CN110396068A - 4-O-alkoxyaryl-1,2,3-triazole derivatives, synthetic method and application - Google Patents

Abstract

The present invention discloses a 4-o-alkoxyaryl-1,2,3-triazole derivative with a structural formula such as formula I or formula II: , wherein R ¹ is selected from H, Me, OMe, OH, CH ₂ OH, F, Cl, Br; R ² is selected from H, Me, OMe, F, Cl, Br; R ³ is selected from H, Me, OMe, OEt, ⁿ PrO, F, Cl, Br; R ⁴ is selected from Me, Et, ⁿ Pr, ⁱ Pr, Cy; the present invention takes 1,4-disubstituted-1,2,3-triazole as raw material, in Under the action of transition metal catalysis, the ortho-position carbon-hydrogen bond of the 4th aryl group is directly converted into an alkoxy group, and the 4-ortho-alkoxy aryl-1,2,3-triazole derivative is selectively synthesized; The compound contains 1,2,3-triazole ring and alkoxy functional group at the same time, and has a good inhibitory effect on the pathogenic bacteria of Panax notoginseng root rot.

Description

4-O-alkoxyaryl-1,2,3-triazole derivatives, synthetic method and application

technical field

The invention relates to a 4-o-alkoxyaryl-1,2,3-triazole derivative, a synthesis method and application, and belongs to the technical field of pesticides and organic synthesis.

Background technique

Triazole compounds have been widely used in the fields of medicine, pesticides and materials, and have always been valued by chemists. Especially after Sharpless discovered the click reaction between organic azides and terminal alkynes, the design, synthesis and application of 1,2,3-triazole compounds have developed rapidly, and have been widely used in antibacterial, anti-influenza, Anti-epileptic, immune and treatment of tumor, arthritis, osteomalacia, etc. (Kantheti S., Narayan R., Raju K. V. S. N. RSC Adv., 2015,5, 3687; Schulze B., Schubert U. S.Chem. Soc. Rev., 2014,43, 2522.). As a valuable cultivated medicinal plant, with the continuous increase of social demand, the planting area of Panax notoginseng continues to expand, and its disease problem is becoming more and more serious, which has become the main obstacle to the production of Panax notoginseng; Root rot has become the most serious disease that directly affects the yield, quality and commodity value of Panax notoginseng. Therefore, the prevention and control of Panax notoginseng root rot and the research and development of new antibacterial agents are particularly important.

The sources of functionalized triazoles are mainly as follows: Method one is through the cycloaddition reaction between alkynes and azides, which can selectively obtain 1,4-disubstituted-1,2, 3-triazole derivatives, and 1,5-disubstituted-1,2,3-triazole derivatives obtained under the catalysis of ruthenium or quaternary amine bases (Luciani, L., et al. Green Chem . , 2018, 20 , 183; Liu, P., et al. J. Org. Chem ., 2018, 83 , 5092.); The second method is to use organic azides and alkenes as substrates to undergo organocatalytic cycloaddition Reaction (Rohilla, S., et al. Eur. J. Org. Chem., 2016, 847; Li, W., et al. RSC Adv. , 2015, 5 , 88816.); Method 3 is directly to 1, 2,3-triazole derivatives were modified (Ma, X.; et al. Synthesis , 2018, 50 , 2567; ZhaoF., et al. Org. Chem. Front ., 2017, 4 , 1112; Zhao S. , et al. Org. Lett ., 2015, 17 , 2828.), including alkenylation, acyloxylation, alkoxylation, arylation and other processes to obtain functionalized 1,2,3-triazoles structure.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a kind of 4-o-alkoxy aryl-1,2,3-triazole derivative, and its chemical structural formula is as follows:

,

Wherein R ¹ is selected from H, Me, OMe, OH, CH ₂ OH, F, Cl, Br; R ² is selected from H, Me, OMe, F, Cl, Br; R ³ is selected from H, Me, OMe, OEt , ⁿ PrO, F, Cl, Br; R ⁴ is selected from Me, Et, ⁿ Pr, ⁱ Pr, Cy.

