CN109810062A - A kind of phenylimidazole derivatives and its synthetic method and the application in pesticide - Google Patents
A kind of phenylimidazole derivatives and its synthetic method and the application in pesticide Download PDFInfo
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Abstract
A kind of application the present invention relates to phenylimidazole derivatives and its synthetic method and in pesticide, the especially application in terms of fungicide pesticide, belong to technical field of pesticide.The structure of application the technical problem to be solved by the present invention is to provide new phenylimidazole derivatives and its synthetic method and in pesticide, the compound is shown in formula I.The compound structure is simple, novel, it is readily synthesized, there is Fungicidally active simultaneously, to the important plant pathogenic fungi such as tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae, Rhizoctonia solani Kuhn, there is preferable antibacterial or bactericidal effect.
Description
Technical field
A kind of application the present invention relates to phenylimidazole derivatives and its synthetic method and in pesticide is especially being killed very
Application in terms of microbial inoculum pesticide, belongs to technical field of pesticide.
Background technique
Carvacrol and Thymol are the main components of many fragment plant volatile oil, are phenols monoterpene.It should
Class compound has extensive bioactivity, and research finds that such compound has analgesic, anti-inflammatory, Antiarthritic, anticancer, anti-sugar
Urine disease, protection cardiac muscle, protection gastrointestinal tract, liver protection, the protection bioactivity such as nerve, also have inhibit to mankind's antibiotic sensitive and
There are the pathogenic bacteria and virus, inhibition pathogenic fungus, anti parasitic of drug resistance, desinsection, sterilization, antimycotic, anti-oxidant etc.
Bioactivity.Therefore, very active to the research of carvacrol and Thymol and its derivative in recent years.
In recent years, heterocyclic compound due to its selectivity it is good, it is active it is high, dosage is few, toxicity is low and in harmful organism it is raw
It manages the specificity in biochemical reaction and shows increasingly important role during the research and development of pesticide.Imidazoles chemical combination
Object has numerous Related products in pesticide and field of medicaments and is able to develop into as one of type most important in heterocyclic compound
Function simultaneously lists production and sales, and due to special structure and biological activity, imidazolium compounds has become pesticide field research and development
Hot spot and forward position.
Using natural activity molecule as lead compound, design synthesis has the compound of application prospect, is novel pesticide discovery
One of method.Imidazole ring is introduced into the structure of natural active matter carvacrol and Thymol by the present invention, and design synthesizes
Some phenylimidazole derivatives, it was found that some structure novels, the reactive compound of superior activity or activity lead compound are
Certain basis has been established in the initiative of novel pesticide.The phenylimidazole derivatives have bactericidal effect.Up to the present, it yet there are no
Report of the phenylimidazole derivatives as disinfectant use in agriculture.
Summary of the invention
The technical problem to be solved by the present invention is to for prior art type it is limited, active it is general, lack natural activity point
The deficiency of sub- compound proposes a kind of structure novel, superior activity, the phenylimidazole derivatives with bactericidal effect and its synthesis
Method and the application in pesticide lay the foundation for the initiative of novel pesticide.
In order to solve the above technical problems, the present invention provides a kind of phenylimidazole derivatives, structure is as shown in formula I:
Wherein, R1For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or new penta
Any one of base；R2For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or
Any one of neopentyl；R3For hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine,
Any one of chlorine, bromine, iodine, nitro；R4For hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl,
Any one of phenyl, fluorine, chlorine, bromine, iodine, nitro；R5For hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
Any one of tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R6For hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl,
Any one of isobutyl group, tert-butyl, acetyl group, propiono, bytyry, benzoyl.
Preferably, the R1For methyl or isopropyl, R2For methyl or isopropyl, R3For hydrogen, methyl, ethyl, fluorine, chlorine
Or any one of bromine, R4For any one of hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R5For hydrogen, methyl, ethyl, fluorine, chlorine or bromine
Any one of, R6For methyl or ethyl.
Scheme as a further preference, the R1For methyl or isopropyl, R2For methyl or isopropyl, R3For hydrogen, first
Any one of base, fluorine or chlorine, R4For any one of hydrogen, methyl, fluorine or chlorine, R5For any one of hydrogen, methyl, fluorine or chlorine,
R6For methyl or ethyl.
