CN104151323A - Compounds with insect anti-feeding and growth inhibition activities and preparation method of compounds - Google Patents
Compounds with insect anti-feeding and growth inhibition activities and preparation method of compounds Download PDFInfo
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- 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
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- C07D313/02—Seven-membered rings
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- 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
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Abstract
The invention belongs to the technical field of medicine, discloses activities and structures of a plurality of Ryanoid diterpenoid compounds separated and extracted from a cinnamon plant and provides a method for separating and preparing the novel Ryanoid diterpenoid compounds. The compounds disclosed by the invention have the advantages of immunosuppressive activity, anti-feeding activity and growth inhibition activity, wherein the compounds with immunosuppressive activity exhibit significant inhibition effect on the proliferation of T cells induced by ConA and the compounds with anti-feeding activity and growth inhibition activity exhibit the anti-feeding activity to beet armyworm larvae and cotton bollworm larvae and the growth inhibition effect on cotton bollworm larvae. The compounds can be used for preparing immunosuppressive drugs and drugs with anti-feeding activity and growth inhibition activity to insects.
Description
Technical field
The invention belongs to medical technical field, relate to method for separating and preparing and the purposes of auspicious promise alkane diterpene compound 1-11.Be specifically related to separation and purification process, structural identification, immunosuppression, insect antifeedant and growth-inhibiting effect etc.
Background technology
Autoimmune disorder is the third-largest disease that is only second to cardiovascular disorder and cancer, has developed a large amount of immunosuppressive drugs at present, is mainly used in preventing rejection and the progress of some autoimmune disorder of inhibition etc. in organ transplantation.Though wherein many medicines have immunosuppressive action, toxic side effect is strong, easily causes general immunosuppression.The immunosuppression lead compound of finding and develop high-efficiency low-toxicity is key subjects of medicine sector of the world.Up-to-date research discovery, autoimmune disorder and T cell relation are especially close.ConA can stimulate the acceptor of T cell surface in vitro, and therefore selectively activate T cell hyperproliferation, utilizes the multiplicative model of the splenic t-cell of ConA foundation can screen fast and efficiently immunosuppressant compound.
Beet armyworm and bollworm are all the omnivory Agricultural pests that extensively distribute in world wide, the crops such as main harm cotton, corn, soybean and vegetables.At present control beet armyworm and bollworm still mainly depend on chemical pesticide, but use unreasonably in a large number chemical pesticide to cause the pollution of soil, water, air, the Genes For Plant Tolerance property of medicine to produce and the disastrous drawback such as harmful to human animal health.Thereby the exploitation of botanical pesticide becomes study hotspot in recent years, insect killing substance in plant is mainly secondary metabolites, do not pollute the environment, comparatively safe to farm crop and ecotope, and insect is also difficult for developing immunity to drugs, therefore the Application and Development of botanical pesticide is being brought into play more and more important effect in current " green food " produced.
Cortex Cinnamomi is the dry bark of canella xylocinnamomum (Cinnamomum cassia Presl (Lauraceae)), and basyleaves are the dry leaf of Chinese cassia tree.Chinese cassia tree energy adjusting immunity of human body, Chinese cassia tree and different auspicious promise alkane diterpene thereof have antialexic activity, the expelling parasite of Chinese cassia tree prodigiosin, purify air, and have the activeconstituents that can make insect antifeedant in Chinese cassia tree.
Summary of the invention:
Task of the present invention is to provide has bioactive compound and method for separating and preparing and application in Chinese cassia tree.
Realizing technical scheme of the present invention is:
From Chinese cassia tree, separating the method that obtains auspicious promise alkane diterpene-kind compound comprises the following steps:
To be dried Cortex Cinnamomi pulverizes, extract by ethanol room temperature, merge ethanol extract reclaim under reduced pressure and be condensed into medicinal extract, obtain total cream, total cream is dispersed to suspendible shape by hot water, and the sherwood oil, chloroform, ethyl acetate, the n-butanol extraction that increase progressively by polarity successively reclaim extraction liquid concentrating under reduced pressure and obtain ethyl acetate extract, n-butanol portion, sherwood oil and chloroform extract are removed.