The synthetic method of above-mentioned 4-o-alkoxyaryl-1,2,3-triazole derivatives is as follows:

(1) According to the molar ratio of 1,4-disubstituted-1,2,3-triazole, catalyst, oxidant and solvent, it is 1:(0.01~0.3):(2~7):(20~80) ratio, add 1,4-disubstituted-1,2,3-triazole, catalyst, oxidant and solvent into the reactor in turn, and react at 70℃-150℃ for 6-24 hours;

(2) After the reaction product is diluted with water, it is extracted several times with ethyl acetate, and the combined extracts are collected, washed and dried, and then distilled under reduced pressure to obtain the crude product, which is then separated and purified to obtain 4-o-alkoxyaryl-1,2, 3-triazole derivatives.

The catalyst is one of palladium acetate, palladium dichloride, tris(dibenzylideneacetone)dipalladium, bisdibenzylideneacetone palladium and tetrakistriphenylphosphine palladium.

The oxidant is one of potassium persulfate, ammonium persulfate, sodium persulfate, potassium hydrogen persulfate and di-tert-butanol peroxide;

The beneficial effects of the invention are as follows: using readily available 1,4-disubstituted-1,2,3-triazole as the starting material, the ortho-position C-H bond of the aryl group at the 4th position is directly converted into an alkoxy group, thereby Selectively obtain 4-o-alkoxyaryl-1,2,3-triazole derivatives. The synthesized compounds contain both 1,2,3-triazole ring and alkoxy functional group structural units. The rot pathogen has a good inhibitory effect, has a certain application prospect, and can also provide a new method for the synthesis and modification of functional molecules.

Detailed ways

The present invention will be described in further detail below with reference to the examples, but the protection scope of the present invention is not limited to the content.

Example 1: Synthesis of 4-(2,6-dimethoxyphenyl)-1-(p-tolyl)-1H- 1,2,3 -triazole (2a), specifically comprising the following steps:

(1) The molar ratio of 1-p-tolyl-4-phenyl-1,2,3-triazole (1a), palladium acetate, potassium persulfate and methanol solvent is 1:0.05:7:80 , 1mmol of 1-p-tolyl-4-phenyl-1,2,3-triazole, 0.05mmol of palladium acetate, 7mmol of potassium persulfate, and 80mmol of methanol solvent were added to the reactor in turn, and the reaction was carried out at 150°C for 24h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted with 120 mL of ethyl acetate for 3 times. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then used ethyl acetate-petroleum ether. The mixed solution (volume ratio of ethyl acetate and petroleum ether: 1:6) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 245 mg of product 4-(2,6-dimethoxyphenyl)-1 -(p- Tolyl )-1H-1,2,3-triazole 2a, the yield is 83%, the reaction equation is as follows:

;

The NMR spectral characterization data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ = 8.07 (s, 1H), 7.67(d, J = 8.4 Hz, 2H), 7.30 (dd, J = 8.3, 2.0 Hz, 3H), 6.66 (d, J = 8.4 Hz, 2H), 3.82 (s, 6H), 2.41 (s, 3H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ = 158.4, 140.3, 138.2, 134.9, 129.9 , 129.8, 122.2, 120.3, 108.4, 104.1, 55.9, 20.9.

Example 2: Synthesis of 1-phenyl-4-(2,6-dimethoxyphenyl)-1H- 1,2,3 -triazole (2b), specifically comprising the following steps:

(1) The molar ratio of 1-phenyl-4-phenyl-1 H -1,2,3-triazole (1b), palladium chloride, ammonium persulfate and methanol solvent is 1:0.01:6:70 The ratio of 1 mmol 1-phenyl-4-phenyl-1 H -1,2,3-triazole, 0.01 mmol palladium chloride, 6 mmol ammonium persulfate, 70 mmol methanol solvent was added to the reactor in turn, and at 140 ℃ reaction 22h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted 4 times with 160 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:2) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 225 mg of product 1-phenyl-4-(2,6-dimethoxyphenyl)-1 H -1 , 2,3-triazole 2b, the yield is 80%, and the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.12 (s, 1H), 7.81 (dd, J = 8.5, 1.0 Hz, 2H), 7.56 – 7.49 (m, 2H), 7.42 (dd, J = 10.7, 4.2 Hz, 1H), 7.33 (t, J = 8.4 Hz, 1H), 6.68 (d, J = 8.4 Hz, 2H), 3.84 (s, 6H). ¹³ C NMR(150 MHz, CDCl ₃ ) δ = 158.4, 140.6, 137.3, 129.9, 129.6, 128.3, 122.3, 120.5, 108.3, 104.1, 56.0.

