CN111018826A - 2-cyano-5-oxo-ethyl valerate compound and application thereof - Google Patents
2-cyano-5-oxo-ethyl valerate compound and application thereof Download PDFInfo
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- CN111018826A CN111018826A CN201911355563.1A CN201911355563A CN111018826A CN 111018826 A CN111018826 A CN 111018826A CN 201911355563 A CN201911355563 A CN 201911355563A CN 111018826 A CN111018826 A CN 111018826A
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- methoxy
- chlorine
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- 150000001875 compounds Chemical class 0.000 claims abstract description 73
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 21
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 235000013311 vegetables Nutrition 0.000 claims abstract description 15
- -1 methoxy, hydroxymethyl Chemical group 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011630 iodine Substances 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 6
- UCFFGYASXIPWPD-UHFFFAOYSA-N methyl hypochlorite Chemical compound COCl UCFFGYASXIPWPD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000007226 seed germination Effects 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 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 10
- 241000209140 Triticum Species 0.000 claims description 8
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 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
- 239000000417 fungicide Substances 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 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
- 239000001387 apium graveolens Substances 0.000 claims description 3
- 230000000855 fungicidal effect Effects 0.000 claims 5
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000035784 germination Effects 0.000 abstract description 10
- 244000000004 fungal plant pathogen Species 0.000 abstract description 5
- 239000000575 pesticide Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 230000000844 anti-bacterial effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003899 bactericide agent Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001819 mass spectrum Methods 0.000 description 10
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000012085 test solution Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 240000007087 Apium graveolens Species 0.000 description 4
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 4
- 235000010591 Appio Nutrition 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- GFBVUFQNHLUCPX-UHFFFAOYSA-N 5-bromothiophene-2-carbaldehyde Chemical compound BrC1=CC=C(C=O)S1 GFBVUFQNHLUCPX-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- WYECURVXVYPVAT-UHFFFAOYSA-N 1-(4-bromophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Br)C=C1 WYECURVXVYPVAT-UHFFFAOYSA-N 0.000 description 2
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 2
- NTPLXRHDUXRPNE-UHFFFAOYSA-N 4-methoxyacetophenone Chemical compound COC1=CC=C(C(C)=O)C=C1 NTPLXRHDUXRPNE-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- CNUDBTRUORMMPA-UHFFFAOYSA-N formylthiophene Chemical compound O=CC1=CC=CS1 CNUDBTRUORMMPA-UHFFFAOYSA-N 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 230000005764 inhibitory process 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
- 229930192474 thiophene Natural products 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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention relates to a 2-cyano-5-oxo-ethyl valerate compound and application thereof, belonging to the field of pesticides. The structural formula of the compound is shown as formula I, wherein R1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Hydrogen, methyl, methoxy, chlorine, bromine or iodine. The compound of the invention has better control effect on plant pathogenic fungi and better promotion effect on the germination of vegetable seeds.
Description
Technical Field
The invention relates to a 2-cyano-5-oxo-ethyl valerate compound and application thereof, belonging to the field of pesticides.
Background
In recent years, heterocyclic compounds have shown an increasingly important role in the research and development of biologically active compounds. The biological activity of the biological enzyme is high, the activity is high, the dosage is small, the toxicity is low, and the specificity in the biological and biological reactions of pests is a main research subject. Among them, compounds such as furan, thiophene, pyridine, pyrimidine, pyrazole, imidazole, thiazole, triazole and the like have attracted attention because of the continuous emergence of novel medicaments with epoch-making significance, and have become hot spots and frontiers for the research of bioactive compounds.
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 are more widely concerned and become hot spots and frontiers for creating new pesticides.
So far, the use of the ethyl 2-cyano-5-oxopentanoate compound as an agricultural bactericide and a vegetable seed germination promoter has not been reported.
Disclosure of Invention
The invention solves the technical problem of providing a novel compound which can be used as an agricultural bactericide and a vegetable seed germination promoter.
