CN108084173A - A kind of pyrazole compound of Han isoxazoles structure and preparation method thereof, application - Google Patents
A kind of pyrazole compound of Han isoxazoles structure and preparation method thereof, application Download PDFInfo
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- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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Abstract
The present invention provides a kind of pyrazole compound of Han isoxazoles structure and preparation method thereof, application, belongs to technical field of organic synthesis.The compound structure such as I：
Description
Technical field
The present invention relates to technical field of organic synthesis, be specifically related to a kind of Han isoxazoles structure pyrazole compound and
Its preparation method, application.
Background technology
Isoxazole is a kind of important five-ring heterocycles structure, and skeleton is universally present in much with wide spectrum pharmacological activity
In the compound molecule of bioactivity.Many have isoxazole structure bioactive compounds have been developed that into fungicide,
The a variety of agricultural chemicals of herbicide, agrochemical.Ru oxazoles phosphorus (Isoxathion) is a kind of contact insecticide of wide spectrum；Evil is mould
Spirit is a kind of systemic fungicide of high-efficiency low-toxicity environmental protection.
Pyrazole compound is a kind of nitrogen-containing heterocycle compound with broad-spectrum biological activity, because it is efficient, low toxicity so that
The compound of many pyrazolyl containing groups has good weeding, desinsection, bactericidal activity, widely should have in pesticide field
With.Such as insecticide：Ethiprole (Fipronil), Tolfenpyrad (Tolfenpyrad), pyraclofos (Pyraclofos), pyrrole mite
Amine (Tebufenpyrad), fenpyroximate (Fenpyroximate) etc.；Fungicide：Fluxapyroxad (Fluxapyroxad), pyrrole thiophene
Bacterium amine (Penthiopyrad), pyraoxystrobin (Pyraoxystrobin), biphenyl pyrrole bacterium amine (Bixafen |) etc..
Therefore, it is rational using Substructure link way in order to find the new compound with high-efficiency broad spectrum bioactivity
Isoxazolyl and pyrazolyl are introduced into same molecule, is therefrom expected to obtain the noval chemical compound with desinsection, bactericidal activity, have
Boundless research and development prospect.
The content of the invention
It is above-mentioned insufficient in the prior art the purpose of the present invention is overcoming, propose a kind of pyrazoles chemical combination of Han isoxazoles structure
Object and preparation method thereof, application.
To achieve these goals, the present invention provides following technical solution：
A kind of pyrazole compound of Han isoxazoles structure, the chemistry knot of the pyrazole compound of the Han isoxazoles structure
Structure is shown in formula I：
Wherein, the Ar in chemical constitution Formulas I is aromatic group.
In the pyrazole compound of Han isoxazoles structure as described above, it is preferable that the aromatic group is selected from one of following：
Phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, 3- methoxyphenyls, 2- methoxyphenyls, 4- fluorophenyls, 4- chlorphenyls, 3- chlorine
Phenyl, 2- chlorphenyls, 4- bromophenyls, 4- tert-butyl-phenyls, 1- naphthalenes and 2- furyls.
A kind of preparation method of the pyrazole compound of Han isoxazoles structure as described above, the preparation method include
Following steps：
The preparation of the pyrazole compound of Han isoxazole structures shown in Formulas I：
(1) by the 5- arylalkenyl -3- methyl -4- nitro Yi Evil shown in the 5- pyrazolones and formula III shown in Formula II
Azoles is added in reactor, is added in solvent and is dissolved；Organic base is added after dissolving, is stirred to react a period of time at room temperature,
And it detects whether to have completely reacted；
(2) after the reaction was complete in step (1), acetylation agents are then added in into reaction system, at room temperature after
Continuous to be stirred to react, after completion of the reaction, washed, extraction, separation, revolving, purifying obtain the pyrrole of target product Han isoxazole structures
Azole compounds.
In preparation method as described above, it is preferable that in step (1), detected whether using thin-layered chromatography completely anti-
It should.
In preparation method as described above, it is preferable that in step (1), the solvent for dichloromethane, toluene, tetrahydrofuran,
Ether, chloroform, ethyl alcohol or acetonitrile；The organic base is triethylamine, pyridine, diisopropyl ethyl amine or 1,8- diazabicylo ten
One carbon -7- alkene.
In preparation method as described above, it is preferable that in step (2), the acetylation agents are chloroacetic chloride or acetic anhydride.
