CN110981864B - N- (4-fluorophenyl) -4, 5-dihydropyrazole compound and application thereof in pesticide - Google Patents
N- (4-fluorophenyl) -4, 5-dihydropyrazole compound and application thereof in pesticide Download PDFInfo
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- -1 N- (4-fluorophenyl) -4, 5-dihydropyrazole compound Chemical class 0.000 title claims abstract description 11
- 239000000575 pesticide Substances 0.000 title abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 14
- 230000007226 seed germination Effects 0.000 claims abstract description 13
- 235000013311 vegetables Nutrition 0.000 claims abstract description 12
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003899 bactericide agent Substances 0.000 claims abstract description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052794 bromium Chemical group 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000011593 sulfur Chemical group 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Chemical group 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 240000008067 Cucumis sativus Species 0.000 claims description 11
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 241000233866 Fungi Species 0.000 claims description 8
- 241000209140 Triticum Species 0.000 claims description 8
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 240000007087 Apium graveolens Species 0.000 claims description 7
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 claims description 7
- 235000010591 Appio Nutrition 0.000 claims description 7
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 claims description 7
- 240000008384 Capsicum annuum var. annuum Species 0.000 claims description 7
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 7
- 240000003768 Solanum lycopersicum Species 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 claims description 6
- 239000000417 fungicide Substances 0.000 claims description 6
- 230000000855 fungicidal effect Effects 0.000 claims description 5
- 241000207199 Citrus Species 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- 241000221785 Erysiphales Species 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 241000233679 Peronosporaceae Species 0.000 claims description 4
- 241000082085 Verticillium <Phyllachorales> Species 0.000 claims description 4
- 235000020971 citrus fruits Nutrition 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 230000035784 germination Effects 0.000 abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000002401 inhibitory effect Effects 0.000 abstract description 6
- 244000000004 fungal plant pathogen Species 0.000 abstract description 5
- 229910052757 nitrogen Chemical group 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 230000004071 biological effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZXBMIRYQUFQQNX-UHFFFAOYSA-N (4-fluorophenyl)hydrazine Chemical compound NNC1=CC=C(F)C=C1 ZXBMIRYQUFQQNX-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000005513 chalcones Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 150000003217 pyrazoles Chemical class 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000012085 test solution Substances 0.000 description 4
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 4
- 241000607479 Yersinia pestis Species 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- MAUHXHSUGFXOEN-UHFFFAOYSA-N 2-(4-fluorophenyl)-3,4-dihydropyrazole Chemical class C1=CC(F)=CC=C1N1N=CCC1 MAUHXHSUGFXOEN-UHFFFAOYSA-N 0.000 description 2
- 230000003110 anti-inflammatory effect Effects 0.000 description 2
- 230000000259 anti-tumor effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 230000003032 phytopathogenic effect Effects 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 1
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 1
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229960005222 phenazone Drugs 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Images
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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
- C07D405/02—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 two hetero rings
- C07D405/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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)
Abstract
The invention relates to an N- (4-fluorophenyl) -4, 5-dihydropyrazole compound and application thereof in pesticides, belonging to the technical field of pesticides. The invention solves the technical problem of providing a new compound which can be used as an agricultural bactericide and a seed germination promoter. The compound has a structural formula shown in formula I, wherein X is oxygen, sulfur or nitrogen, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine. The compound has better inhibitory activity to plant pathogenic fungi and better promotion effect on the germination of vegetable seeds, and lays a better foundation for the creation of new pesticides.
Description
Technical Field
The invention relates to an N- (4-fluorophenyl) -4, 5-dihydropyrazole compound and application thereof in pesticides, belonging to the technical field of pesticides.
Background
Pyrazole compounds have attracted much attention because of their various biological activities, and intensive studies have been made on them. Since Knott discovered that antipyrine containing a pyrazole ring has analgesic, anti-inflammatory and antipyretic effects in 1883, there have been continuous patent and literature reports on novel uses of pyrazole derivatives as bactericides, insecticides, plant growth regulators, herbicides and the like, as shown in FIG. 1. The pyrazole compounds generally have the characteristics of high efficiency, low toxicity, safety to non-target organisms, difficulty in generating resistance to pests and the like. Therefore, the molecular structure design, synthesis and biological activity research of pyrazole compounds are still hot spots and frontiers created by green pesticides at present.
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.
Thiophene is an important member of heterocyclic compounds and plays a very important role. The study of thiophene derivatives also has a very major role in medicine and agrochemical chemistry. Thiophene derivatives have a wide variety of biological activities, for example, antibacterial, antiviral, antitumor, anti-inflammatory, insecticidal, herbicidal, and the like. Meanwhile, the thiophene ring-containing 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, and compounds with novel structures and excellent performance are continuously published. Therefore, in the process of research and development of pesticides, compounds containing thiophene rings will receive more extensive attention and become hot spots for creating new pesticides.