The structural formula of the compound of the invention is shown as formula I:
wherein R is1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Hydrogen, methyl, methoxy, chlorine, bromine or iodine.
Preferably: r1Is chlorine, bromine or methoxy; r2Hydrogen, methyl, methoxy, chlorine, bromine or iodine.
Preferably: r1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Is hydrogen or bromine.
More preferably: r1Is chlorine, bromine or methoxy; r2Is hydrogen or bromine.
Preferably, the compound has the structural formula:
the invention solves a second technical problem by providing the application of the compound in preparing agricultural fungicides.
Researches show that the compound has bactericidal activity and can be used as an agricultural bactericide.
Preferably, the bacteria controlled by the bactericide are fungi; more 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 third technical problem solved by the invention is to provide the application of the compound in preparing the 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; more preferably, the yellow vegetable seed is cucumber seed, green pepper seed, tomato seed or celery seed.
The invention has the beneficial effects that:
1. the invention introduces thiophene ring into the molecular structure of ethyl valerate to synthesize some 2-cyano-5-oxo ethyl valerate compounds, and finds some active compounds or active lead compounds with novel structure and excellent activity, thereby laying a good foundation for the creation of new pesticides.
2. The compound of the general formula (I) has good control effect on plant pathogenic fungi and good promotion effect on the germination of vegetable seeds, and is not reported in the existing bactericides and seed germination promoters.
Drawings
FIG. 1 is 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. 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. 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.
FIG. 13 is a nuclear magnetic hydrogen spectrum of the compound of example 5.
FIG. 14 is a nuclear magnetic carbon spectrum of the compound of example 5.
FIG. 15 is a high resolution mass spectrum of the compound of example 5.
Detailed Description
The invention solves the technical problem of providing a novel compound which can be used as an agricultural bactericide and a vegetable seed germination promoter.
The structural formula of the compound of the invention is shown as formula I:
wherein R is1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Hydrogen, methyl, methoxy, chlorine, bromine or iodine.
Preferably: r1Is chlorine, bromine or methoxy; r2Hydrogen, methyl, methoxy, chlorine, bromine or iodine.
Preferably: r1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Is hydrogen or bromine.
More preferably: r1Is chlorine, bromine or methoxy; r2Is hydrogen or bromine.
Preferably, the compound has the structural formula:
the compound can be prepared by adopting a conventional chemical method;
preferably, the compound can be prepared by the following reaction process:
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 has bactericidal activity and can be used as an agricultural bactericide.
Preferably, the bacteria controlled by the bactericide are fungi; more 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.
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; more preferably, the yellow vegetable seed is cucumber seed, green pepper seed, tomato seed or celery seed.
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
0.01mol of 4-chloroacetophenone was dissolved in 10mL of anhydrous ethanol, and 5mL of a 10% NaOH ethanol solution was added thereto. Under stirring in an ice bath, a mixed solution of 0.01mol of thiophene-2-carbaldehyde and 10mL of absolute ethanol was slowly dropped into the above mixed solution with a constant pressure dropping funnel, reacted at 0 to 5 ℃, and checked for completion with a thin layer silica gel plate (TLC). After completion of the reaction, 5mL of 10% NaOH ethanol solution was added to the reaction mixture, and a mixed solution of 0.02mol of ethyl cyanoacetate and 10mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, and the reaction was continued at 0 to 5 ℃ with TLC to check whether the reaction was completed. After the reaction is finished, adding 1-2 times of distilled water into the solution, adjusting the pH to be neutral by using a 10% hydrochloric acid solution, extracting for 3 times by using ethyl acetate, combining extract liquor, removing the solvent by rotary evaporation, and performing silica gel column chromatography to obtain a target compound, wherein the physicochemical data are as follows:
a yellow liquid; the yield is 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,1HNMR(400MHz,DMSO-d6)δ(ppm):8.02(2H,dd,J＝15.6,8.8Hz),7.63(2H,d,J＝8.8Hz),7.43(1H,dd,J＝5.2,0.8Hz),7.11(1H,d,J＝2.8Hz),7.00(1H,dd,J＝5.2,3.6Hz),4.72-4.63(1H,m),4.37-4.31(1H,m),4.19-4.13(2H,m),3.83-3.57(2H,m),1.24-1.16(3H,m)；13C NMR(100MHz,DMSO-d6)δ(ppm):196.08,165.60,141.33,139.03,135.24,130.46,129.39,127.39,126.45,125.74,116.26,62.84,44.93,42.78,35.76,14.25；HRMS(ESI)m/z:Calcdfor C18H16ClNO3S[M+H]+:362.0612,Found:362.0609.