In preparation method as described above, it is preferable that add in 5- pyrazolones, 5- arylalkenyl -3- first in the preparation method
The molar ratio of base -4- nitros isoxazole, organic base and acetylation agents is according to following ratio：5- pyrazolones: 5- arylalkenyls-
3- methyl -4- nitro isoxazoles: organic base: acetylation agents 1: 1~1.2: 1~1.5: 1~1.2.
In preparation method as described above, it is preferable that the dosage of the solvent for the 5- pyrazolones quality 20~
30 times；
Preferably, the time is stirred to react in step (1) at room temperature as 11-13h；More preferably, stirring is anti-at room temperature
It is 12h between seasonable；
Preferably, continue to be stirred to react the time in step (2) at room temperature as 1-3h；More preferably, continue at room temperature
The time is stirred to react as 2h.
A kind of pyrazole compound of Han isoxazoles structure as described above is in prevention plant pest insects or pathogenic
Application in fungi.
The pyrazole compound of Han isoxazole structures as described above is in prevention plant pest insects or plant pathogenic fungi
In application, the insect include Lepidoptera Noctuidae mythimna separata, Homoptera Cicadellidae rice green leafhopper and Homoptera Aphidiadae aphid；Institute
Stating fungi includes rhizoctonia cerealis, cucumber anthracnose and Pyricularia oryzae.The present invention to the species of harmful insect and fungi not
It limits, as long as desinsection and sterilization are carried out at this using the pyrazole compound of the Han isoxazole structures prepared in the present invention
In application range in invention.
Compared with the immediate prior art, technical solution provided by the invention has the advantages that：
1st, isoxazolyl and pyrazolyl are introduced into same molecule by the present invention using Substructure link way, obtain general formula I institutes
A kind of pyrazole compound of the Han isoxazoles structure for the structure novel shown.
2nd, preparation method of the present invention is easy to operate, mild condition, high income, post processing is relatively easy and is suitable for scale
It prepares.
3rd, the pyrazole compound of Han isoxazole structures prepared by the present invention has desinsection, bactericidal activity, can be used as desinsection
Agent is applied to the prevention of plant pest insects and plant pathogenic fungi with fungicide.
Specific embodiment
The technical solution in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example is only the part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's all other embodiments obtained, belong to the scope of protection of the invention.
Specific embodiments of the present invention provide a kind of pyrazole compound of Han isoxazoles structure and preparation method thereof, answer
With.
A kind of pyrazole compound of Han isoxazoles structure of the present invention, the change of the pyrazole compound of Han isoxazole structures
Learn structure shown in formula I：
Wherein, the Ar in chemical constitution Formulas I is aromatic group；
It is further preferred that aromatic group is selected from one of following：Phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, 3- methoxies
Base phenyl, 2- methoxyphenyls, 4- fluorophenyls, 4- chlorphenyls, 3- chlorphenyls, 2- chlorphenyls, 4- bromophenyls, 4- tert-butyl benzenes
Base, 1- naphthalenes or 2- furyls.
A kind of preparation method of the pyrazole compound of Han isoxazoles structure in the specific embodiment of the invention includes as follows
Step：
The preparation of the pyrazole compound of Han isoxazole structures shown in Formulas I：
(1) by the 5- arylalkenyl -3- methyl -4- nitro Yi Evil shown in the 5- pyrazolones and formula III shown in Formula II
Azoles is added in reactor, is added in solvent and is dissolved；Organic base is added after dissolving, is stirred to react a period of time at room temperature,
And it detects whether to have completely reacted；
(2) after the reaction was complete in step (1), acetylation agents are then added in into reaction system, at room temperature after
Continuous to be stirred to react, after completion of the reaction, washed, extraction, separation, revolving, purifying obtain the pyrrole of target product Han isoxazole structures
Azole compounds.
It is further preferred that it detects whether to have completely reacted using thin-layered chromatography.
It is further preferred that in step (1), solvent is dichloromethane, toluene, tetrahydrofuran, ether, chloroform, ethyl alcohol or
Acetonitrile.Organic base is triethylamine, 11 carbon -7- alkene of pyridine, diisopropyl ethyl amine or 1,8- diazabicylo.In step (2),
Acetylation agents are chloroacetic chloride or acetic anhydride.
5- pyrazolones, 5- arylalkenyl -3- methyl -4- nitros are added in preparation method in a specific embodiment of the present invention
The molar ratio of isoxazole, organic base and acetylation agents is according to following ratio：
5- pyrazolones: 5- arylalkenyl -3- methyl -4- nitro isoxazoles: organic base: acetylation agents 1: 1~1.2
(such as 1.1,1.13,1.15,1.16,1.18,1.19): 1~1.5 (such as 1.1,1.2,1.25,1.3,1.35,1.4,1.45)
: 1~1.2 (such as 1.1,1.13,1.15,1.16,1.18,1.19).
