CN105801596A - Compound with insect antifeedant activity and growth inhibition activity and preparing method thereof - Google Patents
Compound with insect antifeedant activity and growth inhibition activity and preparing method thereof Download PDFInfo
- Publication number
- CN105801596A CN105801596A CN201610242147.0A CN201610242147A CN105801596A CN 105801596 A CN105801596 A CN 105801596A CN 201610242147 A CN201610242147 A CN 201610242147A CN 105801596 A CN105801596 A CN 105801596A
- Authority
- CN
- China
- Prior art keywords
- compound
- activity
- methanol
- chloroform
- silica gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
-
- 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
- A01N43/08—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 oxygen as the ring hetero atom
-
- 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
- A01N43/22—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 rings with more than six members
-
- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
- C07D313/08—Seven-membered rings condensed with carbocyclic rings or ring systems condensed with one six-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/26—Acyclic or carbocyclic radicals, substituted by hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Medicines Containing Plant Substances (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of medicine, discloses activity and structures of various ryanoids diterpene compounds separated and extracted from the plant cinnamon, and provides a method for separation and preparation of a novel ryanoids diterpene compound. The compound has immunity suppression activity, insect antifeedant activity and growth inhibition activity, wherein immunity suppression activity is realized through remarkable suppression of proliferation T cells induced by ConA, and insect antifeedant activity and growth inhibition activity are reflected in beet armyworm larva antifeedant activity, cotton bollworm larva antifeedant activity and cotton bollworm larva growth inhibition. The compounds can be used for preparing drugs which are capable of achieving immunity suppression and have insect antifeedant activity and growth inhibition activity.
Description
The application is the divisional application of No. 2014103695394 patent applications.
The applying date of original application is: on July 30th, 2014.
The application number of original application is: 201410369539.4.
The invention and created name of original application is: have compound of insect antifeedant activity and growth inhibitory activity and preparation method thereof.
Technical field
The invention belongs to pharmaceutical technology field, relate to method for separating and preparing and the purposes of auspicious promise alkane diterpene compound 1-11.It is specifically related to separate purge process, structural identification, immunosuppressant, insect antifeedant and growth inhibited effect etc..
Background technology
Autoimmune disease is the third-largest disease being only second to cardiovascular disease and cancer, has been developed for substantial amounts of immunosuppressive drug at present, is mainly used in preventing the progress etc. of rejection and some autoimmune disease of suppression in organ transplantation.Though wherein many medicines have immunosuppressive action, but toxic and side effects is strong, it is easy to cause systemic immunity to suppress.The immunosuppressant lead compound finding and developing high-efficiency low-toxicity is key subjects of medicine sector of the world.Up-to-date research finds, autoimmune disease and T cell relation are especially close.ConA can stimulate the receptor on T cell surface, selective activation T cell hyper-proliferative in vitro, therefore, utilizes the multiplicative model of the ConA splenic t-cell set up can screen immunosuppressant compound fast and efficiently.
Beet armyworm and bollworm are all the crops such as omnivorousness agricultural pests widely distributed in world wide, main harm Cotton Gossypii, corn and soybean and vegetable.Preventing and treating beet armyworm and bollworm still depend on chemical pesticide at present, but use chemical pesticide causes the disastrous drawbacks such as the pollution of soil, water, air, the generation of the Genes For Plant Tolerance property of medicine and harmful to human animal health unreasonably in a large number.Thus the study hotspot being developed in recent years of botanical pesticide, insect killing substance in plant is mainly secondary metabolites, do not pollute the environment, crops and ecological environment are comparatively safe, and insecticide is not easy to develop immunity to drugs, therefore the exploitation of botanical pesticide is applied in currently " pollution-free food " and plays more and more important effect in producing.
Cortex Cinnamomi is the dry bark of canella xylocinnamomum (CinnamomumcassiaPresl (Lauraceae)), and basyleaves are the dry leaves of Cortex Cinnamomi.Cortex Cinnamomi can regulate body immunity, Cortex Cinnamomi and different auspicious promise alkane diterpene thereof and have antialexic activity, Cortex Cinnamomi prodigiosin anthelmintic, purification air, has the active component that can make insect antifeedant in Cortex Cinnamomi.
