CN116063280B - Eugenol heterocyclic ester derivative, and preparation method and application thereof - Google Patents
Eugenol heterocyclic ester derivative, and preparation method and application thereof Download PDFInfo
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- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a eugenol heterocyclic ester derivative, a preparation method and application thereof, and belongs to the technical field of plant pathogenic fungi resistant medicines. According to the invention, several heterocyclic groups are spliced with natural compound eugenol through ester bonds, 7 heterozygote molecules with novel structures are synthesized, and antibacterial activity tests are carried out on the heterozygote molecules, so that the result shows that the prepared eugenol heterocyclic ester derivative has excellent broad-spectrum plant pathogenic fungi inhibition activity, and can be used as a lead compound for developing novel agricultural bactericides.
Description
Technical Field
The invention belongs to the technical field of plant pathogenic fungi resistant medicines, and particularly relates to a eugenol heterocyclic ester derivative, a preparation method and application thereof.
Background
Plant diseases are one of the main threats for crop growth, often cause crop yield reduction, and seriously cause grain harvest. Most plant diseases are caused by fungal infection, and have the characteristics of wide occurrence range, serious harm, long period, easy transmission and the like, and can penetrate through the whole physiological process of plant growth. Chemical pesticides have been widely used in plant disease control for centuries due to their high efficiency, convenient use, low control cost, etc. Chemical control has so far remained the most dominant means of plant disease control, with irreplaceable status and role in plant protection. However, the unreasonable use of chemical pesticides causes problems such as pesticide residues and environmental pollution. Besides chemical pesticides, plant-derived pesticides are also effective means for controlling plant fungal diseases. With the increasing demands of people for safe and healthy foods, plant-source pesticides are increasingly widely applied in modern agriculture. The botanical pesticide has the advantages of environmental protection, safety and various effective components, and can effectively prevent and treat different plant diseases. Although a botanical pesticide has many advantages, it also has some drawbacks, mainly manifested in: the control effect of a plant-derived pesticide may be relatively weak compared to a chemically synthesized pesticide, and it is difficult to directly use as a pesticide.
Modification of the structure of a natural product refers to a method of obtaining more excellent biological activity or improving other properties by modifying the molecular structure of the natural product. In pesticide development, natural product structural modification has been widely used. Compared with the traditional chemical synthesized pesticide, the natural product structure modification has better environmental protection and sustainability and has smaller influence on the environment. Thus, modification of the structure of natural products has become one of the important directions in the development of pesticides. Eugenol is a natural product and can be extracted from a variety of plants, including clove, cinnamon, laurel, etc. The research shows that eugenol has certain antibacterial activity on various plant pathogenic fungi, but the antibacterial activity at low concentration is poor.
Disclosure of Invention
The invention aims to provide a eugenol heterocyclic ester derivative, and a preparation method and application thereof. By splicing several heterocyclic groups with natural compound eugenol by utilizing ester bonds, 7 heterozygote molecules with novel structures are synthesized, and antibacterial activity tests are carried out on the heterozygote molecules, and the results show that the prepared eugenol heterocyclic ester derivatives have excellent inhibitory activity on three plant pathogenic fungi of Alternaria solani, botrytis cinerea and Rhizoctonia solani, and can be used as active ingredients or lead compounds for developing novel agricultural bactericides.
In order to achieve the above purpose, the present invention provides the following technical solutions:
one of the technical schemes of the invention is as follows: provides a eugenol heterocyclic ester derivative, the structural general formula of which is shown in formula I:
the structure of substituent Ar in formula I is as follows:
the structural formula of the eugenol heterocyclic ester derivative is shown as the following compounds 1-7:
the second technical scheme of the invention is as follows: the preparation method of the eugenol heterocyclic ester derivative comprises the following steps:
mixing a carboxyl compound containing heterocycle with thionyl chloride, concentrating after reaction to obtain acyl chloride containing heterocycle, adding tetrahydrofuran for dissolution, adding eugenol and triethylamine dissolved in the tetrahydrofuran, and continuing reaction to obtain the eugenol heterocyclic ester derivative;
the structural formula of the heterocycle-containing carboxyl compound is one of the following structural formulas:
preferably, the heterocycle-containing carboxylic compound is used in an amount ratio of 1mmol to 1mL of thionyl chloride.