It is furthermore preferred that the structural formula of the phenylimidazole derivatives is one of following:
。
The synthetic method of phenylimidazole derivatives of the present invention, can be according to chemical synthesis, and synthesis technology is as follows:
。
Specific step is as follows for the synthetic method of the phenylimidazole derivatives:
(1) raw material preparation
Take the commercially available chemical reagent raw material for standby such as carvacrol, Thymol, imidazoles.
(2) synthetic intermediate I
Be added phenol (phenol be carvacrol or Thymol), dissolved with DMF in a reservoir, it is to be dissolved completely after be separately added into carbon
Sour potassium and halogenated alkane are stirred to react 10 h-24 h at room temperature.TLC monitoring reaction, distilled water is added after the reaction was completed, uses
Ethyl acetate extraction, decompression boil off solvent.Products therefrom obtains intermediate I by column chromatographic isolation and purification.
(3) synthetic intermediate II
It is under stirring that bromine constant pressure funnel is slow in a reservoir by intermediate I acetic acid and after being cooled to 0 DEG C
It is added dropwise to, by reaction 6 h that are warmed to room temperature that the reaction was continued after being added dropwise to complete.To which compound of reaction is poured into ice water after the reaction was completed
In, and be extracted with dichloromethane, evaporated under reduced pressure after organic phase anhydrous sodium sulfate drying obtains intermediate by column chromatography for separation
Ⅱ。
(4) synthesising target compound
N2Under protection, intermediate II, imidazoles, potassium carbonate and cuprous iodide are added in a reservoir, and dissolved with solvent DMF, it will be anti-
150 DEG C are heated to after answering system vacuum nitrogen gas, reacts 40 hours.Distilled water is added after the reaction was completed, uses ethyl acetate
Extraction, organic phase evaporated under reduced pressure after drying obtain target product through column chromatography for separation.
Phenylimidazole derivatives of the present invention can be applied to inhibit or kill plant pathogenic fungi.
The plant pathogenic fungi is tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae or water
Rhizoctonia solani Kuhn.
In addition, phenylimidazole derivatives of the present invention, moreover it is possible to be prepared into pesticide as active constituent, which has
The effect of sterilization.The present invention also provides a kind of pesticide for having sterilizing function, active constituent is phenylimidazole of the present invention
Derivative.
Compared with prior art, the invention has the following beneficial effects:
Phenylimidazole derivatives of the invention, structure is simple, novel, is readily synthesized, while having bactericidal activity, to tomato morning
The plant pathogenic fungis such as epidemic disease bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae or Rhizoctonia solani Kuhn have preferably
Bactericidal effect.The phenylimidazole derivatives have not been reported in the fungicide being currently known, and establish for the initiative of novel pesticide
Certain basis.
Detailed description of the invention
Fig. 1 is the structural formula of phenylimidazole derivatives of the present invention.
Fig. 2 is four kinds of classic manifestations of phenylimidazole derivatives structural formula of the present invention.
Fig. 3 is the synthetic reaction process figure of phenylimidazole derivatives of the present invention.
Specific embodiment
A specific embodiment of the invention is further described in detail below, the technology or production being not specified in embodiment
The conventional products that product are the prior art or can be obtained by purchase.
The structure of phenylimidazole derivatives of the present invention is as shown in formula I:
Wherein, R1For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or new penta
Base；R2For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or neopentyl；R3For
Hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R4For hydrogen,
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R5For hydrogen, first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R6For hydrogen, methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, acetyl group, propiono, bytyry, benzoyl.
Its synthesis step of the synthetic method of phenylimidazole derivatives of the present invention is as follows:
。
The application of phenylimidazole derivatives of the invention in pesticide is the institute for inhibiting or killing plant pathogenic fungi
The plant pathogenic fungi for inhibiting or killing is tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae or water
Rhizoctonia solani Kuhn.
Embodiment 1: Phenylimidazole compounds(C15H20N2O synthesis).