Summary of the invention:
The task of the present invention is to provide in Cortex Cinnamomi and has bioactive compound and method for separating and preparing thereof and application.
Realization the technical scheme is that
From Cortex Cinnamomi, separate the method obtaining auspicious promise alkane diterpene-kind compound comprise the following steps:
Dry Cortex Cinnamomi is pulverized, extract by ethanol room temperature, merge ethanol extract and recovered under reduced pressure is condensed into extractum, obtain total cream, total cream is dispersed to suspendible shape by hot water, successively with polarity be incremented by petroleum ether, chloroform, ethyl acetate, n-butanol extraction, reclaim extract concentrating under reduced pressure obtain ethyl acetate extract, n-butanol portion, petroleum ether and chloroform extract are removed.
Ethyl acetate extract is carried out silica gel column chromatography, chloroform is to methanol elution gradient (chloroform/methanol 10:1-3:1), one section of Fr.1 is obtained during chloroform/methanol 6:1, Fr.1 obtains a position through reversed-phase silica gel column chromatography (water/methanol 9:1), and this position obtains compound 1 then through gel, preparation liquid phase purification；
N-butanol portion is carried out silica gel column chromatography, and chloroform, to methanol elution gradient (chloroform/methanol 10:1-3:1), obtains Fr.2 during chloroform/methanol 8:1, obtain Fr.3 during chloroform/methanol 6:1, obtains Fr.4 during chloroform/methanol 5:1, obtains Fr.5 during chloroform/methanol 4:1；Fr.2 obtains a position through reversed-phase silica gel column chromatography (water/methanol 9:1), and this position obtains compound 4,5 then through gel, preparation liquid phase purification；Fr.3 obtains two positions respectively Fr.3.1, Fr.3.2 through reversed-phase silica gel column chromatography (water/methanol 9:1-7:3).Fr.3.1 obtains compound 2,6,7 through silica gel, gel, preparation liquid phase purification；Fr.3.2 obtains compound 8,9 through gel, preparation liquid phase purification；Fr.4, through reversed-phase silica gel column chromatography (water/methanol 9:1), obtains compound 3,11 then through silica gel, gel, preparation liquid phase purification；Fr.5 obtains a position through reversed-phase silica gel column chromatography (water/methanol 8:2), and this position obtains compound 10 then through silica gel, gel, preparation liquid phase purification.The structural formula of the auspicious promise alkane diterpene-kind compound 1-11 that present invention separation obtains and title are in Table 1, and separation process is shown in accompanying drawing 1.
Table 1. present invention separates the auspicious promise alkane diterpene-kind compound 1-11 structural formula obtained from Cortex Cinnamomi
Wherein compound Cortex Cinnamomi terpene F, Cortex Cinnamomi terpene G are New skeleton compound, and 19-deoxidation Cortex Cinnamomi terpene G16-glucoside and 18-hydroxyperseanol are noval chemical compound.Accompanying drawing 2 is shown in by the single crystal diffraction structure chart of compound 1, and accompanying drawing 3 is shown in by the single crystal diffraction structure chart of compound 2.
Cortex Cinnamomi active component, under the guidance that immunosuppressive activity is screened, has been carried out systematic study by the present invention.By the research of the T cell inhibited proliferation that ConA is induced by these 11 compounds, present invention discover that the ConA T cell induced is had significant inhibitory action by compound Cortex Cinnamomi terpene G and cinnacaslo, represent that it has significant immunosuppressive action.By compound 1-7 being carried out the research of insect antifeedant and growth inhibitory activity, finding that beet exigua larvae is had antifeedant activity by compound Cortex Cinnamomi terpene F, Cortex Cinnamomi terpene G and 18-hydroxyperseanol, cotton bollworm larvae is had antifeedant activity by compound Cortex Cinnamomi terpene F and 18-hydroxyperseanol；Cotton bollworm larvae is had growth inhibited effect by compound 1-7.
