CN111747943A - 3- (2-furan methylene) quinolinone compound and preparation method and application thereof - Google Patents
3- (2-furan methylene) quinolinone compound and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229930185107 quinolinone Natural products 0.000 title claims abstract description 15
- -1 quinolinone compound Chemical class 0.000 title claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 108
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 40
- 235000013311 vegetables Nutrition 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 230000007226 seed germination Effects 0.000 claims abstract description 11
- 150000002431 hydrogen Chemical group 0.000 claims abstract description 10
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 7
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims abstract description 7
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Chemical group 0.000 claims abstract description 7
- 150000002367 halogens Chemical group 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 229940125782 compound 2 Drugs 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- LISFMEBWQUVKPJ-UHFFFAOYSA-N quinolin-2-ol Chemical compound C1=CC=C2NC(=O)C=CC2=C1 LISFMEBWQUVKPJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 12
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 claims description 10
- 240000008384 Capsicum annuum var. annuum Species 0.000 claims description 10
- 240000008067 Cucumis sativus Species 0.000 claims description 10
- 235000010799 Cucumis sativus var sativus Nutrition 0.000 claims description 10
- 235000007688 Lycopersicon esculentum Nutrition 0.000 claims description 10
- 240000003768 Solanum lycopersicum Species 0.000 claims description 10
- 241000254113 Tribolium castaneum Species 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- 229940126214 compound 3 Drugs 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 7
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 7
- 239000008247 solid mixture Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000001387 apium graveolens Substances 0.000 claims description 6
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- 241000406668 Loxodonta cyclotis Species 0.000 claims description 5
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- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 241000283080 Proboscidea <mammal> Species 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000035784 germination Effects 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000575 pesticide Substances 0.000 abstract description 7
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- 239000002917 insecticide Substances 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 description 19
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 240000007087 Apium graveolens Species 0.000 description 4
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 4
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- 239000003480 eluent Substances 0.000 description 4
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- XQJCCIPREQEDJF-UHFFFAOYSA-N 4-(4-methylphenyl)-1,4-dihydroindeno[1,2-d][1,3]thiazine-2,5-dione Chemical compound C1=CC(C)=CC=C1C1C(C(=O)C=2C3=CC=CC=2)=C3NC(=O)S1 XQJCCIPREQEDJF-UHFFFAOYSA-N 0.000 description 1
- VAUMDUIUEPIGHM-UHFFFAOYSA-N 5-Methyl-2-thiophenecarboxaldehyde Chemical compound CC1=CC=C(C=O)S1 VAUMDUIUEPIGHM-UHFFFAOYSA-N 0.000 description 1
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 1
- VWYFITBWBRVBSW-UHFFFAOYSA-N 5-chlorothiophene-2-carbaldehyde Chemical compound ClC1=CC=C(C=O)S1 VWYFITBWBRVBSW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000254171 Curculionidae Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
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- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YHQFYZYWQCNYSW-UHFFFAOYSA-N n-(2-benzoyl-4-chlorophenyl)thiophene-2-carboxamide Chemical compound C=1C=CC=CC=1C(=O)C1=CC(Cl)=CC=C1NC(=O)C1=CC=CS1 YHQFYZYWQCNYSW-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- 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
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention relates to the field of pesticides, and particularly relates to a 3- (2-furanmethylene) quinolinone compound and a preparation method and application thereof. The invention solves the technical problem of providing a compound which can be used as an insecticide and a seed germination promoter. The structural formula of the compound is shown as formula I; wherein R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen. The compound has good poisoning effect on storage pests and good promotion effect on the germination of vegetable seeds.
Description
Technical Field
The invention relates to the field of pesticides, and particularly relates to a 3- (2-furanmethylene) quinolinone compound and a preparation method and application thereof.
Background
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, no report of the use of 3- (2-furanmethylene) quinolinone compounds as pesticides and vegetable seed germination promoters is available.
Disclosure of Invention
The first technical problem solved by the invention is to provide a compound serving as an insecticide and a vegetable seed germination promoter.
The compound of the invention has a structural formula shown as a formula I:
wherein R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, R is hydrogen, methyl, ethyl, methoxy, hydroxymethyl, chloro, or bromo.
In a specific embodiment, the formula is as follows:
the second technical problem solved by the invention is to provide a preparation method of the compound.
