CN109810062B - Phenylimidazole derivative, synthesis method thereof and application of phenylimidazole derivative in pesticide - Google Patents
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Abstract
The invention relates to a phenylimidazole derivative, a synthesis method thereof and application thereof in pesticides, in particular to application thereof in fungicide pesticides, belonging to the technical field of pesticides. The invention aims to provide a novel phenylimidazole derivative, a synthetic method thereof and application thereof in pesticides, wherein the structure of the compound is shown as a formula I. The compound has simple and novel structure, easy synthesis and fungicidal activity, and has good bacteriostatic or bactericidal effect on important plant pathogenic fungi such as early blight of tomato, gray mold of tomato, cucumber fusarium wilt, rice blast, rice sheath blight and the like.
Description
Technical Field
The invention relates to a phenylimidazole derivative, a synthesis method thereof and application thereof in pesticides, in particular to application thereof in fungicide pesticides, belonging to the technical field of pesticides.
Background
Carvacrol and thymol are the main components of many aromatic plant volatile oils and are phenolic monoterpene compounds. The compound has wide biological activity, and researches show that the compound has the biological activities of relieving pain, resisting inflammation, resisting arthritis, resisting cancer, resisting diabetes, protecting cardiac muscle, protecting gastrointestinal tract, protecting liver, protecting nerves and the like, and also has the biological activities of inhibiting pathogenic bacteria and viruses which are sensitive to human antibiotics and have drug resistance, inhibiting pathogenic fungi, resisting parasites, killing insects, sterilizing, resisting fungi, resisting oxidation and the like. Therefore, in recent years, studies on carvacrol, thymol and derivatives thereof have been actively conducted.
In recent years, heterocyclic compounds have shown more and more important roles in the research and development of pesticides due to their good selectivity, high activity, low dosage, low toxicity and specificity in the physiological and biochemical reactions of pests. Imidazole compounds, one of the most important classes of heterocyclic compounds, have been developed successfully in the pesticide and medicine fields and are marketed for production and sale, and due to the special structure and biological activity, imidazole compounds have become hot spots and frontiers for research and development in the pesticide field.
The natural active molecule is used as a lead compound to design and synthesize a compound with application prospect, and the method is one of new pesticide discovery methods. The imidazole ring is introduced into the structures of natural active substances of carvacrol and thymol, some phenylimidazole derivatives are designed and synthesized, some active compounds or active lead compounds with novel structures and excellent activity are found, and a certain foundation is laid for creating new pesticides. The phenylimidazole derivative has antibacterial effect. So far, the phenylimidazole derivative has not been reported as an agricultural fungicide.
Disclosure of Invention
The invention aims to solve the technical problems of limited types, general activity and lack of natural active molecular compounds in the prior art, provides a phenylimidazole derivative with novel structure, excellent activity and bactericidal effect, a synthesis method and application thereof in pesticides, and lays a foundation for creating new pesticides.
In order to solve the technical problems, the invention provides a phenylimidazole derivative, which has a structure shown in a formula I:
wherein R is1Is any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl; r2Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butylAny of a phenyl group, a naphthyl group, an isopentyl group, or a neopentyl group; r3Is any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine and nitro; r4Is any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine and nitro; r5Is any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine and nitro; r6Any one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, acetyl, propionyl, butyryl and benzoyl.
Preferably, R is1Is methyl or isopropyl, R2Is methyl or isopropyl, R3Is any one of hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R4Is any one of hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R5Is any one of hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R6Is methyl or ethyl.
As a further preferable mode, the R is1Is methyl or isopropyl, R2Is methyl or isopropyl, R3Is any one of hydrogen, methyl, fluorine or chlorine, R4Is any one of hydrogen, methyl, fluorine or chlorine, R5Is any one of hydrogen, methyl, fluorine or chlorine, R6Is methyl or ethyl.
More preferably, the structural formula of the phenylimidazole derivative is one of the following:
the synthetic method of the phenylimidazole derivative can be according to a chemical synthesis method, and the synthetic process is as follows:
the method for synthesizing the phenylimidazole derivative comprises the following specific steps:
(1) raw material preparation
Taking carvacrol, thymol, imidazole and other chemical reagents sold in the market as raw materials for standby.
