CN109400591B - 4- (2-furyl) pyrimidine compound and preparation method and application thereof - Google Patents
4- (2-furyl) pyrimidine compound and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 4- (2-furyl) pyrimidine compound Chemical class 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 48
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- JJVYEIIAFBXFEX-UHFFFAOYSA-N 4-(furan-2-yl)pyrimidine Chemical class C1=COC(C=2N=CN=CC=2)=C1 JJVYEIIAFBXFEX-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
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- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 claims description 8
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RBZRMBCLZMEYEH-UHFFFAOYSA-N 1h-pyrazol-1-ium-1-carboximidamide;chloride Chemical compound Cl.NC(=N)N1C=CC=N1 RBZRMBCLZMEYEH-UHFFFAOYSA-N 0.000 claims description 7
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- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 claims description 6
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- 239000002917 insecticide Substances 0.000 claims description 5
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000008062 acetophenones Chemical class 0.000 claims description 4
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 claims description 3
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- 241001074088 Urophycis Species 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
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- 125000003226 pyrazolyl group Chemical group 0.000 abstract description 2
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- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明提供一种4‑(2‑呋喃基)嘧啶类化合物及其制备方法和应用，其结构通式为：通式中R1为氟原子、氯原子、溴原子、碘原子、甲基、甲氧基，R2为氢原子、溴原子、甲基、羟甲基。本申请提供的化合物将呋喃环和吡唑环引入嘧啶的分子结构中，合成了一些4‑(2‑呋喃基)嘧啶类化合物。该类化合物结构简单，对仓储害虫具有较好的毒杀效果，对植物病原细菌也有较好的抑制活性，将为新农药的创制奠定良好的基础。The present invention provides a 4-(2-furyl) pyrimidine compound, a preparation method and application thereof, and its general structural formula is: In the general formula, R 1 is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a methoxy group, and R 2 is a hydrogen atom, a bromine atom, a methyl group, or a hydroxymethyl group. The compounds provided in this application introduce a furan ring and a pyrazole ring into the molecular structure of pyrimidine, and synthesize some 4-(2-furyl) pyrimidine compounds. The compound has simple structure, good poisoning effect on storage pests, and good inhibitory activity against phytopathogenic bacteria, which will lay a good foundation for the creation of new pesticides.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a 4- (2-furyl) pyrimidine compound and a preparation method and application thereof.
Background
The pyrimidine is a very important heterocyclic compound and is widely applied to the fields of medicines, pesticides, daily chemicals and the like. A large number of researches show that the compounds have good biological activity, such as insecticidal activity, bactericidal activity, acaricidal activity, weeding activity, plant growth regulation activity, antiviral activity, anticancer activity, antioxidant activity, anti-inflammatory activity and the like. Because the pyrimidine compounds have the advantages of high efficiency, low toxicity to human and livestock, unique action mode, difficult generation of drug resistance of pests and the like, the molecular structure design, synthesis and biological activity research are very active fields in the heterocyclic compound research, and the compounds with novel and simple structure and good biological activity are continuously generated.
It is known that furan ring is an electron-rich system, which easily forms intermolecular hydrogen bonds with various biological enzymes, and thus some furan ring-containing compounds, both natural and synthetic, have a broad spectrum of biological activities, such as bacteriostasis, antivirus, antitumor, insecticidal, herbicidal, etc. Meanwhile, the compounds generally have the characteristics of high efficiency, low toxicity, safety to non-target organisms, easiness in degradation in the environment, difficulty in generation of resistance by pests and the like, so that the compounds containing furan rings play more and more important roles in the research and development processes of pesticides.
Pyrazole compounds have been extensively studied for their wide interest due to their diverse biological activities, such as insecticidal, fungicidal, herbicidal, acaricidal, plant growth regulating, antioxidant, etc. Meanwhile, the pyrazole derivative also has the advantages of high efficiency, low toxicity, safety to non-target organisms, difficulty in generating resistance to pests and the like, so that the molecular structure design, synthesis and biological activity research of the pyrazole compound are hot spots and frontiers of the current green pesticide creation.
So far, no report of the use of 4- (2-furyl) pyrimidine compounds as agricultural insecticides and bactericides is found.
Disclosure of Invention
The invention aims to provide a novel compound used as an agricultural insecticide and a bactericide and a preparation method of the compound.
A4- (2-furyl) pyrimidine compound has the following structural general formula:
r in the general formula (I)1Is fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, methoxy group, R2Hydrogen atom, bromine atom, methyl group, hydroxymethyl group.