Preferably, the heterocycle-containing carboxylic compound is used in an amount ratio of 1mmol to 123mg to eugenol.
Preferably, the dosage ratio of the carboxylic compound containing the heterocycle to the triethylamine is 1 mmol:320-350 mu L.
Preferably, the reaction temperature of the heterocycle-containing carboxyl compound and thionyl chloride is 80-90 ℃.
The third technical scheme of the invention: provides an application of the eugenol heterocyclic ester derivative in preparing a medicament for resisting plant pathogenic fungi.
The beneficial technical effects of the invention are as follows:
according to the invention, 7 heterozygote molecules with novel structures are synthesized by splicing several heterocyclic groups with natural product eugenol by utilizing ester bonds. The antibacterial activity test shows that the compound has excellent inhibitory activity on three plant pathogenic fungi of Alternaria solani, botrytis cinerea and Rhizoctonia solani, and can be used as an active ingredient or a lead compound for developing novel agricultural bactericides. And the preparation method is simple and the cost is low.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
Synthesis of Compound 1:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of thiophene-2 carboxylic acid was placed in a 10 mL round bottom flask and 2mL sulfoxide chloride (SOCl) 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); placing the acyl chloride solution into a constant pressure dropping funnel, slowly dropping into the mixed solution of eugenol and triethylamineAfter the completion of the dropwise addition, stirring was carried out at room temperature. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-thiophene-2-carboxylic acid ester (compound 1) in 89.51% yield.
Characterization: 1H NMR (500 MHz, chloride-d) delta 7.98 (d, J=3.8 Hz, 1H, ph-H), 7.65 (d, J=5.0 Hz, 1H, ph-H), 7.19 (m, 1H, ph-H), 7.07 (d, J=8.0 Hz, 1H, -CH), 6.82 (s, 1H, -CH), 6.02 (m, 1H, -CH), 5.13 (m, 2H, -CH) 2 ), 3.81 (s, 3H, -CH 3 ), 3.40 (d, J = 6.7 Hz, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 151.16, 139.23, 137.83, 137.09, 134.64, 133.24, 127.94, 122.67, 121.18, 120.72, 116.19, 115.54, 114.24, 112.91, 111.09, 55.94, 40.13.MS: Cad. for Mol.Wt., 274.43 Found 274.4.
Example 2
Synthesis of Compound 2:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of thiazole-5 carboxylic acid was taken in a 10 mL round bottom flask and 2mL sulfoxide chloride (SOCl) 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfateDrying, filtering and concentrating under reduced pressure to obtain a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-thiazole-5-carboxylic acid ester (compound 2) in 90.24% yield.
Characterization: 1H NMR (500 MHz, chloride-d) δ9.02 (d, J=0.7 Hz, 1H, ph-H), 8.68 (d, J=0.7 Hz, 1H, ph-H), 7.06 (d, J=8.0 Hz, 1H, ph-H), 6.81 (dd, J=8.1, 2.0 Hz, 1H, -CH), 6.04 (m, 1H, -CH), 5.17 (m, 2H, -CH) 2 ), 4.12 (d, J = 7.1 Hz, 1H, -CH), 3.81 (s, 3H, -CH 3 ), 1.25 (s, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 158.69, 150.93, 150.02, 139.66, 136.94, 128.91, 122.45, 120.75, 116.31, 112.89, 60.41, 55.90, 40.12, 21.07, 14.21.MS: Cad. for Mol.Wt., 275.32 Found 275.3.
Example 3
Synthesis of Compound 3:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of 1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxylic acid was taken in a 10 mL round bottom flask and 2mL sulfoxide chloride (SOCl) was added 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-1-methyl-3- (tris)Fluoromethyl) -1H-pyrazole-4-carboxylic acid ester (compound 3) in 92.30% yield.
