CN112079825B - Compound containing 1, 3-dioxolane dimeric bithiophene structure and preparation method and application thereof - Google Patents
Compound containing 1, 3-dioxolane dimeric bithiophene structure and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 title claims abstract description 17
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical group C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 title claims description 6
- 239000000575 pesticide Substances 0.000 claims abstract description 24
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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
- A01N43/02—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
- A01N43/24—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 two or more hetero atoms
- A01N43/26—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 two or more hetero atoms five-membered rings
- A01N43/28—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 two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
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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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a compound containing a 1, 3-dioxolane dimeric dithiophene structure, a preparation method and application thereof. The compound has the structure shown in the formula (1) and the formula (2), and the preparation method comprises the following steps: (1) extracting dry root of donkey-hide gelatin with ethanol to obtain ethanol extract; (2) subjecting the ethanol extract to silica gel column chromatography, and gradient eluting with n-hexane-acetone and petroleum ether-acetone as eluent in sequence to obtain fraction; (3) eluting the fraction obtained in the step (2) by using hydroxypropyl sephadex with chloroform-methanol, and finally obtaining the compound containing the 1, 3-dioxolane dimeric dithiophene structure by using preparative thin-layer chromatography. The invention provides the compound for the first time, and finds that the compound has wide application in the fields of pesticides and the like.
Description
Technical Field
The invention relates to the technical field of phytochemistry, in particular to a compound containing a 1, 3-dioxolane dimeric dithiophene structure extracted and separated from an donkey peristome and application thereof in killing nematodes and resisting plant pathogenic fungi.
Background
Plant resources are an important source for pesticide development. The botanical pesticide has the advantages of environmental friendliness, generally low toxicity, difficulty in causing diseases and pests to generate drug resistance and the like in the prevention and treatment of crop diseases and insect pests, and is a pesticide variety which is preferably selected for producing pollution-free agricultural products.
The donkey is a plant of Echinops (Compositae) genus Echinops (Compositae). The donkey is blue and yellow in flower color, beautiful in flower shape and is a garden plant with high ornamental value. In addition, the roots of the plants have been used as traditional Chinese medicines for a long time due to the effects of resisting inflammation and promoting lactation, and are recorded in the Chinese pharmacopoeia as one of the sources of the radix rhapontici.
To date, researchers at home and abroad have separated various structural compounds from the dry mouth of donkey, which mainly include thiophene, phenylpropanoids, terpenes (monoterpene, sesquiterpene, diterpene and the like), steroids, alkaloids, fatty acids and the like. Among these, natural thiophenes are a very small class of natural compounds, mostly consisting of one to three thiophene rings coupled together via their alpha-carbons and carrying an alkyl chain in their free ortho position. To date, more than 150 thiophene derivatives have been identified. They can be structurally classified according to the number of thiophene rings, including monothiophenes (mono-rings), dithiophenes (bi-rings), and trithiophenes (tri-rings). Bithiophene dimers having four thiophene rings are very rare, and in particular dimers in which two bithiophene units are connected by a new 1, 3-dioxolane backbone are not reported. Thiopheneic compounds are produced as part of the chemical defense mechanism of many plant species and are considered as potential sources of natural alternatives to synthetic pesticides. Therefore, the dimeric dithiophene compound containing 1, 3-dioxolane is separated and extracted from the dry mouth root of donkey and has important practical significance for explaining the nematicidal effect and the anti-plant pathogenic fungi.
At present, no reports are available about the compounds of the present invention, and no reports are available about the use of the compounds of the present invention for their nematicidal and anti-phytopathogenic fungi agricultural activities.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a compound containing a 1, 3-dioxolane dimeric dithiophene structure, and a preparation method and application thereof. The compound with the new framework structure has pesticide application value, and the pharmaceutical composition containing the compound with the 1, 3-dioxolane dimeric dithiophene structure provides more drug selection approaches for killing nematodes and resisting plant pathogenic fungi.
