CN1261436C - Bibenzil compound 13,13'-O-iso-propylidene riccardia D and its extraction and separation method and use - Google Patents

Bibenzil compound 13,13'-O-iso-propylidene riccardia D and its extraction and separation method and use Download PDF

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CN1261436C
CN1261436C CN 200410036044 CN200410036044A CN1261436C CN 1261436 C CN1261436 C CN 1261436C CN 200410036044 CN200410036044 CN 200410036044 CN 200410036044 A CN200410036044 A CN 200410036044A CN 1261436 C CN1261436 C CN 1261436C
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ether
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sherwood oil
acetone
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CN1634923A (en
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娄红祥
牛冲
范培红
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Shandong University
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Abstract

The present invention relates to a compound of 13'-O-isopropylidene substrate Jungermanniaceae D in a general formula (I). The present invention also relates to the extraction and separation method of the compound and the application of the compound in preparing antifungal medications. The compound exploits a new path for developing and applying antifungal medications with natural sources in a new generation.

Description

Bibenzyl compound 13,13 '-O-isopropylidene jungermanniaceae D and extraction and separation method thereof and application
Technical field
The present invention relates to a kind of bibenzyl compound and extraction and separation method and application, relate in particular to a kind of bibenzyl compound 13,13 '-O-isopropylidene jungermanniaceae D (13,13 '-O-isoproylidenericcardin) and by the method for extraction separation in the Hepaticae marchantia marchantia and its application in the preparation antifungal drug.
Background technology
The bibenzyl compound is more common in the bryophyte, structurally with C 6-C 2-C 6Parent nucleus and dimer thereof exist, and are divided into different types of structure with mode of connection difference between the phenyl ring, name according to plant origin usually; Because of the difference of benzene ring substitution group produces numerous compounds, name successively according to affiliated structure type, as the plain B-H of marchantia, J-L, jungermanniaceae C, (Susanne F. such as different jungermanniaceae C, Ulrich HM., Brigirle DN., et al Biosynthesis ofCyclic Bisbibenzyls in Marchantia polymorpha.Phytochemistry, 2001,50 (4): 589-598.).For extremely, from liverwort, obtain more than 80 of bibenzyl compounds up till now, still, do not seen the relevant report that on the bibenzyl structure, has isopropylidene to replace.
At present, because the antifungal compound of natural origin is less, people are at developing new drug and utilize natural matter to extract and done many work aspect the new drug, attempt to find to have stronger antifungic action, overcome that synthesising bacteria anti-reflecting medicine is chemical sproof, the novel cpd of novel structure, yet, in many reports of retrieval, yet there are no about 13 13 '-O-isopropylidene jungermanniaceae D (report of 13,13 '-O-isoproylidenericcardin).
Summary of the invention
At the deficiencies in the prior art, the problem to be solved in the present invention provides a kind of bibenzyl compound 13,13 '-O-isopropylidene jungermanniaceae D (13,13 '-O-isoproylidenericcardin) and by the method for extraction separation in the Hepaticae marchantia marchantia and its application in the preparation antifungal drug.
Compound of the present invention is represented with following general formula (I):
Compound called after 13 of the present invention, (13,13 '-O-isoproylidenericcardin), molecular formula is C to 13 '-O-isopropylidene jungermanniaceae D 31H 28O 4, molecular weight is 464; Fusing point is 235～237 ℃; Be colourless needle crystal; Silica gel thin-layer chromatography shows Rf=0.65～0.85, and spray iron trichloride-Tripotassium iron hexacyanide developer shows blue; HREI-MS:[M] +464.1985, calculated value 464.1687; EI-MS (Rel.Int): 464 (100), 449 (5), 421 (2), 265 (2), 251 (37), 239 (3), 213 (40), 211 (26), 195 (7), 181 (3), 165 (6), 152 (2), 107 (13), 105 (5), 91 (7), 77 (4); 1There are two in the HNMR high field region and are unimodal methyl signals, exists HMBC relevant with the quaternary carbon signal of 110～115ppm, is the feature of isopropylidene.The signal distributions of all the other 28 carbon atoms on carbon spectrum is 24 in δ 110-δ 160 districts, and 4 in δ 36-δ 39 districts present the characteristic feature of duplex benzyl compounds.