Specific step is as follows for the synthetic method of the phenylimidazole derivatives:
(1) synthesis of intermediate 4- isopropyl -3- ethyoxyl toluene
In the round-bottomed flask of 10mL, the Thymol of 10 mmol is dissolved with the DMF of 2 mL, it is to be dissolved completely after be separately added into
The bromoethane of the potassium carbonate of 12mmol and 12 mmol is stirred to react 15 h at room temperature.TLC monitoring reaction, after the reaction was completed plus
Enter distilled water, be extracted with ethyl acetate, anhydrous sodium sulfate is dry, evaporated under reduced pressure.Gained crude product use (petroleum ether: ethyl acetate=
10:1) column chromatographic isolation and purification obtains intermediate 4- isopropyl -3- ethyoxyl toluene.
(2) synthesis of intermediate 2- methyl -5- isopropyl -4- ethyoxyl bromobenzene
10 mmol intermediate 4- isopropyl -3- ethyoxyl toluene, the acetic acid of 20 mL and after being cooled to 0 DEG C, under stirring
The bromine of 11 mmol is added dropwise to constant pressure funnel in 20 min, reaction is warmed to room temperature continuation instead after being added dropwise to complete
Answer 6 h.Stop reaction, reaction solution is poured into the ice water of 50 mL, is extracted three times, merged organic with the methylene chloride of 30 mL
Phase, organic phase is dry with anhydrous sodium sulfate, and evaporated under reduced pressure, column chromatography for separation obtains intermediate 2- methyl -5- isopropyl -4- ethoxy
Bromide benzene.
(3) synthesis of target compound
N2Under protection, by 10 mmol intermediate 2- methyl -5- isopropyl -4- ethyoxyl bromobenzenes, 15mmol imidazoles, 20 mmol
Potassium carbonate, the cuprous iodide of 2 mmol are dissolved in the DMF of 5 mL, 150 DEG C are heated to after vacuum nitrogen gas 3 times, reaction 40
A hour.The distilled water of 30mL is added after the reaction was completed, is extracted three times with the ethyl acetate of 30 mL, merges organic phase, organic phase
Dry, the evaporated under reduced pressure with anhydrous sodium sulfate, column chromatography for separation obtain target compound.
The spectroscopic data of products therefrom is 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。
Antibacterial Activity situation of the gained phenylimidazole derivatives for plant pathogenic fungi is as follows:
Test plant disease fungus: tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae, rice banded sclerotial blight
Germ.
The experimental method of use: taking the untested compound of 5 mg, is dissolved in the mother liquor that various concentration is prepared in acetone, will be female
Liquid is added in PDA culture medium with 1% ratio, and the malicious culture medium of the band that concentration is 50 ppm is obtained after cooling.The acetone of equivalent is taken to add
Enter PDA culture medium, is used as blank control after cooling.Bacteria to be tested after activation is made to the bacteria cake of 5 mm of diameter of punch,
It is seeded in the malicious culture medium of band and blank control culture medium, is repeated 3 times respectively.All culture dishes in 25 ~ 26 DEG C of constant temperature incubations,
When the colony diameter of blank control processing grows to nearly 8cm, each processing colony diameter is measured with crossing method, and by with
Lower formula calculates mycelial growth inhibition rate:
Experimental result: the results are shown in Table 1 for Antibacterial Activity of the phenylimidazole derivatives to plant pathogenic fungi.
1 embodiment of table, 1 compound is in 50mgL-1When to the inhibitory activity of plant pathogenic fungi
As known from Table 1,1 gained compound of embodiment has preferable suppression to cucumber fusarium axysporum, Pyricularia oryzae, Rhizoctonia solani Kuhn
Effect processed.
Embodiment 2: Phenylimidazole compounds(C14H18N2O synthesis).
Specific step is as follows for the synthetic method of the phenylimidazole derivatives:
(1) synthesis of intermediate 4- isopropyl -2- methoxy toluene
In the round-bottomed flask of 10mL, the carvacrol of 10 mmol is dissolved with the DMF of 2 mL, it is to be dissolved completely after be separately added into
The iodomethane of the potassium carbonate of 12mmol and 12 mmol is stirred to react 24 h at room temperature.TLC monitoring reaction, after the reaction was completed plus
Enter distilled water, be extracted with ethyl acetate, anhydrous sodium sulfate is dry, evaporated under reduced pressure.Gained crude product uses column chromatography purifying i.e.
