CN109400576A - A kind of thiophenes and its application - Google Patents
A kind of thiophenes and its application Download PDFInfo
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- CN109400576A CN109400576A CN201811485348.9A CN201811485348A CN109400576A CN 109400576 A CN109400576 A CN 109400576A CN 201811485348 A CN201811485348 A CN 201811485348A CN 109400576 A CN109400576 A CN 109400576A
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- 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
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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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
- A01N43/02—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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- 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
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
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- 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
- C07D333/26—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D333/40—Thiophene-2-carboxylic acid
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Abstract
The present invention relates to a kind of thiophenes and its applications.Thiophenes, including structure shown in formula (1), in formula (1), R1 is independent to be selected from-C ≡ C-CH3Or CH3- CH (OH)-(C=O)-；R2 is independent to be selected from-OH ,=O ,-O-CH3Or-O- (C=O)-CH2‑CH‑(CH3)2；R3 is independent to be selected from-H ,-CH2‑OH、‑CH2‑Cl、‑OH、‑CH3Or-CH2- O-C=O-CH2‑CH‑(CH3)2.Compound provided by the invention has the application of prevention and treatment plant nematode diseases, especially significant to the control efficiency of Meloidogyne incognita, has many advantages, such as that efficient, nontoxic, safety, Environmental compatibility are good, is green plants source nematode killing agent kind.
Description
Technical field
The invention belongs to biological pesticide technical field more particularly to a kind of thiophenes and its applications.
Background technique
Meloidogyne incognita (Meloidogyne incognita) is a kind of omnivorousness pathogenic line of height specialized form
Worm, gonochorism, the root of the various vegetables of main harm, shows as lateral root and fibrous root more normally increases, and in the fibrous root of young root
The upper white root nodule for forming spherical or cone and differing in size, some is in beads shape, and it is short and small, slow to be killed strain aerial growth
Slowly, leaf color is abnormal, as a result few, low output, or even plant is caused to do sth. in advance death.Currently, the prevention and treatment to Meloidogyne incognita is main
It relies on and largely uses various chemical synthetic pesticides for a long time, such as organic phosphorus or carbamates single dose or compound preparation, although
Preferable control efficiency can be played, but as the public is food-safe and the concern of environmental protection is further close, drawback
Also increasingly prominent；Meanwhile gradually quitting listing with high-toxic pesticide, Meloidogyne incognita, which has become, seriously endangers facilities vegetable life
The outstanding problem produce, influence increasing peasant income, restricting China vegetables and other Important Economic crop sustainable developments.Therefore, it studies
Efficient, low toxicity and low residue nematode killing agent is developed, protection environment will effectively be realized that the high-quality and safety of agricultural product produces, expand me
State's agricultural and sideline product export markets promote the development of green agriculture, and rural economy prosperity etc. is promoted to play an important role.
The dry root of echinops grijisii Hance (Echinops grijsii Hance) is also known as radix echinopsis latifolii, has heat-clearing solution
Poison, disappear carbuncle, and lower cream effect is included in 2010 editions " Chinese Pharmacopoeias ".The plant is rich in natural thiophenes, such chemical combination
Object has extensive bioactivity, such as AntiHIV1 RT activity, anti-inflammatory, cell toxicant and antibacterial, but has not yet to see this patent and be related to thiophene to south
Research report in terms of the prevention and treatment of square root-knot nematode.
Summary of the invention
In view of the problems of prior art, the present invention provides a kind of thiophenes and its application, specifically,
It is a kind of plant source thiophenes, inventor is found surprisingly that such compound has prevention and treatment nemas under study for action
Harmful application, it is especially significant to the control efficiency of Meloidogyne incognita, have efficient, nontoxic, safety, Environmental compatibility good etc. excellent
Point is green plants source nematode killing agent kind.
The technical scheme to solve the above technical problems is that
A kind of thiophenes, which is characterized in that including structure shown in formula (1):
Wherein, R1 is independent is selected from-C ≡ C-CH3Or CH3- CH (OH)-(C=O)-；
R2 is independent to be selected from-OH ,=O ,-O-CH3Or-O- (C=O)-CH2-CH-(CH3)2；
R3 is independent to be selected from-H ,-CH2-OH、-CH2-Cl、-OH、-CH3Or-CH2- O-C=O-CH2-CH-(CH3)2。
Beneficial effects of the present invention: the medicine that formula (1) compound represented provided by the invention can be included by " Chinese Pharmacopoeia "
Separation is extracted with the dried roots of plant echinops grijisii Hance and is obtained, it was demonstrated that it is safer to human body；Chemical combination shown in formula (1)
Object derives from natural plants, is easy to degrade in the environment, has low toxicity and low residue characteristic, to non-target organism safety, environment phase
Capacitive is good, meets the needs of environment protective plant protecting and sustainable agriculture production and development；Formula (1) compound represented is to Root Knot line
Worm second instar larvae has strong killing activity, and part of compounds kills line ability better than business nematode killing agent avermectin.With outstanding
Killing the active natural thiophenes of line can be used as main novel pesticide ingredient or lead compound suitable for control agricultural
Plant nematode.
