,CH2),1.63(s,9H,t-Bu).HRMS(ESI)for C28H29N3O m/z:Calculated,424.2383,Found,424.2389[M+H]+.
example 8 preparation of (E) -1- (3- ((4-Fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 4-fluorobenzyl bromide, and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((4-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (A8);
Figure BDA0002526241940000141
(E) 1- (3- ((4-fluorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole as a pale yellow oil in a yield of 23.34%;1H NMR(500MHz,CDCl3):8.06(s,1H,triazole-H),7.53(s,1H,triazole-H),7.46-7.41(m,3H,ArH),7.37-7.33(m,4H,ArH),7.12(m,5H,ArH),6.84(s,1H,＝CH),6.79-6.76(m,2H,ArH),5.39(s,1H,CH),4.74(s,1H,CH2),4.72(s,1H,CH2).HRMS(ESI)for C24H20FN3O m/z:Calculated,386.1663,Found,386.1669[M+H]+.
example 9 preparation of (E) -1- (3- ((4-bromobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 4-bromobenzyl bromide and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((4-bromobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 9);
Figure BDA0002526241940000151
(E) 1- (3- ((4-bromobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole as a pale yellow oil in a yield of 21.66%;1H NMR(500MHz,CDCl3):8.06(s,1H,triazole-H),7.52(s,1H,triazole-H),7.45-7.43(m,3H,ArH),7.36-7.32(m,6H,ArH),7.19-7.16(m,3H,ArH),6.85(s,1H,＝CH),6.80-6.78(m,2H,ArH),5.38(s,1H,CH),4.73(s,1H,CH2),4.72(s,1H,CH2).HRMS(ESI)for C24H20BrN3O m/z:Calculated,446.0863,Found,446.0868[M+H]+.
EXAMPLE 10 preparation of (E) -1- (3- ((2-methylbenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 2-methylbenzyl bromide and the other procedures were the same as in example 1 to obtain (E) -1- (3- ((2-methylbenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 10);
Figure BDA0002526241940000152
Figure BDA0002526241940000161
(E) -1- (3- ((2-methylbenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole: white wax, yield 27.25%;1HNMR(500MHz,CDCl3):8.03(s,1H,triazole-H),7.51(s,1H,triazole-H),7.34-7.30(m,3H,ArH),7.27-7.20(m,6H,ArH),7.12-7.09(m,3H,ArH),6.83(s,1H,＝CH),6.79-6.75(m,2H,ArH),5.42(s,1H,CH),4.63(s,2H,CH2),2.21(s,3H,CH3).HRMS(ESI)for C25H23N3O m/z:Calculated,382.1914,Found,382.1919[M+H]+.
EXAMPLE 11 preparation of (E) -1- (3- ((4-cyanobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 4-cyanobenzyl bromide and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((4-cyanobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 11);
Figure BDA0002526241940000162
(E) -1- (3- ((4-cyanobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole as a white solid, melting point: 201 and 203 ℃ with the yield of 12.34 percent;1H NMR(500MHz,CDCl3):8.06(s,1H,triazole-H),7.51(s,1H,triazole-H),7.42-7.39(m,2H,ArH),7.36-7.33(m,4H,ArH),7.31-7.29(m,2H,ArH),7.20-7.15(m,4H,ArH),6.84(s,1H,＝CH),6.81-6.77(m,2H,ArH),5.38(s,1H,CH),4.55(s,1H,CH2),4.54(s,1H,CH2).HRMS(ESI)for C25H20N4O m/z:Calculated,393.1710,Found,393.1716[M+H]+.
example 12 preparation of ethyl (E) -2- ((1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl) oxy) acetate
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of ethyl 2-bromoacetate and the other operations were the same as in example 1 to obtain ethyl (E) -2- ((1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl) oxy) acetate represented by the formula (a 12);
Figure BDA0002526241940000171
(E) ethyl-2- ((1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) allyl) oxy) acetate, yellow oil, yield 12.15%;1H NMR(500MHz,CDCl3):8.04(s,1H,triazole-H),7.60(s,1H,triazole-H),7.39-7.32(m,3H,ArH),7.31-7.27(m,2H,ArH),7.22-7.17(m,3H,ArH),6.95(s,1H,＝CH),6.83-6.79(m,2H,ArH),5.49(s,1H,CH),4.23-4.20(m,2H,CH2),4.20-4.15(m,2H,CH2),1.26(s,3H,CH3).HRMS(ESI)for C21H21N3O3m/z:Calculated,364.1583,Found,364.1661[M+H]+.