(2) Synthesis of intermediate I
Adding phenol (carvacrol or thymol) into a container, dissolving with DMF, respectively adding potassium carbonate and halogenated alkane after completely dissolving, and stirring at room temperature for reaction for 10-24 h. The reaction was monitored by TLC, and after completion of the reaction, distilled water was added, extracted with ethyl acetate, and the solvent was distilled off under reduced pressure. And separating and purifying the obtained product by column chromatography to obtain an intermediate I.
(3) Synthesis of intermediate II
Dissolving the intermediate I in acetic acid in a container, cooling to 0 ℃, slowly dropwise adding liquid bromine by using a constant-pressure dropping funnel while stirring, and after dropwise adding, raising the temperature of the reaction to room temperature and continuing the reaction for 6 hours. And after the reaction is finished, pouring the reaction compound into ice water, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate, evaporating to dryness under reduced pressure, and separating by column chromatography to obtain an intermediate II.
(4) Synthesis of the target Compound
N2Under the protection, adding the intermediate II, imidazole, potassium carbonate and cuprous iodide into a container, dissolving by using a DMF (dimethyl formamide) solvent, vacuumizing a reaction system, filling nitrogen, heating to 150 ℃, and reacting for 40 hours. And adding distilled water after the reaction is finished, extracting with ethyl acetate, drying an organic phase, evaporating to dryness under reduced pressure, and separating by column chromatography to obtain a target product.
The phenylimidazole derivative can be applied to inhibiting or killing plant pathogenic fungi.
The plant pathogenic fungi are early blight of tomato, gray mold of tomato, cucumber fusarium wilt, rice blast or rice sheath blight.
In addition, the phenylimidazole derivative can be used as an active ingredient to prepare a pesticide, and the pesticide has a bactericidal effect. The invention also provides a pesticide with a sterilization function, and the active ingredient of the pesticide is the phenylimidazole derivative.
Compared with the prior art, the invention has the following beneficial effects:
the phenylimidazole derivative has a simple and novel structure, is easy to synthesize, has bactericidal activity, and has a good bactericidal effect on plant pathogenic fungi such as early blight of tomato, botrytis cinerea, fusarium oxysporum, rice blast or rice sheath blight. The phenylimidazole derivative is not reported in the existing known bactericides, and lays a certain foundation for the creation of new pesticides.
Drawings
FIG. 1 is a structural formula of a phenylimidazole derivative of the present invention.
FIG. 2 is four representative representations of the structural formulae of the phenylimidazole derivatives of the present invention.
FIG. 3 is a reaction scheme for the synthesis of phenylimidazole derivatives according to the present invention.
Detailed Description
In the following, embodiments of the present invention will be described in further detail, and techniques or products not mentioned in the examples are all conventional techniques or conventional products available by purchase.
The phenylimidazole derivative has a structure shown in a formula I:
wherein R is1Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl; r2Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl or neopentyl; r3Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro; r4Is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitreA group; r5Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro; r6Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, acetyl, propionyl, butyryl and benzoyl.
The synthetic method of the phenylimidazole derivative comprises the following synthetic steps:
the application of the phenylimidazole derivative in pesticides is used for inhibiting or killing plant pathogenic fungi, wherein the plant pathogenic fungi which are inhibited or killed are early blight of tomato, botrytis cinerea, cucumber fusarium wilt, rice blast or rice sheath blight.
Example 1: phenylimidazole compounds
（C15H20N2O) synthesis.
The method for synthesizing the phenylimidazole derivative comprises the following specific steps:
(1) synthesis of intermediate 4-isopropyl-3-ethoxytoluene
In a 10mL round-bottomed flask, 10 mmol of thymol was dissolved in 2 mL of DMF, and after complete dissolution, 12mmol of potassium carbonate and 12mmol of ethyl bromide were added, respectively, and the reaction was stirred at room temperature for 15 hours. The reaction was monitored by TLC, and after completion of the reaction, distilled water was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and evaporated to dryness under reduced pressure. The obtained crude product is separated and purified by column chromatography (petroleum ether: ethyl acetate =10: 1) to obtain an intermediate 4-isopropyl-3-ethoxytoluene.