Example 3: Synthesis of 1-o-methylphenyl-4-(2,6-dimethoxyphenyl)-1H- 1,2,3 -triazole (2c), specifically comprising the following steps:

(1) According to 1-o-methylphenyl-4-phenyl- 1H -1,2,3-triazole (1c), tris(dibenzylideneacetone)dipalladium, sodium persulfate, methanol solvent The molar ratio is the ratio of 1: 0.10: 4: 40, and 1 mmol 1-o-methylphenyl-4-phenyl-1 H -1,2,3-triazole, 0.10 mmol tris(dibenzylideneacetone) ) Dipalladium, 4mmol sodium persulfate and 40mmol methanol were added to the reactor, and the reaction was carried out at 80°C for 10h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted 4 times with 160 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:2) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 233 mg of the product 1-o-methylphenyl-4-(2,6-dimethoxyphenyl)-1 H -1,2,3-triazole 2c, the yield is 79%, and the reaction equation is as follows:

The NMR spectral characterization data of the products are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ = 7.92 (s, 1H), 7.46(d, J = 7.6 Hz, 1H), 7.43 – 7.29 (m, 5H), 6.68 ( d, J = 8.4 Hz, 2H), 3.84 (s, 6H), 2.30 (s, 3H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ = 158.4, 139.7, 136.8, 133.6, 131.4, 129.8, 129.5, 126.8, 126.1, 126.0, 108.5, 104.3, 56.1, 18.0.

Example 4: Synthesis of 1-phenyl-4-(2,6-dimethoxy-4-methylphenyl)-1H- 1,2,3 -triazole (2d), which specifically includes the following steps:

(1) According to the molar ratio of 1-phenyl-4-p-tolyl- 1H -1,2,3-triazole (1d), bis-dibenzylideneacetone palladium, potassium hydrogen persulfate and methanol is 1: In a ratio of 0.20:5:50, 1 mmol 1-phenyl-4-p-tolyl-1 H -1,2,3-triazole, 0.20 mmol bis-dibenzylidene acetone palladium, 5 mmol potassium hydrogen persulfate, 50mmol methanol was added to the reactor and reacted at 70°C for 8h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted three times with 120 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:4) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 230 mg of the product 1-phenyl-4-(2,6-dimethoxy-4-methylphenyl) )-1H- 1,2,3 -triazole 2d, the yield is 77%, and the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.08 (s, 1H), 7.99(t, J = 1.9 Hz, 1H), 7.77 (dd, J = 8.1, 1.2 Hz, 1H), 7.54 (dd, J = 8.0, 0.8Hz, 1H), 7.39 (t, J = 8.1 Hz, 1H), 6.50 (s, 2H), 3.82 (s, 6H), 2.41 (s, 3H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 158.1, 141.1, 140.5, 138.2, 131.2, 130.9, 123.4, 123.0, 122.0, 118.9, 105.1, 105.0, 55.9, 22.2.

Example 5: Synthesis of 1-p-tolyl-4-(2-methoxy-6-bromophenyl)-1 H -1,2,3-triazole (2e), including the following steps:

(1) According to the molar ratio of 1-p-tolyl-4-o-bromophenyl-1 H -1,2,3-triazole (1e), tetrakistriphenylphosphine palladium, di-tert-butanol peroxide and methanol In a ratio of 1:0.25:6:70, 1 mmol of 1-p-tolyl-4-o-bromophenyl-1 H -1,2,3-triazole, 0.25 mmol of tetrakistriphenylphosphine palladium, 6 mmol of Oxidized di-tert-butanol and 70 mmol of methanol were added to the reactor and reacted at 100°C for 6 hours;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted 4 times with 120 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then extracted with ethyl acetate-petroleum The ether mixture (volume ratio 1:4) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 248 mg of the product 1-p-tolyl-4-(2-methoxy-6-bromophenyl)- 1 H -1,2,3-triazole 2e, the yield is 72%, the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (400 MHz, CDCl ₃ ) δ = 8.05 (s, 1H), 7.67(d, J = 8.4 Hz, 2H), 7.32 – 7.24 (m, 3H), 7.10 ( dd, J = 8.1, 0.8 Hz, 1H), 6.88 (d, J = 8.3 Hz, 1H), 3.77 (s, 3H), 2.40 (s, 3H). ¹³ C NMR (100 MHz, CDCl ₃ ) δ = 158.6, 140.9, 138.4, 134.9, 134.6, 130.0, 129.9, 122.1, 121.8, 120.1, 118.8, 109.3, 55.9, 20.9.