The technical scheme for solving the technical problems is as follows:
the compound containing the 1, 3-dioxolane dimeric dithiophene structure comprises compounds with structures shown in a formula (1) and/or a formula (2), namely two new skeleton bithiophene dimer compounds which are respectively named as Echinbithiophene dimer A and a formula (1); echinbithiophenedimer B, formula (2); the structure is as follows:
the invention further provides a crystal form of the compound shown in the formula (1) and/or the formula (2), or a stereoisomer thereof, or a pharmaceutically acceptable salt thereof, or a solvate thereof, or a prodrug thereof, or a metabolite thereof.
The invention also provides a pesticide composition which comprises the compound with the structure shown in the formula (1) and/or the formula (2), or a crystal form, a stereoisomer, a pharmaceutically acceptable salt, a solvate, a prodrug or a metabolite of the compound, and pharmaceutically acceptable auxiliary materials. According to different dosage forms, the content of the compound with the structure shown in the formula (1) and/or the formula (2) in the composition can be 0.5-30 wt%, and the balance is pharmaceutically acceptable auxiliary materials.
The pharmaceutically acceptable auxiliary material of the invention refers to a substance contained in a dosage form except for an active ingredient. Pharmaceutically acceptable excipients include any commonly used agricultural pharmaceutical excipients, in the case of liquid formulations, for example, organic solvents such as acetone, aqueous tween (e.g., 0.1% (V/V) aqueous tween-80 solution), and the like, and the mass concentration of the compound having the structure represented by the above formula (1) and/or formula (2) in the liquid formulation for final use may be, for example, 0.5 to 5 wt%. In the case of wettable powders, including, for example, white carbon black, sodium lauryl sulfate, CMC sodium lauryl sulfate, nekal, and attapulgite, the content of the compound having the structure represented by the above formula (1) and/or formula (2) in the wettable powder may be 15 to 30 wt%.
In one embodiment, the wettable powder comprises 15-25 wt% of compound powder with the structure shown in the formula (1) and/or the formula (2), 15-25 wt% of white carbon black, 2-8 wt% of sodium dodecyl sulfate, 0.5-2 wt% of CMC sodium dodecyl sulfate, 1-6 wt% of nekal and the balance of attapulgite; preferably, 20 wt% of powder of the compound having the structure represented by the formula (1) and/or the formula (2), 20 wt% of white carbon black, 5 wt% of sodium dodecyl sulfate, 1 wt% of CMC sodium dodecyl sulfate, 3 wt% of nekal and the balance of attapulgite.
One or more of the compounds of the present invention may be used in combination with each other, or alternatively, in combination with any other active agent. If a group of compounds is used, the compounds may be administered to the subject simultaneously, separately or sequentially.
The invention also provides a preparation method of the compound with the structure shown in the formula (1) and/or the formula (2), which comprises the following steps:
(1) extracting dry root of donkey-hide gelatin with ethanol to obtain ethanol extract;
(2) subjecting the ethanol extract to silica gel column chromatography, and gradient eluting with n-hexane-acetone as eluent to obtain fraction;
(3) and (3) preparing the fraction obtained in the step (2) by adopting hydroxypropyl sephadex silica gel column chromatography and thin-layer preparative chromatography to obtain the compound containing the 1, 3-dioxolane dimeric dithiophene structure.
Specifically, the specific operation steps of step (2) may be:
taking the ethanol extract obtained in the step (1), performing gradient elution by adopting silica gel column chromatography and using n-hexane-acetone volume ratios (15: 1) - (1:1) as eluent, and collecting eluent as fraction;
specifically, the following specific steps may be employed to prepare the compounds having the structures represented by the above formula (1) and/or formula (2):
(A) pulverizing rhizoma Et radix Notopterygii, extracting with ethanol under reflux, mixing extractive solutions, and concentrating under reduced pressure to obtain ethanol extract;
(B) and (2) taking the ethanol extract obtained in the step (1), and performing gradient elution by adopting silica gel column chromatography and using n-hexane-acetone with the volume ratio of 15:1, 10:1, 3:1 and 1:1 as eluent in sequence to obtain four components FA-FD. Detecting by thin layer chromatography, developing, mixing the same elution parts, and concentrating the combined elution parts under reduced pressure to dry.