Obtain intermediate 4- isopropyl -2- methoxy toluene.
(2) intermediate 5- methyl -2- isopropyl -4- methoxybromobenzene synthesizes
10 mmol intermediate 4- isopropyl -2- methoxy toluenes, the acetic acid of 20 mL and after being cooled to 0 DEG C, under stirring
The bromine of 11 mmol is added dropwise to constant pressure funnel in 20 min, reaction is warmed to room temperature continuation instead after being added dropwise to complete
Answer 6 h.Stop reaction, reaction solution is poured into the ice water of 50 mL, is extracted three times, merged organic with the methylene chloride of 30 mL
Phase, organic phase is dry with anhydrous sodium sulfate, evaporated under reduced pressure, and column chromatography for separation obtains intermediate 5- methyl -2- isopropyl -4- first
Methoxyl bromobenzene.
(3) synthesis of target compound
N2Under protection, by 10 mmol intermediate 5- methyl -2- isopropyl -4- methoxybromobenzenes, 15mmol imidazoles, 20 mmol
Potassium carbonate, the cuprous iodide of 2 mmol are dissolved in the DMF of 5 mL, 150 DEG C are heated to after vacuum nitrogen gas 3 times, reaction 40
A hour.The distilled water of 30mL is added after the reaction was completed, is extracted three times with the ethyl acetate of 30 mL, merges organic phase, organic phase
Dry, the evaporated under reduced pressure with anhydrous sodium sulfate, column chromatography for separation obtain target compound.
The spectroscopic data of products therefrom is 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。
Antibacterial Activity situation of the gained phenylimidazole derivatives for plant pathogenic fungi is as follows:
Test plant disease fungus: tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae, rice banded sclerotial blight
Germ.
Using experimental method same as Example 1, the phenylimidazole derivatives are obtained to the antibacterial of plant pathogenic fungi
Determination of activity result is as described in Table 2.
2 embodiment of table, 2 compound is in 50mgL-1When to the inhibitory activity of plant pathogenic fungi
As known from Table 2,2 compound of embodiment to tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae,
Rhizoctonia solani Kuhn has preferable inhibitory effect.
Embodiment 3: Phenylimidazole compounds(C15H20N2O synthesis).
Specific step is as follows for the synthetic method of the phenylimidazole derivatives:
(1) synthesis of intermediate 4- isopropyl -2- ethyoxyl toluene
In the round-bottomed flask of 10mL, the carvacrol of 10 mmol is dissolved with the DMF of 2 mL, it is to be dissolved completely after be separately added into
The bromoethane of the potassium carbonate of 12mmol and 12 mmol is stirred to react 10 h at room temperature.TLC monitoring reaction, after the reaction was completed plus
Enter distilled water, be extracted with ethyl acetate, anhydrous sodium sulfate is dry, evaporated under reduced pressure.Gained crude product use (petroleum ether: ethyl acetate=
10:1) column chromatographic isolation and purification obtains intermediate 4- isopropyl -2- ethyoxyl toluene.
(2) synthesis of intermediate 5- methyl -2- isopropyl -4- ethyoxyl bromobenzene
10 mmol intermediate 4- isopropyl -2- ethyoxyl toluene, the acetic acid of 20 mL and after being cooled to 0 DEG C, under stirring
The bromine of 11 mmol is added dropwise to constant pressure funnel in 20 min, reaction is warmed to room temperature continuation instead after being added dropwise to complete
Answer 6 h.Stop reaction, reaction solution is poured into the ice water of 50 mL, is extracted three times, merged organic with the methylene chloride of 30 mL
Phase, organic phase is dry with anhydrous sodium sulfate, and evaporated under reduced pressure, column chromatography for separation obtains intermediate 5- methyl -2- isopropyl -4- ethoxy
Bromide benzene.
(3) synthesis of target compound
N2Under protection, by 10 mmol intermediate 5- isopropyl -2- methyl -4- ethyoxyl bromobenzenes, 15mmol imidazoles, 20 mmol
Potassium carbonate, the cuprous iodide of 2 mmol are dissolved in the DMF of 5 mL, 150 DEG C are heated to after vacuum nitrogen gas 3 times, reaction 40
A hour.The distilled water of 30mL is added after the reaction was completed, is extracted three times with the ethyl acetate of 30 mL, merges organic phase, organic phase
Dry, the evaporated under reduced pressure with anhydrous sodium sulfate, column chromatography for separation obtain target compound.