So far, the use of N- (4-fluorophenyl) -4, 5-dihydropyrazole compounds as agricultural bactericides and seed germination promoters is not reported.
Disclosure of Invention
The invention solves the technical problem of providing a new compound which can be used as an agricultural bactericide and a seed germination promoter.
The structural formula of the compound of the invention is shown as formula I:
wherein X is oxygen, sulfur or nitrogen, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
Preferably, X is oxygen or sulfur, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
In a preferred embodiment, X is oxygen, sulfur or nitrogen and R is hydrogen, methyl or bromine.
More preferably, X is oxygen or sulfur and R is hydrogen, methyl or bromine.
Preferably, the compound has the structural formula:
the invention solves a second technical problem by providing the application of the compound in the preparation of agricultural fungicides.
Researches show that the compound has bactericidal activity and can be used as an agricultural bactericide.
Preferably, the bacteria controlled by the agricultural fungicide are fungi.
Further preferably, the bacteria controlled by the agricultural bactericide are cucumber downy mildew, wheat powdery mildew, wheat leaf rust, rice blast, cotton verticillium wilt or citrus anthracnose.
The invention also provides application of the compound in preparing a seed germination promoter.
Researches show that the compound can promote seed germination and improve the seed germination rate, and can be prepared into a seed germination promoter.
Preferably, the seeds are vegetable seeds.
Further preferably, the vegetable seeds are cucumber seeds, green pepper seeds, tomato seeds or celery seeds.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, furan rings or thiophene rings are introduced into the molecular structure of pyrazole to synthesize some N- (4-fluorophenyl) -4, 5-dihydropyrazole compounds, some active compounds or active lead compounds with novel structures and excellent activity are found, the synthesis process is simple, the synthesized compounds have a better inhibitory effect on plant pathogenic fungi and a better promotion effect on the germination of seeds, especially vegetable seeds, and a better foundation is laid for the creation of new pesticides.
Drawings
FIG. 1 shows a conventional commercial pyrazole compound having biological activity.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the compound of example 1.
FIG. 3 is a nuclear magnetic carbon spectrum of the compound of example 1.
FIG. 4 is a high resolution mass spectrum of the compound of example 1.
FIG. 5 is a nuclear magnetic hydrogen spectrum of the compound of example 2.
FIG. 6 is a nuclear magnetic carbon spectrum of the compound of example 2.
FIG. 7 is a high resolution mass spectrum of the compound of example 2.
FIG. 8 is a nuclear magnetic hydrogen spectrum of the compound of example 3.
FIG. 9 is a nuclear magnetic carbon spectrum of the compound of example 3.
FIG. 10 is a high resolution mass spectrum of the compound of example 3.
FIG. 11 is a nuclear magnetic hydrogen spectrum of the compound of example 4.
FIG. 12 is a nuclear magnetic carbon spectrum of the compound of example 4.
FIG. 13 is a high resolution mass spectrum of the compound of example 4.
Detailed Description
The structural formula of the compound of the invention is shown as formula I:
wherein X is oxygen, sulfur or nitrogen, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
Preferably, X is oxygen or sulfur, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
In a preferred embodiment, X is oxygen, sulfur or nitrogen and R is hydrogen, methyl or bromine.
More preferably, X is oxygen or sulfur and R is hydrogen, methyl or bromine.
Preferably, the compound has the structural formula:
the compound of the invention can be prepared by adopting a conventional chemical method. Specifically, the compound can be prepared by the following reaction processes:
the compound has bactericidal activity and can be used as an agricultural bactericide.
Preferably, the bacteria controlled by the agricultural fungicide are fungi.
Further preferably, the bacteria controlled by the agricultural bactericide are cucumber downy mildew, wheat powdery mildew, wheat leaf rust, rice blast, cotton verticillium wilt or citrus anthracnose.
The compound of the invention can promote the germination of seeds and improve the germination rate of the seeds, and can be prepared into a seed germination promoter for use.
Preferably, the seeds are vegetable seeds.
Further preferably, the vegetable seeds are cucumber seeds, green pepper seeds, tomato seeds or celery seeds.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Compound (I)
Preparation of
0.02mol of 4-methoxyacetophenone was dissolved in 20mL of anhydrous methanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, slowly dropping a mixed solution of 0.02mol of furfural and 20mL of anhydrous methanol into the mixed solution by using a constant pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). And after the reaction is finished, adding distilled water with the volume of 3-4 times into the mixture, adjusting the pH value of the mixture to be neutral by using 10% HCl, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain the chalcone intermediate.
