CN103910633A - Eight cassane diterpenoid compounds having substantial antitumor activity - Google Patents
Eight cassane diterpenoid compounds having substantial antitumor activity Download PDFInfo
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Abstract
The invention relates to eight new cassane diterpenoid compounds separated from the seed of a leguminous Caesalpinia L. plant Caesalpinia minax Hance through a phytochemical extraction separating process, cytotoxicity of the compounds on the gastric gland cancer, the lung cancer, the liver cancer and the breast cancer, and an application of the compounds in the clinic prevention and treatment of tumors.
Description
Technical field:
The present invention relates to extract from the seed Semen Caesalpiniae Minacis of pulse family Caesalpinia beak pod mysorethorn [Caesalpinia minax Hance] by phytochemical extraction separation means separate and obtain 8 new card mountain alkane type diterpene-kind compounds and the cytotoxicity of this compounds to adenocarcinoma of stomach, lung cancer, liver cancer, mammary cancer and the application in clinical prevention and the treatment of tumour thereof.
Background technology:
Semen Caesalpiniae Minacis is the seed of pulse family Caesalpinia beak pod mysorethorn (Caesalpinia minax Hance).Beak pod mysorethorn is commonly called as southern snake and strangles, dragon's paw thorn, for low brushwood, be born in the mountain region of height above sea level 150-680m, mountain valley, in river valley or roadside shrubbery, mainly be distributed in the Guangxi of southwest and South China in China, Yunnan, Guizhou, Guangxi, the ground such as Guangdong and Hainan. Semen Caesalpiniae Minacis is cool in nature, bitter, there is clearing away heat and eliminating dampness, promoting blood circulation to remove blood stasis, effect of pain relieving, it is south China conventional herbal medicine among the people, it is mainly used in treating common cold due to wind-heat among the people, influenza, hepatitis, dysentery, stranguria with turbid discharge, carbuncle is swollen, skin pruritus, sore tinea, wound, venomous snake bite etc., for China's Chinese medicine ancient books and records " China's book on Chinese herbal medicine " etc. are included, simultaneously by Guangxi Chinese medicinal materials standard, Chinese medicine in Guizhou Province material standard, Chinese Medicinal Materials of Sichuan standard etc. is recorded, it is the valuable strong medicine of tradition.Research shows, the characteristic chemical constituent in Semen Caesalpiniae Minacis and activeconstituents are mainly card mountain alkane type (cassane) diterpene and lactone compound thereof.Through pharmacology activity research, this compounds has well antibacterial, antiviral and anti-malarial, antitumor isoreactivity.
Compound I-VIII involved in the present invention is new compound, and its anti-tumor activity is for finding first, and up to now, above achievement in research not yet has patent or bibliographical information.
The object of the invention is to make full use of the distinctive plant resources that contains card mountain alkane type diterpene of China, deeply research and develop, find and have unique chemical structure, anti-tumor activity is strong, and this compounds that toxic side effect is little, to providing new type antineoplastic medicine for clinical study.
Summary of the invention:
The invention provides the application of card mountain alkane type diterpene-kind compound in pharmacy.