Characterization: 1H NMR (500 MHz, chloroform-d) δ8.13 (s, 1H, ph-H), 7.02 (d, J=8.0 Hz, 1H, ph-H), 6.78 (dd, J=8.1, 1.9 Hz, 1H, ph-H), 6.04 (m, 1H, -CH), 4.12 (d, J=7.1 Hz, 1H, -CH), 4.00 (s, 3H, -CH) 3 ), 3.79 (s, 3H, -CH 3 ), 3.38 (d, J = 6.7 Hz, 2H, -CH 2 ), 1.25 (t, J = 7.2 Hz, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 158.54, 151.06, 139.31, 137.44, 137.06, 136.87, 122.57, 120.72, 116.16, 112.93, 60.41, 55.92, 40.09, 39.90, 21.06, 14.20.MS: Cad. for Mol.Wt., 340.30 Found 340.30.
Example 4
Synthesis of Compound 4:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of 1-methyl-1H-pyrazole-4-carboxylic acid was taken in a 10 mL round bottom flask and 2mL thionyl chloride (SOCl) 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-1-methyl-1H-pyrazole-4-carboxylic acid (compound 4) in 93.75% yield.
Characterization: 1H NMR (500 MHz, chloroform-d) delta 8.05%s, 1H, ph-H), 8.02 (s, 1H, ph-H), 7.02 (d, J = 7.9 Hz, 1H, ph-H), 6.81 (s, 1H, -CH), 6.05 (m, 1H, -CH), 5.19 (m, 2H, -CH 2 ), 4.12 (d, J = 7.2 Hz, 1H, -CH, -CH), 3.96 (s, 3H, -CH 3 ), 3.80 (s, 3H, -CH 3 ), 1.25 (t, J = 7.1 Hz, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 160.86, 151.20, 141.86, 139.01, 137.10, 134.11, 122.76, 120.72, 116.15, 112.82, 60.41, 55.89, 40.12, 39.39, 21.07, 14.21.. MS: Cad. for Mol.Wt., 272.12 Found 272.1.
Example 5
Synthesis of Compound 5:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of 2-chloronicotinic acid was placed in a 10 mL round bottom flask and 2mL thionyl chloride (SOCl) 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-2-chloronicotinic acid ester (compound 5) in 88.57% yield.
Characterization: 1H NMR (500 MHz, chloroform-d) δ8.66 (m, 1H, ph-H), 8.40 (d, J=7.7, 2.0 Hz, 1H, ph-H), 7.39 (d, J=4.8 Hz, 1H, ph-H), 7.09 (d, J=8.0 Hz, 1H, -CH), 6.84 (d, J=1.9 Hz, 2H, -CH) 2 ), 5.97 (d, J = 6.7 Hz, 1H, -CH), 5.12 (m, 1H, -CH), 4.12 (q, J = 7.1 Hz, 1H, -CH), 3.83 (s, 3H, -CH 3 ), 1.25 (s, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 162.52, 152.29, 150.79, 140.91, 139.63, 137.64, 136.96, 126.27, 122.39, 122.15, 120.82, 116.29, 112.87, 60.41, 55.91, 40.12, 21.07, 14.21.MS: Cad. for Mol.Wt., 303.74 Found 303.7.
Example 6
Synthesis of Compound 6:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of nicotinic acid was placed in a 10 mL round bottom flask and 2mL thionyl chloride (SOCl) was added 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-nicotinic acid ester (compound 6) in 86.75% yield.
Characterization: 1H NMR (500 MHz, chloride-d) δ9.40 (d, J=2.3 Hz, 1H, ph-H), 8.84 (d, J=4.9 Hz, 1H, ph-H), 8.45 (d, J=8.0 Hz, 1H, ph-H), 7.49 (m, 1H, -CH), 7.07 (d, J=8.0 Hz, 1H, -CH), 6.84 (s, 2H, -CH) 2 ), 6.03 (m, 1H, -CH), 5.10 (d, J = 4.3 Hz, 1H, -CH), 4.11 (d, J = 7.2 Hz, 1H, -CH), 3.80 (s, 3H, -CH 3 ), 1.25 (s, 2H, -CH 2 ). 13C NMR (126 MHz, CDCl 3 ) δ 163.60, 153.83, 151.53, 150.92, 139.47, 137.71, 137.00, 123.40, 122.48, 120.78, 116.27, 112.86, 60.41, 55.87, 40.13, 21.06, 14.21.MS: Cad. for Mol.Wt., 261.11 Found 269.1.