The preparation method of compound Plagiochin E of the present invention, this method may further comprise the steps:
(1) preparation ether total extract: dried marchantia (Marchantia polymorpa L.) is pulverized, added the ether of 5～10 times of marchantia volumes, under 20 ℃～35 ℃ conditions, soaked 4～7 days, normal pressure filters, collect ether extracted liquid I, repeat united extraction liquid I 3～6 times; With the dregs of a decoction after extracting with the methyl alcohol of its 2～4 times of amounts under 20 ℃～35 ℃ conditions, soak 3～5 times, each 2～3 days, normal pressure filtered, and collected methanol extract liquid, merge, 50 ℃～70 ℃ of Rotary Evaporators, under the vacuum tightness 0.09Mpa condition, concentrating under reduced pressure gets methyl alcohol medicinal extract, with the extracted with diethyl ether medicinal extract that is equivalent to 2～5 times of amounts of medicinal extract 2～4 times, collect, merge ether extraction liquid II; Above-mentioned I, II two portions ether solution are merged, be distilled to fluid extract, volatilize naturally, get the ether total extract in 50 ℃～70 ℃ conditions;
(2) separate: 200～300 purpose silica gel mixed samples of above-mentioned ether total extract with its 1～3 times of amount, carry out silica gel column chromatography (200～300 orders, 6 * 15cm), with sherwood oil-acetone system ratio gradient elution (100% sherwood oil～50% sherwood oil) routinely, at sherwood oil: acetone is that 90～98: 2～10 wash-outs part detects with silica gel thin-layer chromatography, and wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution, merges to collect Rf=0.65～0.85 same stream part, is concentrated into into medicinal extract with ordinary method;
(3) purifying.With above-mentioned medicinal extract carry out Sephadex LH-20 (3 * 50cm) chromatographies, with chloroform: the eluant solution of methyl alcohol=1: 1, elutriant detects with silica gel thin-layer chromatography, wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution, merge to collect Rf=0.65～0.85 same stream part, concentrates with ordinary method and separates out crystallization, and is dry 13,13 '-O-isopropylidene jungermanniaceae D.
Wherein, above-mentioned iron trichloride-potassium ferricyanide solution is 1% iron trichloride and 2% potassium ferricyanide solution equal-volume mixing solutions.
Wherein, the described sherwood oil of step (2): acetone is preferably 95: 5.
Compound 13 of the present invention, the application of 13 '-O-isopropylidene jungermanniaceae D in the preparation antibacterials especially relates to the application in the preparation antifungal drug.
Adopt compound 13 of the present invention, 13 '-O-isopropylidene jungermanniaceae D carries out antibacterial activity test and shows: this compound has stronger antifungic action, and because its novel structure has the applications well prospect in natural new drug development.
Utilization the present invention relates to 13,13 '-O-isopropylidene jungermanniaceae D adopts TLC (thin-layer chromatography) bioautography to carry out the anti-microbial activity test: under the aseptic condition, with getting collarium Candida albicans (Candida allbicans) is inoculated in conventional broth agar culture medium (peptone, sodium-chlor, extractum carnis, nutrient agar medium), constant temperature culture is to test concentrations (about 107CFU/mL).Sample TLC method is launched, treat that solvent on the thin layer plate volatilizes fully after, the ultraviolet sterilization spreads upon bacteria culture fluid on the thin plate uniformly, constant temperature culture is observed its antibacterial spot.After 5 minutes, observe its antibacterial spot with the colour developing of MTT (tetrazolium salts) solution.The result shows 13, and 13 '-O-isopropylidene jungermanniaceae D shows strong anti-microbial activity.