Ethyl acetate extract is carried out to silica gel column chromatography, chloroform is to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), when chloroform/methanol 6:1, obtain one section of Fr.1, Fr.1 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 1 through gel, preparation liquid phase purifying again;
N-butanol portion is carried out to silica gel column chromatography, and chloroform, to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), obtains Fr.2 when chloroform/methanol 8:1, obtain Fr.3 when chloroform/methanol 6:1, obtains Fr.4 when chloroform/methanol 5:1, obtains Fr.5 when chloroform/methanol 4:1; Fr.2 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 4,5 through gel, preparation liquid phase purifying again; Fr.3 obtains two positions through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1-7:3) and is respectively Fr.3.1, Fr.3.2.Fr.3.1 obtains compound 2,6,7 through silica gel, gel, preparation liquid phase purifying; Fr.3.2 obtains compound 8,9 through gel, preparation liquid phase purifying; Fr.4 process reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), then obtain compound 3,11 through silica gel, gel, preparation liquid phase purifying; Fr.5 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 8:2), and this position obtains compound 10 through silica gel, gel, preparation liquid phase purifying again.The present invention separates the structural formula of the auspicious promise alkane diterpene-kind compound 1-11 obtaining and title in table 1, and separation process is shown in accompanying drawing 1.
Table 1. the present invention separates the auspicious promise alkane diterpene-kind compound 1-11 structural formula obtaining from Chinese cassia tree
Wherein compound Chinese cassia tree terpene F, Chinese cassia tree terpene G are New skeleton compound, and 19-deoxidation Chinese cassia tree terpene G16-glucoside and 18-hydroxyperseanol are new compound.Accompanying drawing 2 is shown in by the single crystal diffraction structure iron of compound 1, and accompanying drawing 3 is shown in by the single crystal diffraction structure iron of compound 2.
The present invention, under the guidance of immunosuppressive activity screening, has carried out systematic study to Chinese cassia tree activeconstituents.The research of the T cell inhibitory effect effect by these 11 compounds to ConA induction, the present invention finds that compound Chinese cassia tree terpene G and cinnacaslo have significant restraining effect to the T cell of ConA induction, represent that it has significant immunosuppressive action.By compound 1-7 being carried out to the research of insect antifeedant and growth inhibitory activity, find that compound Chinese cassia tree terpene F, Chinese cassia tree terpene G and 18-hydroxyperseanol have antifeedant activity to beet exigua larvae, compound Chinese cassia tree terpene F and 18-hydroxyperseanol have antifeedant activity to cotton bollworm larvae; Compound 1-7 has growth-inhibiting effect to cotton bollworm larvae.
The invention provides the plant origin of compound 1-11, separation purification method, immunosuppressive activity, insect antifeedant and growth inhibitory activity and application.The present invention, under the guidance of immunosuppressive activity screening, has carried out systematic study to Chinese cassia tree immunosuppressive activity composition, separates and has obtained compound 1-11, and wherein compound 1,2 is New skeleton compound, and compound 3 and 4 is new compound.Structural formula is as shown in table 1.The research of the T cell inhibitory effect effect by these 11 compounds to ConA induction, finds that the T cell of 2 and 11 pairs of ConA inductions of compound has significant restraining effect, represents that it has significant immunosuppressive action.By compound 1,2,4,5,6,8,9 is carried out to the research of insect antifeedant and growth inhibitory activity, find that 1,2 and 4 pairs of beet exigua larvaes of compound have antifeedant activity, 2 and 4 pairs of cotton bollworm larvaes of compound have antifeedant activity; 1,2,4,5,6,8,9 pairs of cotton bollworm larvaes of compound have growth-inhibiting effect.
Immunosuppressive activity provided by the present invention, insect antifeedant structural formula active 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 are: Chinese cassia tree ethyl acetate extract and n-butanol portion are drawn to section by normal phase silicagel column (moving phase: chloroform/methanol 10:1-3:1 gradient elution); Then the part obtaining is all passed through to reverse phase silica gel (moving phase: the water/methyl alcohol 10:0-7:3 gradient elution) section of drawing again; The fragment that separation is obtained further obtains compound 1,2,3,4 through separation such as gel, HPLC.