example 13 preparation of (E) -1- (3- ((3, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of 3, 4-dichlorobenzyl bromide, and the other procedures were carried out as in example 1 to obtain (E) -1- (3- ((3, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (a 13);
Figure BDA0002526241940000181
(E) 1- (3- ((3, 4-dichlorobenzyl) oxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole as a yellow oil in a yield of 41.25%;1H NMR(500MHz,CDCl3):8.07(s,1H,triazole-H),7.60(s,1H,triazole-H),7.40-7.31(m,6H,ArH),7.30-7.24(m,2H,ArH),7.23-7.16(m,3H,ArH),6.90(s,1H,＝CH),6.85-6.79(m,2H,ArH),5.48(s,1H,CH),4.61(s,2H,CH2).HRMS(ESI)forC24H19Cl2N3O m/z:Calculated,436.0978,Found,436.0983[M+H]+.
example 14 preparation of (E) -1- (3- (cyclohexylmethoxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole
The benzyl bromide in step 4) of example 1 was replaced with an equimolar amount of bromomethylcyclohexane, and the other procedure was the same as in example 1 to obtain (E) -1- (3- (cyclohexylmethoxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole represented by the formula (A14);
Figure BDA0002526241940000191
(E) -1- (3- (cyclohexylmethoxy) -1, 3-diphenylprop-1-en-2-yl) -1H-1,2, 4-triazole as a pale yellow oil in a yield of 21.26%;1H NMR(500MHz,CDCl3):8.21(s,1H,triazole-H),8.16(s,1H,triazole-H),7.87-7.81(m,2H,ArH),7.68-7.57(m,2H,ArH),7.55-7.48(m,2H,ArH),7.43-7.36(m,1H,ArH),7.35-7.23(m,3H,ArH),6.90(s,1H,＝CH),5.26(s,1H,CH),3.27-3.23(m,1H,CH),1.70-1.45(m,4H,CH2),1.53-1.43(m,4H,CH2),1.46-1.44(m,1H,CH).HRMS(ESI)forC24H27N3O m/z:Calculated,374.2227,Found,372.2233[M+H]+.
example 15 bactericidal Activity test
Test subjects: tomato gray mold (Botrytis cinerea), cucumber Fusarium wilt (Fusarium oxysporum), cucumber bacterial angular leaf spot (Pseudomonas syringae pv. lachrymans), cucumber Corynespora leaf spot (Corynespora cassiicola), and pepper Phytophthora capsici (Phytophthora capsii).
The compounds represented by the formulae (A1) to (A14) prepared in examples 1 to 14 were labeled as test compounds, and the bactericidal activity test was performed in the following manner:
and (3) test treatment:
each test compound is dissolved in DMSO to form a mother liquor with an effective concentration of 50mg/mL for later use. In addition, a tomato gray mold control medicament is boscalid, a cucumber corymbose leaf spot control medicament is fluopyram, a cucumber fusarium wilt control medicament is thiophanate methyl, a phytophthora capsici control medicament is dimethomorph, and a cucumber bacterial angular leaf spot control medicament is obtained by killing.
The test method comprises the following steps:
and (3) activation: the fungus (Botrytis cinerea, Fusarium oxysporum, Phytophthora capsici or Cordyrhizon polyspora) is obtained by picking mycelium or agar block from the slant of the strain, transferring to PDA/oat plate, and culturing at 25 deg.C for 3 d. Tomato gray mold (botrytis cinerea), cucumber Fusarium wilt (Fusarium oxysporum), cucumber bacterial angular leaf spot (Pseudomonas syringaepv. lachrymans), cucumber corynebacterium sporum (Corynespora cassiicola), and pepper phytophthora capsici (phytophthora capsici).
Propagation: fungus is picked from the activated plate, the mycelium or agar block at the edge of the colony is transferred to a new PDA plate again, and cultured for 3d at 25 ℃. The bacteria were single colonies picked from activated NA plates and transferred to NB for propagation by shaking (28 ℃,180rpm) for 24 h.
Inoculating bacteria: in the fungus determination, a puncher with the diameter of 4mm is fully burned by outer flame of an alcohol lamp, after cooling (ensuring that an incision is cooled), a fungus dish is punched from the edge of a colony after propagation, and one flat plate is taken for only one week. Selecting bacteria dish with mycelium facing downwards, sticking the bacteria dish to the center of the medicated plate, covering the dish with a cover, and culturing at 25 deg.C in the dark for 2 d. In the bacteria determination, 100 mu L of shaken bacterial liquid is absorbed and evenly coated on a poured flat plate, after absorption, a hole is punched in the center of a culture dish, 10 mu L of diluted mother liquid medicine is injected, 10 mu L of sterile water is injected after the hole is punched, and no medicine is added in a blank control without punching. Each treatment was repeated 3 times, and the inoculated dishes were incubated at 28 ℃.