(2) Synthesis of intermediate 2-methyl-5-isopropyl-4-ethoxy bromobenzene
Dissolving 10 mmol of intermediate 4-isopropyl-3-ethoxytoluene in 20 mL of acetic acid, cooling to 0 ℃, dropwise adding 11 mmol of liquid bromine by using a constant-pressure dropping funnel within 20 min under stirring, heating to room temperature after dropwise addition, and continuing to react for 6 h. And stopping the reaction, pouring the reaction solution into 50 mL of ice water, extracting with 30mL of dichloromethane for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, decompressing and evaporating to dryness, and performing column chromatography separation to obtain an intermediate 2-methyl-5-isopropyl-4-ethoxybromobenzene.
(3) Synthesis of target Compound
N2Under protection, 10 mmol of intermediate 2-methyl-5-isopropyl-4-ethoxy bromobenzene, 15mmol of imidazole, 20 mmol of potassium carbonate and 2mmol of cuprous iodide are dissolved in 5 mL of DMF, and the mixture is vacuumized, filled with nitrogen for 3 times, heated to 150 ℃ and reacted for 40 hours. And after the reaction is finished, adding 30mL of distilled water, extracting with 30mL of ethyl acetate for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, evaporating to dryness under reduced pressure, and separating by column chromatography to obtain the target compound.
The spectral data of the product obtained are as follows:1H NMR (500 MHz, DMSO-d 6) δ 7.73 (t, J = 1.1 Hz, 1H, Ar-H), 7.30 (t, J = 1.3 Hz, 1H, Ar-H), 7.07 – 7.01 (m, 2H, Ar-H), 6.95 (s, 1H, Ar-H), 4.09 (m, J = 7.0 Hz, 2H, -CH2), 3.22 (p, J = 6.9 Hz, 1H, -CH), 2.07 (s, 3H, -CH3), 1.37 (t, J = 6.9 Hz, 3H, -CH3), 1.16 (d, J = 6.9 Hz, 6H, -CH3).13C NMR (125 MHz, DMSO-d 6) δ 155.8, 138.3, 135.2, 132.0, 129.7, 128.9, 124.4, 121.6, 114.4, 64.1, 26.8, 22.8, 17.6, 15.2。
the obtained phenylimidazole derivative is used for determining the bacteriostatic activity of the plant pathogenic fungi as follows:
test for phytopathogenic fungi: early blight of tomato, gray mold of tomato, fusarium wilt of cucumber, rice blast and rice sheath blight of rice.
The experimental method used was: dissolving 5 mg of a compound to be detected in acetone to prepare mother liquor with different concentrations, adding the mother liquor into a PDA culture medium in a proportion of 1%, and cooling to obtain a toxic culture medium with a concentration of 50 ppm. An equal amount of acetone was added to the PDA medium and cooled to serve as a blank. Preparing the activated strain to be detected into a bacterial cake with the diameter of 5mm by using a puncher, respectively inoculating the bacterial cake to a culture medium with toxicity and a blank control culture medium, and repeating for 3 times. All culture dishes are cultured at a constant temperature of 25-26 ℃, when the diameter of the colony treated by the blank control grows to be nearly 8cm, the diameter of each treated colony is measured by a cross method, and the hypha growth inhibition rate is calculated by the following formula:
the experimental results are as follows: the result of the determination of the bacteriostatic activity of the phenylimidazole derivative on plant pathogenic fungi is shown in table 1.
TABLE 1 Compound of example 1 at 50 mg.L-1Inhibitory Activity against plant pathogenic fungi
As is clear from Table 1, the compound obtained in example 1 has a good inhibitory effect against Fusarium oxysporum, Pyricularia oryzae, and Rhizoctonia solani.
Example 2: phenylimidazole compounds
（C14H18N2O) synthesis.
The method for synthesizing the phenylimidazole derivative comprises the following specific steps:
(1) synthesis of intermediate 4-isopropyl-2-methoxytoluene
In a 10mL round-bottom flask, 10 mmol of carvacrol is dissolved by 2 mL of DMF, after the carvacrol is completely dissolved, 12mmol of potassium carbonate and 12mmol of methyl iodide are respectively added, and the reaction is stirred at room temperature for 24 hours. The reaction was monitored by TLC, and after completion of the reaction, distilled water was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and evaporated to dryness under reduced pressure. The obtained crude product is separated and purified by column chromatography to obtain an intermediate 4-isopropyl-2-methoxyl toluene.