example 2:
compound (I)
Preparation of
0.01mol of 4-bromoacetophenone was dissolved in 10mL of anhydrous ethanol, and 5mL of a 10% NaOH ethanol solution was added thereto. Under stirring in an ice bath, a mixed solution of 0.01mol of thiophene-2-carbaldehyde and 10mL of absolute ethanol was slowly dropped into the above mixed solution with a constant pressure dropping funnel, reacted at 0 to 5 ℃, and checked for completion with a thin layer silica gel plate (TLC). After completion of the reaction, 5mL of 10% NaOH ethanol solution was added to the reaction mixture, and a mixed solution of 0.02mol of ethyl cyanoacetate and 10mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, and the reaction was continued at 0 to 5 ℃ with TLC to check whether the reaction was completed. After the reaction is finished, adding 1-2 times of distilled water into the solution, adjusting the pH to be neutral by using a 10% hydrochloric acid solution, extracting for 3 times by using ethyl acetate, combining extract liquor, removing the solvent by rotary evaporation, and performing silica gel column chromatography to obtain a target compound, wherein the physicochemical data are as follows:
a white solid; the yield is 67 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,1HNMR(400MHz,DMSO-d6)δ(ppm):7.93(2H,dd,J＝15.6,8.4Hz),7.77(2H,d,J＝8.4Hz),7.43(1H,dd,J＝4.8,0.8Hz),7.11(1H,d,J＝3.2Hz),7.01-6.97(1H,m),4.72-4.63(1H,m),4.34(1H,dd,J＝11.6,6.8Hz),4.17(1H,dd,J＝6.8,2.4Hz),4.14(1H,dd,J＝7.2,2.4Hz),3.83-3.56(2H,m),1.20-1.15(3H,m)；13C NMR(100MHz,DMSO-d6)δ(ppm):196.29,165.61,141.31,135.53,132.36,130.56,128.25,127.40,126.46,125.76,116.27,62.85,44.94,42.73,35.72,14.26；HRMS(ESI)m/z:Calcd for C18H16BrNO3S[M+H]+:406.0107,Found:406.0111.
example 3:
compound (I)
Preparation of
0.01mol of 4-methoxyacetophenone was dissolved in 10mL of anhydrous ethanol, and 5mL of a 10% NaOH ethanol solution was added thereto. Under stirring in an ice bath, a mixed solution of 0.01mol of 5-bromothiophene-2-carbaldehyde and 10mL of absolute ethyl alcohol was slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction was carried out at 0 to 5 ℃, and whether the reaction was completed or not was checked by using a thin layer silica gel plate (TLC). After completion of the reaction, 5mL of 10% NaOH ethanol solution was added to the reaction mixture, and a mixed solution of 0.02mol of ethyl cyanoacetate and 10mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, and the reaction was continued at 0 to 5 ℃ with TLC to check whether the reaction was completed. After the reaction is finished, adding 1-2 times of distilled water into the solution, adjusting the pH to be neutral by using a 10% hydrochloric acid solution, extracting for 3 times by using ethyl acetate, combining extract liquor, removing the solvent by rotary evaporation, and performing silica gel column chromatography to obtain a target compound, wherein the physicochemical data are as follows:
a yellow liquid; the yield is 81 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)δ(ppm):7.98(2H,dd,J＝13.6,8.8Hz),7.10(1H,dd,J＝6.8,4.0Hz),7.07(2H,d,J＝8.8Hz),6.95(1H,d,J＝4.0Hz),4.73-4.65(1H,m),4.29-4.14(3H,m),3.86(3H,s),3.74-3.47(2H,m),1.20(3H,t,J＝7.2Hz)；13C NMR(100MHz,DMSO-d6)δ(ppm):195.06,165.53,164.00,143.64,130.92,130.59,129.43,127.53,116.21,114.47,110.60,62.99,56.06,44.52,41.90,36.20,14.25；HRMS(ESI)m/z:Calcd for C19H18BrNO4S[M+H]+:436.0213,Found:436.0211.