Embodiment 6: Synthesis of 1-m-tolylmethyl-4-o-isobutoxyphenyl-1 H -1,2,3-triazole (2f), which specifically includes the following steps:

(1) According to the molar ratio of 1-m-tolylmethyl-4-phenyl-1 H -1,2,3-triazole (1f), palladium chloride, potassium persulfate and isobutanol, it is 1:0.30: In the ratio of 3:40, 1mmol of benzyl-4-phenyl- 1H -1,2,3-triazole, 0.30mmol of palladium chloride, 3mmol of potassium persulfate and 40mmol of isobutanol were successively added to the reactor , react at 90°C for 12h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted three times with 120 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:6) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 268 mg of the product 1-m-tolylmethyl-4-isobutoxyphenyl-1 H -1,2,3 -triazole 2f, the yield is 83%, and the reaction equation is as follows:

The NMR spectral characterization data of the products are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.33 (dd, J = 7.7, 1.6 Hz, 1H), 7.94 (s, 1H), 7.28 – 7.24 (m, 2H), 7.16 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 5.7 Hz, 2H), 7.05 (t, J = 7.5 Hz, 1H), 6.90 (d, J = 8.3 Hz, 1H), 5.53 ( s, 2H), 3.78 (d, J = 6.3 Hz, 2H), 2.33 (s, 3H), 2.01 (dp, J = 13.2, 6.6Hz, 1H), 0.92 (d, J = 6.8 Hz, 6H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 155.1, 143.5, 138.9, 134.6, 129.3, 128.9, 128.8, 127.6, 125.3, 122.9, 120.7, 119.3, 111.4, 75.6, 54.0, 19.28.3

Example 7: Synthesis of 4-(2,6-diethoxyphenyl)-1-(p-tolyl)-1H- 1,2,3 -triazole (2g), specifically including the following steps:

(1) According to the molar ratio of 4-phenyl-1-(p-tolyl)-1 H -1,2,3-triazole (1a), tridibenzylideneacetone dipalladium, potassium hydrogen persulfate and ethanol In a ratio of 1:0.25:2:30, 1 mmol 4-phenyl-1-(p-tolyl)-1 H -1,2,3-triazole, 0.25 mmol tridibenzylideneacetone dipalladium, 2 mmol potassium hydrogen persulfate and 30 mmol ethanol were added to the reactor, and the reaction was carried out at 100 °C for 14 h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted 4 times with 150 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:4) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 262 mg of product 4-(2,6-diethoxyphenyl)-1-(p-tolyl)- 1 H -1,2,3-triazole 2g, the yield is 81%, the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.10 (s, 1H), 7.67 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H) , 7.26 (dd, J = 10.3, 6.4Hz, 1H), 6.64 (d, J = 8.4 Hz, 2H), 4.07 (q, J = 7.0 Hz, 4H), 2.42 (s, 3H), 1.35 (t, J = 7.0 Hz, 6H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 157.8, 140.6, 138.2, 135.0, 130.1, 129.6, 122.2, 120.2, 109.3, 105.5, 64.5, 21.0, 14.7.

Example 8: Synthesis of 4-(2,6-dipropyl)-1-(p-tolyl)-1H- 1,2,3 -triazole (2h), specifically including the following steps:

(1) The molar ratio of 4-phenyl-1-(p-tolyl)-1H- 1,2,3 -triazole (1a), palladium acetate, ammonium persulfate and n-propanol is 1:0.20: In a ratio of 3:40, 1 mmol 4-phenyl-1-(p-tolyl)-1 H -1,2,3-triazole, 0.20 mmol palladium acetate, 3 mmol ammonium persulfate and 40 mmol n-propanol were added to the mixture in turn. In the reactor, the reaction was carried out at 110°C for 16h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted three times with 100 mL of ethyl acetate. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then extracted with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:3) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 278 mg of the product 4-(2,6-dipropyl)-1-(p-tolyl)-1 H -1 , 2,3-triazole 2h, the yield is 79%, and the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.08 (s, 1H), 7.67(d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.3 Hz, 2H) , 7.26 (d, J = 2.6 Hz, 1H), 6.64(d, J = 8.4 Hz, 2H), 3.96 (t, J = 6.5 Hz, 4H), 2.43 (s, 3H), 1.79 – 1.72 (m, 4H), 0.95 (t, J = 7.4 Hz, 6H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 158.0, 140.7, 138.2, 135.1, 130.1, 129.7, 122.1, 120.3, 109.3, 105.4, 70.5, 22.5 , 21.1, 10.5.