Present patent application embodiment 1 has stated that the present invention separates the concrete grammar that obtains auspicious promise alkane diterpene-kind compound from Chinese cassia tree.
Brief description of the drawings
Fig. 1: embodiment 1 schema;
Fig. 2: the single crystal diffraction structure iron of compound 1;
Fig. 3: the single crystal diffraction structure iron of compound 2.
Embodiment
Embodiment 1: the separation preparation of compound.
50Kg is dry, and Cortex Cinnamomi is pulverized, with ethanol room temperature extraction 3 times, each 7 days, merge ethanol extract reclaim under reduced pressure and be condensed into medicinal extract, obtain total cream 5.1Kg, total cream is dispersed to suspendible shape by hot water, the sherwood oil, chloroform, ethyl acetate, the n-butanol extraction that increase progressively by polarity successively, reclaim extraction liquid concentrating under reduced pressure and obtain ethyl acetate extract 70g, n-butanol portion 320g, sherwood oil and chloroform extract are removed.
Compound 1 (22mg): ethyl acetate extract 70g carries out silica gel column chromatography, chloroform is to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), when chloroform/methanol 6:1, obtain one section of Fr.1, Fr.1 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 1 through gel, preparation liquid phase purifying again.
Compound 4 (3mg), 5 (6mg): n-butanol portion 320g carries out silica gel column chromatography, chloroform is to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), when chloroform/methanol 8:1, obtain Fr.2, when chloroform/methanol 6:1, obtain Fr.3, when chloroform/methanol 5:1, obtain Fr.4, when chloroform/methanol 4:1, obtain Fr.5.Fr.2 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 4,5 through gel, preparation liquid phase purifying again.
Compound 2 (4mg), 6 (21mg), 7 (42mg): Fr.3 obtain two positions through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1-7:3) and are respectively Fr.3.1, Fr.3.2.Fr.3.1 obtains compound 2,6,7 through silica gel, gel, preparation liquid phase purifying.Compound 8 (12mg), 9 (28mg): Fr.3.2 obtain compound 8,9 through gel, preparation liquid phase purifying.
Compound 3,11:Fr.4 process reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), then obtain compound 3 (3mg), 11 (57mg) through silica gel, gel, preparation liquid phase purifying.
Compound 10:Fr.5 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 8:2), and this position obtains compound 10 through silica gel, gel, preparation liquid phase purifying again.
Separate preparation flow figure and see Fig. 1.
Through NMR, the absolute configuration that has obtained compound 1,2,3,4 is resolved in X-Ray and chemical reaction test.
Compound 1, Chinese cassia tree terpene F (cinncassiol F) is colorless prismatic crystal,
uV (MeOH) λ
max(log ε): 204 (3.78) nm; IR (KBr) V
max3394,2968,2881,1709,1445,1388,1367,1331,1257,1086,1039,999,851,787,758,683cm
– 1; The quasi-molecular ion peak [M+Na] that HRESIMS provides
+m/z421.1822.Its
1h NMR and
13c NMR spectral data is shown in Table 1 and Table 2.
Compound 2, Chinese cassia tree terpene G (cinncassiol G) is water white transparency styloid,
uV (MeOH) λ
max(log ε)=202 (3.7) nm; IR (KBr) V
max3418,2969,2886,2115,1641,1581,1412,1388,1269,1103,1026,833cm
– 1; The quasi-molecular ion peak [M+H] that HRESIMS provides
+m/z383.2066, determines that in conjunction with hydrogen spectrum and carbon spectrum data its molecular formula is C
20h
30o
7(calculated value C
20h
32o
7h[M+H]
+, 383.2065), 196 DEG C of fusing point 195 –.Its
1h NMR and
13c NMR spectral data is shown in Table 1 and Table 2.
Compound 3,19-deoxidation Chinese cassia tree terpene G16-glucoside (19-deoxycinncassiol G16-O-β-D-glucopyranoside) is colourless oil liquid,
uV (MeOH) λ
max(log ε)=204 (3.7) nm; IR (KBr) V
max3391,2960,2931,1716,1629,1459,1376,1240,1214,1165,1081,1027,943,869,774,693cm
– 1; The quasi-molecular ion peak [M+Na] that HRESIMS provides
+(calculated value is C to m/z567.2385
26h
40o
12[M+Na]
+, 567.2412).Its
1h NMR and
13c NMR spectral data is shown in Table 1 and Table 2.