Compound of the present invention is the compound that new rare bibenzyl connects isopropylidene, utilize of the present invention from the marchantia plant extraction separation compound 13, the method of 13 '-O-isopropylidene jungermanniaceae D, the extraction productive rate is higher, the compound purity that obtains reaches more than 98%, antibacterial activity test shows that this compound has stronger antifungic action, though it is active not as good as the synthetic antibacterial drug miconazole nitrate, but the antifungal compound of natural origin is more rare, cause that drug-fast possibility is less, under present synthesising bacteria anti-reflecting medicine resistance serious environmental, adopt compound 13 of the present invention, 13 '-O-isopropylidene jungermanniaceae D has excellent development, utilize and development prospect, also provide lead compound to open up a new approach simultaneously for researching and developing new antibacterials.
Description of drawings
Fig. 1 13,13 '-O-isopropylidene jungermanniaceae D 1The HNMR spectrogram
Fig. 2 13,13 '-O-isopropylidene jungermanniaceae D 13The CNMR spectrogram
Fig. 3 13,13 '-O-isopropylidene jungermanniaceae D 1H- 1The HCOSY spectrogram
Fig. 4 13, the HMBC spectrogram of 13 '-O-isopropylidene jungermanniaceae D
Fig. 5 13, the HMQC collection of illustrative plates of 13 '-O-isopropylidene jungermanniaceae D
Fig. 6 13, the EI-MS spectrogram of 13 '-O-isopropylidene jungermanniaceae D
Fig. 7 TLC bioautography is carried out anti-microbial activity test minimal inhibitory concentration (MID) test-results:
Wherein: A figure is a miconazole nitrate, antibacterial spot occurs since the 3rd point, shows that MID is 0.01 μ g;
B figure is 13, and 13 '-O-isopropylidene jungermanniaceae D antibacterial spot occurs since the 3rd point, shows that MID is 0.4 μ g.
Embodiment
Embodiment 1:
To pick up from the geographic marchantia of Mt.E'mei, Sichuan Province height above sea level 1000-1500 rice (Marchantia polymorpa L.) dry in the shade naturally pulverize 8.95Kg, ether with 8 times of marchantia volumes soaked 5 days for 28 ℃, and normal pressure filters, and collects ether extracted liquid I, repeat united extraction liquid I 4 times.The dregs of a decoction after extracting are for the last time soaked 4 times for 28 ℃ with 3 times of amount methyl alcohol, each 3 days, normal pressure filtered, and collected methanol extract liquid, merge, 60 ℃ of Rotary Evaporators, decompression (vacuum tightness 0.09Mpa) concentrate methyl alcohol medicinal extract, with the extracted with diethyl ether medicinal extract that is equivalent to 3 times of amounts of medicinal extract 3 times, collect, merge ether extraction liquid II, I, II two portions ether solution are merged the back be distilled to fluid extract, volatilize naturally, get the ether total extract in 60 ℃ of conditions.With 200～300 purpose silica gel mixed samples of above-mentioned ether total extract with its 2 times of amounts, carry out silica gel column chromatography (Qingdao Haiyang Chemical Manufacture 200～300 orders, 6 * 15cm), sherwood oil-acetone system convention ratio gradient elution (100% sherwood oil～50% sherwood oil), partly use silica gel thin-layer chromatography (developping agent, sherwood oil: acetone=6: 4 at sherwood oil-acetone (95: 5) wash-out; Developer, iron trichloride-potassium ferricyanide solution) detect, merge and collect Rf=0.65～0.85 same stream part, be concentrated into into medicinal extract with ordinary method.With gained medicinal extract carry out Sephadex LH-20 (3 * 50cm) chromatographies, with chloroform: the eluant solution of methyl alcohol=1: 1, elutriant detects with silica gel thin-layer chromatography, wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution (described iron trichloride-potassium ferricyanide solution is 1% iron trichloride and 2% potassium ferricyanide solution equal-volume mixing solutions), merge and collect Rf=0.65～0.85 same stream part, concentrate with ordinary method and to separate out crystallization, dry 13,13 '-O-isopropylidene jungermanniaceae D 5.9mg.
This compound is colourless needle crystal, and mp:235.8-236.3 ℃, (sherwood oil: Rf=0.77 acetone=6: 4), iron trichloride-potassium ferricyanide solution show blue to TLC.