The preparation method of the compound comprises the following steps:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding a NaOH ethanol solution, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction liquid into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine until a precipitate is separated out, filtering to obtain a precipitate, washing the precipitate by using water, and recrystallizing by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in tetrahydrofuran, and adding potassium tert-butoxide thereto; adding a mixed solution of furfural and tetrahydrofuran, reacting at 20-30 ℃, removing the solvent after the reaction is finished to obtain a solid mixture, and performing chromatographic separation by using a silica gel column to obtain a target compound;
wherein the compound A is
And R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
The invention also provides application of the compound in preparing a medicament for preventing and treating pests.
The compound of the invention has excellent insecticidal effect.
In one embodiment, the pest is a storage pest;
in one embodiment, the pest is elephant corn, clothes of grain or tribolium castaneum;
in another embodiment, when the pest is a zealand, the compound is compound 1 or compound 2; when the pests are the grain, the compound is compound 2, compound 3 or compound 4; when the pest is tribolium castaneum, the compound is compound 1 or compound 3;
in a specific embodiment, when the pest is a corn elephant, the compound is compound 2; when the pests are the clothes, the compound is compound 2; when the pest is tribolium castaneum, the compound is compound 3.
The invention also provides application of the compound in preparing a seed germination promoter.
Researches show that the compound can promote the germination of seeds and improve the germination rate of the seeds, and can be prepared into a seed germination promoter.
In one embodiment, the seed is a vegetable seed.
In a specific embodiment, the vegetable seed is a cucumber seed, a green pepper seed, a tomato seed, or a celery seed.
In a specific embodiment, when the vegetable seed is cucumber seed, the compound is compound 4; when the vegetable seed is a green pepper seed, the compound is compound 1; when the vegetable seed is a tomato seed, the compound is compound 2; when the vegetable seed is celery seed, the compound is compound 1.
The invention has the beneficial effects that:
according to the invention, furan rings and thiophene rings are introduced into the molecular structure of quinolinone to synthesize some 3- (2-furanmethylene) quinolinone 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 better poisoning and killing effects on storage pests and better promotion effect on the germination of vegetable seeds, and a better foundation is laid for the creation of new pesticides.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound of example 1.
FIG. 1-a is a detailed view of a nuclear magnetic hydrogen spectrum of the compound of example 1.
FIG. 2 is a nuclear magnetic carbon spectrum of the compound of example 1.
FIG. 3 is a high resolution mass spectrum of the compound of example 1.
FIG. 4 is a nuclear magnetic hydrogen spectrum of the compound of example 2.
FIG. 5 is a nuclear magnetic carbon spectrum of the compound of example 2.
FIG. 6 is a high resolution mass spectrum of the compound of example 2.
FIG. 7 is a nuclear magnetic hydrogen spectrum of the compound of example 3.
FIG. 7-a is a detailed view of a nuclear magnetic hydrogen spectrum of the compound of example 3.
FIG. 8 is a nuclear magnetic carbon spectrum of the compound of example 3.
FIG. 9 is a high resolution mass spectrum of the compound of example 3.
FIG. 10 is a nuclear magnetic hydrogen spectrum of the compound of example 4.
FIG. 10-a is a detailed view of a nuclear magnetic hydrogen spectrum of the compound of example 4.
FIG. 11 is a nuclear magnetic carbon spectrum of the compound of example 4.
FIG. 12 is a high resolution mass spectrum of the compound of example 4.
Detailed Description
The compound of the invention has a structural formula shown as a formula I:
wherein R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
In one embodiment, R is hydrogen, methyl, ethyl, methoxy, hydroxymethyl, chloro, or bromo.
In a specific embodiment, the formula is as follows:
the second technical problem solved by the invention is to provide a preparation method of the compound.
The compound of the invention can be prepared by adopting a conventional chemical method.
In one embodiment, the following reaction process can be adopted for preparation:
wherein R is a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a hydroxymethyl group, a chlorine atom or a bromine atom.
The following steps may be specifically employed:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding a NaOH ethanol solution, stirring in an ice bath, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
wherein the compound A is
R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction solution into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine until a precipitate is separated out, filtering, washing the precipitate by using water until the washing water is neutral, and recrystallizing the precipitate by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in tetrahydrofuran, and adding potassium tert-butoxide thereto; and adding a mixed solution of furfural and tetrahydrofuran, reacting at 20-30 ℃, removing the solvent to obtain a solid mixture after the reaction is finished, and performing chromatographic separation by using a silica gel column to obtain the target compound.