A preparation method of 4- (2-furyl) pyrimidine compounds comprises the following steps: dissolving substituted acetophenone in anhydrous ethanol, adding 10% NaOH solution, stirring in ice bath, slowly dropping the mixture of furfural and anhydrous ethanol or the mixture of 5-methylfurfural and anhydrous ethanol into the above mixed solution with a constant pressure dropping funnel, reacting at 0-5 deg.C, and checking whether the reaction is completed with thin-layer silica gel plate (TLC). After the reaction was completed, 13X molecular sieve was added to the reaction mixture, and a mixed solution of 1H-pyrazole-1-carboxamidine hydrochloride and absolute ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, followed by reaction at 40 to 50 ℃ and completion of the reaction was checked by TLC. And after the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain the target compound.
Further, according to the method, the substituted acetophenone is one of 4-chloroacetophenone, 4-methoxyacetophenone, 4-bromoacetophenone and 4-methylacetophenone.
Further, in the method described above, the 13X molecular sieve is 60-80 mesh.
An application of 4- (2-furyl) pyrimidine compounds as agricultural insecticides or bactericides.
Further, as the above-mentioned application, the pesticide can kill one or more of corn elephant, corn bagel and corn beetle.
Further, the bactericide can inhibit one or more of bacterial brown spot of corn, bacterial black spot of rape, citrus canker, potato black shank, onion bulb rot and melon bacterial fruit blotch.
Has the advantages that:
the invention introduces furan rings and pyrazole rings into the molecular structure of pyrimidine to synthesize some 4- (2-furyl) pyrimidine compounds, which have simple structure and excellent activity and lay a good foundation for the creation of new pesticides.
The compound of the general formula (I) has simple synthesis process, and adopts a one-pot method, namely, the intermediate is not separated out according to the traditional method and then subjected to the next reaction, but the next reaction is directly performed, so that the operation steps are reduced, the reaction efficiency is improved, and the energy conservation and consumption reduction are facilitated. The compound of the general formula (I) has better control effect on storage pests and plant pathogenic bacteria, and is not reported in the currently known pesticides and bactericides.
Drawings
FIG. 1 is a hydrogen spectrum of the compound prepared in example 1;
FIG. 2 is a carbon spectrum of the compound prepared in example 1;
FIG. 3 is a high resolution mass spectrum of the compound prepared in example 1;
FIG. 4 is a hydrogen spectrum of the compound prepared in example 2;
FIG. 5 is a carbon spectrum of the compound prepared in example 2;
FIG. 6 is a high resolution mass spectrum of the compound prepared in example 2;
FIG. 7 is a hydrogen spectrum of the compound prepared in example 3;
FIG. 8 is a carbon spectrum of the compound prepared in example 3;
FIG. 9 is a high resolution mass spectrum of the compound prepared in example 3;
FIG. 10 is a hydrogen spectrum of the compound prepared in example 4;
FIG. 11 is a carbon spectrum of the compound prepared in example 4;
FIG. 12 is a high resolution mass spectrum of the compound prepared in example 4;
FIG. 13 is a hydrogen spectrum of the compound prepared in example 5;
FIG. 14 is a carbon spectrum of the compound prepared in example 5;
FIG. 15 is a high resolution mass spectrum of the compound prepared in example 5.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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 invention provides a compound with insecticidal and bacteriostatic activity, which has the following structural general formula:
r in the general formula (I)1Is fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, methoxy group, R2Is a hydrogen atom, a bromine atom, a methyl group,A hydroxymethyl group.
The main reaction equation in the preparation of the compound of formula (I) is:
in the formula R1、R2The same as above.
The compound of the general formula (I) has simple synthesis process, and adopts a one-pot method, namely, the intermediate is not separated out according to the traditional method and then subjected to the next reaction, but the next reaction is directly performed, so that the operation steps are reduced, the reaction efficiency is improved, and the energy conservation and consumption reduction are facilitated. The compound of the general formula (I) has better control effect on storage pests and plant pathogenic bacteria, and is not reported in the currently known pesticides and bactericides.
Example 1:
compound (I)
Preparation of
0.02mol of 4-methylacetophenone was dissolved in 20mL of anhydrous ethanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, a mixed solution of 0.02mol of furfural and 20mL of absolute ethyl alcohol is slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 0-5 ℃, and whether the reaction is finished or not is checked by using a thin-layer silica gel plate (TLC). After completion of the reaction, 2 g of 13X molecular sieve (60-80 mesh) was added to the reaction mixture, and a mixed solution of 0.02mol of 1H-pyrazole-1-carboxamidine hydrochloride and 20mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, reacted at 40-50 ℃ and checked for completion by TLC. After the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a black solid product, wherein the yield is 88%. Spectral data for the product are as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):8.88(1H,s),8.36(2H,d,J＝8.4Hz),8.26(1H,s),8.09(1H,s),7.91(1H,s),7.81(2H,d,J＝8.0Hz),7.69(1H,d,J＝2.4Hz),6.84(1H,s),6.65(1H,s),2.42(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):161.84,154.87,153.26,148.17,144.40,140.74,132.16,129.49,127.38,126.92,123.03,112.15,110.60,106.16,105.17,23.02；HRMS(ESI)m/z:Calcd for C18H14N4O[M+H]+:303.1246,Found:303.1248.
the hydrogen spectrogram, carbon spectrogram and high-resolution mass spectrogram of the product are shown in figures 1-3.