Further, above-mentioned thiophenes, which is characterized in that there is compound 1, compound 4, compound 6, compound
7, structure shown in compound 8, compound 9, compound 10, compound 11 or compound 12, structure shown in above-mentioned each compound point
Not are as follows:
The present invention also provides a kind of thiophenes, including structure shown in formula (2):
Wherein, R4 is independent is selected from-H ,-(C=O)-CH3Or-(C=O)-CH2-CH-(CH3)2, R5 is independent to be selected from-Cl
Or-O- (C=O)-CH2-CH2-(CH3)2。
Beneficial effects of the present invention: the medicine that formula (2) compound represented provided by the invention can be included by " Chinese Pharmacopoeia "
Separation is extracted with the dried roots of plant echinops grijisii Hance and is obtained, it was demonstrated that it is safer to human body；Chemical combination shown in formula (2)
Object derives from natural plants, is easy to degrade in the environment, has low toxicity and low residue characteristic, to non-target organism safety, environment phase
Capacitive is good, meets the needs of environment protective plant protecting and sustainable agriculture production and development；Formula (2) compound represented is to Root Knot line
Worm second instar larvae has strong killing activity, and part of compounds kills line ability better than business nematode killing agent avermectin.With outstanding
Killing the active natural thiophenes of line can be used as main novel pesticide ingredient or lead compound suitable for control agricultural
Plant nematode.
Further, above-mentioned thiophenes, which is characterized in that there is knot shown in compound 2, compound 3 or compound 5
Structure；Compound 2, compound 3, structure is respectively as follows: shown in compound 5
The present invention also provides a kind of salt compounds of thiophenes, can pass through above-mentioned thiophenes and nothing
Machine acid or organic acid are prepared.
In the specific application process, the thiophenes of the invention can be formed with inorganic acid or organic acid
Physiologically acceptable salt keeps compound structure more stable, is conducive to save and wire work is killed in preparation, it is living to play nematicidal
Property.
The present invention also provides application of the above-mentioned thiophenes in prevention and treatment nematode.It can be used for preparing pest-resistant product.
It is especially more significant to the control efficiency of Meloidogyne incognita.
The present invention provides application of the salt compounds of above-mentioned thiophenes in prevention and treatment nematode.It can be used for preparing
Pest-resistant product.It is especially more significant to the control efficiency of Meloidogyne incognita.
When above-mentioned thiophenes or its esters compound are used as agricultural nematode killing agent, can directly it use, or with agriculture
The form of drug composition uses.
The present invention also provides a kind of nematicidal products, including above-mentioned thiophenes and/or above-mentioned thiophenes
Salt compounds.The salt compounds of above-mentioned thiophenes and/or above-mentioned thiophenes, which can be used as, kills line work
Property ingredient.Nematicidal product has many advantages, such as that efficient, nontoxic, environmentally friendly, safety, Environmental compatibility are good.
In above-mentioned nematicidal product, solvent, auxiliary agent etc. can also be added other than killing line active constituent, for being made not
With the product of dosage form.
For example, the present invention separates all thiophenes obtained, C can be used10Aromatic hydrocarbons, ethyl alcohol, acetonitrile etc. are as molten
Agent is added tween, glycerol etc. and is used as cosolvent, nematicidal product is made, for killing nematode, improves the yield and product of vegetables
Matter.
Since the compound that present invention separation obtains is to extract and obtain from the root of medicinal plant echinops grijisii Hance, certainly
It is easily decomposed under the conditions of so, therefore biological concentration phenomenon will not be caused, and to safety of human and livestock, can be used as natural pesticide makes for a long time
The problem of with being polluted without generation environment.In some embodiments of the invention, the nematicidal product also may include
Compatible others are known in the art with the active compound of line is killed on, to enhance nematicidal effect.
The various dosage forms of above-mentioned pesticide or combinations thereof object can be prepared according to the conventional production process of pesticide field.Such as
It mixes active constituent with one or more carriers, is then made into required dosage form.It can also be prepared into and contain containing difference
The product of the thiophenes of amount.
Such as: a kind of wettable powder, including following mass percent component: the powder of above-mentioned thiophenes
20%, white carbon black 20%, lauryl sodium sulfate 5%, CMC lauryl sodium sulfate 1% and pull open powder 3%, more than attapulgite
Amount.
Preparation method is the following steps are included: above-mentioned each raw material is uniformly mixed, 0-50 DEG C of processing temperature of control, in air-flow powder
In broken machine or other high mesh pulverizers, 150 mesh or more are crushed to, moisture control exists in 6-8% (mass percentage), pH control
7-7.5。
Nematicidal product can be prepared by the following method: be carried out on separating-purifying and acquisition by raw material of echinops grijisii Hance
State the salt compounds of thiophenes and/or above-mentioned thiophenes.
The present invention provides a kind of preparation side of the salt compounds of above-mentioned thiophenes or above-mentioned thiophenes
Method, comprising the following steps: carry out separating-purifying by raw material of echinops grijisii Hance.