The compound of the invention has excellent insecticidal effect.
In one embodiment, the pest is a storage pest;
in one embodiment, the pest is elephant corn, clothes of grain or tribolium castaneum;
in another embodiment, when the pest is a zealand, the compound is compound 1 or compound 2; when the pests are the grain, the compound is compound 2, compound 3 or compound 4; when the pest is tribolium castaneum, the compound is compound 1 or compound 3;
in a specific embodiment, when the pest is a corn elephant, the compound is compound 2; when the pests are the clothes, the compound is compound 2; when the pest is tribolium castaneum, the compound is compound 3.
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.
In one embodiment, the seed is a vegetable seed.
In a specific embodiment, the vegetable seed is a cucumber seed, a green pepper seed, a tomato seed, or a celery seed.
In a specific embodiment, when the vegetable seed is cucumber seed, the compound is compound 4; when the vegetable seed is a green pepper seed, the compound is compound 1; when the vegetable seed is a tomato seed, the compound is compound 2; when the vegetable seed is celery seed, the compound is compound 1.
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 1:
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of thiophene-2-formaldehyde and 10mL of absolute ethyl alcohol 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). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the self-prepared intermediate was dissolved in 10mL of tetrahydrofuran, and 0.001mol of potassium tert-butoxide was added thereto. And slowly dropping a mixed solution of 0.01mol of furfural and 10mL of tetrahydrofuran into the mixed solution by using a constant-pressure dropping funnel, reacting at the temperature of 20-30 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 10) to obtain the target compound, wherein the physical and chemical properties of the target compound are as follows:
orange granular crystals; yield: 80 percent; the hydrogen spectrum is shown in figure 1, the carbon spectrum is shown in figure 2, the high resolution mass spectrum is shown in figure 3, and particularly,1H NMR(400MHz,DMSO-d6)(ppm):7.98(1H,d,J＝1.6Hz),7.69(1H,dd,J＝8.0,1.6Hz),7.64(1H,d,J＝3.6Hz),7.46(1H,s),7.35-7.31(1H,m),7.29(1H,dd,J＝5.2,1.2Hz),7.09(1H,d,J＝3.6Hz),6.96(1H,dt,J＝3.6,1.2Hz),6.90(1H,dd,J＝5.2,3.6Hz),6.84(1H,d,J＝8.0Hz),6.72(1H,dd,J＝3.6,1.6Hz),6.68-6.64(1H,m),6.51(1H,d,J＝3.2Hz)；13C NMR(100MHz,DMSO-d6)(ppm):182.08,151.06,150.70,147.17,146.91,135.94,130.79,127.72,127.22,125.40,125.31,121.76,119.66,118.24,117.54,116.63,113.41,52.26；HRMS(ESI)m/z:Calcd for C18H13NO2S[M+H]+:308.0740,Found:308.0732.
example 2:
compound 2:
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-methylthiophene-2-formaldehyde and 10mL of absolute ethyl alcohol 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). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the self-prepared intermediate was dissolved in 10mL of tetrahydrofuran, and 0.001mol of potassium tert-butoxide was added thereto. And slowly dropping a mixed solution of 0.01mol of furfural and 10mL of tetrahydrofuran into the mixed solution by using a constant-pressure dropping funnel, reacting at the temperature of 20-30 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 10) to obtain the target compound, wherein the physical and chemical properties of the target compound are as follows:
orange needle crystals; yield: 85 percent; the hydrogen spectrum is shown in fig. 4, the carbon spectrum is shown in fig. 5, the high resolution mass spectrum is shown in fig. 6, and particularly,1H NMR(400MHz,DMSO-d6)(ppm):7.98(1H,d,J＝1.6Hz),7.67(1H,dd,J＝7.6,1.2Hz),7.59(1H,d,J＝3.2Hz),7.43(1H,s),7.34-7.30(1H,m),7.08(1H,d,J＝3.6Hz),6.81(1H,d,J＝4.0Hz),6.73-6.71(2H,m),6.67-6.63(1H,m),6.56(1H,dd,J＝3.6,1.2Hz),6.41(1H,d,J＝3.2Hz),2.29(3H,s)；13C NMR(100MHz,DMSO-d6)(ppm):182.08,151.07,150.73,147.16,144.16,135.91,130.75,127.70,125.24,125.14,121.62,119.61,118.20,117.46,116.61,113.40,52.33,15.33；HRMS(ESI)m/z:Calcd for C19H15NO2S[M+H]+:322.0896,Found:322.0898.