This laboratory utilizes modern separation technology and structure determination means to carry out in chemical constitution study process the seed Semen Caesalpiniae Minacis of pulse family Caesalpinia beak pod mysorethorn, therefrom separate and obtain 8 new card mountain alkane type diterpene, be respectively 1 α, 6 α-diacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-7 (8), 13 (14)-diene (I); 1 α, 6 α, 7 β-triacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-13 (14)-diene (II); 1 α, 6 α, 7 β-triacetoxy-5 α-hydroxy-16,16-dimethoxy-12-oxocassa-13 (14)-diene (III); 1 α-acetoxy-7-oxo-14-methylvoucapane-5 (6), 8 (14), 9 (11)-diene (IV); 1 α, 6 α-diacetoxy-5 α, 7 β-dihydroxyl-14-methylvoucapane-8 (14), 9 (11)-diene (V); 1 α, 2 α-diacetoxy-5 α-hydroxyl-12 α-methoxy-14 α-methylcassa-13 (15)-en-16,12-olide (VI); 1 α-acetoxy-5 α, 7 β-dihydroxyl-12 α-methoxycassa-14 (17), 13 (15)-diene-16,12-olide (VII); 1 α, 6 α-diacetoxy-5 α, 7 β-dihydroxyl-12 α-methoxycassa-14 (17), 13 (15)-diene-16,12-olide (VIII).By these compounds are carried out to extracorporeal anti-tumor pharmacodynamic study, find that it all has certain restraining effect to people's adenocarcinoma of stomach, lung cancer, liver cancer, mammary cancer, sees the following form:
Technical scheme of the present invention comprises following steps according to this:
The seed Semen Caesalpiniae Minacis 8.0kg of beak pod mysorethorn is adopted to obtain in Nanning, is accredited as [Caesalpinia minax Hance] by the Yuan Jingquan researcher of Medicinal Plants of Guangxi institute.After Semen Caesalpiniae Minacis 8.0kg pulverizes, methyl alcohol heating and refluxing extraction secondary, each two hours, united extraction liquid, decompression and solvent recovery, obtains total medicinal extract 2020g after concentrating.After the total medicinal extract of Semen Caesalpiniae Minacis dissolves with chloroform-methanol, with 100～200 object silica gel mixed samples, use successively sherwood oil, chloroform, ethyl acetate, acetone, methanol-eluted fractions, elutriant concentrating under reduced pressure, finally obtain sherwood oil part 130g, chloroform part 325g, ethyl acetate part 160g, partial acetone 305g, methyl alcohol part 1100g.(extracting flow process sees shown in accompanying drawing 5).Get chloroform part through silica gel column chromatography, with petroleum ether-ethyl acetate eluent 1: 0-1: 1 gradient elution, obtain 12 cuts (Fr.A-L), therefrom choose cut C (15.4g), cut D (8.9g), cut E (6.8g), through LH20 gel filtration chromatography, removes pigment with 40: 60 wash-outs of chloroform-methanol.Cut C is through anti-phase MCI column chromatography, with methanol-water (30: 70-100: 0) gradient elution, obtains 8 components (C1-C8).C7-C8 merges after thin layer inspection is known, and merges component and separates through anti-phase high pressure preparative chromatography with methanol-water (60: 40), obtains Compound I (9.0mg).Cut D is through anti-phase MCI column chromatography, with methanol-water (30: 70-100: 0) gradient elution, obtains 6 components (D1-D6).D2-D3 merges after thin layer inspection is known, and merges component through 300～400 order silica gel column chromatographies, chloroform-sherwood oil (1: 1-1: 0) gradient elution, obtains Compound I I (7.8mg), compound III (5.5mg).D4-D5 merges after thin layer inspection is known, merge component through 300～400 order silica gel column chromatographies, chloroform-sherwood oil (1: 1-1: 0) gradient elution, obtain compound IV (8.0mg), the standby liquid phase of compacting in compound V (6.3mg) cut E warp, with methanol-water (40: 70-100: 0) gradient elution, obtains 4 components (E1-E4).E2 component separates through anti-phase high pressure preparative chromatography with methanol-water (68: 32), obtains compound VI (3.2mg).E3-E4 component separates through anti-phase high pressure preparative chromatography with methanol-water (60: 40), obtains compound VI I (6.2mg), VIII (6.8mg).
Compound I: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:485.2137[M+Na]
+(Calcd for:485.2151) infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
25h
34o
8.IR (KBr) cm
-1: 3468,1746,1780 infer that it exists hydroxyl and carbonyl.
1h-NMR (table 1) shows that it exists four angular methyl(group) proton signal: δ
h1.15,1.16,1.22,2.03; The methyl proton signal of two ethanoyl: δ
h2.09,2.19; Carboxymethyl proton signal a: δ
h3.66; Alkene hydrogen proton signal a: δ
h5.83 (d, J=2.4), in conjunction with
13four olefinic carbon signal δ that occur in C-NMR (table 4)
c127.0,130.4,136.4,149.9 and a carbonyl carbon signal δ
c197.2, infer that this compound skeleton is tricyclic antidepressants card mountain alkane type diterpene, Pulcherralpin is similar with compound
[1].Difference is the conjugated double bond of substituent difference and Compound I.