Further preferably, the dosage of solvent for the 5- pyrazolones quality 20~30 times (such as 21 times, 22 times,
23 times, 24 times, 25 times, 26 times, 27 times, 28 times, 29 times).
Preferably, be stirred to react at room temperature in step (1) time for 11-13h (such as 11.1h, 11.5h, 12h,
12.3h、12.5h、12.8h)；More preferably, the time is stirred to react at room temperature as 12h；
Preferably, continue to be stirred to react at room temperature in step (2) time for 1-3h (such as 1.1h, 1.5h, 2h, 2.3h,
2.5h、2.8h)；More preferably, continue to be stirred to react the time at room temperature as 2h.
The pyrazole compound of Han isoxazole structures prepared by the present invention has desinsection, bactericidal activity, can be used as insecticide
It is applied to the prevention of plant pest insects and plant pathogenic fungi with fungicide, can be applied to pesticide field.
The compound of the present invention is adapted for use in the prevention of plant pest insects, and insect includes Lepidoptera Noctuidae mythimna separata,
Homoptera Cicadellidae rice green leafhopper and Homoptera Aphidiadae aphid etc..Certainly, the plant pest that the compound of the present invention can prevent
Insect is not limited to the scope of the example above, and this is not limited by the present invention.
The compound of the present invention is adapted for use in the prevention of plant pathogenic fungi, and fungi includes rhizoctonia cerealis, cucumber
Anthrax bacteria and Pyricularia oryzae etc..Certainly, the plant pathogenic fungi that the compound of the present invention can prevent is not limited to the example above
Scope, this is not limited by the present invention.
Prepare embodiment：
Embodiment 1：
It is added in 100mL round-bottomed bottles shown in 5- pyrazolones (1.74g, 10.0mmol) shown in Formula II and formula III a
5- phenylakenyl -3- methyl -4- nitros isoxazoles (2.76g, 12.0mmol) and 30mL dichloromethane, then add in triethylamine
(2.0mL, 15.0mmol) is placed in and is stirred to react 12h at room temperature, and TLC detections are after the reaction was complete；Then it is added dropwise into reaction system
Chloroacetic chloride (0.85mL, 12.0mmol) continues to be stirred to react 2h at room temperature, and 50mL water, liquid separation, water phase are added in reaction system
It is extracted with dichloromethane (30mLx2), merges organic phase, anhydrous MgSO4Dry, concentrated by rotary evaporation, residue carries out column chromatography (leaching
Washing lotion：Petrol ether/ethyl acetate=10/1), obtain target product 4.15g shown in corresponding Formulas I a, white solid, yield
93%, 40-41 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.11 (s, 3H), 2.16 (s, 3H), 2.48 (s, 3H), 3.88 (dd, J=
14.4Hz, 8.8Hz, 1H), 3.96 (dd, J=14.8Hz, 8.0Hz, 1H), 4.60 (t, J=8.0Hz, 1H), 7.19-7.24 (m,
1H), 7.25-7.34 (m, 5H), 7.35-7.46 (m, 4H)；13C NMR (100MHz, CDCl3) δ 172.6,167.2,155.5,
147.3,141.4,140.1,137.6,130.5,129.1,128.6,127.3,127.2,127.0,122.7,109.0,37.1,
31.5,20.0,13.3,11.5.
Embodiment 2：
Identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- shown in formula III b are to toluene
Base alkenyl -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, obtain Formulas I
Target product 4.19g shown in b, white solid, yield 91%, 56-57 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.12 (s, 3H), 2.17 (s, 3H), 2.30 (s, 3H), 2.48 (s, 3H), 3.88
(dd, J=14.4Hz, 8.8Hz, 1H), 3.96 (dd, J=14.8Hz, 7.6Hz, 1H), 4.57 (t, J=7.6Hz, 1H), 7.11
(d, J=6.4Hz, 2H), 7.19 (d, J=6.8Hz, 2H), 7.24-7.34 (m, 1H), 7.35-7.47 (m, 4H)；13C NMR
(100MHz, CDCl3) δ 172.7,167.3,155.5,147.3,141.4,137.6,137.1,136.6,130.4,129.2,
128.0,127.3,127.1,122.7,109.1,36.8,31.7,20.9,20.1,13.4,11.5.