Example 2:
compound (I)
Preparation of
0.02mol of 4-methoxyacetophenone was dissolved in 20mL of anhydrous ethanol, and 15mL of 10% NaOH solution was added thereto. Under the stirring of ice bath, a mixed solution of 0.02mol of furfural and 20mL of absolute ethyl alcohol is slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 0-5 ℃, and whether the reaction is finished or not is checked by using a thin-layer silica gel plate (TLC). After completion of the reaction, 2 g of 13X molecular sieve (60-80 mesh) was added to the reaction mixture, and a mixed solution of 0.02mol of 1H-pyrazole-1-carboxamidine hydrochloride and 20mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, reacted at 40-50 ℃ and checked for completion by TLC. After the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a yellow powdery solid product, wherein the yield is 90%. Spectral data for the product are as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):8.88(1H,s),8.39(2H,d,J＝8.4Hz),8.16(1H,s),8.08(1H,s),7.90(1H,s),7.65(1H,d,J＝3.2Hz),7.15(2H,d,J＝8.4Hz),6.83(1H,s),6.65(1H,s),3.89(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):164.15,157.18,155.57,150.48,146.70,143.04,134.47,131.80,129.86,129.23,125.33,114.45,112.90,108.47,107.47,53.40；HRMS(ESI)m/z:Calcd for C18H14O2N4[M+H]+:319.1195,Found:319.1179.
the hydrogen spectrogram, carbon spectrogram and high-resolution mass spectrogram of the product are shown in FIGS. 4-6.
Example 3:
compound (I)
Preparation of
0.02mol of 4-chloroacetophenone was dissolved in 20mL of anhydrous ethanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, a mixed solution of 0.02mol of 5-methylfurfural and 20mL of anhydrous ethanol is slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 0-5 ℃, and whether the reaction is finished or not is checked by using a thin-layer silica gel plate (TLC). After completion of the reaction, 2 g of 13X molecular sieve (60-80 mesh) was added to the reaction mixture, and a mixed solution of 0.02mol of 1H-pyrazole-1-carboxamidine hydrochloride and 20mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, reacted at 40-50 ℃ and checked for completion by TLC. After the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a white needle-shaped crystal product, wherein the yield is 88%. Spectral data for the product are as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):8.88(1H,d,J＝2.4Hz),8.48(2H,dd,J1＝5.6Hz,J2＝5.2Hz),8.14(1H,s),7.90(1H,s),7.59(1H,d,J＝3.6Hz),7.44(2H,t,J＝8.4Hz),6.65-6.64(1H,m),6.47(1H,d,J＝3.2Hz),2.48(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):159.72,156.32,154.51,146.97,146.01,142.56,135.59,135.10,131.49,129.69,129.58,109.44,107.60,106.09,104.60,14.50；HRMS(ESI)m/z:Calcd for C18H13N4OCl[M+H]+:337.0856,Found:337.0825.
the hydrogen spectrogram, carbon spectrogram and high-resolution mass spectrogram of the product are shown in FIGS. 7-9.
Example 4:
compound (I)
Preparation of
0.02mol of 4-methylacetophenone was dissolved in 20mL of anhydrous ethanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, a mixed solution of 0.02mol of 5-methylfurfural and 20mL of anhydrous ethanol is slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 0-5 ℃, and whether the reaction is finished or not is checked by using a thin-layer silica gel plate (TLC). After completion of the reaction, 2 g of 13X molecular sieve (60-80 mesh) was added to the reaction mixture, and a mixed solution of 0.02mol of 1H-pyrazole-1-carboxamidine hydrochloride and 20mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, reacted at 40-50 ℃ and checked for completion by TLC. After the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a black powdery solid product, wherein the yield is 83%. Spectral data for the product are as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):8.73(1H,s),8.21(2H,d,J＝8.4Hz),8.11(1H,s),7.94(1H,s),7.76(1H,s),7.66(2H,d,J＝8.0Hz),7.54(1H,d,J＝2.4Hz),6.69(1H,s),2.36(3H,s),2.25(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):159.72,156.32,154.51,146.97,146.02,142.56,135.60,135.10,131.50,129.69,129.59,109.44,107.60,106.09,104.60,24.12,14.50；HRMS(ESI)m/z:Calcd for C19H16N4O[M+H]+:317.1402,Found:317.1475.
the hydrogen spectrum, carbon spectrum and high resolution mass spectrum of the product are shown in FIGS. 10-12.