(2) Synthesis of intermediate 5-methyl-2-isopropyl-4-methoxy bromobenzene
Dissolving 10 mmol of intermediate 4-isopropyl-2-methoxytoluene in 20 mL of acetic acid, cooling to 0 ℃, dropwise adding 11 mmol of liquid bromine by using a constant-pressure dropping funnel within 20 min under stirring, heating to room temperature after dropwise adding, and continuing to react for 6 h. And stopping the reaction, pouring the reaction solution into 50 mL of ice water, extracting with 30mL of dichloromethane for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, decompressing, evaporating to dryness, and performing column chromatography separation to obtain an intermediate 5-methyl-2-isopropyl-4-methoxybromobenzene.
(3) Synthesis of target Compound
N2Under protection, 10 mmol of intermediate 5-methyl-2-isopropyl-4-methoxy bromobenzene, 15mmol of imidazole, 20 mmol of potassium carbonate and 2mmol of cuprous iodide are dissolved in 5 mL of DMF, and the mixture is vacuumized, filled with nitrogen for 3 times, heated to 150 ℃ and reacted for 40 hours. And after the reaction is finished, adding 30mL of distilled water, extracting with 30mL of ethyl acetate for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, evaporating to dryness under reduced pressure, and separating by column chromatography to obtain the target compound.
The spectral data of the product obtained are as follows:1H NMR (500 MHz, DMSO-d 6) δ 7.70 (s, 1H, Ar-H), 7.27 (s, 1H, Ar-H), 7.18 – 7.02 (m, 2H, Ar-H), 6.97 (s, 1H, Ar-H), 3.86 (s, 3H, -CH3), 2.57 – 2.45 (m, 1H, -CH), 2.13 (s, 3H, -CH3), 1.13 (d, J = 6.9 Hz, 6H, -CH3).13C NMR (125 MHz, DMSO-d 6) δ 158.3, 143.8, 129.2, 127.8, 124.5, 108.2, 56.1, 28.0, 24.2, 15.7。
the obtained phenylimidazole derivative is used for determining the bacteriostatic activity of the plant pathogenic fungi as follows:
test for phytopathogenic fungi: early blight of tomato, gray mold of tomato, fusarium wilt of cucumber, rice blast and rice sheath blight of rice.
The results of the determination of the bacteriostatic activity of the phenylimidazole derivatives against phytopathogenic fungi using the same experimental method as in example 1 are shown in table 2.
TABLE 2 Compounds of example 2 at 50 mg. L-1Inhibitory Activity against plant pathogenic fungi
As is clear from Table 2, the compound of example 2 has a good inhibitory effect on early blight of tomato, Botrytis cinerea, Fusarium oxysporum of cucumber, Pyricularia oryzae and Rhizoctonia solani.
Example 3: phenylimidazole compounds
（C15H20N2O) synthesis.
The method for synthesizing the phenylimidazole derivative comprises the following specific steps:
(1) synthesis of intermediate 4-isopropyl-2-ethoxytoluene
In a 10mL round-bottom flask, 10 mmol of carvacrol is dissolved in 2 mL of DMF, and after the carvacrol is completely dissolved, 12mmol of potassium carbonate and 12mmol of bromoethane are respectively added, and the reaction is stirred at room temperature for 10 hours. The reaction was monitored by TLC, and after completion of the reaction, distilled water was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and evaporated to dryness under reduced pressure. The obtained crude product is separated and purified by column chromatography (petroleum ether: ethyl acetate =10: 1) to obtain an intermediate 4-isopropyl-2-ethoxytoluene.
(2) Synthesis of intermediate 5-methyl-2-isopropyl-4-ethoxy bromobenzene
Dissolving 10 mmol of intermediate 4-isopropyl-2-ethoxytoluene in 20 mL of acetic acid, cooling to 0 ℃, dropwise adding 11 mmol of liquid bromine by using a constant-pressure dropping funnel within 20 min under stirring, heating to room temperature after dropwise addition, and continuing to react for 6 h. And stopping the reaction, pouring the reaction solution into 50 mL of ice water, extracting with 30mL of dichloromethane for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, decompressing and evaporating to dryness, and performing column chromatography separation to obtain an intermediate 5-methyl-2-isopropyl-4-ethoxybromobenzene.