Further, the method for separating-purifying is the following steps are included: alcohol steep, n-hexane, methylene chloride, silica gel column layer
Analysis.
Detailed description of the invention
Fig. 1 is molecular structure of the shown compound 1 to compound 6.
Fig. 2 is that the HRESIMS of shown compound 1 schemes.
Fig. 3 is shown compound 11H NMR figure.
Fig. 4 is shown compound 113C NMR figure.
Fig. 5 is that the HRESIMS of shown compound 2 schemes.
Fig. 6 is shown compound 21H NMR figure.
Fig. 7 is shown compound 213C NMR figure.
Fig. 8 is that the HRESIMS of shown compound 3 schemes.
Fig. 9 is shown compound 31H NMR figure.
Figure 10 is shown compound 313C NMR figure.
Figure 11 is that the HRESIMS of shown compound 4 schemes.
Figure 12 is shown compound 41H NMR figure.
Figure 13 is shown compound 413C NMR figure.
Figure 14 is that the HRESIMS of shown compound 5 schemes.
Figure 15 is shown compound 51H NMR figure.
Figure 16 is shown compound 513C NMR figure.
Figure 17 is that the HRESIMS of shown compound 6 schemes.
Figure 18 is shown compound 61H NMR figure.
Figure 19 is shown compound 613C NMR figure.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, by following embodiments and kills line experiment knot
Fruit can further illustrate and understand the present invention, but be not intended to limit protection scope of the present invention.
The present invention is based at present in medicinal plant echinops grijisii Hance (Echinops grijsii Hance) dried roots
Thiophenes and its prevent and treat Meloidogyne incognita present Research, and it is an object of the present invention to provide it is a kind of without any chemical pesticide at
Point, to people, animal low toxicity, the plant source thiophenes of drug resistance are not likely to produce using rear Meloidogyne incognita, in agricultural
New nematode killing agent is provided to the sustainable prevention and treatment of plant nematode in production.
The echinops grijisii Hance dried roots that the present invention uses are rich in thiophenes, therefrom extract the thiophene-based of separation
Compounds content is high, it is good to kill Meloidogyne incognita second instar larvae activity, it can be achieved that efficiently preventing and treating the purpose of Meloidogyne incognita.
To realize above-mentioned task, the technical solution adopted by the present invention is that: extracting from echinops grijisii Hance dried roots has
The active thiophenes of line are killed by force, molecular structure is respectively as follows:
The preparation method of above compound, comprising the following steps:
1) by echinops grijisii Hance dry root, ethyl alcohol is extracted, and obtains ethanol extract；
2) it by ethanol extract disperse water, is successively extracted with n-hexane, methylene chloride, obtains methylene chloride medicinal extract；
3) by the methylene chloride medicinal extract in step 2), use silica gel column chromatography successively with n-hexane-ethyl acetate volume ratio
50:1,40:1,30:1,20:1,10:1,5:1,1:1 are that eluant, eluent carries out gradient elution, obtain 7 fractions, are followed successively by Fr.A-
Fr.G；
4) Fr.A uses silica gel column chromatography, using n-hexane-chloroform volume ratio 30:1 as eluent, obtained elution portion
It is divided into Ac, disperses silica gel column chromatography for Ac, with n-hexane-ethyl acetate 25:1 elution, obtains compound 6 and washed in addition multiple
De- part.The elution fraction that Rf value is 0.38 is passed through into prefabricated TLC chromatographic sheet, with petroleum ether-ethyl acetate volume ratio 15:
1 elution, obtains compound 4.
5) Fr.B is used into silica gel column chromatography, is 10:1 elution with petroleum ether-ethyl acetate volume ratio, obtains compound 3；
Silica gel column chromatography is used, for 5:1 elution, to obtain compound 5 with petroleum ether-ethyl acetate volume ratio Fr.B.
6) Fr.C is used into silica gel column chromatography, using n-hexane-ethyl acetate volume ratio 20:1 as eluent, by Rf value
Silica gel column chromatography is used for 0.41 elution fraction, is eluted using petroleum ether-ethyl acetate 10:1 as eluant, eluent, obtains chemical combination
Object 8 and compound 12.
7) Fr.E obtains compound 10 using n-hexane-acetone volume ratio 8:1 as eluent using silica gel column chromatography
With multiple elution fractions.The elution fraction that Rf value is 0.35 is used into prefabricated TLC chromatographic sheet, with chloroform-methanol volume ratio
20:1, which makees solvent, to be unfolded, and compound 11 is obtained.The elution fraction that Rf value is 0.35 is used into prefabricated TLC chromatographic sheet
Solvent is made with chloroform-methanol volume ratio 16:1 to be unfolded, and compound 9 is obtained.By Rf value be 0.42 elution fraction with pre-
TLC chromatographic sheet chloroform-methanol volume ratio 50:3 processed is unfolded, and compound 2 is obtained.
8) Fr.F is washed using silica gel column chromatography using petroleum ether-ethyl acetate volume ratio 10:1 as eluent
De- part, is further separated with petroleum ether-acetone volume ratio 8:1 silica gel column chromatography, obtains compound 7.