Example 5:
compound (I)
Preparation of
0.02mol of 4-bromoacetophenone was dissolved in 20mL of anhydrous ethanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, a mixed solution of 0.02mol of furfural and 20mL of absolute ethyl alcohol is slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 0-5 ℃, and whether the reaction is finished or not is checked by using a thin-layer silica gel plate (TLC). After completion of the reaction, 2 g of 13X molecular sieve (60-80 mesh) was added to the reaction mixture, and a mixed solution of 0.02mol of 1H-pyrazole-1-carboxamidine hydrochloride and 20mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, reacted at 40-50 ℃ and checked for completion by TLC. After the reaction is finished, filtering, adding a large amount of ice water into the filtrate, adjusting the pH value to be neutral by using a 10% hydrochloric acid solution, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a brown powdery solid product, wherein the yield is 86%. Spectral data for the product are as follows:
1H NMR(400MHz,DMSO-d6)δ(ppm):8.89(1H,s),8.37(2H,d,J＝8.4Hz),8.26(1H,s),8.10(1H,s),7.91(1H,s),7.82(2H,d,J＝8.0Hz),7.70(1H,d,J＝2.4Hz),6.85(1H,s),6.66(1H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):164.84,157.87,156.26,151.17,147.40,143.74,135.16,132.49,130.38,129.92,126.03,115.15,113.60,109.16,108.17；HRMS(ESI)m/z:Calcd for C17H11N4OBr[M+H]+:367.0189,Found:367.0183.
the hydrogen spectrum, carbon spectrum and high resolution mass spectrum of the product are shown in FIGS. 13-15.
Example 6: determination of insecticidal Activity of Compounds of the present invention
(1) Test pest
Adult corn weevils, adult corn clothes and adult tribolium castaneum, which are all sensitive strains bred indoors for years.
(2) Measurement method
Adopting a feed mixing method: mixing the compound to be tested and the wheat feed uniformly according to a certain dosage. Weighing 100 g of the drug-mixed feed into 500mL wide-mouth bottles, putting 30 heads of tested pests into each bottle, wrapping the bottle mouth with white cloth, placing the bottles in a pest feeding room with the temperature of 28-30 ℃ and the relative humidity of 70-80% for continuous feeding, and taking the feed without the drug as a blank control. Mortality was recorded after 14 days, each experiment was repeated 3 times, and corrected mortality was calculated using the following formula:
(3) experimental results the pesticidal results of the compounds of the present invention are shown in table 1.
TABLE 1 poisoning Activity of Compounds of the invention against storage pests
a: average of three replicates.
From Table 1 above, it is clear that the compounds of the present invention have a good poisoning activity against these pests.
Example 7: determination of the bacteriostatic Activity of Compounds of the invention
(1) Test for plant pathogenic bacteria
Bacterial brown spot of corn, bacterial black spot of rape, canker of citrus, black shank of potato, bulb rot of onion, and bacterial fruit blotch of melon.
(2) Measurement method
(a) Activation of strains: the bacterial strain to be tested is inoculated on a beef extract peptone solid medium slant and cultured overnight at 37 ℃.
(b) Preparation of bacterial suspension: inoculating a loop of activated test strain in a conical flask containing 100mL beef extract peptone liquid medium, culturing at 37 deg.C for 18h to obtain initial bacterial suspension, and diluting with sterile normal saline to appropriate concentration (10)6～107CFU/mL) of the suspension.
(c) Determination of Minimum Inhibitory Concentration (MIC): dissolving the test compound in dimethyl sulfoxide, diluting with sterile normal saline containing 0.1% Tween-80 by two-fold dilution method to obtain solutions with different concentrations, and mixing. 1mL of the diluted sample solution was added to 19mL of a sterilized medium, and mixed well to prepare a plate. After the culture medium has solidified, the above-mentioned concentration of 10% is added by coating method6CFU/mL of 200. mu.L bacterial suspension, cultured at 37 ℃ in 16 &The bacteria growth was observed at 18h, with the concentration of completely sterile growth as the MIC value for the test sample solution, and the corresponding solution without test compound as a blank.
(3) Results of the experiment
The bacteriostatic activity of the compounds of the invention is shown in table 2.
TABLE 2 inhibitory Activity of the Compounds of the present invention against plant pathogenic bacteria
From the above table 2, it can be seen that the compounds of the present invention have a good inhibitory effect on these plant pathogenic bacteria.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
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