0.02mol of the self-made intermediate was dissolved in 20mL of anhydrous methanol, and 0.005mol of p-toluenesulfonic acid was added thereto. Under the stirring condition, a mixed solution of 0.02mol of 4-fluorophenylhydrazine and 20mL of methanol is slowly dripped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 50-60 ℃, and the completion of the reaction is checked by TLC. After the reaction is finished, adjusting the pH value of the solution to be neutral by using 10% NaOH, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a target product, wherein the physical and chemical properties of the target product are as follows:
light yellow crystals; the yield is 86 percent; the hydrogen spectrum is shown in figure 2, the carbon spectrum is shown in figure 3, the high resolution mass spectrum is shown in figure 4, and particularly,1H NMR(400MHz,DMSO-d6)δ(ppm):7.71(2H,d,J＝8.8Hz),7.57(1H,d,J＝0.8Hz),7.12(2H,dd,J＝9.2,4.8Hz),7.06(2H,d,J＝8.8Hz),7.01(2H,d,J＝8.8Hz),6.43(1H,d,J＝2.8Hz),6.40-6.38(1H,m),5.51(1H,dd,J＝12.0,6.4Hz),3.81(3H,s),3.74(1H,dd,J＝17.6,12.4Hz),3.34(1H,dd,J＝17.2,6.4Hz)；13C NMR(100MHz,DMSO-d6)δ(ppm):160.39,156.43(d,J＝234.0Hz),153.61,148.43,143.30,142.15(d,J＝1.0Hz),127.79,125.17,115.74(d,J＝22.0Hz),114.94(d,J＝7.0Hz),114.60,110.88,108.34,57.73,55.70；HRMS(ESI)m/z:Calcd for C20H17FN2O2[M+H]+:337.1347,Found:337.1346.
example 2
Compound (I)
Preparation of
0.02mol of 4-methoxyacetophenone was dissolved in 20mL of anhydrous methanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, slowly dropping a mixed solution of 0.02mol of 5-methylfurfural and 20mL of anhydrous methanol into the mixed solution by using a constant-pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). And after the reaction is finished, adding distilled water with the volume of 3-4 times into the mixture, adjusting the pH value of the mixture to be neutral by using 10% HCl, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain the chalcone intermediate.
0.02mol of the self-made intermediate was dissolved in 20mL of anhydrous methanol, and 0.005mol of p-toluenesulfonic acid was added thereto. Under the stirring condition, a mixed solution of 0.02mol of 4-fluorophenylhydrazine and 20mL of methanol is slowly dripped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 50-60 ℃, and the completion of the reaction is checked by TLC. After the reaction is finished, adjusting the pH value of the solution to be neutral by using 10% NaOH, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a target product, wherein the physical and chemical properties of the target product are as follows:
yellow crystals; the yield is 87%; the hydrogen spectrum is shown in fig. 5, the carbon spectrum is shown in fig. 6, the high resolution mass spectrum is shown in fig. 7, and particularly,1H NMR(400MHz,DMSO-d6)δ(ppm):7.71(2H,d,J＝8.8Hz),7.11(2H,dd,J＝9.2,4.8Hz),7.06(2H,d,J＝8.8Hz),7.01(2H,d,J＝9.2Hz),6.30(1H,d,J＝3.2Hz),5.99(1H,d,J＝2.0Hz),5.41(1H,dd,J＝12.0,6.8Hz),3.81(3H,s),3.73(1H,dd,J＝17.2,12.0Hz),3.33-3.29(1H,m),2.19(3H,s)；13C NMR(100MHz,DMSO-d6)δ(ppm):160.37,156.43(d,J＝233.0Hz),151.94,151.73,148.30,142.31(d,J＝2.0Hz),127.77,125.20,115.72(d,J＝22.0Hz),114.90(d,J＝8.0Hz),114.59,109.14,106.90,57.97,55.69,13.75；HRMS(ESI)m/z:Calcd for C21H19FN2O2[M+H]+:351.1503,Found:351.1496.
example 3
Compound (I)
Preparation of
0.02mol of 4-methoxyacetophenone was dissolved in 20mL of anhydrous methanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, slowly dropping a mixed solution of 0.02mol of thiophene-2-formaldehyde and 20mL of anhydrous methanol into the mixed solution by using a constant pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). And after the reaction is finished, adding distilled water with the volume of 3-4 times into the mixture, adjusting the pH value of the mixture to be neutral by using 10% HCl, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain the chalcone intermediate.