HREI-MS:[M] +464.1985, calculated value 464.1987, molecular formula is C 31H 28O 4 1There are two in the HNMR high field region and are unimodal methyl signals, exists HMBC relevant with the quaternary carbon signal of 110～115ppm, is the feature of isopropylidene.The signal distributions of all the other 28 carbon atoms on carbon spectrum is 24 in δ 110-δ 160 districts, and 4 in δ 36-δ 39 districts present the characteristic feature of duplex benzyl compounds.
1What HNMR demonstrated that 13 fragrant hydrogen signals possess fragrant hydrogen on four kinds of different substituted benzene rings splits branch feature (formula A～D structure fragment as follows), and the coupled relation of saturation region proton signal shows two groups of adjacent methylene radical features (formula E-F as follows).
δ 33.76 and δ 7.31 remote couplings among the HMBC, δ 37.49 and δ 6.72 and δ 5.14 have coupling, δ 37.96 and δ 6.88 and δ 6.11 remote couplings.Thereby can be with A in the following formula and D, B is connected by the methylene radical that links to each other respectively with C.
There is remote couplings in δ 7.10 with δ 113 among the HMBC, and δ 1.58 and δ 1.55 have remote couplings with δ 151.1 and δ 151.4 respectively, finally draws following formula one-piece construction G.
EI-MS (Rel.Int): 464 (100), 449 (5), 421 (2), 265 (2), 251 (37), 239 (3), 213 (40), 211 (26), 195 (7), 181 (3), 165 (6), 152 (2), 107 (13), 105 (5), 91 (7), 77 (4) can both obtain proper explanations, and its possible lytic pathway is shown below.
Figure C20041003604400071
Through consulting document, the parent nucleus of this compound is the plain D of sheet page or leaf tongue, pertinent literatures such as retrieval CA, do not find this compound, determine that this compound is a new compound, called after 13,13 '-O-isopropylidene jungermanniaceae D (13,13 '-O-isoproylidenericcardin D).
The compounds of this invention 13, the MS that 13 '-O-isopropylidene jungermanniaceae D relates in identifying, 1HNMR, 13CNMR, 1H- 1HCOSY, HMBC, HMQC collection of illustrative plates are seen accompanying drawing 1-6.
1The H-NMR data see Table 1, 13The C-NMR data see Table 2.
Table 1 13, the plain D's of 13 '-O-isopropylidene substrate page or leaf tongue 1H (CDCl 3, 600MHz)
Sequence number 1H(ppm) Sequence number 1H(ppm)
2 3 5 6 6.78(m) 6.96(m) 6.54(m) 6.56(m) 2′ 3′ 5′ 6′ 5.14(d，J＝1.80Hz) 6.71(dd，J＝8.0，1.8Hz) 6.90(d，J＝8.0Hz)
7 8 10 11 12 R-CH 3 R-CH 3 2.72(m)，2.97(m)， 3.18(m) 7.31(dd，J＝7.8，1.5Hz) 7.34(d，J＝7.8Hz) 6.96(dd，J＝7.8，1.5Hz) 1.45(3H，s) 1.58(3H，s) 7′ 8′ 10′ 11′ 14′ 2.92(m)，2.49(m) 3.01(m)，2.41(m) 6.88(dd，J＝7.9，1.8Hz) 7.10(d，J＝7.9Hz) 6.11(d，J＝7.80Hz)
Table 2 13, the plain D's of 13 '-O-isopropylidene substrate page or leaf tongue 13C-NMR data (CDCl 3, 150MHz)
Figure C20041003604400081
Embodiment 2:
To pick up from the geographic marchantia of Mt.E'mei, Sichuan Province height above sea level 1000-1500 rice (Marchantia polymorpa L.) dry in the shade naturally pulverize 9.50Kg, ether with 5 times of marchantia volumes soaked 4 days for 23 ℃, and normal pressure filters, and collects ether extracted liquid I, repeat united extraction liquid I 6 times; The dregs of a decoction after extracting are for the last time soaked 5 times for 35 ℃ with 2 times of amount methyl alcohol, each 2 days, normal pressure filtered, and collected methanol extract liquid, merge, 70 ℃ of Rotary Evaporators, decompression (vacuum tightness 0.09Mpa) concentrate methyl alcohol medicinal extract, with the extracted with diethyl ether medicinal extract that is equivalent to 2 times of amounts of medicinal extract 4 times, collect, merge ether extraction liquid II, I, II two portions ether solution are merged the back be distilled to fluid extract, volatilize naturally, get the ether total extract in 70 ℃ of conditions.With the 200 purpose silica gel mixed samples of above-mentioned ether total extract with its 1 times of amount, with silica gel column chromatography (200 orders, 6 * 15cm) sherwood