Compound 4,18-hydroxyperseanol is colourless oil liquid,
uV (MeOH) λ
max(log ε)=206 (3.4) nm; IR (KBr) V
max3388,2963,2879,1602,1465,1387,1177,1110,1029,962,892,829,699cm
– 1; The quasi-molecular ion peak [M+Na] that HRESIMS provides
+(calculated value is C to m/z423.1979
20h
32o
8h[M+Na]
+, 423.1989).Its
1h NMR and
13c NMR spectral data is shown in Table 1 and Table 2.
Table 1 compound 1-4's
1h NMR data
Table 2 compounds 1 ?4
13c NMR data
Embodiment 2
The T cell proliferation of 2 and 11 pairs of ConA inductions of compound has remarkable restraining effect, and compound 1-11 all has no side effect to splenocyte, and splenocyte survival rate is all greater than 90%.The impact of the external immunosuppressive activity of compound 1-11 T cell proliferation on ConA induction by CCK-8 method is evaluated, and result is as shown in following table Table 3:
The inhibiting rate of the T cell proliferation of Table 3 compounds to ConA induction
Experiment conclusion: compound 2 has the restraining effect of highly significant to the mouse T cell of ConA induction, it is relevant that its restraining effect is concentration, and the inhibiting rate of its different concns is all greater than 85%, and inhibition can be compared with positive control CsA.Compound 11 also has the restraining effect of very strong highly significant to the mouse boosting cell of ConA induction, under experimental concentration, its inhibiting rate is all greater 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, 7 compounds have growth-inhibiting effect to cotton bollworm larvae.Antifeedant activity is observed in 24h in table 4 compound by leaf dish method and beet armyworm and cotton bollworm larvae are taken food to blade area is evaluated its antifeedant activity.Growth inhibitory activity is mixed malicious method by feed and is observed the impact of compound (50 μ g/ml) on cotton bollworm larvae body weight in following table in 24h, evaluates its growth inhibitory activity to larva.Result is as shown in following table Table 4.
Table 4. compounds are to concentration and growth inhibition ratio in the food refusal of larva
Experiment conclusion: except the most diterpene of compound 5 all has antifeedant activity in various degree to beet armyworm or bollworm.1,2 and 4 pairs of beet exigua larvaes of compound have remarkable antifeedant activity, and 1 and 4 pairs of cotton bollworm larvaes of compound have remarkable antifeedant activity; Compound is chosen in all experiments has growth-inhibiting effect to cotton bollworm larvae, and compound 2 even makes the bollworm body weight in the growth stage alleviate.
Claims (10)
1. there is the compound of structure shown in following compound 1, compound 2, compound 3 or compound 4:
2. from Chinese cassia tree, separate the method that obtains structural compounds shown in following compounds 1, comprise the following steps:
Step 1: will be dried Cortex Cinnamomi and pulverize, extract by ethanol room temperature, merge ethanol extract reclaim under reduced pressure and be condensed into medicinal extract, obtain total cream, total cream is dispersed to suspendible shape by hot water, and the sherwood oil, chloroform, ethyl acetate, the n-butanol extraction that increase progressively by polarity successively reclaim extraction liquid concentrating under reduced pressure and obtain ethyl acetate extract, n-butanol portion, sherwood oil and chloroform extract are removed;
Step 2: ethyl acetate extract is carried out to silica gel column chromatography, chloroform is to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), when chloroform/methanol 6:1, obtain one section of Fr.1, Fr.1 obtains a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 1 through gel, preparation liquid phase purifying again.