(C) And (3) subjecting the FB component in the step (B) to silica gel column chromatography, performing gradient elution by using petroleum ether-acetone solvents with the volume ratio of (10:1) to (1:1), detecting by using thin layer chromatography, developing, and combining the same elution parts. Subjecting to hydroxypropyl dextran gel chromatography, eluting with chloroform-methanol at volume ratio of 1:1, detecting by thin layer chromatography, developing, and mixing the same eluates to obtain three fractions FBA-FBC.
(D) And (3) preparing the FBA fraction obtained in the step (C) into the compounds Echinbithiophenedimer A and Echinbithiophenedimer B by using petroleum ether-n-hexane-acetone (5: 1: 0.2) as a developing solvent by adopting preparative thin-layer chromatography.
Preferably, in the step (B), an eluent obtained by eluting with an eluent having a volume ratio of n-hexane to acetone of 10:1 is collected as a fraction.
Preferably, in the step (C), the eluate obtained by eluting with an eluent having a petroleum ether-acetone volume ratio of 8:1 is collected as a fraction.
The invention also provides application of the compound with the structure shown in the formula (1) and/or the formula (2), or a crystal form, a stereoisomer, a pharmaceutically acceptable salt, a solvate, a prodrug or a metabolite of the compound in preparation of pesticides. Further, the pesticide is a pesticide for preventing and controlling nematodes or a pesticide for preventing and controlling plant pathogenic fungi (alternaria, rice blast, fusarium oxysporum, colletotrichum gloeosporum, potato late blight, and the like).
The compound containing the 1, 3-dioxolane dimeric dithiophene structure can be applied to preparation of nematicidal pesticides, and the inventor finds that the nematicidal capability of the compound is superior to that of the existing nematicidal pesticide fenamiphos in the process of research. The compound containing the 1, 3-dioxolane dimeric dithiophene structure has better application prospect in the direction of killing nematodes when being used as a plant source pesticide. Can be further prepared into nematicidal botanical pesticides for nematode control.
The compound containing the 1, 3-dioxolane dimeric dithiophene structure can be applied to preparation of plant pathogenic fungus resistant pesticides. Can be further prepared into plant pathogenic fungus resisting botanical pesticide for preventing and treating pathogenic fungi.
In the application process, the compound containing the 1, 3-dioxolane dimeric dithiophene structure can be prepared into a proper dosage form or added with one or more auxiliary materials which are conventional in the art to prepare a pharmaceutical composition for application according to the actual use requirement.
Test results show that the compound has good effects of killing nematodes and plant pathogenic fungi, and provides a new choice for screening and/or preparing nematodes and plant pathogenic fungi in agriculture.
Obviously, according to the above-mentioned contents of the present invention, many other modifications, substitutions or changes can be made without departing from the basic technical idea of the present invention, and the modifications, substitutions or changes are also within the protection scope of the present invention.
Drawings
FIG. 1 is a schematic view of a compound represented by the formula (1)1H NMR spectrum.
FIG. 2 shows a process for producing a compound represented by the formula (1)13C NMR spectrum.
FIG. 3 is a nuclear magnetic resonance COSY spectrum of a compound represented by the formula (1).
FIG. 4 is a diagram of a nuclear magnetic resonance HSQC spectrum of the compound represented by formula (1).
FIG. 5 is a nuclear magnetic resonance HMBC spectrum of the compound of formula (1).
FIG. 6 is a NOESY signal diagram of the compound represented by the formula (1).
FIG. 7 is a HRESIMS mass spectrum of the compound represented by the formula (1).