Embodiment 3：
Identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- shown in formula III c are to methoxy
Phenylakenyl -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, are obtained
Target product 4.29g shown in Formulas I c, white solid, yield 90%, 55-56 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.07 (s, 3H), 2.08 (s, 3H), 2.42 (s, 3H), 3.69 (s, 3H), 3.76
(dd, J=14.4Hz, 8.0Hz, 1H), 3.87 (dd, J=14.8Hz, 8.0Hz, 1H), 4.47 (t, J=7.6Hz, 1H), 6.75
(d, J=7.2Hz, 2H), 7.14 (d, J=7.6Hz, 2H), 7.18-7.26 (m, 1H), 7.29-7.39 (m, 4H)；13C NMR
(100MHz, CDCl3) δ 172.7,167.4,158.4,155.5,147.3,141.4,137.7,132.2,130.5,129.1,
128.3,127.3,122.8,113.9,109.3,55.1,36.5,31.8,20.1,13.4,11.5.
Embodiment 4：
Identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- shown in formula III d are to fluorobenzene
Base alkenyl -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, obtain Formulas I
Target product 4.37g shown in d, white solid, yield 94%, 101-103 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.06 (s, 6H), 2.42 (s, 3H), 3.78 (dd, J=13.6Hz, 8.0Hz,
1H), 3.86 (dd, J=14.8Hz, 7.6Hz, 1H), 4.50 (t, J=7.6Hz, 1H), 6.91 (t, J=7.6Hz, 2H), 7.12-
7.27 (m, 3H), 7.28-7.41 (m, 4H)；13C NMR (100MHz, CDCl3) δ 172.4,167.3,161.6 (d, JC-F=
244.6Hz), 155.5,147.2,141.4,137.6,136.0 (d, JC-F=3.0Hz), 130.5,129.1,128.9 (d, JC-F
=8.0Hz), 127.4,122.8,115.4 (d, JC-F=21.2Hz), 108.8,36.6,31.7,20.1,13.4,11.5.
Embodiment 5：
Identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- shown in formula III e are to chlorobenzene
Base alkenyl -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, obtain Formulas I
Target product 4.42g shown in e, white solid, yield 92%, 112-113 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.07 (s, 6H), 2.42 (s, 3H), 3.77 (dd, J=13.2Hz, 8.0Hz,
1H), 3.85 (dd, J=14.4Hz, 7.6Hz, 1H), 4.49 (t, J=7.6Hz, 1H), 7.10-7.27 (m, 5H), 7.27-7.40
(m, 4H)；13C NMR (100MHz, CDCl3) δ 172.2,167.3,155.5,147.2,141.4,138.7,137.5,132.8,
130.5,129.1,128.8,128.7,127.4,122.8,108.6,36.6,31.5,20.1,13.4,11.5.
Embodiment 6：
Identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- shown in formula III f are to bromobenzene
Base alkenyl -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, obtain Formulas I
Target product 4.73g shown in f, white solid, yield 90%, 109-110 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.14 (s, 3H), 2.15 (s, 3H), 2.50 (s, 3H), 3.84 (dd, J=
14.8Hz, 8.4Hz, 1H), 3.93 (dd, J=14.8Hz, 8.0Hz, 1H), 4.55 (t, J=8.0Hz, 1H), 7.18 (d, J=
8.0Hz, 2H), 7.27-7.34 (m, 1H), 7.35-7.69 (m, 6H)；13C NMR (100MHz, CDCl3) δ 172.2,167.3,
155.6,147.2,141.4,139.3,137.5,131.7,130.5,129.1,129.0,127.5,122.8,121.0,
108.5,36.7,31.5,20.1,13.4,11.5.
Embodiment 7：
It is identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- naphthalene alkenyls -3- in formula III g
Methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, are obtained shown in Formulas I g
Target product 4.22g, colourless oil liquid, yield 85%, 45-46 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.05 (s, 3H), 2.19 (s, 3H), 2.49 (s, 3H), 3.98 (dd, J=
14.8Hz, 8.4Hz, 1H), 4.11 (dd, J=14.4Hz, 8.0Hz, 1H), 4.78 (t, J=8.0Hz, 1H), 7.30 (t, J=
6.0Hz, 1H), 7.36-7.52 (m, 7H), 7.72-7.85 (m, 4H)；13C NMR (100MHz, CDCl3) δ 172.6,167.3,
155.6,147.4,141.6,137.6,137.5,133.1,132.3,130.6,129.1,128.5,127.7,127.5,
127.4,126.3,126.1,126.0,125.1,122.8,108.8,37.3,31.5,20.0,13.4,11.5.