The invention provides the plant origin of compound 1-11, isolation and purification method, immunosuppressive activity, insect antifeedant and growth inhibitory activity and application.Cortex Cinnamomi immunosuppressive activity composition, under the guidance that immunosuppressive activity is screened, has been carried out systematic study by the present invention, separates and obtains compound 1-11, and wherein compound 1,2 is New skeleton compound, and compound 3 and 4 is noval chemical compound.Structural formula is as shown in table 1.By the research of the T cell inhibited proliferation that ConA is induced by these 11 compounds, it has been found that the T cell of compound 2 and 11 pairs of ConA inductions has significant inhibitory action, represents that it has significant immunosuppressive action.By compound 1,2,4,5,6,8,9 being carried out the research of insect antifeedant and growth inhibitory activity, it has been found that 1,2 and 4 pairs of beet exigua larvaes of compound have antifeedant activity, compound 2 and 4 pairs of cotton bollworm larvaes to have antifeedant activity；1,2,4,5,6,8,9 pairs of cotton bollworm larvaes of compound have growth inhibited effect.
Immunosuppressive activity provided by the present invention, the structural formula of insect antifeedant activity and growth inhibitory activity compound 1,2,3,4 and 5 is as follows:
The compounds of this invention 1,2,3,4 method for separating and preparing is: by normal phase silicagel column (mobile phase: chloroform/methanol 10:1-3:1 gradient elution), Cortex Cinnamomi ethyl acetate extract and n-butanol portion are drawn section；Then all again carry out drawing section through reverse phase silica gel (mobile phase: water/methanol 10:0-7:3 gradient elution) by the part obtained；Compound 1,2,3,4 is obtained further across the separation such as gel, HPLC by separating the fragment obtained.
Present patent application embodiment 1 set forth the present invention and separates the concrete grammar obtaining auspicious promise alkane diterpene-kind compound from Cortex Cinnamomi.
Accompanying drawing explanation
Fig. 1: embodiment 1 flow chart；
Fig. 2: the single crystal diffraction structure chart of compound 1；
Fig. 3: the single crystal diffraction structure chart of compound 2.
Detailed description of the invention
Embodiment 1: prepared by the separation of compound.
50Kg is dry, and Cortex Cinnamomi is pulverized, extract 3 times by ethanol room temperature, each 7 days, merging ethanol extract and recovered under reduced pressure is condensed into extractum, obtain total cream 5.1Kg, total cream is dispersed to suspendible shape by hot water, successively with polarity be incremented by petroleum ether, chloroform, ethyl acetate, n-butanol extraction, reclaim extract concentrating under reduced pressure and obtain ethyl acetate extract 70g, n-butanol portion 320g, petroleum ether and chloroform extract removal.
Compound 1 (22mg): ethyl acetate extract 70g carries out silica gel column chromatography, chloroform is to methanol elution gradient (chloroform/methanol 10:1-3:1), one section of Fr.1 is obtained during chloroform/methanol 6:1, Fr.1 obtains a position through reversed-phase silica gel column chromatography (water/methanol 9:1), and this position obtains compound 1 then through gel, preparation liquid phase purification.
Compound 4 (3mg), 5 (6mg): n-butanol portion 320g carries out silica gel column chromatography, chloroform is to methanol elution gradient (chloroform/methanol 10:1-3:1), Fr.2 is obtained during chloroform/methanol 8:1, Fr.3 is obtained during chloroform/methanol 6:1, obtain Fr.4 during chloroform/methanol 5:1, during chloroform/methanol 4:1, obtain Fr.5.Fr.2 obtains a position through reversed-phase silica gel column chromatography (water/methanol 9:1), and this position obtains compound 4,5 then through gel, preparation liquid phase purification.
Compound 2 (4mg), 6 (21mg), 7 (42mg): Fr.3 obtain two positions respectively Fr.3.1, Fr.3.2 through reversed-phase silica gel column chromatography (water/methanol 9:1-7:3).Fr.3.1 obtains compound 2,6,7 through silica gel, gel, preparation liquid phase purification.
Compound 8 (12mg), 9 (28mg): Fr.3.2 obtain compound 8,9 through gel, preparation liquid phase purification.
Compound 3,11:Fr.4, through reversed-phase silica gel column chromatography (water/methanol 9:1), obtain compound 3 (3mg), 11 (57mg) then through silica gel, gel, preparation liquid phase purification.
Compound 10:Fr.5 obtains a position through reversed-phase silica gel column chromatography (water/methanol 8:2), and this position obtains compound 10 then through silica gel, gel, preparation liquid phase purification.
Separate preparation flow figure and see Fig. 1.