(3) Synthesis of target Compound
N2Under protection, 10 mmol of intermediate 5-isopropyl-2-methyl-4-ethoxy bromobenzene, 15mmol of imidazole, 20 mmol of potassium carbonate and 2mmol of cuprous iodide are dissolved in 5 mL of DMF, and the mixture is vacuumized, filled with nitrogen for 3 times, heated to 150 ℃ and reacted for 40 hours. And after the reaction is finished, adding 30mL of distilled water, extracting for three times by using 30mL of ethyl acetate, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, evaporating to dryness under reduced pressure, and separating by using column chromatography to obtain the target compound.
The spectral data of the product obtained are as follows:1H NMR (500 MHz, DMSO-d 6) δ: 7.67 (s, 1H), 7.24 (s, 1H), 7.07 – 7.01 (m, 2H), 6.95 (s, 1H), 4.12 (m, J = 6.9 Hz, 2H, -CH2), 2.56 – 2.46 (m, 1H,-CH), 2.13 (s, 3H), 1.37 (t, J = 6.9 Hz, 3H), 1.12 (d, J = 6.9 Hz, 6H). 13C NMR (125 MHz, DMSO-d6) δ: 157.5, 143.7, 129.3, 129.0, 127.7, 124.7, 109.2, 64.1, 27.9, 24.2, 15.7, 15.2。
the obtained phenylimidazole derivative is used for determining the bacteriostatic activity of the plant pathogenic fungi as follows:
test for phytopathogenic fungi: early blight of tomato, gray mold of tomato, fusarium wilt of cucumber, rice blast and rice sheath blight of rice.
The results of the determination of the bacteriostatic activity of the phenylimidazole derivatives against phytopathogenic fungi using the same experimental method as in example 1 are shown in table 3.
TABLE 3 Compound of example 3 at 50 mg.L-1Inhibitory Activity against plant pathogenic fungi
As is clear from Table 3, the compound of example 3 has a good inhibitory effect on early blight of tomato, Botrytis cinerea, Fusarium oxysporum of cucumber, Pyricularia oryzae, and Rhizoctonia solani.
Example 4: phenylimidazole compounds
（C14H18N2O) synthesis.
The method for synthesizing the phenylimidazole derivative comprises the following specific steps:
(1) synthesis of intermediate 4-isopropyl-3-methoxytoluene
In a 10mL round bottom flask, 10 mmol carvacrol is dissolved by 2 mL DMF, after the carvacrol is completely dissolved, 12mmol potassium carbonate and 12mmol iodoalkane are respectively added, and the reaction is stirred at room temperature for 24 h. The reaction was monitored by TLC, and after completion of the reaction, distilled water was added, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and evaporated to dryness under reduced pressure. The obtained crude product is separated and purified by column chromatography to obtain an intermediate 4-isopropyl-3-methoxytoluene.
(2) Synthesis of intermediate 5-methyl-2-isopropyl-4-methoxy bromobenzene
Dissolving 10 mmol of intermediate 4-isopropyl-3-methoxytoluene in 20 mL of acetic acid, cooling to 0 ℃, dropwise adding 11 mmol of liquid bromine by using a constant-pressure dropping funnel within 20 min under stirring, heating to room temperature after dropwise adding, and continuing to react for 6 h. And stopping the reaction, pouring the reaction solution into 50 mL of ice water, extracting with 30mL of dichloromethane for three times, combining organic phases, drying the organic phases with anhydrous sodium sulfate, decompressing and evaporating to dryness, and performing column chromatography separation to obtain an intermediate 5-methyl-2-isopropyl-4-methoxybromobenzene.
(3) Synthesis of target Compound
N2Under protection, 10 mmol of intermediate 2-isopropyl-5-methyl-4-methoxy bromobenzene, 15mmol of imidazole, 20 mmol of potassium carbonate and 2mmol of cuprous iodide are dissolved in 5 mL of DMF, and the mixture is vacuumized, filled with nitrogen for 3 times, heated to 150 ℃ and reacted for 40 hours. And after the reaction is finished, adding 30mL of distilled water, extracting for three times by using 30mL of ethyl acetate, combining organic phases, drying the organic phases by using anhydrous sodium sulfate, evaporating to dryness under reduced pressure, and separating by using column chromatography to obtain the target compound.