13c-NMR shows, has two oxygen containing methine carbon δ
c75.0 (C-1), 72.3 (C-6), the methyl carbon δ of two ethanoyl
c21.5,21.9 infer that C-1 and C-6 position respectively have an ethanoyl to replace.HMBC shows, δ
h5.82 (H-6, d, J=2.4) and δ
c127.0 136.4 is relevant; δ
h2.03 (H
3-17, s) and δ
c130.4,136.4,149.9 is relevant, infers that conjugated double bond is 7,8,13 and 14.HSQC shows, 3.36 (1H, d, J=16.8); 3.62 (1H, d, J=16.8) and methylene radical δ
c31.8 is relevant, points out this methylene radical to be connected with quaternary carbon; According to being correlated with in HMBC, infer that this methylene radical is connected with the carboxymethyl of 15 with the olefinic carbon of 13.Two dimension NOESY shows, δ
h4.85 (1-H, s); 5.82 (6-H, d, J=2.4) and δ
h1.16 (H
3-20, s) relevant, the ethanoyl of prompting C-1 and C-6 position is α.Comprehensive above information, can be by compound identification: 1 α, 6 α-diacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-7 (8), 13 (14)-diene.
Compound I I: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MSm/z:545.2390[M+Na]
+(Calcd for:545.2363), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
27h
38o
10.This compound
1h-NMR and
13c-NMR (table 1) is similar with Compound I, and difference is that Compound I I has three ethanoyl (δ
h2.02,2.07,2.08; δ
c21.4,21.7,21.9), two olefinic carbon (δ
c130.7,158.6).In conjunction with two-dimensional spectrum HSQC, HMBC finally determines that three ethanoyl are the substituting group of 1,6,7; Two olefinic carbons are C-13 and C-14 position.Compound I I is the product after Compound I hydrogenating reduction.Comprehensive above information, in conjunction with the NOESY spectrum of this compound, by the Structural Identification of this compound is: 1 α, 6 α, 7 β-triacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-13 (14)-diene.
Compound III: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:561.2648[M+Na]
+(Calcd for:561.2676), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
28h
42o
10.This compound
1h-NMR and
13c-NMR (table 1) and Compound I I are similar, in conjunction with the HSQC of this compound, and HMBC, known the two the difference of COSY is the CH (OCH of the C-16 position of compound III
3)
2substituting group has replaced the carboxymethyl of Compound I I.Therefore, by this compound called after: 1 α, 6 α, 7 β-triacetoxy-5 α-hydroxy-16,16-dimethoxy-12-oxocassa-13 (14)-diene.
Compound IV: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:375.1572[M+Na]
+(Calcd for:375.1588), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
22h
24o
4.This compound
1h-NMR (table 2) shows that it exists four angular methyl(group) proton signal: δ
h1.34,1.39,1.58,2.93; Two alkene hydrogen proton signal: δ
h6.53,7.41.
13c-NMR (table 2) shows that it exists ten olefinic carbon signal δ
c104.9,106.1,124.7,127.9,128.2,135.5,145.8,148.7,156.4,167.3.Thus, infer that this compound is the furan type card mountain alkyl compound that contains phenyl ring, similar with compound S ucutinirane C skeleton
[2].The difference of the two is that compound IV is than the many ethanoyl of Sucutinirane C, a pair of key and a ketone carbonyl.HSQC and HMBC two-dimensional spectrum show, δ
h(5.77 s, H-1), 1.67 (s ,-OCOCH
3) and δ
c170.4 all have relevant, infer 1 have one ethanoyl replace; δ
h6.53 with δ
c36.6 (C-4), 167.3,188.0 relevant deduction C-5, C-6 is two keys, C-7 is ketone carbonyl.Comprehensive above information is in conjunction with the two-dimentional NOESY spectrum of this compound, by this compound called after 1 α-acetoxy-7-oxo-14-methylvoucapane-5 (6), 8 (14), 9 (11)-diene.
Compound V: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:453.1907[M+Na]
+(Calcd for:453.1889), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
24h
30o
7.This compound
1h-NM and
13c-NMR (table 2) is extremely similar to compound S ucutinirane C, in conjunction with HSQC, HMBC, known the two the difference of COSY two-dimensional spectrum be compound more than 5 C-1 ethanoyl replace and the hydroxyl replacement of C-7.Therefore, by this compound called after: 1 α, 6 α-diacetoxy-5 α, 7 β-dihydroxyl-14-methylvoucapane-8 (14), 9 (11)-diene.