0.02mol of the self-made intermediate was dissolved in 20mL of anhydrous methanol, and 0.005mol of p-toluenesulfonic acid was added thereto. Under the stirring condition, a mixed solution of 0.02mol of 4-fluorophenylhydrazine and 20mL of methanol is slowly dripped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 50-60 ℃, and the completion of the reaction is checked by TLC. After the reaction is finished, adjusting the pH value of the solution to be neutral by using 10% NaOH, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a target product, wherein the physical and chemical properties of the target product are as follows:
yellow crystals; the yield is 88%; the hydrogen spectrum is shown in fig. 8, the carbon spectrum is shown in fig. 9, the high resolution mass spectrum is shown in fig. 10, and specifically,1H NMR(400MHz,DMSO-d6)δ(ppm):7.71(2H,d,J＝8.4Hz)7.39(1H,d,J＝4.8Hz),7.14(1H,d,J＝3.2Hz),7.09(2H,J＝8.8,5.2Hz),7.04(2H,d,J＝8.8Hz),7.01(2H,d,J＝8.0Hz),6.97-6.95(1H,m),5.73(1H,dd,J＝11.2,6.4Hz),3.89-3.80(4H,m),3.22(1H,dd,J＝17.2,6.4Hz)；13C NMR(100MHz,DMSO-d6)δ(ppm):160.48,156.53(d,J＝234.0Hz),148.73,145.98,142.22(d,J＝2.0Hz),127.89,127.34,125.93,125.70,125.13,115.76(d,J＝22.0Hz),115.24(d,J＝7.0Hz),114.63,60.43,55.73,44.03；HRMS(ESI)m/z:Calcd for C20H17FN2OS[M+H]+:353.1118,Found:353.1113.
example 4
Compound (I)
Preparation of
0.02mol of 4-methoxyacetophenone was dissolved in 20mL of anhydrous methanol, and 15mL of a 10% NaOH solution was added thereto. Under the stirring of ice bath, slowly dropping a mixed solution of 0.02mol of 5-bromothiophene-2-formaldehyde and 20mL of anhydrous methanol into the mixed solution by using a constant pressure dropping funnel, reacting at 0-5 ℃, and checking whether the reaction is finished by using a thin-layer silica gel plate (TLC). And after the reaction is finished, adding distilled water with the volume of 3-4 times into the mixture, adjusting the pH value of the mixture to be neutral by using 10% HCl, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain the chalcone intermediate.
0.02mol of the self-made intermediate was dissolved in 20mL of anhydrous methanol, and 0.005mol of p-toluenesulfonic acid was added thereto. Under the stirring condition, a mixed solution of 0.02mol of 4-fluorophenylhydrazine and 20mL of methanol is slowly dripped into the mixed solution by using a constant pressure dropping funnel, the reaction is carried out at 50-60 ℃, and the completion of the reaction is checked by TLC. After the reaction is finished, adjusting the pH value of the solution to be neutral by using 10% NaOH, separating out a precipitate, filtering, washing, and recrystallizing by using absolute ethyl alcohol to obtain a target product, wherein the physical and chemical properties of the target product are as follows:
yellow crystals; the yield is 74 percent; the hydrogen spectrum is shown in fig. 11, the carbon spectrum is shown in fig. 12, the high resolution mass spectrum is shown in fig. 13, and specifically,1H NMR(400MHz,DMSO-d6)δ(ppm):7.71(2H,d,J＝8.8Hz),7.10(2H,dd,J＝9.2,4.8Hz),7.08(1H,d,J＝2.0Hz),7.06(2H,d,J＝2.8Hz),7.02(2H,d,J＝2.4Hz),7.00(1H,d,J＝2.4Hz),5.73(1H,dd,J＝11.2,6.0Hz),3.83-3.79(4H,m),3.27(1H,dd,J＝17.6,6.0Hz)；13C NMR(100MHz,DMSO-d6)δ(ppm):160.58,156.67(d,J＝234.0Hz),149.13,147.69,142.01(d,J＝2.0Hz),130.54,127.99,126.73,124.94,115.88(d,J＝22.0Hz),115.39(d,J＝8.0Hz),114.64,110.94,60.59,55.74,43.55；HRMS(ESI)m/z:Calcd for C20H16BrFN2OS[M+H]+:431.0224,Found:431.0229.
test example 1 measurement of inhibitory Activity of the Compound of the present invention against plant pathogenic fungi
(1) Test for plant pathogenic fungi
Cucumber downy mildew, wheat powdery mildew, wheat leaf rust, rice blast, cotton verticillium wilt and citrus anthracnose.