The spectroscopic data of products therefrom is 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。
Antibacterial Activity situation of the gained phenylimidazole derivatives for plant pathogenic fungi is as follows:
Test plant disease fungus: tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae, rice banded sclerotial blight
Germ.
Using experimental method same as Example 1, the phenylimidazole derivatives are obtained to the antibacterial of plant pathogenic fungi
Determination of activity result is as described in Table 3.
3 embodiment of table, 3 compound is in 50mgL-1When to the inhibitory activity of plant pathogenic fungi
As known from Table 3,3 compound of embodiment to tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae,
Rhizoctonia solani Kuhn has preferable inhibitory effect.
Embodiment 4: Phenylimidazole compounds(C14H18N2O synthesis).
Specific step is as follows for the synthetic method of the phenylimidazole derivatives:
(1) synthesis of intermediate 4- isopropyl -3- methoxy toluene
In the round-bottomed flask of 10mL, the carvacrol of 10 mmol is dissolved with the DMF of 2 mL, it is to be dissolved completely after be separately added into
The iodine of the potassium carbonate of 12mmol and 12 mmol add alkane, are stirred to react 24 h at room temperature.TLC monitoring reaction, after the reaction was completed plus
Enter distilled water, be extracted with ethyl acetate, anhydrous sodium sulfate is dry, evaporated under reduced pressure.Gained crude product uses column chromatography purifying i.e.
Obtain intermediate 4- isopropyl -3- methoxy toluene.
(2) intermediate 5- methyl -2- isopropyl -4- methoxybromobenzene synthesizes
10 mmol intermediate 4- isopropyl -3- methoxy toluenes, the acetic acid of 20 mL and after being cooled to 0 DEG C, under stirring
The bromine of 11 mmol is added dropwise to constant pressure funnel in 20 min, reaction is warmed to room temperature continuation instead after being added dropwise to complete
Answer 6 h.Stop reaction, reaction solution is poured into the ice water of 50 mL, is extracted three times, merged organic with the methylene chloride of 30 mL
Phase, organic phase is dry with anhydrous sodium sulfate, and evaporated under reduced pressure, column chromatography for separation obtains intermediate 5- methyl -2- isopropyl -4- methoxy
Bromide benzene.
(3) synthesis of target compound
N2Under protection, by 10 mmol intermediate 2- isopropyl -5- methyl -4- methoxybromobenzenes, 15mmol imidazoles, 20 mmol
Potassium carbonate, the cuprous iodide of 2 mmol are dissolved in the DMF of 5 mL, 150 DEG C are heated to after vacuum nitrogen gas 3 times, reaction 40
A hour.The distilled water of 30mL is added after the reaction was completed, is extracted three times with the ethyl acetate of 30 mL, merges organic phase, organic phase
Dry, the evaporated under reduced pressure with anhydrous sodium sulfate, column chromatography for separation obtain target compound.
The spectroscopic data of products therefrom is 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。
Antibacterial Activity situation of the gained phenylimidazole derivatives for plant pathogenic fungi is as follows:
Test plant disease fungus: tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae, rice banded sclerotial blight
Germ.
Using experimental method same as Example 1, the phenylimidazole derivatives are obtained to the antibacterial of plant pathogenic fungi
Determination of activity result is as described in Table 4.
4 embodiment of table, 4 compound is in 50mgL-1When to the inhibitory activity of plant pathogenic fungi
As known from Table 4,4 compound of embodiment to tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae,
Rhizoctonia solani Kuhn has preferable inhibitory effect.
Technology contents of the invention are described above, but protection scope of the present invention is not limited to the content,
Those skilled in the art within the scope of knowledge, can also be without departing from the purpose of the present invention to this hair
Bright technology contents make a variety of changes, all within the spirits and principles of the present invention, any modification for being made, equivalent replacement,
Improve etc., it should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of phenylimidazole derivatives, which is characterized in that its structure is as shown in formula I:
Wherein, R1For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or new penta
Base；R2For methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl or neopentyl；R3For
Hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R4For hydrogen,
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R5For hydrogen, first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, phenyl, fluorine, chlorine, bromine, iodine, nitro；R6For hydrogen, methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, acetyl group, propiono, bytyry, benzoyl.