Example 7
Synthesis of Compound 7:
the reaction formula is:
the method comprises the following specific steps:
(1) 2 mmol of furan-3 carboxylic acid was placed in a 10 mL round bottom flask and 2mL sulfoxide chloride (SOCl) 2 ) Dissolving, heating and refluxing for 2h at 85 ℃, decompressing and concentrating to obtain acyl chloride, and adding 2mL of anhydrous tetrahydrofuran for later use.
(2) 246 mg eugenol was placed in a 10 mL round bottom flask, 3 mL anhydrous Tetrahydrofuran (THF) was added for dissolution, and 685. Mu.L triethylamine (Et) was added 3 N); and (3) placing the acyl chloride solution in a constant-pressure dropping funnel, slowly dropping the acyl chloride solution into a mixed solution of eugenol and triethylamine, and stirring at room temperature after the dropping is finished. The progress of the reaction was monitored by Thin Layer Chromatography (TLC). After the reaction was completed, 10% mL distilled water was added thereto to quench, and methylene chloride (20. 20 mL ×3) was extracted. The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The oily liquid obtained was prepared using PE: EA (20:1, V/V) column chromatography to give the target compound: 4-propenyl-2-methoxyphenyl-furan-3-carboxylic acid ester (compound 7) in 89.55% yield.
Characterization: 1H NMR (500 MHz, chloride-d) δ8.22 (m, 1H), 7.49 (s, 1H, ph-H), 7.03 (d, J=8.0 Hz, 1H, ph-H), 6.79 (dd, J=7.9, 2.0 Hz, 1H, ph-H), 5.98 (d, J=6.8 Hz, 1H, -CH), 5.11 (m, 1H, -CH), 4.12 (d, J=7.2 Hz, 1H, -CH), 3.81 (s, 3H, -CH) 3 ), 3.40 (d, J = 6.8 Hz, 2H, -CH 2 ), 1.26 (t, J = 7.1 Hz, 2H, -CH 2 ).13C NMR (126 MHz, CDCl 3 ) δ 161.09, 151.14, 148.70, 143.88, 137.08, 122.67, 120.73, 116.18, 112.84, 110.23, 60.41, 55.89, 55.86, 40.12, 21.06, 14.21.MS: Cad. for Mol.Wt., 258.27 Found 258.2.
Antibacterial activities of the eugenol heterocyclic ester derivatives, eugenol phenyl ester compounds (controls 1 to 2) and eugenol fatty acid ester compounds (controls 3 to 6) prepared in examples 1 to 7 were measured:
the method comprises the following steps: PDA medium was prepared at a ratio of potato to glucose to agar=200 g to 20g in 1000 mL. The mother solution of 5000 mug/mL is prepared by dissolving each object to be tested by acetone, the obtained mother solution is added into PDA culture medium according to the proportion of 1:100 and is uniformly shaken, and the PDA culture medium with the medicine with the final concentration of 50 mug/mL is obtained (taking no medicine and only equal volume of acetone as a control group). A9 cm diameter petri dish was used and poured into 15mL of PDA medium from either the treatment or control group and allowed to cool for use. Selecting a position with good growth vigor of the outermost ring of the strain, taking out a bacterial cake by a 5 mm puncher, inoculating a bacterial cake on each flat plate with the drug by an inoculating needle in a reverse way, placing a culture dish with the inoculated strain into an incubator for dark culture at 25 ℃, measuring the diameter of a bacterial colony by a crisscross method when the bacterial colony of a control group grows to be close to the edge of the culture dish, and calculating the bacterial inhibition rate, wherein the calculation result is shown in table 1. The calculation formula of the bacteriostasis rate is as follows:
antibacterial ratio (%) = (control colony diameter-treated colony diameter)/(control colony diameter) ×100%.