The inhibition (%) was calculated by referring to the following formula:
Figure BDA0002526241940000201
the pure growth of the control colony in the above calculation formula refers to the pure growth of the colony under the test of the sterile water control (QCK).
The bactericidal activity test results are shown in table 1.
In vivo fungicidal Activity of Compounds at Table 150 mg/mL (% control)
Figure BDA0002526241940000211
As can be seen from Table 1, each compound of the A series shows certain bactericidal activity and has no control effect on cucumber bacterial leaf spot. The bactericidal activity of part of compounds is excellent, wherein the inhibition rate of A9 and A10 on tomato gray mold reaches more than 55%, and the effect is better than that of a reference medicament, namely boscalid; the inhibition rate of A4 on cucumber fusarium wilt reaches 73.82%. In general, although each compound has certain bactericidal activity, the activity is not high in general, and no compound with particularly outstanding bactericidal activity is known, and the activity is not as good as that of a control medicament.
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 (9)

1. A novel allyl ether compound containing triazole is characterized in that the structural formula is shown as the formula (I):
Figure FDA0002526241930000011
in formula (I): r is phenyl, substituted phenyl, methyl acetate or cyclohexane;
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 halogen, cyano or C1-C4 alkyl.
2. The novel triazole-containing allyl ether compound according to claim 1, wherein R in formula (I) is one of the following: phenyl, 2-chlorophenyl, 2-fluorophenyl, 4-chlorophenyl, 2, 4-dichlorophenyl, 3-fluorophenyl, 4-tert-butylphenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 4-cyanophenyl, carbomethoxy acetate, 3, 4-dichlorophenyl or cyclohexyl.
3. The process for producing a novel triazole-containing allyl ether compound according to claim 1 or 2, which comprises 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 FDA0002526241930000012
Figure FDA0002526241930000021
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 and piperidine in an organic reagent C for reflux reaction, and tracking the reaction process by TLC; cooling to room temperature after the reaction is finished, transferring the reaction liquid into a separating funnel, layering after washing, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, and carrying out column chromatography separation and purification treatment to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown in the formula (III);
Figure FDA0002526241930000022
3) dispersing (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown as a formula (III) obtained in the step 2) in an organic reagent D, adding PEG600 and sodium borohydride, stirring and reacting under the condition of ice bath at 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 with an organic reagent E, combining organic phases, drying with anhydrous sodium sulfate, filtering, and treating with a spin-dried solvent to obtain (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol shown in the formula (IV);
Figure FDA0002526241930000023
4) dispersing (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol shown in the formula (IV) obtained in the step 3) in an organic reagent F, adding NaH and halide, stirring for reaction at room temperature, and tracking the reaction process by TLC; after the reaction is finished, washing with water, extracting with an organic reagent G, layering, washing an organic phase with saturated saline solution for 1-3 times, drying with anhydrous sodium sulfate, filtering, and performing column chromatography separation and purification treatment to obtain the novel triazole-containing allyl ether compound shown in the formula (I);
wherein the halide is substituted benzyl halide, 2-bromoethyl acetate or halogenated methylcyclohexane, the number of the substituent groups on the benzene ring of the substituted benzyl halide is one or more, and each substituent group is independently selected from H, halogen, cyano or C1-C4 alkyl.
4. The method for preparing a novel allyl ether compound containing triazole as claimed in claim 3, wherein the organic solvent A in 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 solvent F in the step 4) is DMF, and the organic reagent E in the step 3) and the organic solvent G in the step 4) are dichloromethane.
5. The method for preparing the novel triazole-containing allyl ether compound according to 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 benzaldehyde is 1: 1.1-1.5; in the step 3), the feeding molar ratio of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-one shown in the formula (III) to sodium borohydride is 1: 1.1-1.5; in the step 4), the feeding molar ratio of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazole-1-yl) prop-2-ene-1-ol shown as the formula (IV) and halide is 1: 1.1-1.5.
6. 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 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 substance of (E) -1, 3-diphenyl-2- (1H-1,2, 4-triazol-1-yl) prop-2-en-1-ol shown in the formula (IV).
7. The method for preparing a novel allyl ether compound containing triazole as claimed in claim 3, wherein in step 2) and step 4), the eluent for column chromatography separation and purification is a mixture of ethyl acetate and petroleum ether at a volume ratio of 1: 0.5-2.
8. The use of the novel allyl ether compound containing triazole as claimed in claim 1 or 2 for the preparation of a bactericide.
9. The use according to claim 8, wherein the novel triazole-containing allyl ether compounds are used for the preparation of a fungicide for the inhibition of cucumber fusarium oxysporum.
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