2. phenylimidazole derivatives according to claim 1, it is characterised in that: preferably, the R1For methyl or isopropyl
Base, R2For methyl or isopropyl, R3For hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R4For hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R5For
Hydrogen, methyl, ethyl, fluorine, chlorine or bromine, R6For methyl or ethyl.
3. phenylimidazole derivatives according to claim 1, it is characterised in that: as further preferred, the R1For methyl
Or isopropyl, R2For methyl or isopropyl, R3For hydrogen, methyl, fluorine or chlorine, R4For hydrogen, methyl, fluorine or chlorine, R5For hydrogen, methyl, fluorine
Or chlorine, R6For methyl or ethyl.
4. phenylimidazole derivatives according to claim 1, it is characterised in that: preferably, the phenylimidazole is derivative
The structural formula of object is one of following:
。
5. a kind of synthetic method of phenylimidazole derivatives described in -4 according to claim 1, it is characterised in that: the phenyl miaow
The synthesis step of Zole derivatives is as follows:
。
6. the synthetic method of phenylimidazole derivatives according to claim 5, it is characterised in that: the tool of the synthetic method
Steps are as follows for body:
6.1 raw material preparation
Take the commercially available chemical reagent raw material for standby such as carvacrol, Thymol, imidazoles；
6.2 synthetic intermediates I
Be added phenol (phenol be carvacrol or Thymol), dissolved with DMF in a reservoir, it is to be dissolved completely after be separately added into carbon
Sour potassium and halogenated alkane are stirred to react 10 h-24 h at room temperature；TLC monitoring reaction, distilled water is added after the reaction was completed, uses
Ethyl acetate extraction, decompression boil off solvent, and products therefrom obtains intermediate I by column chromatographic isolation and purification；
6.3 synthetic intermediates II
It is under stirring that bromine constant pressure funnel is slow in a reservoir by intermediate I acetic acid and after being cooled to 0 DEG C
It is added dropwise to, by reaction 6 h that are warmed to room temperature that the reaction was continued after being added dropwise to complete；To which compound of reaction is poured into ice water after the reaction was completed
In, and be extracted with dichloromethane, evaporated under reduced pressure after organic phase anhydrous sodium sulfate drying obtains intermediate by column chromatography for separation
Ⅱ；
6.4 synthesising target compound
N2Under protection, intermediate II, imidazoles, potassium carbonate and cuprous iodide is added in a reservoir, and dissolved with solvent DMF, will react
It is heated to 150 DEG C after system vacuum nitrogen gas, reacts 40 hours；Distilled water is added after the reaction was completed, is extracted with ethyl acetate
It takes, organic phase evaporated under reduced pressure after drying, obtains target product through column chromatography for separation.
7. a kind of application of described in any item phenylimidazole derivatives of Claims 1 to 4 in pesticide, it is characterised in that: institute
Phenylimidazole derivatives are stated for inhibiting or killing plant pathogenic fungi.
8. application of the phenylimidazole derivatives according to claim 7 in pesticide, it is characterised in that: the pathogenic
Fungi is tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum, Pyricularia oryzae or Rhizoctonia solani Kuhn.
9. application of the phenylimidazole derivatives according to claim 7 in pesticide, it is characterised in that: the phenyl miaow
Zole derivatives prepare pesticide as active constituent, which has effects that sterilization.
10. application of the phenylimidazole derivatives according to claim 9 in pesticide, it is characterised in that: the phenyl miaow
The pesticide that Zole derivatives are prepared as active constituent for kill tomato early blight bacterium, botrytis cinerea, cucumber fusarium axysporum,
Pyricularia oryzae or Rhizoctonia solani Kuhn.
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| CN201910067302.3A CN109810062B (en) | 2019-01-24 | 2019-01-24 | Phenylimidazole derivative, synthesis method thereof and application of phenylimidazole derivative in pesticide |
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