CN105418594A - Compound, preparation method and antibacterial application thereof - Google Patents
Compound, preparation method and antibacterial application thereof Download PDFInfo
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- CN105418594A CN105418594A CN201510982510.8A CN201510982510A CN105418594A CN 105418594 A CN105418594 A CN 105418594A CN 201510982510 A CN201510982510 A CN 201510982510A CN 105418594 A CN105418594 A CN 105418594A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- 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
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Indole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a preparation method of a novel medicine for inhibiting Cylindrocladium parasiticum, Colletotrichum corda and Phomopsis(Sacc.)Bubak. Indoleacetic acid, bromoethanol and carbendazim active compounds are used as synthetic raw materials to prepare an indoleacetic acid-carbendazim conjugate, which is the finish product, through a reaction. The invention also discloses nuclear magnetic resonance structure data, a hydrogen spectrogram and a carbon spectrogram of the novel compound. The compound has excellent antibacterial effects on the Cylindrocladium parasiticum, the Colletotrichum corda and the Phomopsis(Sacc.)Bubak.
Description
Technical field
The invention belongs to pesticide field, be specifically related to a kind of compound and its preparation method and application.
Background technology
Due to the broad spectrum of derosal, it has certain restraining effect to peanut black rot, anthrax bacteria, Phomopsis bacterium.Anthrax bacteria (ColletotrichumCorda) is global phytopathogen, various plants can be caused to produce disease, cause very large financial loss, especially in tropical and subtropical region to crop.Wherein colletotrichum gloeosporioides Penz host range is extensive, and the various crop such as oranges and tangerines, coffee, mango, papaya can be caused to produce disease.Control for anthrax bacteria focuses mostly on triazolone, benzimidazoles chemical control etc., but research shows, the colletotrichum gloeosporioides Penz of mango anthracnose and Oil Tea Anthracnose to benzimidazole germicide as derosal, thiophanate_methyl etc. create resistance.
Phomopsis germ (Phomopsis (Sacc.) Bubak) also can cause various plants such as asparagus, peach, mango etc. to produce disease, and the kind of subtropical and tropical zones is especially common.Research shows, derosal etc. have certain prevention effect to this germ Asparagus Stem Blight, but its action site is single, easily make germ develop immunity to drugs.
Peanut Black Rotten is serious and various crop is all had to the disease of threat as a class harm peanut, and it is reported, there is no effective medicament at present can prevent and treat.Derosal has certain restraining effect to this germ, but its more and more extensive He serious resistance, makes the control that it is not suitable for for this germ.Generally speaking, occur that the area of resistant strain can form resistance cause of disease colony very soon, cause prevention effect to decline.
Indolylacetic acid is a kind of plant hormone, has the effect of directed transport and Promoting plant growth, is widely used in farm crop.Although there is report derosal and indolylacetic acid to be jointly applied in medicament, both are only simple superposition at effect, to the plant developed immunity to drugs to derosal without any change.
Summary of the invention
The object of the invention is to the defect overcoming prior art, the compound that a kind of fungistatic effect is remarkable, economic is provided, and its preparation method and antibacterial application are provided simultaneously.
To achieve these goals, the technical scheme taked of the present invention is as follows:
Technical scheme one:
One aspect of the present invention provides the compound of a kind of structural formula such as formula (I):
Technical scheme two:
Further aspect of the present invention provides a kind of fungistat, its contained (I) compound:
Technical scheme three:
Another aspect of the invention provides the preparation method of the compound of a kind of formula (I):
3) there is esterification by indolylacetic acid (II) and bromoethanol (III) and obtain formula (IV) compound:
4) formula (I) compound is obtained by reacting in the basic conditions by formula (IV) compound and derosal (V):
Further improve as the present invention, described step 1) in also there is catalyzer, described catalyzer is selected from lN, N '-dicyclohexylcarbodiimide (DCC), EDCI, DIC, DMAP and HOBT.
Further improve as the present invention, specifically comprise the steps:
1) by 10mmol indolylacetic acid, 10mmolN, N '-dicyclohexylcarbodiimide (DCC), the DMAP (DMAP) of catalytic amount and 12mmol bromoethanol are added in 30mL methylene dichloride, stirring at room temperature 2h, after completion of the reaction, add water extraction, concentrated, column chromatography obtains colourless midbody compound (IV);
2) 5mmol carbendazim active compound is added in 20mL dimethyl formamide, stirring at room temperature, adds 7.5mmol cesium carbonate, after stirring 30min, be cooled to 0 DEG C, drip the DMF solution 30mL being dissolved with 6mmol midbody compound (IV), slowly be warming up to room temperature, stirring reaction, after completion of the reaction, adjusts pH value to neutral with the HCl solution of 3mol/L, extraction into ethyl acetate, column chromatography obtains indolylacetic acid-derosal.