9) Fr.G is washed using silica gel column chromatography using petroleum ether-ethyl acetate volume ratio 8:1 as eluent
De- part is unfolded with prefabricated TLC chromatographic sheet petroleum ether-acetone volume ratio 4:1, obtains compound 1.
Embodiment 1: the preparation of thiophenes
1, experimental material:
1) medicinal material
Echinops grijisii Hance root is bought in June, 2017 from Anguo medicine city, Hebei province, through present inventor doctor Liu Tingting
It is accredited as the dry root of composite family Echinops plant echinops grijisii Hance (Echinops grijsii Hance).
2) reagent and filler
Column chromatography silica gel, 200~300 mesh (SILVER REAGENT) are purchased from Qingdao Haiyang silica-gel desiccant factory；
Tlc silica gel GF254 (chemistry is pure), is purchased from Qingdao Haiyang silica-gel desiccant factory；
Sephadex LH-20 sephadex is purchased from Amersham company, Sweden；
GF254 silica gel prepares thin layer, is purchased from Yantai Jiang You silica gel development corporation, Ltd.；
The analytical reagents such as petroleum ether, n-hexane, chloroform, ethyl acetate, acetone, methanol, are purchased from Beijing Chemical Plant.
3) laboratory apparatus
Bruker-AVIIIHD-600 Nuclear Magnetic Resonance (Switzerland Bruker)；5700 infrared spectrometer (the U.S. Nicolet
Thermo company)；341 polariscopy instrument (U.S. PerkinElmer) of Perkin-Elmer；Ten a ten thousandth electronics of BP211D
Balance (Switzerland Sartorius)；R-210 rotary evaporator (Switzerland BUCHI)；(Shanghai is gloomy for DZG-6050 type vacuum oven
Letter).
2, ingredient isolates and purifies:
1) echinops grijisii Hance dry root 10kg is taken, after crushing, is extracted 3 times with 95% alcohol reflux of volume fraction, merging mentions
Liquid is taken, ethanol extract 800g is concentrated under reduced pressure to give；
2) gained ethanol extract in step 1) is taken, is dispersed in water, successively with n-hexane, methylene chloride and ethyl acetate extraction
It takes, respectively obtains n-hexane medicinal extract 257.3g, methylene chloride medicinal extract 218.8g and ethyl acetate extract 124.6g；
3) gained methylene chloride medicinal extract in step 2) is taken, using silica gel column chromatography, successively with n-hexane-ethyl acetate volume
It is that eluant, eluent carries out gradient elution than 50:1,40:1,30:1,20:1,10:1,5:1,1:1, is detected, shown through thin-layer chromatography
Color merges identical elution fraction, obtains 7 fractions, Fr.A-Fr.G (wherein, Fr.A is n-hexane-ethyl acetate volume ratio 50:
1 fraction, Fr.B are n-hexane-ethyl acetate volume ratio 40:1 fraction, and Fr.C is that n-hexane-ethyl acetate volume ratio 30:1 evaporates
Point, Fr.D is n-hexane-ethyl acetate volume ratio 20:1 fraction, and Fr.E is n-hexane-ethyl acetate volume ratio 10:1 fraction,
Fr.F is n-hexane-ethyl acetate volume ratio 5:1 fraction, and Fr.G is n-hexane-ethyl acetate volume ratio 1:1 fraction, successively class
It pushes away, totally 7 fractions).
4) part Fr.A is taken in step 3) to use silica gel column chromatography, with n-hexane-chloroform volume ratio 50:1,40:1,30:1,
20:1,10:1,5:1 are that eluant, eluent successively elutes, and obtaining 6 elution fraction Aa-Af, (wherein, Aa is positive hexane-chloroform volume ratio
The elution fraction of 50:1, Ab are positive the elution fraction of hexane-chloroform volume ratio 40:1, and Ac is positive hexane-chloroform volume ratio 30:1
Elution fraction, Ad is positive the elution fraction of hexane-chloroform volume ratio 20:1, and Ae is positive the washing of hexane-chloroform volume ratio 10:1
De- part, Af are positive the elution fraction of hexane-chloroform volume ratio 5:1).Ac is scattered in silica gel column chromatography, with n-hexane-acetic acid second
Ester volume ratio 25:1 elution, obtains monomeric compound 6 and other mixed components, detects to the further thin-layer chromatography of mixed component,
10% sulfuric acid ethyl alcohol chromogenic reagent obtains two elution fraction 1AC according to Rf value elution fraction identical with colour developing color merging
(Rf=0.25) and 2AC (Rf=0.38).Wherein prefabricated TLC chromatographic sheet is passed through in the part 2AC, with petroleum ether-ethyl acetate
Volume ratio 15:1 elution, obtains compound 4.
5) part Fr.B is taken in step 3) to use silica gel column chromatography, with petroleum ether-ethyl acetate volume ratio 30:1,20:1,
10:1,5:1 are that eluant, eluent successively elutes, and obtain compound 3, petroleum in petroleum ether-ethyl acetate volume ratio 10:1 elution fraction
Ether-ethyl acetate volume ratio 5:1 elution fraction obtains compound 5.