FIG. 8 is an infrared spectrum of a compound represented by the formula (1).
FIG. 9 shows a schematic representation of a compound of formula (2)1H NMR spectrum.
FIG. 10 shows a process for producing a compound represented by the formula (2)13C NMR spectrum.
FIG. 11 is a COSY spectrum of a compound represented by the formula (2).
FIG. 12 is a nuclear magnetic resonance HSQC spectrum of the compound represented by formula (2).
FIG. 13 is a nuclear magnetic resonance HMBC spectrum of the compound of formula (2).
FIG. 14 is a HRESIMS mass spectrum of the compound represented by the formula (2).
FIG. 15 is an infrared spectrum of a compound represented by the formula (2).
Detailed Description
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Unless otherwise specified, the raw materials and equipment used in the embodiments of the present invention are known and commercially available products are obtained.
EXAMPLE 1 preparation of the Compounds of the invention
1. Experimental materials:
firstly, medicinal materials
The root of donkey was collected from Mentou ditch of Beijing city in 2017 in 9 months and identified as a dry root of donkey (Echinops latifolius Tausch.) belonging to Echinops of Compositae.
② reagents and fillers
Column chromatography silica gel of 200-300 mesh (reagent grade) purchased from Qingdao ocean silica gel desiccant factory;
thin layer chromatography silica gel GF254 (chemical purity) purchased from Qingdao ocean silica gel desiccant factory;
sephadex LH-20 sepharose, available from Amersham, Sweden;
a GF254 silica gel preparation thin layer purchased from Yangtze river friend silica gel development Co., Ltd;
analytically pure reagents such as petroleum ether, n-hexane, trichloromethane, ethyl acetate, acetone, methanol and the like are purchased from Beijing chemical plants.
(iii) laboratory instruments
Bruker-AVIIIHD-600 NMR (Bruker, Switzerland); nicolet 5700 Infrared Spectroscopy (Thermo corporation, USA); Perkin-Elmer 341 polarimeter (Perkin Elmer, USA); BP211D one tenth ten million electronic balance (Sartorius, switzerland); r-210 rotary evaporator (BUCHI, Switzerland); model DZG-6050 vacuum drying oven (shanghai semen).
2. Separation and purification of components:
1) taking 1.8kg of dry donkey root, crushing, extracting with ethanol under reflux for 3 times, mixing the extracting solutions, and concentrating under reduced pressure to obtain 90g of ethanol extract;
2) taking the ethanol extract obtained in the step 1), performing gradient elution by adopting silica gel column chromatography (column chromatography silica gel, 200-300 meshes (reagent grade) purchased from Qingdao ocean silica gel desiccant factory) with n-hexane-acetone as eluent at the volume ratio of 15:1, 10:1, 3:1 and 1:1 in sequence, detecting by thin-layer chromatography, developing, and combining the same elution parts to obtain 4 components, namely FA-FD. (FA is a fraction of n-hexane-acetone 15:1, FB is a fraction of n-hexane-acetone 10:1, FC is a fraction of n-hexane-acetone 3:1, FD is a fraction of n-hexane-acetone 1:1, 4 components in total).
3) Subjecting the FB component in the step 2) to silica gel column chromatography (Sephadex LH-20 Sephadex), gradient eluting with petroleum ether-acetone at volume ratio of (10:1) - (1:1), detecting with thin layer chromatography, developing with 10% ethanol sulfate developer, and mixing the same eluate according to Rf value and color development to obtain 3 fractions FBA-FBC (FBA is petroleum ether-acetone 10:1 fraction, FBB is petroleum ether-acetone 5:1 fraction, and FBC is petroleum ether-acetone 1:1 fraction).
4) Preparing the FBA fraction obtained in the step 3) by using petroleum ether-n-hexane-acetone (5: 1: 0.2) as a developing agent and adopting preparative thin-layer chromatography (GF254 silica gel prepared thin layer) to respectively obtain a compound Echinbithiophenedimer A and a compound Echinbithiophenedimer B.