Technical scheme four:
Last aspect of the present invention provides the application of formula (I) compound in antibacterial, sterilization and sterilizing.
Further, formula (I) compound is suppressing the application in peanut black rot, anthrax bacteria or Phomopsis germ.
Alkaline condition described in the application is selected from mineral alkali, organic bases, or its arbitrary combination, they exist with any suitable concentration, wherein, mineral alkali is selected from sodium hydroxide, sodium carbonate, salt of wormwood, cesium carbonate, saleratus, sodium bicarbonate and Sodium phosphate dibasic, preferred cesium carbonate, salt of wormwood or sodium carbonate; Organic bases is selected from triethylamine, pyridine, diisopropylethylamine, Diisopropylamine, ammoniacal liquor, preferred ammoniacal liquor.
In order to find a kind of novel fungistat that can substitute derosal, present inventor has carried out a large amount of research work, in order to overcome the resistance of germ to derosal, contriver attempts to carry out structure of modification to derosal, consider the root of initial site of pathological change plant of peanut black rot, the tip of a root is the initial site that it is injured.And growth hormone is as the important carrier of a class, the growth of its class have naphthylacetic acid (NAA), indolebutyric acid etc., has the effect such as directional transmissions, Promoting plant growth.Contriver attempts indolylacetic acid and fungicide carbendazim to splice, both can keep the sterilization idiocratic of derosal, and the directed conductivity of indolylacetic acid can have been utilized again, transported to root, reach antibacterial object, and the result of this trial is heartening and successful.
Compared with prior art, the beneficial effect acquired by the present invention is as follows:
The compounds of this invention all has remarkable restraining effect to germs such as peanut black rot, anthrax bacteria or Phomopsis germs.
Indolylacetic acid-the derosal of 100 μ g/mL all has fabulous restraining effect to three kinds of germs, and bacteriostasis rate all reaches 100%,
25 μ g/mL medicaments to the restraining effect of three kinds of germs all more than 50%.Compared with former medicine derosal, compound maintains the sterilization idiocratic of derosal, and has the effect to root transporting.Chemical combination synthesis material of the present invention is few and economical.The compounds of this invention belongs to a kind of pharmaceutical preparations, and its resistance can be ignored, and its action site is not only confined to blade, can also transporting to root.
Accompanying drawing explanation
Accompanying drawing 1 is formula (I) compound
1hNMR collection of illustrative plates;
Accompanying drawing 2 is formula (I) compound
13cNMR collection of illustrative plates;
Embodiment
Below in conjunction with specific embodiment, detailed further describing is carried out to the present invention.
The preparation of embodiment 1 formula (I) compound
By 10mmol indolylacetic acid (II), 10mmolN, N '-dicyclohexylcarbodiimide (DCC), DMAP (DMAP) and the 12mmol bromoethanol (III) of catalytic amount are added in 30mL methylene dichloride, stirring at room temperature 2h.After completion of the reaction, strengthen water gaging extraction, concentrated, column chromatography obtains colourless midbody compound (IV).
5mmol carbendazim active compound (V) is added in 20mL dimethyl formamide, stirring at room temperature, add 7.5mmol cesium carbonate, after stirring 30min, be cooled to 0 DEG C, drip DMF (DMF) the solution 30mL containing 6mmol midbody compound (IV), slowly be warming up to room temperature, stir 36h.After completion of the reaction, adjust pH value to neutral with the HCl solution of 3mol/L, extraction into ethyl acetate, column chromatography obtains white solid formula (I) compound indolylacetic acid-derosal.
The nuclear magnetic data of formula (I) compound:
1hNMR (400MHz, CDCl
3) δ 10.83 (s, 1H), 8.08 (s, 1H), 7.66 – 7.58 (m, 1H), 7.51 (d, J=7.9Hz, 1H), 7.35 (dd, J=6.5,2.2Hz, 1H), 7.29 (d, J=8.1Hz, 1H), 7.24 – 7.18 (m, 2H), 7.16 (d, J=7.3Hz, 1H), 7.08 (t, J=7.4Hz, 1H), 6.96 (d, J=2.1Hz, 1H), 4.49 (s, 4H), 3.78 (s, 3H), 3.69 (s, 2H).