Embodiment 8：
It is identical with the preparation method step of embodiment 1,5- pyrazolones shown in Formula II, 5- furans alkene shown in formula III h
Base -3- methyl -4- nitros isoxazole, triethylamine, the mol ratio that feeds intake of chloroacetic chloride are 1: 1.2: 1.5: 1.2, are obtained in Formulas I h
Shown target product 3.84g, white solid, yield 88%, 52-53 DEG C of fusing point.
1H NMR (400MHz, CDCl3) δ 2.12 (s, 3H), 2.18 (s, 3H), 2.49 (s, 3H), 3.88 (dd, J=
14.4Hz, 8.8Hz, 1H), 3.96 (dd, J=14.8Hz, 8.0Hz, 1H), 7.19-7.24 (m, 2H), 7.25-7.34 (m, 5H),
7.38 (d, J=4.0Hz, 1H)；13C NMR (100MHz, CDCl3) δ 172.6,167.2,155.5,147.3,141.4,140.1,
137.6,130.5,129.1,128.6,127.3,127.2,127.0,122.7,109.0,37.1,31.5,20.0,13.3,
11.5。
Application Example：
Embodiment 9：
The insecticidal activity survey carried out to plant pest insects of the pyrazole compound of Han isoxazoles structure in the present embodiment
Examination.
Mythimna separata has been carried out to compound I a~I h that above-described embodiment 1~8 synthesizes using Potter spray-on processes
The insecticidal activity test of (Mythimna separata), concentration 500mg/L；Using leaf worm with change of the leaching method to synthesis
Close the insecticidal activity test that object has carried out bean aphid (Aphis fabae), concentration 500mg/L；Using dipping plant
Method has carried out the compound of synthesis the insecticidal activity test of green rice leafhopper (Nephotettix bipunctatus), uses
Concentration is 500mg/L.
The test result that the compound that above-described embodiment 1~8 synthesizes carries out insecticidal activity experiment is as shown in table 1：
The preliminary insecticidal activity data of compound I a~I h in 1 Examples 1 to 8 of table
Insecticidal activity test result shows that the pyrazole compound of Han isoxazole structures all shows certain kill in table 1
Worm activity.Compound I d, I e, I f are relatively preferable to the insecticidal activity of mythimna separata, aphid and leafhopper, especially compound I d's
Insecticidal activity is relatively high.
Embodiment 10：The pyrazole compound of Han isoxazoles structure plant pathogenic fungi is killed in the present embodiment
Bacterium active testing.
The compound synthesized to above-described embodiment 1~8 is carried out using the toxic potato agar culture medium method of excised leaf
The bactericidal activity test of rhizoctonia cerealis (Rhizoctonia cerealis), concentration 100mg/L；Using mycelia
The sterilization that growth inhibition assay has carried out the compound of synthesis cucumber anthracnose (Colletotrichum orbiculare) is lived
Property test, concentration 100mg/L.
The compound that above-described embodiment 1~8 synthesizes carries out the test result of the bactericidal activity test of plant pathogenic fungi such as
Shown in table 2：
The preliminary bactericidal activity data of compound I a~I h of 2 Examples 1 to 8 of table synthesis
Bactericidal activity test result in table 2 shows that the pyrazole compound of the Han isoxazole structures supplies two kinds
Trying fungi has certain bactericidal activity.The inhibition of compound I d, I e, I f to rhizoctonia cerealis and cucumber anthracnose
Activity is relatively preferable, and the bactericidal activity of especially compound I d is relatively high.
More than experimental data shows that isoxazolyl and pyrazolyl are introduced into same molecule using Substructure link way, obtains
To compounds show good bioactivity, these experimental datas are also the pyrazoles of new Han isoxazoles structure from now on
MOLECULE DESIGN, synthesis and the bioactivity research of class compound provide certain theoretical direction.
In conclusion the present invention has following advantageous effects：
1st, isoxazolyl and pyrazolyl are introduced into same molecule by the present invention using Substructure link way, obtain general formula I institutes
A kind of pyrazole compound of the Han isoxazoles structure for the structure novel shown.
2nd, preparation method of the present invention is easy to operate, mild condition, high income, post processing is relatively easy and is suitable for scale
It prepares.