Test through NMR, X-Ray and chemical reaction and resolve the absolute configuration obtaining compound 1,2,3,4.
Compound 1, Cortex Cinnamomi terpene F (cinncassiolF) is colorless prismatic crystal,UV(MeOH)λmax(logε):204(3.78)nm；IR(KBr)Vmax3394,2968,2881,1709,1445,1388,1367,1331,1257,1086,1039,999,851,787,758,683cm–1；The quasi-molecular ion peak [M+Na] that HRESIMS provides+m/z421.1822.Its1HNMR and13CNMR spectral data is shown in Table1 and Table2.
Compound 2, Cortex Cinnamomi terpene G (cinncassiolG) is water white transparency column crystal,UV(MeOH)λmax(log ε)=202 (3.7) nm；IR(KBr)Vmax3418,2969,2886,2115,1641,1581,1412,1388,1269,1103,1026,833cm–1；The quasi-molecular ion peak [M+H] that HRESIMS provides+In conjunction with hydrogen spectrum and carbon modal data, m/z383.2066, determines that its molecular formula is C20H30O7(value of calculation C20H32O7H[M+H]+, 383.2065), fusing point 195 196 DEG C.Its1HNMR and13CNMR spectral data is shown in Table1 and Table2.
Compound 3,19-deoxidation Cortex Cinnamomi terpene G16-glucoside (19-deoxycinncassiolG16-O-β-D-glucopyranoside) is colourless oil liquid,UV(MeOH)λmax(log ε)=204 (3.7) nm；IR(KBr)Vmax3391,2960,2931,1716,1629,1459,1376,1240,1214,1165,1081,1027,943,869,774,693cm–1；The quasi-molecular ion peak [M+Na] that HRESIMS provides+(value of calculation is C to m/z567.238526H40O12[M+Na]+,567.2412).Its1HNMR and13CNMR spectral data is shown in Table1 and Table2.
Compound 4,18-hydroxyperseanol is colourless oil liquid,UV(MeOH)λmax(log ε)=206 (3.4) nm；IR(KBr)Vmax3388,2963,2879,1602,1465,1387,1177,1110,1029,962,892,829,699cm–1；The quasi-molecular ion peak [M+Na] that HRESIMS provides+(value of calculation is C to m/z423.197920H32O8H[M+Na]+,423.1989).Its1HNMR and13CNMR spectral data is shown in Table1 and Table2.
Table1 compound 1-4's1HNMR data
Table2 compound 1-4's13CNMR data
Embodiment 2
The T cell propagation of compound 2 and 11 pairs of ConA inductions significantly inhibits effect, and splenocyte is all had no side effect by compound 1-11, and splenocyte survival rate is all higher than 90%.The impact that the ConA T cell induced is bred by compound 1-11 ion vitro immunization inhibitory activity by CCK-8 method is evaluated, and result is such as shown in following table Table3:
The suppression ratio that the ConA T cell induced is bred by Table3 compound
Experiment conclusion: the ConA mouse T cell induced is had the inhibitory action of highly significant by compound 2, its inhibitory action is that concentration is correlated with, and the suppression ratio of its variable concentrations is all higher than 85%, it is suppressed that effect can be compared with positive control CsA.The ConA mouse boosting cell induced also is had the inhibitory action of very strong highly significant by compound 11, and under experimental concentration, its suppression ratio is all higher than 50%.
Embodiment 3: 1,2 and 4 pairs of beet exigua larvaes of compound have the antifeedant activity of antifeedant activity and cotton bollworm larvae；In table, cotton bollworm larvae is had growth inhibited effect by 7 compounds.Beet armyworm and cotton bollworm larvae are taken food blade area by compound in table 4 in leaf dish method observation 24h and evaluate its antifeedant activity by antifeedant activity.Growth inhibitory activity observes the compound (the 50 μ g/ml) impact on cotton bollworm larvae body weight in following table in 24h by feedstuff mixed poison method, evaluates its growth inhibitory activity to larva.Result is such as shown in following table Table4.