6) it takes the part Fr.C in step 3) to use silica gel column chromatography, is elution with n-hexane-ethyl acetate volume ratio 20:1
Agent elution, further by all elution fractions by thin-layer chromatography detect, 10% sulfuric acid ethyl alcohol chromogenic reagent, according to Rf value with
The color that develops the color merges identical elution fraction, obtains 4 elution fraction Ca-Cd.The part Cc (Rf=0.41) uses silica gel column chromatography,
It is eluted using petroleum ether-ethyl acetate 10:1 as eluant, eluent, obtains compound 8 and compound 12.
7) it takes the part Fr.E in step 3) to use silica gel column chromatography, is washed using n-hexane-acetone volume ratio 8:1 as eluant, eluent
It is de-, compound 10 and other mixed components are obtained, the further thin-layer chromatography of mixed component is detected, 10% sulfuric acid ethyl alcohol color developing agent
Colour developing obtains other 4 elution fraction Ea-Ed according to Rf value elution fraction identical with colour developing color merging.The part Eb (Rf=
0.35) multiple prefabricated TLC chromatographic sheets are used, solvent is done with chloroform-methanol 20:1, obtains compound 11.Eb is adopted part
Solvent is done with chloroform-methanol 16:1 with multiple prefabricated TLC thin-layer chromatography versions, obtains compound 9.Ed part (Rf=0.42) with
Prefabricated TLC chromatographic sheet chloroform-methanol 50:3 is unfolded, and compound 2 is obtained.
8) part Fr.F is taken in step 3) to use silica gel column chromatography, with petroleum ether-ethyl acetate volume ratio 30:1,20:1,
10:1 and 5:1 is that eluant, eluent successively elutes, and obtaining 4 elution fraction Fa-Fd, (wherein, Fa is petroleum ether-ethyl acetate volume ratio
The elution fraction of 30:1, Fb are the elution fraction of petroleum ether-ethyl acetate volume ratio 20:1, and Fc is petroleum ether-ethyl acetate body
Elution fraction of the product than 10:1, Fd are the elution fraction of petroleum ether-ethyl acetate volume ratio 5:1).Wherein the part Fc is further used
Petroleum ether-acetone 8:1 silica gel column chromatography is separated, and compound 7 is obtained.
9) part Fr.G is taken in step 3) to use silica gel column chromatography, with petroleum ether-ethyl acetate volume ratio 15:1,10:1,
8:1,5:1 and 3:1 be eluant, eluent successively elute, obtain 5 elution fraction Ga-Ge (wherein, Ga be petroleum ether-ethyl acetate 15:
1 elution fraction, Gb are the elution fraction of petroleum ether-ethyl acetate 10:1, and Gc is the elution portion of petroleum ether-ethyl acetate 8:1
Point, Gd is the elution fraction of petroleum ether-ethyl acetate 5:1, and Ge is the elution fraction of petroleum ether-ethyl acetate 3:1).Wherein Gc
Elution fraction is unfolded with prefabricated TLC chromatographic sheet petroleum ether-acetone 4:1, obtains compound 1.
3, compound identification:
After isolated each compound, its physicochemical property and molecular structure are identified, obtain compound 1 to change
Conjunction object 12 be new thiophenes (molecular structure of compound 1 to compound 6 is as shown in Figure 1), specific physicochemical property and
Spectral data is as follows:
Compound 1: yellow oil；[α] 25D=+3.8 (c 0.10, MeOH)；HRESIMS m/z,299.0403[M+
H]+,calcd for C13H15O4S2,299.0412；1H-NMR(MeOH-d4)δH:7.30(1H,d,3.6,H-3),7.00(1H,
d,3.5,H-4),4.92(1H,m,H-6),3.71(1H,m,H-7a),3.70(1H,m,H-7b),7.28(1H,d,3.4,H-
3'),7.90(1H,d,3.2,H-4'),4.93(1H,m,H-7'),1.45(3H,d,6.8,H-8')；13C-NMR(MeOH-d4)
δC:134.9(C-2),125.2(C-3),124.9(C-4),148.2(C-5),70.3(C-6),66.9(C-7),138.1(C-
2'),123.8(C-3'),134.8(C-4'),146.5(C-5'),195.1(C-6'),70.4(C-7'),20.4(C-8').Change
The HRESIMS figure of conjunction object 1,1H NMR figure and13C NMR figure is as shown in Figure 1 to Figure 3 respectively.
Compound 2: yellow oil；[α] 25D=+16.4 (c 0.10, MeOH)；HRESIMS m/z,270.9963[M+
Na]+,calcd for C13H9ONaSCl,270.9960；1H-NMR(CDCl 3)δH:7.23(1H,d,3.6,H-3),6.89
(1H,d,3.7,H-4),5.11(1H,dd,8.0,3.3,H-6),3.78(1H,dd,11.3,3.6,H-7a),3.69(1H,dd,
11.3,8.0,H-7b),2.02(3H,s,H-8')；13C-NMR(CDCl3)δC:121.6(C-2),135.2(C-3),124.5(C-
4),147.0(C-5),70.3(C-6),50.1(C-7),67.8(C-2'),79.4(C-3'),58.5(C-4'),64.9(C-
5'),70.1(C-6'),79.7(C-7'),4.7(C-8').The HRESIMS figure of compound 2,1H NMR figure and13C NMR figure difference
As shown in Figures 5 to 7.