Antibacterial Activity of Compounds of Table 1
As can be seen from Table 1, at a drug concentration of 50. Mu.g/mL, compounds 1-7 all showed relatively broad-spectrum and excellent antibacterial activity, and the antibacterial activity of 7 compounds against three plant pathogenic fungi of Alternaria solani, botrytis cinerea and Rhizoctonia solani was higher than that of the parent compound eugenol, and the antibacterial activity was higher than or equivalent to that of the positive commercial bactericide chlorothalonil. Compared with homologous control matters, the overall activity of the compounds 1-7 is higher than that of eugenol phenyl ester compounds (control matters 1-2) and eugenol fatty acid ester compounds (control matters 3-6), and the eugenol heterocyclic ester derivatives have potential application prospects in the field of plant pathogenic fungi resistance.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (5)
1. The application of the eugenol heterocyclic ester derivative in preparing the anti-plant pathogenic fungi drug is characterized in that the structural general formula of the eugenol heterocyclic ester derivative is shown in formula I:
the structure of substituent Ar in formula I is as follows:
2. the use according to claim 1, wherein the step of preparing the eugenol heterocyclic ester derivative comprises:
mixing a carboxyl compound containing heterocycle with thionyl chloride, concentrating after reaction to obtain acyl chloride containing heterocycle, adding tetrahydrofuran for dissolution, adding eugenol and triethylamine dissolved in the tetrahydrofuran, and continuing reaction to obtain the eugenol heterocyclic ester derivative;
the structural formula of the heterocycle-containing carboxyl compound is one of the following structural formulas:
3. the use according to claim 2, wherein the ratio of the heterocycle-containing carboxylic compound to thionyl chloride is 1 mmol/1 ml.
4. The use according to claim 2, wherein the ratio of the heterocycle-containing carboxylic compound to eugenol is 1 mmol/123 mg.
5. The use according to claim 2, wherein the reaction temperature of the heterocyclic carboxylic compound and thionyl chloride is 80-90 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE10327136A1 (en) * | 2003-06-17 | 2005-01-13 | Henkel Kgaa | Inhibiting asexual reproduction of fungi, especially Aspergillus strains, using eugenol and/or its derivatives e.g. by incorporation in detergents, adhesives or sealants |
| KR20120124084A (en) * | 2011-05-03 | 2012-11-13 | 주식회사 케이알셀코리아 | Eugenol derivatives and its use |
| CN105767168A (en) * | 2016-03-08 | 2016-07-20 | 中国农业科学院农产品加工研究所 | Application of eugenol and/or derivatives thereof in inhibition of aspergillus ochraceus growth |
| CN108191665A (en) * | 2018-01-19 | 2018-06-22 | 湖南省农业生物技术研究所 | Eugenol ester analog and preparation method thereof and insecticide |
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| KR20060022279A (en) * | 2003-06-17 | 2006-03-09 | 헨켈 코만디트게젤샤프트 아우프 악티엔 | Inhibition of the asexual reproduction of fungi by eugenol and/or the derivatives thereof |
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| DE10327136A1 (en) * | 2003-06-17 | 2005-01-13 | Henkel Kgaa | Inhibiting asexual reproduction of fungi, especially Aspergillus strains, using eugenol and/or its derivatives e.g. by incorporation in detergents, adhesives or sealants |
| KR20120124084A (en) * | 2011-05-03 | 2012-11-13 | 주식회사 케이알셀코리아 | Eugenol derivatives and its use |
| CN105767168A (en) * | 2016-03-08 | 2016-07-20 | 中国农业科学院农产品加工研究所 | Application of eugenol and/or derivatives thereof in inhibition of aspergillus ochraceus growth |
| CN108191665A (en) * | 2018-01-19 | 2018-06-22 | 湖南省农业生物技术研究所 | Eugenol ester analog and preparation method thereof and insecticide |
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