3. Identification of the compounds:
after separating to obtain each compound, identifying the physical and chemical properties and molecular structure of the compound, and obtaining a new skeleton compound containing 1, 3-dioxolane dimeric bithiophene as compounds 1 to 2, wherein the specific physical and chemical properties and spectral data are as follows:
echinbithiophenedimer A (1): a yellow amorphous solid;
UV(CH3CN)λmax(log ε)243(0.53)，332(1.75)nm；ECD(CH3CN)λmax(Δε)222(-7.9)，258(+2.1)nm；IR(KBr)vmax 1633 and 1027 cm-1；HR-ESI-MS[M+Na]+ m/z 515.0236(calcd for C26H20NaO2S4，515.0238).
echinbithiophenedimer B (2): a yellow amorphous solid;
UV(CH3CN)λmax(log ε)243(0.49)，340(1.47)nm；ECD(CH3CN)λmax(Δε)231(-15.4)，250(+4.3)nm；IR(KBr)vmax 1653 and 1055cm-1；HR-ESI-MS[M+H]+m/z 493.0420(calcd for C26H21O2S4，493.0419).
4. nuclear magnetic resonance hydrogen spectrum (1H-NMR): Bruker-AVIII HD-600spectrometer assay, data are shown in Table 1.
5. Nuclear magnetic resonance carbon spectrum (13C-NMR): Bruker-AVIII HD-600spectrometer assay, data are shown in Table 1.
TABLE 1 of Echinbithiophenedimer A-B1H-NMR(600MHz)、13C-NMR (150MHz) nuclear magnetic data
(measuring solvent: CDCl)3；δ：ppm；J：Hz)
To illustrate the advantageous effects of the present invention, the present invention further provides the following examples.
Example 2: virulence determination for second instar larvae of meloidogyne incognita
1) Preparing a sample:
the compound to be tested and the commercial nematicide ethoprophos are dissolved by acetone to prepare the compound with the concentration of 104mu.g/mL of the mother liquor. And (3) diluting the compound to be detected by using a 0.1% (V/V) Tween-80 aqueous solution to ensure that the content of the organic solvent in the final compound to be detected is not more than 1% (V/V).
2) Preparing second-instar larvae of Meloidogyne incognita:
collecting tomato roots infected by meloidogyne incognita (M.incognita), washing the tomato roots with sterilized distilled water, gently peeling off egg masses with tweezers under a stereoscopic microscope, placing the eggs in a culture dish containing a small amount of distilled water, and incubating in an incubator at 28 ℃ for 3-5 days. The hatched 2-year-old root-knot nematodes can be used as target organisms for bioassays.
3) And (3) biological activity determination:
taking a 96-well biochemical test plate, putting 100 μ L of test solution into small holes, adding isovolumetric nematode suspension, ensuring that the number of second-instar nematodes in each hole is 80-100, and covering the plate to prevent water evaporation. The 96-well plate was placed in an incubator at 28 ℃ in the dark. Each treatment was repeated 4 times. Survival and mortality of second instar larvae of Meloidogyne incognita were checked 24 hours after treatment, and mortality and corrected mortality were calculated. And calculating LC of the medicament by SAS software50. Mortality and corrected mortality were calculated as follows:
4) and (4) the result of bioassay:
TABLE 2 toxicity of Echinbithiophenedimer A-B to Meloidogyne incognita (μ g/mL)
The test results show that the high-temperature-resistant steel,
as can be seen from the data in Table 2, Echinbithiophenedimer A-B has varying degrees of nematicidal activity against second instar larvae of Meloidogyne incognita. And the inventor unexpectedly finds that Echinbithiophenedimer A-B is superior to the existing commercial bactericide ethoprophos. Can be further prepared into a nematicidal pesticide.