Example 9: Synthesis of 4-(2-isopropoxyphenyl)-1-(p-tolyl)-1H- 1,2,3 -triazole (2i), including the following steps:

(1) According to the molar ratio of 4-phenyl-1-(p-tolyl)-1 H -1,2,3-triazole (1a), tetrakistriphenylphosphine palladium, sodium persulfate, and isobutanol: The ratio of 1:0.15:4:50, followed by 1mmol 4-phenyl-1-(p-tolyl)-1H-1,2,3-triazole, 0.15mmol tetrakistriphenylphosphine palladium, 4mmol persulfuric acid Sodium and 50mmol isobutanol were added to the reactor, and the reaction was carried out at 120°C for 18h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted with 120 mL of ethyl acetate for 5 times. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:2) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 235 mg of product 4-(2-isopropoxyphenyl)-1-(p-tolyl) -1H -1,2,3-triazole 2i, the yield is 80%, and the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.49 (s, 1H), 8.41 (dd, J = 7.7, 1.5 Hz, 1H), 7.65 (d, J = 8.3 Hz, 2H), 7.35 – 7.30 (m, 3H), 7.09 (t, J = 7.5 Hz, 1H), 6.98 (d, J = 8.3 Hz, 1H), 3.91 (d, J = 6.4 Hz, 2H), 2.43 ( s, 3H), 2.27 – 2.21 (m, 1H), 1.12 (d, J = 6.7 Hz, 6H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 155.2, 143.8, 138.5, 135.0, 130.2, 129.0, 127.8, 120.9, 120.8, 120.2, 119.0, 111.5, 74.8, 28.4, 21.1, 19.6.

Example 10: Synthesis of 4-(2-(cyclohexyloxy)phenyl)-1-(p-tolyl)-1H- 1,2,3 -triazole (2j), which specifically includes the following steps:

(1) The molar ratio of 4-phenyl-1-(p-tolyl)-1H- 1,2,3 -triazole (1a), palladium chloride, potassium persulfate and cyclohexanol is 1:0.10 : 5:60 ratio, followed by 1mmol 4-phenyl-1-(p-tolyl)-1H-1,2,3-triazole, 0.10mmol palladium chloride, 5mmol potassium persulfate, 60mmol cyclohexanol added to the reactor and reacted at 130°C for 20h;

(2) The obtained reaction product was diluted with 40 mL of water, and the reaction product was extracted with 120 mL of ethyl acetate for 5 times. The combined extracts were collected, washed with water and dried, and the solvent was distilled off under reduced pressure to obtain a crude product, which was then mixed with ethyl acetate-petroleum ether. The mixed solution (volume ratio 1:3) was used as the eluent and purified by column chromatography (400 mesh silica gel) to obtain 260 mg of product 4-(2-(cyclohexyloxy)phenyl)-1-(p-tolyl)- 1 H -1,2,3-triazole 2j, the yield is 78%, the reaction equation is as follows:

The NMR spectral characterization data of the product are as follows: ¹ H NMR (600 MHz, CDCl ₃ ) δ = 8.50 (s, 1H), 8.41 (dd, J = 7.7, 1.7 Hz, 1H), 7.67 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.1 Hz, 2H), 7.31 – 7.28 (m, 1H), 7.09 – 7.05 (m, 1H), 7.01 (d, J = 8.3 Hz, 1H), 4.48 – 4.42 (m , 1H), 2.44 (s, 3H), 2.13 (dd, J = 12.9, 3.7 Hz, 2H), 1.84 – 1.80(m, 2H), 1.64 – 1.59 (m, 4H), 1.44 (tdd, J = 10.5 , 7.1, 3.5 Hz, 2H). ¹³ C NMR (150 MHz, CDCl ₃ ) δ = 153.9, 143.9, 138.5, 135.1, 130.2, 128.8, 128.0, 120.9,120.7, 120.3, 119.9, 111.0, 5.5.9, , 23.9, 21.1.