(2) Experimental methods
The test compound is dissolved in dimethyl sulfoxide, added into tap water containing 0.1% Tween-80, and mixed uniformly to prepare a test solution of 20 mg/L. The solution was added to sterilized PDA medium, and streptomycin was added thereto at a concentration of 50mg/L to obtain a toxic medium. The corresponding solution without the test compound is used as a blank control, and a control culture medium with uniform thickness is prepared for standby application and is repeated three times. Selecting a fungus cake with phi 5mm, good growth, no pollution and uniform growth by using a sterilized puncher, inoculating the fungus cake into centers of a toxic culture medium and a control culture medium (one fungus cake is inoculated on each plate) under an aseptic condition, and culturing at the constant temperature of 28 +/-1 ℃. When the colony diameter of the blank control grows to about 50mm, the diameter of the colony is measured by a cross method, the average value is taken, and the inhibition rate is calculated by the following formula:
(3) results of the experiment
The results of the measurement of the inhibitory activity of the compounds of the present invention against phytopathogenic fungi are shown in Table 1.
TABLE 1 inhibitory Activity of the Compounds of examples 1 to 4 against phytopathogenic fungi at 20mg/L
a: average of three replicates.
As is clear from Table 1, the compounds of examples 1 to 4 showed a good inhibitory effect against all of the 6 types of germs.
Test example 2 measurement of the Germination-promoting Effect of the Compound of the present invention on vegetable seeds
(1) Test seeds
Cucumber seeds (Zhongnong No. 8), green pepper seeds (Fengyuan No. 8), tomato seeds (Dongfeng No. 4), and celery seeds (Jinnanshi No. 1).
(2) Measurement method
The test compounds were dissolved in dimethyl sulfoxide and diluted to 20mg/L in tap water containing 0.1% Tween-80 for use. 10 g of cucumber seeds, 10 g of green pepper seeds, 5 g of tomato seeds and 5 g of celery seeds are respectively weighed. And respectively soaking the test solution into 20mL of the test solution, stirring for 30 minutes, fishing out the test solution into a small sieve, washing for 3-4 times by using tap water, and air-drying for later use. The corresponding solution without test compound was used as a blank. 100 seeds with uniform size and no defect treated by the liquid medicine are respectively selected and are horizontally placed in a culture dish (9cm) paved with double-layer filter paper. The water adding amount for the 1 st time is as follows: 9mL of cucumber, 7mL of green pepper, 5mL of tomato and 5mL of celery are put into a constant temperature box (25 +/-2 ℃) for accelerating germination, observed for 1 time every day and quantitatively supplemented when water is deficient. Each treatment was repeated 3 times. The germination of cucumber was checked after 1 day, the germination of green pepper after 5 days, the germination of tomato after 3 days, and the germination of celery after 9 days, and the average germination percentage was calculated for 3 replicates.
(3) Results of the experiment
The germination-promoting effect of the compounds of the present invention on vegetable seeds is shown in table 2.
TABLE 2 accelerating effect of the compounds of examples 1 to 4 on seed germination at 20mg/L
a: average of three replicates.
As is clear from Table 2, the example compounds 1 to 4 all had a good accelerating effect on the germination of the 4 vegetable seeds.
In conclusion, the compound can be prepared into an agricultural bactericide which has a good inhibition effect on plant pathogenic fungi, and can also be prepared into a seed germination promoter which has a good promotion effect on the germination of vegetable seeds.
Claims (9)
1. A compound having the structural formula I:
wherein X is oxygen or sulfur, and R is hydrogen, methyl, methoxy, hydroxymethyl, chlorine or bromine.
2. The compound of claim 1, wherein: r is hydrogen, methyl or bromine.
3. The compound of claim 1, wherein: the structural formula is as follows:
4. use of a compound according to any one of claims 1 to 3 for the preparation of an agricultural fungicide.
5. Use of a compound according to claim 4 for the preparation of an agricultural fungicide, characterized in that: the bacteria for preventing and controlling the agricultural bactericide are fungi.
6. Use of a compound according to claim 4 for the preparation of an agricultural fungicide, characterized in that: the bacteria controlled by the agricultural bactericide are cucumber downy mildew, wheat powdery mildew, wheat leaf rust, rice blast, cotton verticillium wilt or citrus anthracnose.
7. Use of a compound according to any one of claims 1 to 3 for the preparation of a seed germination promoter.
8. Use of a compound according to claim 7 for the preparation of a seed germination promoter, wherein: the seeds are vegetable seeds.
9. Use of a compound according to claim 8 for the preparation of a seed germination promoter, wherein: the vegetable seeds are cucumber seeds, green pepper seeds, tomato seeds or celery seeds.
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