Table4. compound is to concentration and growth inhibition ratio in the refusing to eat of larva
Experiment conclusion: except beet armyworm or bollworm are all had antifeedant activity in various degree by the most diterpene of compound 5.1,2 and 4 pairs of beet exigua larvaes of compound have notable antifeedant activity, compound 1 and 4 pairs of cotton bollworm larvaes to have notable antifeedant activity；Compound is chosen in all experiments growth inhibited effect to cotton bollworm larvae, and compound 2 even makes the bollworm in the growth stage lose weight.
Claims (7)
1. there is the compound of structure shown in following compound 4:
2. from Cortex Cinnamomi, separate one or more the method obtaining in following auspicious promise alkane diterpene-kind compound 4-10, comprise the following steps:
Step one: dry Cortex Cinnamomi is pulverized, extract by ethanol room temperature, merge ethanol extract and recovered under reduced pressure is condensed into extractum, obtain total cream, total cream is dispersed to suspendible shape by hot water, successively with polarity be incremented by petroleum ether, chloroform, ethyl acetate, n-butanol extraction, reclaim extract concentrating under reduced pressure obtain ethyl acetate extract, n-butanol portion, petroleum ether part and chloroform extract；
Step 2: the n-butanol portion obtained in step one is carried out silica gel column chromatography, chloroform, to methanol elution gradient (chloroform/methanol 10:1-3:1), obtains Fr.2 during chloroform/methanol 8:1, obtain Fr.3 during chloroform/methanol 6:1, obtains Fr.5 during chloroform/methanol 4:1；
Step 3: through reversed-phase silica gel column chromatography (water/methanol 9:1), Fr.2 is obtained a position, this position obtains compound 4,5 then through gel, preparation liquid phase purification；Or
Fr.3 is obtained two positions respectively Fr.3.1, Fr.3.2 through reversed-phase silica gel column chromatography (water/methanol 9:1-7:3)；Fr.3.1 obtains compound 6,7 through silica gel, gel, preparation liquid phase purification；Or Fr.3.2 obtains compound 8,9 through gel, preparation liquid phase purification；Or
Through reversed-phase silica gel column chromatography (water/methanol 8:2), Fr.5 is obtained a position, and this position obtains compound 10 then through silica gel, gel, preparation liquid phase purification.
3. any one compound in following compounds 4 to compound 7 is preparing application insecticide being had in antifeedant activity and/or growth inhibitory activity medicine:
4. application according to claim 3, it is characterised in that described insecticide is bollworm or beet armyworm.
5. application according to claim 3, it is characterised in that described insecticide is cotton bollworm larvae or beet exigua larvae.
6. following compounds 4 (18-hydroxyperseanol) is preparing application beet exigua larvae being had in antifeedant activity medicine,
7. following compounds 4 (18-hydroxyperseanol) is preparing application cotton bollworm larvae being had in antifeedant activity medicine,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610242147.0A CN105801596B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610242147.0A CN105801596B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201410369539.4A CN104151323B (en) | 2014-07-30 | 2014-07-30 | There is compound of insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410369539.4A Division CN104151323B (en) | 2014-07-30 | 2014-07-30 | There is compound of insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105801596A true CN105801596A (en) | 2016-07-27 |
| CN105801596B CN105801596B (en) | 2018-04-24 |
Family
ID=51876976
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410369539.4A Active CN104151323B (en) | 2014-07-30 | 2014-07-30 | There is compound of insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610238948.XA Active CN105859676B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610242147.0A Active CN105801596B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410369539.4A Active CN104151323B (en) | 2014-07-30 | 2014-07-30 | There is compound of insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610238948.XA Active CN105859676B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN104151323B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478832B (en) * | 2015-01-05 | 2016-04-20 | 项敬来 | Diterpene compound, containing its pharmaceutical composition and its preparation method and application |