The spectral data of the product obtained are as follows:1H NMR (500 MHz, DMSO-d 6) δ: 7.73 (s, 1H, Ar-H), 7.30 (s, 1H, Ar-H), 7.05 (d, J = 6.7 Hz, 2H, Ar-H), 6.97 (s, 1H, Ar-H), 3.84 (s, 3H, -CH3), 3.21 (p, J = 6.9 Hz, 1H, -CH), 2.08 (s, 3H, -CH3), 1.15 (d, J = 7.0 Hz, 6H, -CH3). 13C NMR (125 MHz, DMSO-d6) δ: 156.5, 138.3, 135.0, 132.1, 129.7, 128.9, 124.4, 121.6, 113.5, 56.3, 26.5, 22.8, 17.7。
the obtained phenylimidazole derivative is used for determining the bacteriostatic activity of the plant pathogenic fungi as follows:
test for phytopathogenic fungi: early blight of tomato, gray mold of tomato, fusarium wilt of cucumber, rice blast and rice sheath blight of rice.
The results of the determination of the bacteriostatic activity of the phenylimidazole derivatives against phytopathogenic fungi using the same experimental method as in example 1 are shown in table 4.
TABLE 4 Compound of example 4 at 50 mg.L-1Inhibitory Activity against plant pathogenic fungi
As is clear from Table 4, the compound of example 4 has a good inhibitory effect on early blight of tomato, Botrytis cinerea, Fusarium oxysporum of cucumber, Pyricularia oryzae, and Rhizoctonia solani.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (4)
1. A phenylimidazole derivative is characterized in that the structure of the phenylimidazole derivative is shown as a formula I:
the structural formula of the phenylimidazole derivative is one of the following formulas:
2. a method for synthesizing a phenylimidazole derivative according to claim 1, which comprises: the synthesis steps of the phenylimidazole derivative are as follows:
the synthesis method comprises the following specific steps:
2.1 preparation of the starting Material
Taking carvacrol, thymol and imidazole as chemical reagent raw materials sold in markets for standby;
2.2 Synthesis of intermediate I
Adding carvacrol or thymol into a container, dissolving with DMF, respectively adding potassium carbonate and halogenated alkane after complete dissolution, and stirring at room temperature for reaction for 10-24 h; monitoring the reaction by TLC, adding distilled water after the reaction is finished, extracting by using ethyl acetate, evaporating the solvent under reduced pressure, and separating and purifying the obtained product by column chromatography to obtain an intermediate I;
2.3 Synthesis of intermediate II
Dissolving the intermediate I in acetic acid in a container, cooling to 0 ℃, slowly dropwise adding liquid bromine by using a constant-pressure dropping funnel while stirring, and heating the reaction to room temperature after dropwise adding is finished to continue reacting for 6 hours; after the reaction is finished, pouring the reaction compound into ice water, extracting with dichloromethane, drying an organic phase with anhydrous sodium sulfate, then evaporating to dryness under reduced pressure, and separating by column chromatography to obtain an intermediate II;
2.4 Synthesis of the target Compound
N2Under protection, adding the intermediate II, imidazole, potassium carbonate and cuprous iodide into a container, dissolving with a solvent DMF, vacuumizing a reaction system, filling nitrogen, and addingHeating to 150 ℃, and reacting for 40 hours; and adding distilled water after the reaction is finished, extracting with ethyl acetate, drying an organic phase, evaporating to dryness under reduced pressure, and separating by column chromatography to obtain a target product.
3. Use of the phenylimidazole derivatives according to claim 1 or 2 in pesticides characterized in that: the phenylimidazole derivatives are useful for inhibiting or killing phytopathogenic fungi.
4. The use of phenylimidazole derivatives according to claim 3 in pesticides, characterized in that: the plant pathogenic fungi are early blight of tomato, gray mold of tomato, cucumber fusarium wilt, rice blast or rice sheath blight.
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| Substituent and solvent eff ects on the fl uorescent and photochromic properties of 2-(2-pyridyl)imidazole containing diarylethene derivatives;Xuefeng Peng 等;《RSC Adv.》;20131231;第3卷;第24147页scheme 1、第24151页第1栏第2段 * |
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