Compound VI: white powder (chloroform), is soluble in chloroform, methyl alcohol .HR-ESI-MS m/z:487.2325[M+Na]
+(Calcd for:487.2308), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
25h
36o
8.This compound
1h-NMR and
13c-NMR (table 2) is similar to compound N eocaesalpin AA
[3], known in conjunction with HSQC and HMBC, the difference of the two is that the C-14 position of compound VI is methyne, only has methyl substituted, does not have hydroxyl to replace.Therefore, be 1 α by the Structural Identification of this compound, 2 α-diacetoxy-5 α-hydroxyl-12 α-methoxy-14 α-methylcassa-13 (15)-eh-16,12-olide.
Compound VI I: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:443.2046[M+Na]
+(Calcd for:443.2030), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
23h
32o
7.This compound
1h-NMR and
13c-NMR (table 3) is similar with compound VI, in conjunction with the HSQC of this compound, HMBC, COSY by the Structural Identification of this compound is: 1 α-acetoxy-5 α, 7 β-dihydroxyl-12 α-methoxycassa-14 (17), 13 (15)-diene-16,12-olide.
Compound VI II: white powder (chloroform), is soluble in chloroform, methyl alcohol.HR-ESI-MS m/z:501.2101[M+Na]
+(Calcd for:501.2125), infers that in conjunction with hydrogen spectrum and carbon spectrum the molecular formula of this compound is C
25h
34o
9.This compound
1h-NMR and
13c-NMR and compound sucutinirane I are similar
[3], difference has been more than compound VI II two alkene hydrogen proton: δ
h(5.60 d, J=1.8), 5.40 (d, J=1.8) and two olefinic carbon signal: δ
c: 116.2,139.9, in conjunction with the 17-CH on HSQC and the known sucutinirane I of HMBC
3be oxidized into C-14 on compound VI II and two keys of 17.Therefore, by this compound called after: 1 α, 6 α-diacetoxy-5 α, 7 β-dihydroxyl-12 α-meth oxycassa-14 (17), 13 (15)-diene-16,12-olide.
Table1.NMR?data(600MHz，in?CDCl
3)for?compounds1-3
Table2.NMR?data(600MHz)for?compounds4-6.
aspectra?were?recorded?in?CDCl
3.
bspecral?were?recorded?in?MeOD.
Table3.NMR?data(600MHz?in?CDCl
3)for?compounds7-8.
Invention effect:
8 card mountain alkane type diterpene-kind compounds that the present invention relates to described in formula 1 treat and/or prevent the application in tumour medicine in preparation.Through experimental results show that the compounds of this invention has the effect of the tumour for the treatment of and/or preventing, the present invention has carried out the test of extracorporeal anti-tumor pharmacodynamic study, tests as follows:
Embodiment:
Listed embodiment contributes to those skilled in the art to understand better the present invention below, but does not limit the present invention in any way.
Embodiment 1
Cytotoxicity experiment:
Utilize MTT colorimetry, each compound is carried out to screening active ingredients.Choose after adenocarcinoma of stomach (ASG), lung cancer (A549), liver cancer (HepG-2), the dilution of mammary cancer (MCF-7) substratum, with 6 × 10
4the density of/ml is inoculated in 96 orifice plates, normal cultivation after 24 hours in the 100 μ l. incubators of every hole, dosing.Make the ultimate density of medicine be respectively 2.5 μ g/ml (1 group), 5 μ g/ml (2 groups), 10 μ g/ml (3 groups), 20 μ g/ml (four groups), 40 μ g/ml (5 groups).Establish altogether 5 concentration, 3 multiple holes of each concentration, and establish blank group.Cultivate after 48 hours, add MTT10 μ l dyeing in every hole.Continue to cultivate after four hours, inhale and abandon original fluid, every hole adds DMSO100 μ l, puts low-speed oscillation 10min on shaking table, and crystallisate is fully dissolved, and detects optical density value in enzyme-linked immunosorbent assay instrument 570nm wavelength place.
Reference
[1]Che?C?T，McPherson?D?D，Cordell?G?A，Fong?H?H.Pulcherralpin，a?new?diterpene?ester?from?Caesalpinia?pulcherrima[J].J.Nat.Prod.1986，49(4)：561-569.