| CN108935473B (en) * | 2018-09-28 | 2021-01-05 | 广东省农业科学院果树研究所 | Application of eurycollactone in antifeedant activity and inhibition of growth and development of insects |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55136283A (en) * | 1979-03-29 | 1980-10-23 | Itsuo Nishioka | Novel diterpene derivative |
-
2014
- 2014-07-30 CN CN201410369539.4A patent/CN104151323B/en active Active
- 2014-07-30 CN CN201610238948.XA patent/CN105859676B/en active Active
- 2014-07-30 CN CN201610242147.0A patent/CN105801596B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55136283A (en) * | 1979-03-29 | 1980-10-23 | Itsuo Nishioka | Novel diterpene derivative |
Non-Patent Citations (5)
| Title |
|---|
| AZUCENA GONZALEZ-COLOMA 等: "Selective Insect Antifeedant and Toxic Action of Ryanoid Diterpenes", 《J. AGRIC. FOOD CHEM.》 * |
| BRAULIO M. FRAGA 等: "Insect Antifeedant Isoryanodane Diterpenes from Persea indica", 《JOURNAL OF NATURAL PRODUCTS》 * |
| TOSHIHIRO NOHARA 等: "Constituents of Cinnamomi cortex. V. Structures of five novel diterpenes, cinncassiols D1, D1 glucoside,D2, D2 glucoside and D3", 《CHEMICAL & PHARMACEUTICAL BULLETIN》 * |
| TOSHIHIRO NOHARA 等: "Two novel diterpenes from bark of Cinnamomum cassia", 《PHYTOCHEMISTRY》 * |
| 赵凯 等: "肉桂的化学成分及其生物活性研究进展", 《内蒙古医科大学学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104151323B (en) | 2016-09-28 |
| CN104151323A (en) | 2014-11-19 |
| CN105859676A (en) | 2016-08-17 |
| CN105859676B (en) | 2018-03-09 |
| CN105801596B (en) | 2018-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101190258A (en) | Total sesquiterpene lactone extract containing rich parthenolide and preparation method and application thereof | |
| CN103804443B (en) | Flavonoid glycoside compound and preparation method thereof | |
| Qnais et al. | Analgesic and anti-inflammatory effects of an extract and flavonoids from Artemisia Herba-Alba and their mechanisms of action | |
| CN102212093A (en) | Flavonoid glycoside compounds, method for preparing same and application | |
| Vasconcelos et al. | Anti-inflammatory activities of the hydroalcoholic extracts from Erythrina velutina and E. mulungu in mice | |
| CN105801596A (en) | Compound with insect antifeedant activity and growth inhibition activity and preparing method thereof | |
| CN102178688B (en) | Preparation method of ivy saponins ingredient and application of the ingredient to resisting tumors | |
| Manosroi et al. | In vivo immunomodulating activity of wood extracts from Clausena excavata Burm. f. | |
| CN105031072A (en) | Anti-tumor radix tetrastigme extract, as well as preparation method and application thereof | |
| Rajesh et al. | Antifungal metabolite from Muntingia calabura root against early leaf blight of tomato | |
| CN105777772A (en) | Compounds with insect antifeedant activity and growth inhibitory activity and preparation method thereof | |
| CN103626812B (en) | Gloomy glycosides compound of a kind of new Bali and uses thereof in rhizoma Gastrodiae | |
| Fehri et al. | Effects of Globularia alypum L. on the gastrointestinal tract | |
| CN102451220A (en) | Erythrophleum fordii Oliver extract, preparation method and pharmaceutical composition thereof and application | |
| Di Toto Blessing et al. | Structural factors of annonaceous acetogenins and their semisynthetic analogues related with the toxicity on Spodoptera frugiperda | |
| EP1968575B1 (en) | Immunomodulatory pharmaceutical composition containing a combination of three coumarinolignoids | |
| Hossain et al. | Chemical and pesticidal studies on Acorus calamus rhizomes | |
| Umaru et al. | Antidiabetic potentials of leaves extract of Barringtonia Racemosa (L) in Alloxan-induced Albino rats | |
| Zomborszki et al. | Development of an optimized processing method for withania frutescens | |
| Rawat et al. | Study on characterization and pesticidal evaluation of diterpenes isolated from chloroform extract of Hedychium spicatum Sm. rhizomes | |
| Mata et al. | Bioactive natural products of medicinal and agrochemical interest from selected Mexican medicinal plants | |
| CN104829529B (en) | Artabotrys pilosus total alkaloid extract and application thereof | |
| CN104586837B (en) | Purposes of the gray wool Cipadessa baecifera Miq A and the like in anti-depression drug is prepared | |
| Huang et al. | Novel selective cytotoxicity of wild sarsaparilla rhizome extract | |
| Blessing et al. | Structural factors of annonaceous acetogenins and their semisynthetic analogues related with the toxicity on Spodoptera frugiperda |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |