CN108794471B - Synthesis method of benzimidazole compound and agricultural biological activity thereof - Google Patents
Synthesis method of benzimidazole compound and agricultural biological activity thereof Download PDFInfo
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Abstract
The invention provides a synthesis method of a benzimidazole compound and agricultural biological activity thereof, belonging to the field of organic synthesis. The technical scheme includes that a phenylimidazole compound and a phenolic compound are respectively added into a reaction container, and the reaction is carried out for 4-6 hours under the illumination condition of blue LED light at 20-25 ℃ under the action of palladium acetate and isopropanol; and after the reaction is finished, performing column chromatography separation to obtain the benzimidazole compound. The invention can be applied to the preparation of benzimidazole compounds and the prevention and treatment of germs of crops.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of a benzimidazole compound and agricultural biological activity of the benzimidazole compound.
Background
The benzimidazole compound is widely existed in various natural products, has various biological activities such as antimicrobial, antibacterial and the like, and is an important intermediate for synthesizing spices, medicines, pesticides and dyes.
There are many existing methods for synthesizing benzimidazole compounds, such as: halogen benzene and phenylimidazole compounds are used as raw materials, and react for 16 hours in N, N-dimethyl ether at 100 ℃ under the action of palladium diacetate, potassium carbonate, tricyclohexylphosphine tetrafluoroboric acid and trimethylacetic acid, and the product yield is 95% (Marhadour Sophie et al, tetrahedron letters,2012, vol.53, #3, p.297-300); phenylboronic acid and a phenylimidazole compound are used as raw materials, and react for 2 hours in 1, 2-ethanedioic acid dimethyl ether and water at 100 ℃ under the action of tetrakis (triphenylphosphine) palladium and sodium carbonate, so that the product yield is 88% (XiaoXinsheng et al, Organic Letters,2015, vol.17, #16, p.3998-4001).
However, when the benzimidazole compound is synthesized by the method, raw materials such as phenylhydrazine, phenylboronic acid or halobenzene which are difficult to synthesize are used, and a reaction system needs to be heated, so that the method is high in cost and environment-friendly.
Disclosure of Invention
The invention provides a synthesis method of a benzimidazole compound and agricultural biological activity thereof, the method has the advantages of low cost of used raw materials, no need of heating a reaction system, low energy consumption, environmental friendliness and high product yield, and a novel method is provided for the synthesis of the benzimidazole compound.
In order to achieve the above purpose, the invention provides a method for synthesizing benzimidazole compounds, which comprises the following steps:
respectively adding a phenylimidazole compound and a phenolic compound into a reaction container, and reacting for 4-6 hours under the illumination condition of blue LED light at 20-25 ℃ under the action of palladium acetate and isopropanol;
and after the reaction is finished, performing column chromatography separation to obtain the benzimidazole compound.
Preferably, the phenylimidazole compound has the following structural formula (a):
wherein R is1Is selected from-OCH3or-H, R2Is selected from-CH3or-H, R3Is selected from-CH3-H or-Cl.
Preferably, the phenolic compound is phenol or p-trifluoromethylphenol.
Preferably, the benzimidazole compound has the following structural formula (B):
wherein R is1Is selected from-Ph or-H, R2Is selected from OCH3or-H, R3Is selected from-CF3or-H, R4Is selected from-CH3or-H, R5Is selected from-CH3-H or-Cl.
Preferably, the millimole ratio of the phenylimidazole compound to the phenol compound is 1:1-1: 2.
Preferably, the millimole ratio of the phenylimidazole compound to the palladium acetate and isopropanol is 1:0.001:2-1:0.002: 3.
Preferably, the chromatographic column used in the column chromatography is a silica gel column, and the eluent used is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:5-2: 1.
The invention also provides application of the compound synthesized by the synthesis method according to any one technical scheme in prevention and treatment of crop germs.
Compared with the prior art, the invention has the advantages and positive effects that:
the synthesis method provided by the invention directly uses cheap and easily-obtained phenyl imidazole compounds and phenolic compounds as raw materials to promote the synthesis reaction of the compounds, the cost of the used raw materials is low, the reaction system does not need heating, the energy consumption is low, the environment is friendly, the product yield is high, and a novel method is provided for the synthesis of the benzimidazole compounds.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a method for synthesizing a benzimidazole compound, which comprises the following steps:
s1: respectively adding a phenylimidazole compound and a phenolic compound into a reaction container, and reacting for 4-6 hours under the illumination condition of blue LED light at 20-25 ℃ under the action of palladium acetate and isopropanol.
In the step, the benzimidazole compound is synthesized by utilizing the benzimidazole compound and the phenolic compound, specifically, under the condition of illumination, a palladium catalyst reacts with the phenolic compound to generate an aryl palladium intermediate, and the intermediate reacts with the benzimidazole compound to generate a target product. The reaction in the step does not need heating, the dosage of the catalyst is extremely low, the cost of raw materials can be reduced, the energy consumption can be reduced, and the environment friendliness can be kept; in addition, the method has good selectivity, and the product yield can reach more than 95%. It is understood that the reaction time set in this step is set under the illumination condition of 10W of LED lamp, and those skilled in the art can adjust the reaction time according to the illumination condition of LED lamp and the actual reaction condition, as long as the reaction of the reaction raw material is ensured to be sufficient.
S2: and after the reaction is finished, performing column chromatography separation to obtain the benzimidazole compound.
In a preferred embodiment, the phenylimidazole compounds have the following structural formula (a):
wherein R is1Is selected from-OCH3or-H, R2Is selected from-CH3or-H, R3Is selected from-CH3-H or-Cl.
In a preferred embodiment, the phenolic compound is phenol or p-trifluoromethylphenol.
In a preferred embodiment, the benzimidazole compound has the following structural formula (B):
wherein R is1Is selected from-Ph or-H, R2Is selected from OCH3or-H, R3Is selected from-CF3or-H, R4Is selected from-CH3or-H, R5Is selected from-CH3-H or-Cl.
The specific structural formula of the benzimidazole compound used in the above embodiment is specifically defined, and it is understood that the benzimidazole compound defined in this embodiment is a compound derived based on benzimidazole, and the structure is relatively simple, but this embodiment does not exclude the benzimidazole compound finally obtained in the present invention from being prepared from benzimidazole derivatives having a relatively complex structure.
In a preferred embodiment, the millimolar ratio of the phenylimidazole compound to the phenolic compound is 1:1-1: 2. In the embodiment, the addition amount of the raw materials participating in the reaction is specifically given, wherein the addition amount of the phenolic compound can be equal to or excessive relative to the phenylimidazole compound, so that the sufficient reaction of the phenylimidazole compound and the phenolic compound can be ensured; in a preferred embodiment, the millimolar ratio of the phenylimidazole compound to palladium acetate and isopropanol is 1:0.001:2 to 1:0.002: 3. In this example, the amounts of palladium acetate and isopropyl alcohol added may be equal or excessive relative to the phenylimidazole compound, so as to ensure complete reaction of the whole system and prepare the desired compound.
In a preferred embodiment, the chromatographic column used in the column chromatography is a silica gel column, and the eluent used is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:5-2: 1. In this example, the product obtained by the reaction was subjected to gradient elution with a silica gel column to separate the desired synthesized product. In this embodiment, gradient elution is performed by using a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1:5 to 2:1, according to the principle of similar phase solubility and considering the polarity of the synthesized product, and within this range, the skilled person can adjust the gradient elution according to the actual situation.
The embodiment of the invention also provides application of the compound synthesized by the synthesis method according to any one of the embodiments in prevention and treatment of crop pathogens. Specifically, the prepared compound can be effectively applied to the control of apple canker and botrytis cinerea, and can be selected to be used singly or in combination according to requirements.
In order to more clearly and specifically describe the synthesis method and the agricultural biological activity of the benzimidazole compounds provided in the examples of the present invention, the following description will be given with reference to the specific examples.
Example 1
Respectively adding 1mmol of 2-phenylimidazo [1,2- α ] pyridine, 1mmol of phenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel, reacting for 4 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED light, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (1):
the white solid powder was subjected to nuclear magnetic spectrum analysis, and the data were as follows:
1HNMR(400MHz,CDCl3)：δ7.96(d,J＝6.9Hz,1H),7.77-7.58(m,3H),7.60-7.46(m,5H),7.38-7.19(m,4H),6.79(ddd,J＝6.8,6.8,1.2Hz,1H)；
13CNMR(100MHz,CDCl3)：δ144.9,142.6,134.0,130.8,129.9,129.6,128.6,128.3,128.1,128.0,127.3,124.7,123.0,121.2,117.5,112.7；
after identification, the spectral data correspond to the structural formula, and the synthesized 2, 3-dibenzoimidazo [1,2- α pyridine ] is proved to have the yield of 98%.
Example 2
Respectively adding 1mmol of 3- (2-methoxyphenyl) imidazo [1,2- α ] pyridine, 1mmol of phenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel, reacting for 4 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED lamp, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (2):
the light brown solid powder was subjected to nuclear magnetic spectroscopy and the data were as follows:
1HNMR(400MHz,CDCl3)：δ8.26(ddd,J＝7.0,1.2,1.1Hz,1H),7.70(ddd,J＝9.1,1.2,1.1Hz,1H),7.63(dd,J＝7.5,1.8Hz,1H),7.46-7.33(m,5H),7.20(ddd,J＝9.1,6.7,1.3Hz,1H),7.02(ddd,J＝7.5,7.4,1.1Hz,1H),6.82(dd,J＝8.3,1.0Hz,1H),6.78(ddd,J＝6.9,6.8,1.2Hz,1H),3.36(s,3H)；
13CNMR(100MHz,CDCl3)：δ156.8,144.6,140.8,132.0,130.9,129.4,129.2,128.7,127.9,124.3,123.8,123.2,122.9,120.7,118.0,112.5,111.0,54.9；
after identification, the spectral data correspond to the structural formula, and the synthesized 2-phenyl-3- (2-methoxyphenyl) imidazo [1,2- α ] pyridine is proved to have the yield of 97%.
Example 3
Respectively adding 1mmol of 3-phenylimidazo [1,2- α ] pyridine, 1mmol of p-trifluoromethylphenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel, reacting for 6 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED light, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (3):
the light brown solid powder was subjected to nuclear magnetic spectroscopy and the data were as follows:
1HNMR(400MHz,CDCl3)：δ8.02(d,J＝6.9Hz,1H),7.76(d,J＝8.1Hz,2H),7.72(d,J＝9.1Hz,1H),7.66-7.54(m,4H),7.36-7.16(m,4H),6.77(dd,J＝6.7,6.5Hz,1H)；
13CNMR(100MHz,CDCl3)：δ145.2,143.6,133.8,131.0,130.8,128.6,128.4,127.9,126.6,126.2,125.2,123.0,121.9,119.7,117.9,117.5,112.9；
after identification, the spectral data corresponded to the structural formula, demonstrating that 2- (4-trifluoromethylphenyl) -3-benzimidazolo [1,2- α ] pyridine was synthesized in 96% yield.
Example 4
Respectively adding 1mmol of 7-methyl-3-phenylimidazo [1,2- α ] pyridine, 1mmol of phenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel, reacting for 6 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED lamp, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (4):
the light brown solid powder was subjected to nuclear magnetic spectroscopy and the data were as follows:
1HNMR(400MHz,CDCl3)：δ7.85(d,J＝7.0Hz,1H),7.68(d,J＝7.6Hz,2H),7.59-7.36(m,6H),7.34-7.24(m,3H),6.59(d,J＝6.8Hz,1H),2.43(s,3H)；
13CNMR(100MHz,CDCl3)：δ145.5,142.1,135.8,134.4,130.9,130.1,129.6,128.8,128.4,128.1,127.4,122.8,120.6,115.7,115.0,21.6；
after identification, the spectral data corresponded to the structural formula, demonstrating that 7-methyl-2, 3-dibenzoimidazo [1,2- α ] pyridine was synthesized in 95% yield.
Example 5
Adding 1mmol of 8-trifluoromethyl-3-phenylimidazo [1,2- α ] pyridine, 1mmol of phenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel respectively, reacting for 5 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED lamp, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (5):
the above yellow solid powder was subjected to nuclear magnetic spectrum analysis, and the data were as follows:
1HNMR(400MHz,CDCl3)：δ8.26(s,1H),7.82-7.71(m,1H),7.70-7.65(m,2H),7.58-7.52(m,3H),7.48-7.43(m,2H),7.39-7.25(m,4H)；
13CNMR(100MHz,CDCl3)：δ144.8,144.4,133.5,130.6,130.0,129.8,128.9,128.6,128.2,128.2,125.9,122.4,121.8,120.6,118.4,116.8；
after identification, the spectral data correspond to the structural formula, and the synthesized 8-trifluoromethyl-2, 3-dibenzoimidazo [1,2- α ] pyridine is proved to have the yield of 98%.
Example 6
Adding 1mmol of 8-chloro-3-phenylimidazo [1,2- α ] pyridine, 1mmol of phenol, 0.001mmol of palladium acetate and 2ml of isopropanol into a reaction vessel respectively, reacting for 5 hours at the temperature of 20-25 ℃ under the illumination condition of 10W blue LED light, and after the reaction is finished, carrying out column chromatography separation to obtain the following compound (6):
the above yellow solid powder was subjected to nuclear magnetic spectrum analysis, and the data were as follows:
1HNMR(400MHz,CDCl3)：δ7.98(dd,J＝2.0,0.9Hz,1H),7.67-7.58(m,3H),7.57-7.49(m,3H),7.46-7.40(m,2H),7.32-7.21(m,3H),7.15(dd,J＝9.5,2.0Hz,1H)；
13CNMR(100MHz,CDCl3)：δ143.7,143.2,133.6,130.7,129.8,129.4,129.4,128.4,128.1,127.9,126.3,121.7,121.1,120.7,118.2；
after identification, the spectral data corresponded to the structural formula, demonstrating that 8-chloro-2, 3-dibenzoimidazo [1,2- α ] pyridine was synthesized in 95% yield.