oils-acetone system convention ratio gradient elution (100% sherwood oil～50% sherwood oil), partly use silica gel thin-layer chromatography (developping agent, sherwood oil: acetone=6: 4 at sherwood oil-acetone (98: 2) wash-out; Developer, iron trichloride-potassium ferricyanide solution) detect, merge and collect Rf=0.65～0.85 same stream part, be concentrated into into medicinal extract with ordinary method.Gained medicinal extract is carried out Sephadex LH-20, and (elutriant detects with silica gel thin-layer chromatography for 3 * 50cm) chromatographies, chloroform-methanol (1: 1) wash-out, and wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution (described iron trichloride-potassium ferricyanide solution is 1% iron trichloride and 2% potassium ferricyanide solution equal-volume mixing solutions), merge and collect Rf=0.65～0.85 same stream part, concentrate with ordinary method and to separate out crystallization, dry 13,13 '-O-isopropylidene jungermanniaceae D 6.2mg.
Embodiment 3:
With the marchantia of adopting (Marchantia polymorpa L.) dry in the shade naturally pulverize 8.25Kg, soaked 7 days for 35 ℃ with the ether of 10 times of marchantia volumes, normal pressure filters, and collects ether extracted liquid I, repeats united extraction liquid I 3 times.The dregs of a decoction after extracting are for the last time measured the methyl alcohol soaking at room temperature 3 times with 4 times, each 2 days, normal pressure filtered, and collected methanol extract liquid, merge, 50 ℃ of Rotary Evaporators, decompression (vacuum tightness 0.09Mpa) concentrate methyl alcohol medicinal extract, with the extracted with diethyl ether medicinal extract that is equivalent to 5 times of amounts of medicinal extract 2 times, collect, merge ether extraction liquid II, I, II two portions ether solution are merged the back be distilled to fluid extract, volatilize naturally, get the ether total extract in 50 ℃ of conditions.With the 300 purpose silica gel mixed samples of above-mentioned ether total extract with its 3 times of amounts, with silica gel column chromatography (300 orders, 6 * 15cm) sherwood oils-acetone system convention ratio gradient elution (100% sherwood oil～50% sherwood oil), partly use silica gel thin-layer chromatography (developping agent, sherwood oil: acetone=6: 4 at sherwood oil-acetone (90: 10) wash-out; Developer, iron trichloride-potassium ferricyanide solution) detect, merge and collect Rf=0.65～0.85 same stream part, be concentrated into into medicinal extract with ordinary method.Gained medicinal extract is carried out Sephadex LH-20, and (elutriant detects with silica gel thin-layer chromatography for 3 * 50cm) chromatographies, chloroform-methanol (1: 1) wash-out, and wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution (described iron trichloride-potassium ferricyanide solution is 1% iron trichloride and 2% potassium ferricyanide solution equal-volume mixing solutions), merge and collect Rf=0.65～0.85 same stream part, concentrate with ordinary method and to separate out crystallization, dry 13,13 '-O-isopropylidene jungermanniaceae D 5.4mg.
Embodiment 4:
Under the aseptic condition, with getting collarium Candida albicans (Candida allbicans) is inoculated in broth agar culture medium (peptone, sodium-chlor, extractum carnis, nutrient agar medium), in 30 ℃ of 1 weeks of constant temperature culture, bacteria concentration reaches 107CFU/mL.With 13, the preparation of 13 '-O-isopropylidene jungermanniaceae D is as the serial gradient concentration of table 3, with miconazole nitrate (table 4) product in contrast, sample through TLC launch (sherwood oil: acetone=6: 4), treat that solvent on the thin plate volatilizes fully after, ultraviolet sterilization 30 minutes, bacteria culture fluid is spread upon on the thin plate uniformly, and 30 ℃ of constant temperature culture 36 hours are with the MTT solution colour developing of 2.5mg/mL, after 5 minutes, observe its antibacterial spot.