Compound 3: yellow oil；[α] 25D=+18.2 (c 0.10, MeOH)；HRESIMS m/z,313.0066[M+
Na]+,calcd for C15H11O2NaSCl,313.0066；1H-NMR(CDCl3)δH:7.25(1H,d,3.5,H-3),6.99
(1H,d,3.6,H-4),6.17(1H,dd,7.2,4.8,H-6),3.82(1H,dd,11.5,7.3,H-7a),3.78(1H,dd,
11.5,5.0,H-7b),2.02(3H,s,H-8'),2.16(3H,s,H-8")；13C-NMR(CDCl3)δC:122.4(C-2),
134.9(C-3),126.6(C-4),142.8(C-5),70.2(C-6),45.9(C-7),67.5(C-2'),79.7(C-3'),
58.5(C-4'),64.9(C-5'),70.2(C-6'),79.8(C-7'),4.7(C-8'),169.5(C-1”),20.8(C-2”)。
The HRESIMS figure of compound 3,1H NMR figure and13C NMR figure is respectively as shown in Fig. 8 to Figure 10.
Compound 4: yellow oil；[α] 25D=+76.3 (c 0.10, MeOH)；HRESIMS m/z,389.0414[M+
Na]+,calcd for C18H19O2NaS2Cl,389.0413；1H-NMR(CDCl3)δH:7.04(1H,d,3.4,H-3),7.01
(1H,d,3.5,H-4),6.21(1H,dd,7.5,4.9,H-6),3.88(1H,dd,11.5,7.8,H-7a),3.83(1H,dd,
11.6,4.8,H-7b),6.99(1H,d,3.5,H-3'),7.02(1H,d,3.5,H-4'),2.11(3H,s,H-8'),2.30
(2H,d,6.8,H-2"),2.10(1H,m,H-3"),0.99(3H,d,6.6,H-4"),0.99(3H,d,6.6,H-5")；13C-
NMR(CDCl3)δC:137.7(C-2),123.6(C-3),127.4(C-4),138.7(C-5),70.3(C-6),46.0(C-7),
136.8(C-2'),123.6(C-3'),131.7(C-4'),123.4(C-5'),72.8(C-6'),91.5(C-7'),4.7(C-
8'),171.8(C-1"),43.3(C-2"),25.7(C-3"),22.4(C-4"),22.4(C-5").The HRESIMS of compound 4
Figure,1H NMR figure and13C NMR figure is as shown in Figure 11 to Figure 13 respectively.
Compound 5: yellow oil；[α] 25D=+32.2 (c 0.10, MeOH)；HRESIMS m/z,421.1446[M+
Na]+,calcd for C23H26O4NaS,421.1449；1H-NMR(CDCl3)δH:7.24(1H,d,3.6,H-3),6.97(1H,
d,3.6,H-4),6.25(1H,dd,6.8,4.0,H-6),4.45(1H,dd,11.7,3.8,H-7a),4.33(1H,dd,11.8,
7.1,H-7b),2.05(3H,s,H-8'),2.24(2H,d,7.9,H-2”),2.11(1H,m,H-3”),0.96(3H,d,6.6,
H-4”),0.96(3H,d,6.6,H-5”),2.22(2H,d,7.9,H-2”'),2.11(1H,m,H-3”'),0.96(3H,d,
6.6,H-4"'),0.96(3H,d,6.6,H-5"')；13C-NMR(CDCl3)δC:122.2(C-2),134.9(C-3),126.4
(C-4),142.6(C-5),68.5(C-6),65.0(C-7),67.6(C-2'),79.5(C-3'),58.5(C-4'),64.9(C-
5'),70.1(C-6'),79.7(C-7'),4.7(C-8'),171.7(C-1”),43.2(C-2”),25.7(C-3”),22.3(C-
4”),22.3(C-5”),172.4(C-1”'),43.1(C-2”'),25.6(C-3”'),22.3(C-4”'),22.3(C-5”')。
The HRESIMS figure of compound 5,1H NMR figure and13C NMR figure is respectively as shown in Figure 14 to Figure 16.