example 4:
compound (I)
Preparation of
0.01mol of 4-chloroacetophenone was dissolved in 10mL of anhydrous ethanol, and 5mL of a 10% NaOH ethanol solution was added thereto. Under stirring in an ice bath, a mixed solution of 0.01mol of 5-bromothiophene-2-carbaldehyde and 10mL of absolute ethyl alcohol was slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction was carried out at 0 to 5 ℃, and whether the reaction was completed or not was checked by using a thin layer silica gel plate (TLC). After completion of the reaction, 5mL of 10% NaOH ethanol solution was added to the reaction mixture, and a mixed solution of 0.02mol of ethyl cyanoacetate and 10mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, and the reaction was continued at 0 to 5 ℃ with TLC to check whether the reaction was completed. After the reaction is finished, adding 1-2 times of distilled water into the solution, adjusting the pH to be neutral by using a 10% hydrochloric acid solution, extracting for 3 times by using ethyl acetate, combining extract liquor, removing the solvent by rotary evaporation, and performing silica gel column chromatography to obtain a target compound, wherein the physicochemical data are as follows:
white crystals; the yield is 82 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,1HNMR(400MHz,DMSO-d6)δ(ppm):8.02(2H,dd,J＝14.4,8.8Hz),7.63(2H,d,J＝8.8Hz),7.11(1H,dd,J＝7.2,4.0Hz),6.98(1H,d,J＝3.6Hz),4.72-4.66(1H,m),4.29-4.15(3H,m),3.81-3.57(2H,m),1.22-1.17(3H,m)；13C NMR(100MHz,DMSO-d6)δ(ppm):195.91,165.49,143.44,139.09,135.12,130.62,130.49,129.39,127.65,116.15,110.67,63.03,44.52,42.33,36.00,14.26；HRMS(ESI)m/z:Calcd for C18H15BrClNO3S[M+H]+:439.9717,Found:439.9729.
example 5:
compound (I)
Preparation of
0.01mol of 4-bromoacetophenone was dissolved in 10mL of anhydrous ethanol, and 5mL of a 10% NaOH ethanol solution was added thereto. Under stirring in an ice bath, a mixed solution of 0.01mol of 5-bromothiophene-2-carbaldehyde and 10mL of absolute ethyl alcohol was slowly dropped into the mixed solution by using a constant pressure dropping funnel, the reaction was carried out at 0 to 5 ℃, and whether the reaction was completed or not was checked by using a thin layer silica gel plate (TLC). After completion of the reaction, 5mL of 10% NaOH ethanol solution was added to the reaction mixture, and a mixed solution of 0.02mol of ethyl cyanoacetate and 10mL of anhydrous ethanol was slowly dropped into the mixture using a constant pressure dropping funnel, and the reaction was continued at 0 to 5 ℃ with TLC to check whether the reaction was completed. After the reaction is finished, adding 1-2 times of distilled water into the solution, adjusting the pH to be neutral by using a 10% hydrochloric acid solution, extracting for 3 times by using ethyl acetate, combining extract liquor, removing the solvent by rotary evaporation, and performing silica gel column chromatography to obtain a target compound, wherein the physicochemical data are as follows:
white crystals; the yield is 81 percent; the hydrogen spectrum is shown in fig. 13, the carbon spectrum is shown in fig. 14, the high-resolution mass spectrum is shown in fig. 15, and specifically,1HNMR(400MHz,DMSO-d6)δ(ppm):7.94(2H,dd,J＝14.0,8.8Hz),7.77(2H,d,J＝8.8Hz),7.10(1H,dd,J＝7.2,3.6Hz),6.97(1H,d,J＝4.0Hz),4.72-4.65(1H,m),4.29-4.15(3H,m),3.80-3.56(2H,m),1.22-1.16(3H,m)；13C NMR(100MHz,DMSO-d6)δ(ppm):196.12,165.49,144.44,143.43,135.45,132.35,130.58,128.30,127.64,116.14,110.67,63.03,44.52,42.31,35.99,14.26；HRMS(ESI)m/z:Calcd for C18H15Br2NO3S[M+Na]+:505.9032,Found:505.9027.