3. from Chinese cassia tree, separate one or more the method obtaining in following auspicious promise alkane diterpene-kind compound 2 to 11, comprise the following steps:
Steps A: the n-butanol portion obtaining in the step 1 of claim 2 is carried out to silica gel column chromatography, chloroform is to methyl alcohol gradient elution (chloroform/methanol 10:1-3:1), when chloroform/methanol 8:1, obtain Fr.2, when chloroform/methanol 6:1, obtain Fr.3, when chloroform/methanol 5:1, obtain Fr.4, when chloroform/methanol 4:1, obtain Fr.5;
Step B: Fr.2 is obtained to a position through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), and this position obtains compound 4,5 through gel, preparation liquid phase purifying again; Or
Fr.3 is obtained to two positions through reversed-phase silica gel column chromatography (water/methyl alcohol 9:1-7:3) and be respectively Fr.3.1, Fr.3.2; Fr.3.1 obtains compound 2,6,7 through silica gel, gel, preparation liquid phase purifying; Or Fr.3.2 obtains compound 8,9 through gel, preparation liquid phase purifying; Or
By Fr.4 process reversed-phase silica gel column chromatography (water/methyl alcohol 9:1), then obtain compound 3,11 through silica gel, gel, preparation liquid phase purifying; Or
Fr.5 is obtained to a position through reversed-phase silica gel column chromatography (water/methyl alcohol 8:2), and this position obtains compound 10 through silica gel, gel, preparation liquid phase purifying again.
4. there is the compound of structure shown in following compound 2 in the application of preparing in immunosuppression,
5. there is the compound of structural formula shown in following compound 11 in the application of preparing in immunosuppression,
6. following compounds 1 to any compound in compound 7 has the application in antifeedant activity and/or growth inhibitory activity medicine in preparation to insect:
7. application according to claim 6, is characterized in that, described insect is bollworm or beet armyworm.
8. application according to claim 6, is characterized in that, described insect is cotton bollworm larvae or beet exigua larvae.
9. a kind of in following compounds 1 (Chinese cassia tree terpene F), compound 2 (Chinese cassia tree terpene G) and compound 4 (18-hydroxyperseanol) has an application in antifeedant activity medicine in preparation to beet exigua larvae,
10. a kind of in following compounds 1 (Chinese cassia tree terpene F) and compound 4 (18-hydroxyperseanol) has an application in antifeedant activity medicine in preparation to cotton bollworm larvae,
Priority Applications (4)
| 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 |
| CN201610238969.1A CN105777772B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610238948.XA CN105859676B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610242147.0A Division CN105801596B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610238969.1A Division CN105777772B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
| CN201610238948.XA Division CN105859676B (en) | 2014-07-30 | 2014-07-30 | Compound with insect antifeedant activity and growth inhibitory activity and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN104151323A true CN104151323A (en) | 2014-11-19 |
| CN104151323B CN104151323B (en) | 2016-09-28 |
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| 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 |
| 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 |
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| 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 |
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| CN104478832A (en) * | 2015-01-05 | 2015-04-01 | 富阳鸿祥技术服务有限公司 | Diterpene compound, pharmaceutical composition containing same and preparation method and usage thereof |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55136283A (en) * | 1979-03-29 | 1980-10-23 | Itsuo Nishioka | Novel diterpene derivative |
Non-Patent Citations (3)
| Title |
|---|
| AZUCENA GONZALEZ-COLOMA ET AL.: "Selective Insect Antifeedant and Toxic Action of Ryanoid Diterpenes", 《J.AGRIC.FOOD.CHEM》, vol. 47, 31 December 1999 (1999-12-31), pages 4419 - 4424 * |
| BRAULIO M. FRAGA ET AL.: "Insect Antifeedant Isoryanodane Diterpenes from Persea indica", 《J. NAT. PROD.》, vol. 60, 31 December 1997 (1997-12-31), pages 880 - 883 * |
| TRAN MINH NGOC ET AL.: "Two New Dierpenes from the Twigs of Cinnamomum cassia", 《HELCETICA CHIMICA ACTA》, vol. 92, 31 December 2009 (2009-12-31), pages 2058 - 2062 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104478832A (en) * | 2015-01-05 | 2015-04-01 | 富阳鸿祥技术服务有限公司 | Diterpene compound, pharmaceutical composition containing same and preparation method and usage thereof |
| CN104478832B (en) * | 2015-01-05 | 2016-04-20 | 项敬来 | Diterpene compound, containing its pharmaceutical composition and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105859676B (en) | 2018-03-09 |
| CN105801596B (en) | 2018-04-24 |
| CN105859676A (en) | 2016-08-17 |
| CN104151323B (en) | 2016-09-28 |
| CN105801596A (en) | 2016-07-27 |
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