Compound 6: yellow oil；[α] 25D=+52.4 (c 0.10, MeOH)；HRESIMS m/z,455.1318[M+
Na]+,calcd for C23H28O4NaS2,455.1327；1H-NMR(CDCl3)δH:7.02(1H,d,3.5,H-3),7.01(1H,
d,3.6,H-4),6.28(1H,dd,7.5,4.1,H-6),4.46(1H,dd,11.6,3.9,H-7a),4.39(1H,dd,11.7,
7.6,H-7b),6.99(1H,d,3.6,H-3'),7.01(1H,d,3.6,H-4'),2.11(3H,s,H-8'),2.25(2H,d,
7.9,H-2”),2.13(1H,m,H-3”),0.97(3H,d,6.6,H-4”),0.97(3H,d,6.6,H-5”),2.24(2H,d,
7.9,H-2"'),2.15(1H,m,H-3"'),0.97(3H,d,6.6,H-4"'),0.97(3H,d,6.6,H-5"')；13C-NMR
(CDCl3)δC:137.6(C-2),123.5(C-3),127.3(C-4),138.1(C-5),68.5(C-6),65.2(C-7),
136.9(C-2'),123.5(C-3'),131.7(C-4'),126.3(C-5'),72.8(C-6'),91.4(C-7'),4.7(C-
8'),171.9(C-1”),43.3(C-2”),25.7(C-3”),22.4(C-4”),22.4(C-5”),172.5(C-1”'),43.2
(C-2"'),25.7(C-3"'),22.4(C-4"'),22.3(C-5"').The HRESIMS figure of compound 6,1H NMR figure and13C
NMR figure is as shown in Figures 17 to 19 respectively.
Compound 7: yellow oil；HRESIMS m/z,287.3468[M+Na]+,calcd for C13H12O2NaS2,
287.0176；1H-NMR(CDCl3)δH:7.20(1H,d,5.2,H-3),7.14(1H,d,5.2,H-4),4.79(1H,t,6.5,
H-6),3.89(2H,t,6.5,H-7),7.02(1H,d,3.8,H-3'),7.12(1H,d,3.6,H-4'),2.10(3H,s,H-
8')。
Compound 8: yellow oil；HRESIMS m/z,305.7898[M+Na]+,calcd for C13H11ONaClS2,
304.9838；1H-NMR(CDCl3)δH:6.96(1H,d,4.0,H-3),7.01(1H,d,4.0,H-4),5.14(1H,m,H-6),
3.84(1H,dd,11.6,3.9,H-7a),3.76(1H,dd,11.7,7.6,H-7b),7.02(1H,d,4.0,H-3'),6.99
(1H,d,4.0,H-4'),2.11(3H,s,H-8')。
Compound 9: yellow oil；HRESIMS m/z,301.0336[M+Na]+,calcd for C14H14S2NaO2,
301.0327；1H-NMR(CDCl3)δH:7.05(1H,d,3.5,H-3),6.94(1H,d,3.5,H-4),4.51(1H,dd,7.0,
4.0,H-6),3.82(1H,dd,12.0,7.0Hz,H-7a),3.76(1H,dd,12.0,4.0Hz,H-7b),6.99(1H,d,
3.5,H-3'),7.02(1H,d,3.5,H-4'),2.10(3H,s,H-8'),3.40(3H,s,OCH3)。
Compound 10: yellow oil；HRESIMS m/z,455.1318[M+Na]+,calcd for C23H28O4NaS2,
455.1327；1H-NMR(CDCl3)δH:7.78(1H,d,4.0,H-3),7.16(2H,d,4.0,H-4,H-4'),7.10(1H,d,
4.0,H-3'),2.12(3H,s,H-8')。
Compound 11: yellow oil；HRESIMS m/z,269.3318[M+Na]+,calcd for C13H10ONaS2,
269.0071；1H-NMR(CDCl3)δH:7.14(1H,d,3.9,H-3),7.57(1H,d,3.9,H-4),2.55(3H,s,H-7),
7.24(1H,d,3.8,H-3'),7.04(1H,d,3.6,H-4'),2.10(3H,s,H-8')。
Compound 12: yellow oil；HRESIMS m/z,255.3048[M+Na]+,calcd for C12H8ONaS2,
254.9914；1H-NMR(CDCl3)δH:7.12(1H,d,3.9,H-3),7.57(1H,d,3.9,H-4),7.12(1H,d,3.9,
H-3'),6.95(1H,d,3.9,H-4'),2.03(3H,s,H-8'),9.80(1H,s,CHO)。
Embodiment 2: to the toxicity test of Meloidogyne incognita second instar larvae
1) configuration of sample:
It is 10 that untested compound and commercial nematode killing agent avermectin, which are prepared into concentration with organic solvent methanol or acetone solution,4
The mother liquor of μ g/mL.Untested compound is diluted with 0.1% (V/V) Tween-80 aqueous solution, is guaranteed organic in final untested compound
Solvent content is no more than 1% (V/V).
2) preparation of Meloidogyne incognita second instar larvae:
The tomato root infected by Meloidogyne incognita (M.incognita) is acquired, rinses tomato root with the distilled water of sterilizing,
Under stereomicroscope, pieces of an egg are gently removed with tweezers, are placed in the culture dish containing a small amount of distilled water, 28 DEG C of incubator hatchings
3-5 days.The 2 age root-knot nematode nematodes hatched can be used as the target organism of bioassay.