13CNMR(125MHz,CDCl
3)δ171.90,155.14,148.39,140.73,135.99,132.24,127.15,123.08,122.07,122.03,121.78,119.58,118.65,118.00,111.12,110.30,107.94,61.99,53.84,44.85,31.06。
The indoor antibacterial test of effect example 1 pair of peanut black rot
Formula (I) compound 0.01g embodiment 1 obtained joins in 10mL sterilized water and (includes 1mL alcohol), after it fully dissolves, obtains 10
3the mother liquor of μ g/mL.Mother liquor being got 5mL joins in 45mL substratum, fully shake up after alcohol volatilization, on average be poured in three culture dish, each access diameter is the peanut black rot bacterium block of 5mm respectively, the diameter of bacterium colony is measured after cultivating 72h, calculate the mean value of bacteriostasis rate, obtain 100 μ g/mL medicaments to the effect of germ.Separately getting mother liquor 2.39mL, 1.15mL, 0.57mL, 0.28mL, 0.14mL respectively joins in 45ml substratum, by above-mentioned test operation, obtain 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicament to the effect of germ.As stated above, the derosal aqueous solution of equivalent is joined in bacterium block respectively, survey its inhibiting rate to germ.Blank then only adds 5mL sterilized water.
Result shows, 100 μ g/mL, 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicaments, relative to blank, are respectively the bacteriostatic action of peanut black rot: 100%, 80.6%, 52.0%, 29.6%, 24.63%, 19.90%.The inhibiting rate of derosal to germ of each concentration is 100%.
The indoor antibacterial test of effect example 2 pairs of anthrax-bacilus
Formula (I) compound 0.01g embodiment 1 obtained joins in 10mL sterilized water and (includes 1mL alcohol), after it fully dissolves, obtains 10
3the mother liquor of μ g/mL.Mother liquor being got 5mL joins in 45mL substratum, fully shake up after alcohol volatilization, on average be poured in three culture dish, each access diameter is the anthrax-bacilus bacterium block of 5mm respectively, the diameter of bacterium colony is measured after cultivating 72h, calculate the mean value of bacteriostasis rate, obtain 100 μ g/mL medicaments to the effect of germ.Separately getting mother liquor 2.39mL, 1.15mL, 0.57mL, 0.28mL, 0.14mL respectively joins in 45mL substratum, by above-mentioned test operation, obtain 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicament to the effect of germ.As stated above, the derosal aqueous solution of equivalent is joined in bacterium block respectively, survey its inhibiting rate to germ.Blank then only adds 5mL sterilized water.
Result shows, 100 μ g/mL, 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicaments, relative to blank, are respectively the bacteriostatic action of anthrax-bacilus: 100%, 81.86%, 64.42%, 30.7%, 14.65%, 6.98%.The inhibiting rate of derosal to germ of each concentration is 100%.
The indoor antibacterial test of effect example 3 pairs of Phomopsis germs
Formula (I) compound 0.01g embodiment 1 obtained joins in 10mL sterilized water and (includes 1mL alcohol), after it fully dissolves, obtains 10
3the mother liquor of μ g/mL.Mother liquor being got 5mL joins in 45mL substratum, fully shake up after alcohol volatilization, on average be poured in three culture dish, each access diameter is the Phomopsis germ bacterium block of 5mm respectively, the diameter of bacterium colony is measured after cultivating 72h, calculate the mean value of bacteriostasis rate, obtain 100 μ g/mL medicaments to the effect of germ.Separately getting mother liquor 2.39mL, 1.15mL, 0.57mL, 0.28mL, 0.14mL respectively joins in 45mL substratum, by above-mentioned test operation, obtain 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicament to the effect of germ.As stated above, the derosal aqueous solution of equivalent is joined in bacterium block respectively, survey its inhibiting rate to germ.Blank then only adds 5mL sterilized water.
Result shows, 100 μ g/mL, 50 μ g/mL, 25 μ g/mL, 12.5 μ g/mL, 6.25 μ g/mL, 3.125 μ g/mL medicaments, relative to blank, are respectively the bacteriostatic action of Phomopsis germ: 100%, 93.59%, 57.18%, 48.21%, 32.82%, 17.95%.The inhibiting rate of derosal to germ of each concentration is 100%.
Effect example 4 transporting is tested
Accurately take a certain amount of indolylacetic acid-derosal, be dissolved in the acetone of about 5mL, add 0.2mL tween-80 as tensio-active agent, be diluted with water to the solution that concentration is 0.5mmol/L after mixing, even spraying is on the peanut plant of 10-15cm.During spraying, with plastic paper, flowerpot is covered, prevent liquid from entering in soil.Get peanut root 10g after 36h, join in the mixed solution of 90mL methyl alcohol and 10mL water, tissue refiner smashs to pieces, and 10h is soaked in rear taking-up.After suction filtration, residue is poured in extraction flask and is extracted 2 times, merging filtrate with 100mL methanol aqueous solution again, and use dichloromethane extraction 3 times after concentrated, after anhydrous sodium sulfate drying, water-bath is concentrated into dry.After 5mL acetone solution, through glass chromatography column purifying, obtain sample after water-bath is concentrated, be settled to 2mL after acetone solution, it is 1.03 ± 0.02 μ g/g that liquid phase chromatography detects its content.By above-mentioned same method, root does not then detect derosal.