Example 3: activity test against plant pathogenic fungi
1) Sample preparation:
the compound to be tested and the commercial bactericide carbendazim are dissolved by organic solvent acetone to prepare the solution with the concentration of 104mu.g/mL of the mother liquor. And (3) diluting the compound to be detected by using a 0.1% (V/V) Tween-80 aqueous solution to ensure that the content of the organic solvent in the final compound to be detected is not more than 1% (V/V).
2) Preparation of pathogenic fungi:
alternaria alternata (Alternaria alternate), Pyricularia oryzae (Pyricularia oryzae), Fusarium oxysporum (Fusarium oxysporum), Colletotrichum gloeosporioides (Colletotrichum gloeosporioides) and potato late blight (Phytophthora infestans) are the main pathogens to test antifungal activity.
3) And (3) biological activity determination:
the antifungal activity of 96-well plates was determined by a microtissues broth dilution method using Potato Dextrose (PD) medium. Briefly, each purified compound was diluted sequentially starting at 256. mu.g/mL to a suspension containing fungal pathogen spores (1X 10)6CFU) in wells of a 96-well plate, antifungal activity was measured by the broth microdilution method. Briefly, each purified compound was diluted sequentially starting at 256. mu.g/mL to a suspension containing fungal pathogen spores (1X 10)6cfu) in 96-well plates. Carbendazim was used as a positive control. Incubation in dark at 28. + -. 0.5 ℃ for 3d, Minimal Inhibitory Concentration (MIC) as test compound in 96-well platesAt the lowest concentration there was no microbial growth. Three replicates of each compound were performed at all concentrations investigated.
4) And (4) the result of bioassay:
TABLE 3 Echinbithiophenedimer A-B anti-phytopathogenic fungi Activity (MIC, μ g/mL)
A., Alternaria alternata; p.o., Pyricularia oryzae (magnaporthe oryzae); f.o., Fusarium oxysporum (Fusarium oxysporum); c.g., Colletotrichum gloeosporioides (Colletotrichum gloeosporioides); p.i., Phytophthora infestans (potato late blight)
The data in Table 3 show that the compound Echinbithiophenedimer A-B shows remarkable antifungal activity (MIC value is 8-16 mu g/mL) on Alternaria and Magnaporthe grisea. The compound Echinbithiophenedimer A-B has good bacteriostatic activity (MIC value is 16-64 mu g/mL) on fusarium oxysporum and colletotrichum gloeosporum. The MIC value of the compound Echinbithiophenedimer A-B to phytophthora infestans is 128 mug/mL, which is better than that of carbendazim (the MIC value is 256 mug/mL).
Example 4: wettable powder
The formula (weight ratio) and the preparation method are as follows: 20% of powder of the compound obtained in example 1, 20% of white carbon black, 5% of sodium dodecyl sulfate, 1% of CMC sodium dodecyl sulfate, 3% of nekal, and the balance of attapulgite. Mixing the above materials uniformly, controlling processing temperature at 0-50 deg.C, pulverizing in jet mill or other high mesh pulverizer to more than 150 mesh, controlling water content at 6-8% (by mass), and controlling pH at 7-7.5. So as to prepare 20 percent of wettable powder of the compound shown in the formula (1). The water dispersivity, the diluent stability and the cold and hot storage stability of the preparation meet the requirements of commercial pesticide preparations. The verification proves that the plant growth regulator has good line killing and plant pathogenic fungi inhibiting capabilities.
In conclusion, the invention provides two novel framework compounds containing 1, 3-dioxolane dimeric dithiophene and an extraction and separation method thereof, the compounds are extracted from a common traditional Chinese medicine donkey, and experimental results show that the compounds have the activities of killing nematodes and resisting plant pathogenic fungi, so the compounds have wide application prospects in the field of pesticides as plant source natural products.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The compound containing a 1, 3-dioxolane dimeric bithiophene structure is characterized by being a compound having a structure shown in a formula (1) and/or a formula (2), or a pharmaceutically acceptable salt thereof:
2. a pesticidal composition, which comprises a compound having a structure represented by formula (1) and/or formula (2) of claim 1, or a stereoisomer thereof, or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable excipient.