3) biological activity determination:
96 hole biochemical test plates are taken, 100 μ L is respectively taken to be placed in aperture for reagent liquid, isometric nematode suspension is added,
Guarantee every Kong Erling nematode number 80-100 head, cover board is to prevent moisture evaporation.96 orifice plates are placed in 28 DEG C of incubators, are protected from light.Each place
Reason is repeated 4 times.The amount of survival and The dead quantity that Meloidogyne incognita second instar larvae is checked after processing 24 hours, calculate the death rate
And corrected mortality.And the LC of medicament is calculated with SAS software50.The death rate and corrected mortality are calculated as follows:
4) raw to survey result:
Toxicity (μ g/mL) of 1 thiophenes of table to Meloidogyne incognita
Antibacterial activity of the invention experiments have shown that: compound 1 to compound 12 to Meloidogyne incognita second instar larvae all
Have and different degrees of kills line activity, LD50=0.86-18.41 μ g/mL.
Above it can be concluded that the excellent benefit that the present invention has compared with prior art is: compound 1 to compound 4,
Compound 8, compound 9, compound 11 and compound 12 kill line activity (LD to Meloidogyne incognita second instar larvae50=0.86-
9.23 μ g/mL) it is superior to existing commercial sterilization agent avermectin (LD50=9.38 μ g/mL), it is obvious to kill line effect.Especially change
The line ability of killing for closing object 8 reaches 1 μ g/mL or less (0.86 μ g/mL).
Embodiment 3: wettable powder
It is formulated (weight ratio) and preparation method: the powder 20% of 1 gained compound of embodiment, white carbon black 20%, dodecane
Base sodium sulphate 5%, CMC lauryl sodium sulfate 1% and pull open powder 3%, attapulgite surplus.Above-mentioned raw materials are uniformly mixed,
0-50 DEG C of processing temperature of control is crushed to 150 mesh or more in airslide disintegrating mill or other high mesh pulverizers, and moisture control exists
6-8% (mass percentage), pH are controlled in 7-7.5.It can be prepared by the wettable powder of compound shown in 20% formula (1).Through
Dispersibility in the water of preparation, dilution stability, cold heat storage stability meet the requirement of commercially available agricultural chemical preparation.It is verified to have very
Line ability is killed well.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of thiophenes, which is characterized in that including structure shown in formula (1):
Wherein, R1 is independent is selected from-C ≡ C-CH3Or CH3- CH (OH)-(C=O)-；
R2 is independent to be selected from-OH ,=O ,-O-CH3Or-O- (C=O)-CH2-CH-(CH3)2；
R3 is independent to be selected from-H ,-CH2-OH、-CH2-Cl、-OH、-CH3Or-CH2- O-C=O-CH2-CH-(CH3)2。
2. thiophenes according to claim 1, which is characterized in that there is compound 1, compound 4, compound 6, change
Structure shown in conjunction object 7, compound 8, compound 9, compound 10, compound 11 or compound 12；Knot shown in above-mentioned each compound
Structure is respectively as follows:
3. a kind of thiophenes, which is characterized in that including structure shown in formula (2):
Wherein, R4 is independent is selected from-H ,-(C=O)-CH3Or-(C=O)-CH2-CH-(CH3)2, R5 is independent to be selected from-Cl or-O-
(C=O)-CH2-CH2-(CH3)2。
4. thiophenes according to claim 3, which is characterized in that have 5 institute of compound 2, compound 3 or compound
Show structure；Compound 2, compound 3, structure is respectively as follows: shown in compound 5
5. a kind of salt compounds of thiophenes, which is characterized in that any one of claim 1-4 thiophene-based chemical combination
Object is prepared with inorganic acid or organic acid.
6. application of any one of the claim 1-4 thiophenes in prevention and treatment nematode.
7. application of the salt compounds of any one of the claim 1-4 thiophenes in prevention and treatment nematode.
8. a kind of nematicidal product, which is characterized in that including any one of the claim 1-4 thiophenes and/or power
Benefit requires the salt compounds of any one of 1-4 thiophenes.
9. the preparation method of a kind of any one of claim 1-4 thiophenes or its esters compound, feature exist
In, comprising the following steps: separating-purifying is carried out by raw material of echinops grijisii Hance.
10. preparation method according to claim 9, which is characterized in that the method for separating-purifying is the following steps are included: ethyl alcohol soaks
It mentions, the extraction of n-hexane extraction, methylene chloride, silica gel column chromatography.
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| 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 |
| FR2958500A1 (en) * | 2010-04-07 | 2011-10-14 | Jd Invest | Insecticide, insect repellent, ovicide, larvicide, nymphicide composition, useful to destruct flying and crawling insects, their eggs, larvae, and nymphs, comprises essential oil, proteolytic enzyme, and amphoteric surfactant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| FR2958500A1 (en) * | 2010-04-07 | 2011-10-14 | Jd Invest | Insecticide, insect repellent, ovicide, larvicide, nymphicide composition, useful to destruct flying and crawling insects, their eggs, larvae, and nymphs, comprises essential oil, proteolytic enzyme, and amphoteric surfactant |
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| QINGHAO JIN ET AL.: ""Dimeric sesquiterpene and thiophenes from the roots of Echinops latifolius"", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
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