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 1-5 on phytopathogenic fungi at 20mg/L
a: average of three replicates.
As is clear from Table 1, the compounds 1 to 5 of examples have a good inhibitory effect on all of the above 6 types of pathogens.
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. 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 the test solution for 3-4 times by using tap water, and air-drying the test solution 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 5 on seed germination at 20mg/L
a: average of three replicates.
As is clear from Table 2, the compounds 1 to 5 of the examples have a good accelerating effect on the germination of the seeds of the above 4 vegetables.
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 (10)
1. A compound having the structural formula I:
wherein R is1Is methyl, methoxy, hydroxymethyl, chlorine or bromine; r2Is hydrogen, methyl, methoxy, chlorine, bromineOr iodine.
2. The compound of claim 1, wherein: r1Is chlorine, bromine or methoxy.
3. The compound of claim 1 or 2, wherein: r2Is hydrogen or bromine.
4. The compound of claim 1, having the formula:
5. use of a compound according to any one of claims 1 to 4 for the preparation of an agricultural fungicide.
6. The use of a compound according to claim 5 in the preparation of an agricultural fungicide, wherein the fungus controlled by the agricultural fungicide is a fungus.
7. The use of the compound according to claim 5 in the preparation of an agricultural fungicide, wherein the fungus to be controlled by the agricultural fungicide is cucumber downy mildew, wheat powdery mildew, wheat leaf rust, rice blast, cotton verticillium or citrus anthracnose.
8. Use of a compound according to any one of claims 1 to 4 for the preparation of a seed germination promoter.
9. Use of a compound according to claim 8 for the preparation of a seed germination promoter, wherein the seed is a vegetable seed.
10. Use of a compound according to claim 9 for the preparation of a seed germination promoter, wherein the yellow vegetable seed is a cucumber seed, a green pepper seed, a tomato seed or a celery seed.
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| CN109879841A (en) * | 2019-03-26 | 2019-06-14 | 江苏省农药研究所股份有限公司 | (Z) -3- imino group -1- allyl alcohol-like compound, preparation method and applications |
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| WO2007060164A1 (en) * | 2005-11-22 | 2007-05-31 | Bayer Cropscience Sa | N-(1-alkyl-2-phenylethyl)-carboxamide derivatives and use thereof as fungicides |
| WO2009117467A2 (en) * | 2008-03-18 | 2009-09-24 | Allergan, Inc. | Therapeutic compounds |
| CN102239160A (en) * | 2008-11-13 | 2011-11-09 | 拜尔农科股份公司 | Substituted (pyridyl)-azinylamine derivatives as fungicides |
| CN108347939A (en) * | 2015-11-25 | 2018-07-31 | 吉利德阿波罗公司 | Fungicidal composition containing the 2,4- dioxo -1,4- dihydro-thiophenes simultaneously derivative of [2,3-D] pyrimidine |
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