example 3:
compound 3:
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-chlorothiophene-2-formaldehyde and 10mL of absolute ethyl alcohol 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). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the self-prepared intermediate was dissolved in 10mL of tetrahydrofuran, and 0.001mol of potassium tert-butoxide was added thereto. And slowly dropping a mixed solution of 0.01mol of furfural and 10mL of tetrahydrofuran into the mixed solution by using a constant-pressure dropping funnel, reacting at the temperature of 20-30 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 10) to obtain the target compound, wherein the physical and chemical properties of the target compound are as follows:
orange powder; yield: 86 percent; the hydrogen spectrum is shown in fig. 7, the carbon spectrum is shown in fig. 8, the high resolution mass spectrum is shown in fig. 9, and specifically,1HNMR(400MHz,DMSO-d6)(ppm):8.00(1H,d,J＝1.6Hz),7.69(1H,dd,J＝8.0,1.6Hz),7.66(1H,d,J＝3.6Hz),7.49(1H,s),7.37-7.33(1H,m),7.13(1H,d,J＝3.6Hz),6.90(1H,d,J＝4.0Hz),6.85(1H,d,J＝8.0Hz),6.80(1H,dd,J＝3.6,0.8Hz),6.73(1H,dd,J＝3.6,2.0Hz),6.70-6.66(1H,m),6.43(1H,d,J＝3.2Hz)；13C NMR(100MHz,DMSO-d6)(ppm):181.75,150.90,150.38,147.43,146.19,136.09,129.78,127.77,127.03,127.00,125.17,122.26,120.17,118.30,117.89,116.67,113.51,52.42；HRMS(ESI)m/z:Calcd for C18H12ClNO2S[M+H]+:342.0350,Found:342.0332.
example 4:
compound 4:
preparation of
0.01mol of 2-aminoacetophenone was dissolved in 10mL of anhydrous ethanol, and 10mL of 10% NaOH ethanol solution was added thereto. Stirring in an ice bath, slowly dropping a mixed solution of 0.01mol of 5-bromothiophene-2-formaldehyde and 10mL of absolute ethyl alcohol 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). After the reaction was complete, the pH of the solution was adjusted to neutral with 10% HCl. Then, 0.01mol of p-toluenesulfonic acid is added into the reaction mixture, the reaction is carried out at 65-70 ℃, and the completion of the reaction is checked by TLC. And after the reaction is finished, pouring the reaction solution into 100mL of ice water, adjusting the pH value of the solution to 7-9 by using triethylamine, separating out a precipitate, filtering, washing with distilled water to be neutral, and recrystallizing with absolute ethyl alcohol to obtain a quinolinone intermediate.
0.01mol of the self-prepared intermediate was dissolved in 10mL of tetrahydrofuran, and 0.001mol of potassium tert-butoxide was added thereto. And slowly dropping a mixed solution of 0.01mol of furfural and 10mL of tetrahydrofuran into the mixed solution by using a constant-pressure dropping funnel, reacting at the temperature of 20-30 ℃, and checking whether the reaction is finished by using TLC. After the reaction is finished, removing the solvent by rotary evaporation to obtain a solid mixture, and separating by silica gel column chromatography (eluent is a mixture of ethyl acetate and petroleum ether with the volume ratio of 1: 10) to obtain the target compound, wherein the physical and chemical properties of the target compound are as follows:
brick red powder; yield: 81 percent; the hydrogen spectrum is shown in fig. 10, the carbon spectrum is shown in fig. 11, the high resolution mass spectrum is shown in fig. 12, and specifically,1H NMR(400MHz,DMSO-d6)(ppm):8.00(1H,d,J＝2.0Hz),7.69(1H,dd,J＝8.0,1.6Hz),7.66(1H,d,J＝3.6Hz),7.48(1H,s),7.37-7.33(1H,m),7.13(1H,d,J＝3.2Hz),7.01(1H,d,J＝3.6Hz),6.85(1H,d,J＝8.0Hz),6.78(1H,dd,J＝4.0,1.2Hz),6.73(1H,dd,J＝3.6,2.0Hz),6.70-6.66(1H,m),6.44(1H,d,J＝3.2Hz)；13C NMR(100MHz,DMSO-d6)(ppm):181.76,150.90,150.40,148.83,147.44,136.09,130.56,129.82,127.77,126.18,122.20,120.17,118.28,117.88,116.67,113.52,110.10,52.43；HRMS(ESI)m/z:Calcd forC18H12BrNO2S[M+H]+:385.9845,Found:385.9825.
experimental example 1: 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) results of the experiment
The insecticidal 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.