[2]Matsuno?Y，Deguchi?J，Hosoya?T，Hirasawa?Y，Hirobe?C，Shiro?M，Morita?H.Sucutiniranes?C-F，CassaneType?Diterpenes?from?Bowdichia?nitida[J].J.Nat.Prod.2009，72(5)：976-979.
[3]Ma?G?X，Yuan?J?Q，Wu?H?F，Fang?K，Yang?J?S，MaL?Y，Xu?X?D.Novel?cassane?diterpenes?fromthe?seeds?of?Caesalpinia?mmax[J].Phytochemistry?Letters.2012，5(3)：617-620.
Accompanying drawing explanation:
The structure of Fig. 1: Compound I-VIII
Fig. 2: Compound I
1h-NMR spectrum
Fig. 3: Compound I
13c-APT spectrum
Fig. 4: Compound I I's
1h-NMR spectrum
Fig. 5: Compound I I's
13c-APT spectrum
Fig. 6: compound III
1h-NMR spectrum
Fig. 7: compound III
13c-APT spectrum
Fig. 8: compound IV
1h-NMR spectrum
Fig. 9: compound IV
13c-APT spectrum
Figure 10: compound V's
1h-NMR spectrum
Figure 11: compound V's
13c-APT spectrum
Figure 12: compound VI
1h-NMR spectrum
Figure 13: compound VI
13c-APT spectrum
Figure 14: compound VI I's
1h-NMR spectrum
Figure 15: compound VI I's
13c-APT spectrum
Figure 16: compound VI II's
1h-NMR spectrum
Figure 17: compound VI II's
13c-APT spectrum.
Claims (3)
1. have eight card mountain alkane type diterpene-kind compounds of anti-tumor activity, it is characterized in that it is to obtain by extracting in the seed Semen Caesalpiniae Minacis of leguminous plants beak pod mysorethorn to separate, chemical structural formula is:
According to 8 new card mountain alkane type diterpene-kind compounds claimed in claim 1, it is characterized in that:
Compound I is 1 α, 6 α-diacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-7 (8), and 13 (14)-diene, molecular formula is C
25h
34o
8, be white powder, Compound I is new compound.
Compound I I is 1 α, 6 α, and 7 β-triacetoxy-5 α-hydroxy-15-carboxymethyl-12-oxocassa-13 (14)-diene, molecular formula is C
27h
38o
10, be white powder, Compound I I is new compound.
Compound III is 1 α, 6 α, and 7 β-triacetoxy-5 α-hydroxy-16,16-dimethoxy-12-oxocassa-13 (14)-diene, molecular formula is C
28h
42o
10, be white powder, compound III is new compound.
Compound IV is 1 α-acetoxy-7-oxo-14-methylvoucapane-5 (6), 8 (14), and 9 (11)-diene, molecular formula is C
22h
24o
4, be colorless solid, compound IV is new compound.
Compound V is 1 α, 6 α-diacetoxy-5 α, and 7 β-dihydroxyl-14-methylvoucapane-8 (14), 9 (11)-diene, molecular formula is C
24h
30o
7, be colorless solid, compound V is new compound.
Compound VI is 1 α, 2 α-diacetoxy-5 α-hydroxyl-12 α-methoxy-14 α-methylcassa-13 (15)-en-16, and 12-olide, molecular formula is C
25h
36o
8, be colorless solid, compound VI is new compound.
Compound VI I is 1 α-acetoxy-5 α, 7 β-dihydroxyl-12 α-methoxycassa-14 (17), and 13 (15)-diene-16,12-olide, molecular formula is C
23h
32o
7, be colorless solid, compound VI I is new compound.
Compound VI II is 1 α, 6 α-diacetoxy-5 α, and 7 β-dihydroxyl-12 α-methoxycassa-14 (17), 13 (15)-diene-16,12-olide, molecular formula is C
25h
34o
9, be colorless solid, compound VI II is new compound.