Experimental result: 13, the MID of 13 '-O-isopropylidene jungermanniaceae D anti-candida albicans is 0.4 μ g, the MID of positive control miconazole nitrate is 0.01 μ g (seeing accompanying drawing 7).
Table 3 13,13 '-O-isopropylidene jungermanniaceae D point sample amount
F 1 F 2 F 3 F 4 F 5 F 6
C (μ g/ μ l) point sample amount (μ g) 0.05 0.1 0.1 0.2 0.2 0.4 0.3 0.6 0.4 0.8 0.5 1
Table 4 miconazole nitrate point sample amount
A 1 A 2 A 3 A 4 A 5 A 6
C (μ g/ μ l) point sample amount (μ g) 0.0025 0.005 0.00375 0.0075 0.005 0.01 0.00625 0.0125 0.0125 0.025 0.025 0.05

Claims (6)

1. the compound of following general formula (I):
2. the preparation method of the described compound of claim 1, this method may further comprise the steps:
(1) preparation ether total extract: dried marchantia (Marchantia polymorpa L.) is pulverized, added the ether of 5～10 times of marchantia volumes, under 20 ℃～35 ℃ conditions, soaked 4～7 days, normal pressure filters, collect ether extracted liquid I, repeat united extraction liquid I 3～6 times; With the dregs of a decoction after extracting with the methyl alcohol of its 2～4 times of amounts under 20 ℃～35 ℃ conditions, soak 3～5 times, each 2～3 days, normal pressure filtered, and collected methanol extract liquid, merge, 50 ℃～70 ℃ of Rotary Evaporators, under the vacuum tightness 0.09Mpa condition, concentrating under reduced pressure gets methyl alcohol medicinal extract, with the extracted with diethyl ether medicinal extract that is equivalent to 2～5 times of amounts of medicinal extract 2～4 times, collect, merge ether extraction liquid II; Above-mentioned I, II two portions ether solution are merged, be distilled to fluid extract, volatilize naturally, get the ether total extract in 50 ℃～70 ℃ conditions;
(2) separate: 200～300 purpose silica gel mixed samples of above-mentioned ether total extract with its 1～3 times of amount, carry out silica gel column chromatography, with sherwood oil-acetone system ratio gradient elution routinely, at sherwood oil: acetone is that 90～98: 2～10 wash-outs part detects with silica gel thin-layer chromatography, and wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution, merges to collect Rf=0.65～0.85 same stream part, is concentrated into into medicinal extract with ordinary method;
(3) purifying: above-mentioned medicinal extract is carried out Sephadex LH-20 chromatography, with chloroform: the eluant solution of methyl alcohol=1: 1, elutriant detects with silica gel thin-layer chromatography, and wherein developping agent is a sherwood oil: acetone=6: 4; Developer is iron trichloride-potassium ferricyanide solution, merge to collect Rf=0.65～0.85 same stream part, concentrates with ordinary method and separates out crystallization, and is dry 13,13 '-0-isopropylidene jungermanniaceae D.
3. the preparation method of compound as claimed in claim 2 is characterized in that, described iron trichloride-potassium ferricyanide solution is 1% iron trichloride and 2% potassium ferricyanide solution equal-volume mixing solutions.
4. the preparation method of compound as claimed in claim 2 is characterized in that, the described sherwood oil of step (2): acetone is 95: 5.
5. the application of the described compound of claim 1 in the preparation antibacterials.
6. application as claimed in claim 5, antibacterials wherein are antifungal drug.
CN 200410036044 2004-10-29 2004-10-29 Bibenzil compound 13,13'-O-iso-propylidene riccardia D and its extraction and separation method and use Expired - Fee Related CN1261436C (en)

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