Experimental example 2: measurement of 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 compound of the present invention on seed germination at 20mg/L
a: average of three replicates.
As is clear from Table 2, the compounds of the present invention have a good accelerating effect on the germination of the seeds of all of the above 4 vegetables.
The foregoing embodiments are intended to illustrate that the invention may be implemented or used by those skilled in the art, and modifications to the above embodiments will be apparent to those skilled in the art, and therefore the invention includes, but is not limited to, the above embodiments, any methods, processes, products, etc., consistent with the principles and novel and inventive features disclosed herein, and fall within the scope of the invention.
Claims (10)
1. A compound of formula I:
wherein R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
2. A compound according to claim 1, wherein R is hydrogen, methyl, ethyl, methoxy, hydroxymethyl, chloro or bromo.
3. The compound of claim 1, having the formula:
4. a process for the preparation of a compound according to any one of claims 1 to 3, comprising the steps of:
a. dissolving 2-aminoacetophenone in absolute ethyl alcohol, adding a NaOH ethanol solution, adding a mixed solution of a compound A and the absolute ethyl alcohol, and reacting at 0-5 ℃;
b. after the reaction is finished, adjusting the pH value of the reaction solution to be neutral, then adding p-toluenesulfonic acid into the reaction solution, and reacting at 65-70 ℃;
c. after the reaction is finished, pouring the reaction liquid into ice water, adjusting the pH value of the solution to 7-9 by using triethylamine until a precipitate is separated out, then filtering to obtain a precipitate, washing the precipitate by using water, and recrystallizing by using absolute ethyl alcohol to obtain a quinolinone intermediate;
d. dissolving the quinolinone intermediate in tetrahydrofuran, and adding potassium tert-butoxide thereto; adding a mixed solution of furfural and tetrahydrofuran, reacting at 20-30 ℃, removing the solvent after the reaction is finished to obtain a solid mixture, and separating by using silica gel column chromatography to obtain the compound of any one of claims 1-3;
wherein the compound A is
And R is hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 hydroxyalkyl or halogen.
5. Use of a compound according to any one of claims 1 to 3 for the preparation of a medicament for controlling pests.
6. The use of a compound according to claim 5 for the manufacture of a medicament for the control of pests, wherein the pests are stored-grain pests; preferably, the pests are elephants, clothes of corn or tribolium castaneum; more preferably, when the pest is a corn elephant, the compound is compound 1 or compound 2; when the pests are the grain, the compound is compound 2, compound 3 or compound 4; when the pest is tribolium castaneum, the compound is compound 1 or compound 3; further preferably, when the pest is a zeamais pest, the compound is compound 2; when the pests are the clothes, the compound is compound 2; when the pest is tribolium castaneum, the compound is compound 3.
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 seed is a vegetable seed.
9. Use of a compound according to claim 8 for the preparation of a seed germination promoter, wherein the vegetable seed is cucumber seed, green pepper seed, tomato seed or celery seed.
10. Use of a compound according to claim 9 for the preparation of a seed germination promoter, wherein when the vegetable seed is cucumber seed, the compound is compound 4; when the vegetable seed is a green pepper seed, the compound is compound 1; when the vegetable seed is a tomato seed, the compound is compound 2; when the vegetable seed is celery seed, the compound is compound 1.
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| CN112979621A (en) * | 2021-03-11 | 2021-06-18 | 西华大学 | 2,3,4, 6-tetra-substituted pyridine compound and application thereof in pesticides |
| CN113004260A (en) * | 2021-03-11 | 2021-06-22 | 西华大学 | 2- (2-furoylamino) benzopyran compounds and their use in pesticides |
| CN112979621B (en) * | 2021-03-11 | 2023-08-29 | 山东淏源生物科技有限公司 | 2,3,4, 6-tetra-substituted pyridine compound and application thereof in pesticides |
| CN113004260B (en) * | 2021-03-11 | 2023-12-26 | 西华大学 | 2- (2-furoylamino) benzopyran compounds and their use in pesticides |
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