Example 11: Activation of pathogenic bacteria

(1) Potato dextrose agar medium (PDA): 200 g of potato, 20 g of glucose, 20 g of agar, and 1000 mL of distilled water;

(2) Purify and identify the pathogenic bacteria isolated from the roots of Panax notoginseng, and identify them as Fusarium oxysporum , Fusarium solani and Cylindrocarpon destructans . Inoculate on PDA medium for activation, after inoculation 3 to 4 times, take the vigorously growing strains for use.

Example 12: Compound Minimum Inhibitory Concentration (MIC) Determination

(1) Compounds 2a, 2b, 2c, 2d, 2e, 2f, and 2j synthesized in the examples were dissolved in DMSO and prepared into an aqueous solution of 6 mg/mL;

(2) Take the pathogenic bacteria grown for 7 days in Example 11, wash the medium with 20mL 1/4 PDA liquid medium (without adding agar, the amount of potato and glucose is 1/4 of the conventional medium), and then prepare the spore concentration It is a spore suspension of 1×10 ⁴ /mL;

(3) Add 4 μL of the monomer compound and 156 μL of the spore suspension prepared in step (2) into a 96-well plate; the concentration range is 150 μg/mL- Multiple concentration gradient liquids of 0.146μg/mL;

(4) The blank control is 4 μL DMSO and 156 μL 1/4PDA liquid medium; the positive control is 4 μL DMSO and 150 μL spore suspension in step (3);

(5) The 96-well plate was incubated at a constant temperature of 28°C for 36 hours, and then the fungal growth in the wells was checked; the absorbance of each well was measured with a microplate reader (Thermo 1510) at 595 nm, and the results are shown in the following table;

Compounds 2a, 2b, 2d, and 2f have strong broad-spectrum antibacterial activities against the three pathogenic strains causing Panax notoginseng root rot, which are in the same order of magnitude as the antibacterial activities of the positive drugs oxamidil and fenconazole. The antibacterial activity was higher than that of ripper and propamocarb. Compounds 2c and 2e had higher bacteriostatic activities against Fusarium oxysporum and Fusarium solani, and compound 2j had better antibacterial activity against Cylindrosporium.

Claims (6)

1. The 4-o-alkoxyaryl-1,2,3-triazole derivatives represented by the structural formula I or II: , Wherein R ¹ is selected from H, Me, OMe, OH, CH ₂ OH, F, Cl, Br; R ² is selected from H, Me, OMe, F, Cl, Br; R ³ is selected from H, Me, OMe, OEt , ⁿ PrO, F, Cl, Br; R ⁴ is selected from Me, Et, ⁿ Pr, ⁱ Pr, Cy. 2. the synthetic method of 4-o-alkoxyaryl-1,2,3-triazole derivatives according to claim 1, is characterized in that: by 1,4-disubstituted-1,2,3-triazol The molar ratio of azole, catalyst, oxidant and solvent is 1:(0.01~0.3):(2~7):(20~80), and 1,4-disubstituted-1,2,3-triazine The azole, catalyst, oxidant, and solvent were added to the reactor, and the reaction was carried out at 70°C to 150°C for 6 to 24 hours; the reaction product was diluted with water and then extracted with ethyl acetate for several times. The combined extracts were collected, washed, dried, and decompressed. The crude product is obtained by distillation, and then separated and purified to obtain 4-o-alkoxyaryl-1,2,3-triazole derivatives. 3. the synthetic method of 4-o-alkoxyaryl-1,2,3-triazole derivatives according to claim 2, is characterized in that: catalyzer is palladium acetate, palladium dichloride, tris(dibenzylidene) acetone) dipalladium, bisdibenzylideneacetone palladium, tetrakistriphenylphosphine palladium. 4. the synthetic method of 4-o-alkoxyaryl-1,2,3-triazole derivatives according to claim 2, is characterized in that: oxidant is potassium persulfate, ammonium persulfate, sodium persulfate, persulfate One of potassium hydrogen sulfate and di-tert-butanol peroxide. 5. the synthetic method of 4-o-alkoxy aryl-1,2,3-triazole derivatives according to claim 2, it is characterized in that: solvent is methanol, ethanol, n-propanol, isobutanol, ring One of the hexanol solvents. 6. The application of the 4-o-alkoxyaryl-1,2,3-triazole derivative of claim 1 in inhibiting the pathogenic bacteria of Panax notoginseng root rot.