Performance testing
Respectively weighing 30mg of the synthesized compounds to be tested, then adding 3mL of acetone, and respectively dissolving and preparing liquid medicine mother liquor with the concentration of 10000 mg/L; 0.5mL of the above mother liquor was added with 2mL of acetone, and dissolved to prepare a 2000mg/L solution. Adding 1mL of each of the two liquid medicines into 100mL of molten PDA culture medium, mixing well to obtain toxic culture medium, mixing the toxic culture medium uniformly, pouring into 6 culture dishes of 6cm, and cooling to obtain flat plate. 1mL of acetone was added to 100mL of melted PDA medium as a blank (CK). The fungus cakes were cultured on the above PDA medium containing the liquid medicine, and each treatment was repeated three times. The inoculated plate was sealed and placed in an incubator (28 ℃ C.) for culture, and when the colony of the white control strain grew to about 3/4 on the petri dish, the diameter of the colony was measured, and the colony growth inhibition rate was calculated, and the measurement results are shown in Table 1.
Colony growth inhibition rate: inhibition/% ([ control colony diameter-treated colony diameter ]/control colony diameter × 100)
TABLE 1 percent inhibition of pathogen growth at 20mg/L for each compound
| Compound (I) | Rot of apple | Botrytis cinerea |
| Example 1 | 93 | 86 |
| Example 2 | 99.6 | 98 |
| Example 3 | 96 | 88.2 |
| Example 4 | 76 | 81 |
| Example 5 | 85.8 | 98.3 |
| Example 6 | 99 | 97 |
As can be seen from the data in Table 1, the compounds prepared in the above examples 1-6 of the present invention have good bacteriostatic effects on both apple rot and Botrytis cinerea, wherein the bacteriostatic effects on apple rot in examples 2 and 6 can reach more than 99%, and the bacteriostatic effects on Botrytis cinerea in examples 2 and 5 can reach more than 98%. Therefore, in order to effectively inhibit the above germs, the compounds prepared in the above examples can be selected to be used alone or in combination in order to obtain a better bacteriostatic effect.
Claims (5)
1. A method for synthesizing benzimidazole compounds is characterized by comprising the following steps:
respectively adding the compound of the formula (A) and the phenolic compound into a reaction container, and reacting for 4-6 hours under the illumination condition of blue LED light at 20-25 ℃ under the action of palladium acetate and isopropanol;
after the reaction is finished, carrying out column chromatographic separation to obtain the benzimidazole compound shown as the formula (B);
wherein the compound of formula (a) has the following structural formula:
in the formula (A), R1Is selected from-OCH3or-H, R2Is selected from-CH3or-H, R3Is selected from-CH3-H or-Cl;
the phenolic compound is phenol or p-trifluoromethylphenol;
the benzimidazole compound of the formula (B) has the following structural formula:
in the formula (B), R1Is selected from-OCH3or-H, R2Is selected from-CH3or-H, R3Is selected from-CH3-H or-Cl, R4Selected from phenyl or trifluoromethylphenyl.
2. The synthesis process according to claim 1, characterized in that the millimolar ratio of the compound of formula (a) and the phenolic compound is from 1:1 to 1: 2.
3. The method of synthesis of claim 1, wherein the millimolar ratio of the compound of formula (a) to palladium acetate and isopropanol is 1:0.001:2 to 1:0.002: 3.
4. The synthesis method according to claim 1, wherein the column used in the column chromatography is a silica gel column, and the eluent used is a mixed solvent of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 1:5-2: 1.
5. The compound synthesized by the synthesis method according to any one of claims 1 to 4 is applied to preventing and controlling crop pathogens.
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| WO2002048146A2 (en) * | 2000-12-13 | 2002-06-20 | Basf Aktiengesellschaft | Use of substituted imidazoazines, novel imidazoazines, methods for the production thereof, and agents containing these compounds |
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| WO2002048146A2 (en) * | 2000-12-13 | 2002-06-20 | Basf Aktiengesellschaft | Use of substituted imidazoazines, novel imidazoazines, methods for the production thereof, and agents containing these compounds |
Non-Patent Citations (2)
| Title |
|---|
| Direct Arylation of Imidazo[1,2-a]pyridine at C-3 with Aryl Iodides, Bromides, and Triflates via Copper(I)-Catalyzed C-H Bond Functionalization;Joana F. Campos et al.;《Organic Letters》;20120314;第14卷(第7期);第1688–1691页 * |
| On water direct arylation of imidazo[1,2-a]pyridines with aryl halides;Saradhi Kalari et al.;《Tetrahedron Letters》;20171231;第58卷;第2818-2821页 * |
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