Liquid chromatograph is equipped with automatic sampler, diode battle array row detector.Chromatographic condition: chromatographic column is the inverse bonded post of Hewlett-Packard Corporation of U.S. C18 (250mm × 4mm), column temperature 25 DEG C, and eluent is methyl alcohol: water (80: 20, volume ratio), flow velocity 1mL/min, sample size 10 μ L, determined wavelength 250nm.
The above embodiment is only the preferred embodiments of the present invention, and and the feasible enforcement of non-invention exhaustive.For persons skilled in the art, to any apparent change done by it under the prerequisite not deviating from the principle of the invention and spirit, all should be contemplated as falling with within claims of the present invention.
Claims (7)
1. a structural formula is such as formula the compound of (I):
2. a fungistat, is characterized in that, its contained (I) compound:
3. the preparation method of formula as claimed in claim 1 (I) compound: it is characterized in that, comprise following steps:
1) there is esterification by indolylacetic acid (II) and bromoethanol (III) and obtain formula (IV) compound:
2) formula (I) compound is obtained by reacting in the basic conditions by formula (IV) compound and derosal (V):
4. the preparation method of a kind of formula (I) compound according to claim 3: it is characterized in that, described step 1) in also there is catalyzer, described catalyzer is selected from lN, N '-dicyclohexylcarbodiimide (DCC), EDCI, DIC, DMAP and HOBT.
5. the preparation method of a kind of formula (I) compound according to claim 3 or 4: it is characterized in that, specifically comprise the steps:
1) by 10mmol indolylacetic acid, 10mmolN, N '-dicyclohexylcarbodiimide (DCC), the DMAP (DMAP) of catalytic amount and 12mmol bromoethanol are added in 30mL methylene dichloride, stirring at room temperature 2h, after completion of the reaction, add water extraction, concentrated, column chromatography obtains colourless midbody compound (IV);
2) 5mmol carbendazim active compound is added in 20mL dimethyl formamide, stirring at room temperature, adds 7.5mmol cesium carbonate, after stirring 30min, be cooled to 0 DEG C, drip the DMF solution 30mL being dissolved with 6mmol midbody compound (IV), slowly be warming up to room temperature, stirring reaction, after completion of the reaction, adjusts pH value to neutral with the HCl solution of 3mol/L, extraction into ethyl acetate, column chromatography obtains indolylacetic acid-derosal.
6. formula as claimed in claim 1 (I) compound application in antibacterial, sterilization and sterilizing.
7. formula as claimed in claim 1 (I) compound is suppressing the application in peanut black rot, anthrax bacteria or Phomopsis germ.
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| CN201510982510.8A CN105418594B (en) | 2015-12-23 | 2015-12-23 | A kind of compound and preparation method thereof and antibacterial application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299276A (en) * | 2018-01-11 | 2018-07-20 | 中国农业科学院植物保护研究所 | A kind of Benzazole compounds and its application in prevention agricultural fungal evil |
| CN108299307A (en) * | 2018-01-26 | 2018-07-20 | 仲恺农业工程学院 | A kind of compound and preparation method thereof and antibacterial application |
| CN108728367A (en) * | 2017-04-25 | 2018-11-02 | 中国海洋大学 | A kind of marine fungi in two discrimination wick gorgonian source of flower bud and its application in preparing antibacterials |
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2015
- 2015-12-23 CN CN201510982510.8A patent/CN105418594B/en not_active Expired - Fee Related
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| 俞文渊等: "新型杀菌剂苯并咪唑喹啉铜对辣椒疫霉的抑菌活性", 《农药》 * |
| 张英等: "苯并咪唑类化合物杀菌活性的研究进展", 《农药》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108728367A (en) * | 2017-04-25 | 2018-11-02 | 中国海洋大学 | A kind of marine fungi in two discrimination wick gorgonian source of flower bud and its application in preparing antibacterials |
| CN108728367B (en) * | 2017-04-25 | 2022-01-21 | 中国海洋大学 | Marine fungus from dichotomous juncus effusum and application of marine fungus in preparation of antibacterial drugs |
| CN108299276A (en) * | 2018-01-11 | 2018-07-20 | 中国农业科学院植物保护研究所 | A kind of Benzazole compounds and its application in prevention agricultural fungal evil |
| CN108299276B (en) * | 2018-01-11 | 2020-07-31 | 中国农业科学院植物保护研究所 | Indole compound and application thereof in preventing and treating agricultural fungal diseases |
| CN108299307A (en) * | 2018-01-26 | 2018-07-20 | 仲恺农业工程学院 | A kind of compound and preparation method thereof and antibacterial application |
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