2. eight Compound I-VIII claimed in claim 1 prove to have remarkable anti-tumor activity through tumour pharmacodynamic experiment, the results are shown in following table:
3. the preparation method of 8 card mountain alkane type diterpene claimed in claim 1 (Compound I-VIII), comprises the following steps:
The seed Semen Caesalpiniae Minacis 8.0kg of beak pod mysorethorn is adopted to obtain in Nanning, is accredited as [Caesalpinia minax Hance] by the Yuan Jingquan researcher of Medicinal Plants of Guangxi institute.After Semen Caesalpiniae Minacis 8.0kg pulverizes, methyl alcohol heating and refluxing extraction secondary, each two hours, united extraction liquid, decompression and solvent recovery, obtains total medicinal extract 2020g after concentrating.After the total medicinal extract of Semen Caesalpiniae Minacis dissolves with chloroform-methanol, with 100～200 object silica gel mixed samples, use successively sherwood oil, chloroform, ethyl acetate, acetone, methanol-eluted fractions, elutriant concentrating under reduced pressure, finally obtain sherwood oil part 130g, chloroform part 325g, ethyl acetate part 160g, partial acetone 305g, methyl alcohol part 1100g.(extracting flow process sees shown in accompanying drawing 5).Get chloroform part through silica gel column chromatography, with petroleum ether-ethyl acetate eluent 1: 0-1: 1 gradient elution, obtain 12 cuts (Fr.A-L), therefrom choose cut C (15.4g), cut D (8.9g), cut E (6.8g), through LH20 gel filtration chromatography, removes pigment with 40: 60 wash-outs of chloroform-methanol.Cut C is through anti-phase MCI column chromatography, with methanol-water (30: 70-100: 0) gradient elution, obtains 8 components (C1-C8).C7-C8 merges after thin layer inspection is known, and merges component and separates through anti-phase high pressure preparative chromatography with methanol-water (60: 40), obtains Compound I (9.0mg).Cut D is through anti-phase MCI column chromatography, with methanol-water (30: 70-100: 0) gradient elution, obtains 6 components (D1-D6).D2-D3 merges after thin layer inspection is known, and merges component through 300～400 order silica gel column chromatographies, chloroform-sherwood oil (1: 1-1: 0) gradient elution, obtains Compound I I (7.8mg), compound III (5.5mg).D4-D5 merges after thin layer inspection is known, merge component through 300～400 order silica gel column chromatographies, chloroform-sherwood oil (1: 1-1: 0) gradient elution, obtain compound IV (8.0mg), the standby liquid phase of compacting in compound V (6.3mg) cut E warp, with methanol-water (40: 70-100: 0) gradient elution, obtains 4 components (E1-E4).E2 component separates through anti-phase high pressure preparative chromatography with methanol-water (68: 32), obtains compound VI (3.2mg).E3-E4 component separates through anti-phase high pressure preparative chromatography with methanol-water (60: 40), obtains compound VI I (6.2mg), VIII (6.8mg).
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| CN103910633A true CN103910633A (en) | 2014-07-09 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045819A (en) * | 2016-06-29 | 2016-10-26 | 吉首大学 | Mysorethorn tricyclic diterpene, and preparation method and application thereof |
| CN106045951A (en) * | 2016-06-29 | 2016-10-26 | 吉首大学 | Mysorethorn lactone, and preparation method and application thereof |
| CN106810563A (en) * | 2017-01-13 | 2017-06-09 | 中国科学院昆明植物研究所 | Furans card mountain alkane forskolin and its pharmaceutical composition and its application in pharmacy |
-
2013
- 2013-01-08 CN CN201310005537.2A patent/CN103910633A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045819A (en) * | 2016-06-29 | 2016-10-26 | 吉首大学 | Mysorethorn tricyclic diterpene, and preparation method and application thereof |
| CN106045951A (en) * | 2016-06-29 | 2016-10-26 | 吉首大学 | Mysorethorn lactone, and preparation method and application thereof |
| CN106045951B (en) * | 2016-06-29 | 2018-03-02 | 吉首大学 | A kind of mysorethorn lactone and its preparation method and purposes |
| CN106045819B (en) * | 2016-06-29 | 2018-03-30 | 吉首大学 | A kind of mysorethorn tricyclic diterpene and its preparation method and purposes |
| CN106810563A (en) * | 2017-01-13 | 2017-06-09 | 中国科学院昆明植物研究所 | Furans card mountain alkane forskolin and its pharmaceutical composition and its application in pharmacy |
| CN106810563B (en) * | 2017-01-13 | 2019-07-26 | 中国科学院昆明植物研究所 | Furans card mountain alkane forskolin and its pharmaceutical composition and its application in pharmacy |
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Application publication date: 20140709 |