3rd, the pyrazole compound of Han isoxazole structures prepared by the present invention has desinsection, bactericidal activity, can be used as desinsection
Agent is applied to the prevention of plant pest insects and plant pathogenic fungi with fungicide.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God and principle within, any modifications, equivalent replacements and improvements are made, accompanying claims protection domain of the present invention it
It is interior.
Claims (10)
- A kind of 1. pyrazole compound of Han isoxazoles structure, which is characterized in that the pyrazoles chemical combination of the Han isoxazoles structure The chemical constitution of object is shown in formula I：Wherein, the Ar in chemical constitution Formulas I is aromatic group.
- 2. the pyrazole compound of Han isoxazoles structure as described in claim 1, which is characterized in that the aromatic group is selected from It is one of following：Phenyl, 4- aminomethyl phenyls, 4- methoxyphenyls, 3- methoxyphenyls, 2- methoxyphenyls, 4- fluorophenyls, 4- chlorine Phenyl, 3- chlorphenyls, 2- chlorphenyls, 4- bromophenyls, 4- tert-butyl-phenyls, 1- naphthalenes and 2- furyls.
- 3. a kind of preparation method of the pyrazole compound of Han isoxazoles structure as claimed in claim 1 or 2, feature exist In the preparation method includes the following steps：The preparation of the pyrazole compound of Han isoxazole structures shown in Formulas I：(1) the 5- arylalkenyl -3- methyl -4- nitro isoxazoles shown in the 5- pyrazolones and formula III shown in Formula II are added Enter in reactor, add in solvent and dissolved；Organic base is added after dissolving, a period of time is stirred to react at room temperature, and examines Whether survey has completely reacted；(2) after the reaction was complete in step (1), acetylation agents is then added in into reaction system, continue to stir at room temperature Reaction is mixed, after completion of the reaction, washed, extraction, separation, revolving, purifying obtain the pyrazoles of target product Han isoxazole structures Compound.
- 4. preparation method as claimed in claim 3, which is characterized in that in step (1), detected whether using thin-layered chromatography Through reacting completely.
- 5. preparation method as claimed in claim 3, which is characterized in that in step (1), the solvent for dichloromethane, toluene, Tetrahydrofuran, ether, chloroform, ethyl alcohol or acetonitrile；The organic base is triethylamine, 11 carbon -7- alkene of pyridine, diisopropyl ethyl amine or 1,8- diazabicylo.
- 6. the preparation method as described in claim 3 or 5, which is characterized in that in step (2), the acetylation agents are second Acyl chlorides or acetic anhydride.
- 7. preparation method as claimed in claim 3, which is characterized in that 5- pyrazolones, 5- virtues are added in the preparation method The molar ratio of alkenyl -3- methyl -4- nitros isoxazole, organic base and acetylation agents is according to following ratio：5- pyrazolones: 5- arylalkenyl -3- methyl -4- nitro isoxazoles: organic base: acetylation agents 1: 1~1.2: 1~ 1.5: 1~1.2.
- 8. preparation method as claimed in claim 7, which is characterized in that the dosage of the solvent is the matter of the 5- pyrazolones 20~30 times of amount；Preferably, the time is stirred to react in step (1) at room temperature as 11-13h；More preferably, when being stirred to react at room temperature Between be 12h；Preferably, continue to be stirred to react the time in step (2) at room temperature as 1-3h；More preferably, continue to stir at room temperature Reaction time is 2h.
- 9. the pyrazole compound of the Han isoxazole structures as described in claim 1-8 is any is in prevention plant pest insects or plant Application in object disease fungus.
- 10. the pyrazole compound of Han isoxazoles structure as claimed in claim 9 is in prevention plant pest insects or phytopathy Application in fungal pathogens,The insect includes Lepidoptera Noctuidae mythimna separata, Homoptera Cicadellidae rice green leafhopper and Homoptera Aphidiadae aphid；The fungi includes rhizoctonia cerealis, cucumber anthracnose and Pyricularia oryzae.
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| CN1189823A (en) * | 1995-04-20 | 1998-08-05 | G·D·瑟尔公司 | Cyclic amidino agents useful as nitric oxide synthase inhibitors |
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| JP3216673B2 (en) * | 1993-11-26 | 2001-10-09 | 宇部興産株式会社 | Method for producing 3-hydroxyisoxazole |
| CN1189823A (en) * | 1995-04-20 | 1998-08-05 | G·D·瑟尔公司 | Cyclic amidino agents useful as nitric oxide synthase inhibitors |
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