3. The pesticide composition as set forth in claim 2, wherein the pesticide composition is a liquid preparation, and the mass concentration of the compound of the structure represented by the formula (1) and/or the formula (2) as set forth in claim 1 in the liquid preparation is 0.5-5 wt%; or the pesticide composition is wettable powder, and the content of the compound with the structure shown in the formula (1) and/or the formula (2) in the wettable powder is 15-30 wt%.
4. The pesticide composition as claimed in claim 3, wherein the wettable powder comprises 15-25 wt% of compound powder with the structure shown in formula (1) and/or formula (2) as claimed in claim 1, 15-25 wt% of white carbon black, 2-8 wt% of sodium dodecyl sulfate, 0.5-2 wt% of CMC sodium dodecyl sulfate, 1-6 wt% of nekal, and the balance of attapulgite.
5. A process for preparing a compound of formula (1) and/or formula (2) according to claim 1, comprising the steps of:
(A) pulverizing rhizoma Et radix Notopterygii, extracting with ethanol under reflux, mixing extractive solutions, and concentrating under reduced pressure to obtain ethanol extract;
(B) taking the ethanol extract obtained in the step (A), performing gradient elution by adopting silica gel column chromatography and using n-hexane-acetone volume ratios of 15:1, 10:1, 3:1 and 1:1 as an eluent in sequence to obtain four components FA-FD, detecting by thin-layer chromatography, developing, combining the same elution parts, and concentrating the combined elution parts under reduced pressure until the combined elution parts are dry for later use;
(C) subjecting the FB component in the step (B) to silica gel column chromatography, gradient eluting with petroleum ether-acetone solvent at volume ratio of (10:1) - (1:1), detecting by thin layer chromatography, developing, mixing the same elution parts, subjecting to hydroxypropyl sephadex chromatography, eluting with chloroform-methanol at volume ratio of (1:1), detecting by thin layer chromatography, developing, mixing the same elution parts, and obtaining three fractions FBA-FBC;
(D) mixing the fraction of FBA obtained in the step (C) with petroleum ether-n-hexane-acetone 5: 1: 0.2 is developing agent, and the compound of the formula (1) and the compound of the formula (2) are prepared by adopting preparative thin layer chromatography.
6. The production method according to claim 5, wherein in the step (B), an eluate obtained by eluting with an eluent at a n-hexane-acetone volume ratio of 10:1 is collected as a fraction.
7. The production method according to claim 5 or 6, wherein, in the step (C), an eluate obtained by eluting with an eluent at a petroleum ether-acetone volume ratio of 8:1 is collected as a fraction.
8. Use of a compound of formula (1) and/or formula (2), or a pharmaceutically acceptable salt thereof, according to claim 1, for the preparation of a pesticide for the control of nematodes or for the control of phytopathogenic fungi.
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| CN101277696A (en) * | 2005-08-03 | 2008-10-01 | 詹森药业有限公司 | Quinoline derivatives as antibacterial agents |
| CN101723940A (en) * | 2009-12-07 | 2010-06-09 | 中国科学院昆明植物研究所 | Bithiophene compound and pharmaceutical composite and application thereof |
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| CN101277696A (en) * | 2005-08-03 | 2008-10-01 | 詹森药业有限公司 | Quinoline derivatives as antibacterial agents |
| CN101723940A (en) * | 2009-12-07 | 2010-06-09 | 中国科学院昆明植物研究所 | Bithiophene compound and pharmaceutical composite and application thereof |
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| Adjusting the Local Arrangement of π-Stacked Oligothiophenes through Hydrogen Bonds: A Viable Route to Promote Charge Transfer;Hongguang Liu et al.;《J. Phys. Chem. Lett.》;20140617;第5卷;第2320-2324页 * |
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