CN105439843B - A kind of noval chemical compound and its preparation method and application - Google Patents
A kind of noval chemical compound and its preparation method and application Download PDFInfo
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- CN105439843B CN105439843B CN201510875204.4A CN201510875204A CN105439843B CN 105439843 B CN105439843 B CN 105439843B CN 201510875204 A CN201510875204 A CN 201510875204A CN 105439843 B CN105439843 B CN 105439843B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The invention discloses a kind of noval chemical compound, the compound be colorless oil, molecular formula C10H12O4, degree of unsaturation 5, structural formula such as formula is
Description
Technical field
The invention belongs to organic compound technical fields, and in particular to a kind of noval chemical compound and its preparation method and application.
Background technology
Tibet Paeonia ludlowii (Paeonia ludlowii) be Ranunculaceae (Ranunculacea), Paeonia
(Paeonia), Section Moutan (Sect.Moutan DC.) plant.Only be grown in the Milin in China Tibet, Linzhi, Bomi, Chayu,
In the open river valley in the Yarlung Zangbo River of the 2500~3500m of height above sea level in the counties such as Longzi and hillside border shrubbery, quantity is few, and in by
Year reduces trend, belongs to the distinctive endangered protection plant in Tibet.It is recorded according to local local chronicle, Tibetan are before the centuries
Tibet Paeonia ludlowii root skin treatment gynecological disease, cardiovascular and cerebrovascular disease, dermatophytosis etc. are just used.
At present, there is correlative study to the medicinal effects of Paeonia ludlowii root skin, but due in Paeonia ludlowii root skin
Chemical composition is varied, yet there are no relevant report for the research of its active ingredient, applicant utilizes normal phase silicagel column color
The technologies such as spectrum, reverse phase (MCI-Gel) column chromatography, gel (Sephadex LH-20) column chromatography, high performance liquid chromatography are yellow to great Hua
The ethyl acetate extraction components of moutan root bark are separated, purified, and obtain monomeric compound 23, by ultraviolet spectra, infrared
Spectrum, mass spectrum, nuclear magnetic resoance spectrum simultaneously determine its structure with reference to document report, including monoterpenes compound 7, monoterpene glycosides
Compound 3, phenolic compound 8, phenol glycosides compound 3, alkaloid compound 1, triterpene compound 1,
Middle noval chemical compound 4, it is known that compound 19, it is isolated from the Paeonia ludlowii of Tibet for the first time.
The content of the invention
For the present invention by the further investigation to Paeonia ludlowii root skin, provide a kind of has similar structure to Paeonol
Noval chemical compound and its preparation method.
The present invention is realized especially by following technical scheme：
A kind of noval chemical compound, structural formula is shown in formula I：
Compound described in Formulas I is colorless oil, is composed ([M-H] by ESI-MS-M/z 195) and HR-ESI-MS spectrums ([M-
H]-m/z,195.0655calcd for C10H11O4, 195.0663), determine the molecular formula C of the compound10H12O4, insatiable hunger
It is 5 with degree.IR spectrums (KBr tablettings) give hydroxyl (3419cm-1), carbonyl (1671cm-1) and aromatic rings (1592,1516,
1464,1428cm-1) signal.Ultraviolet spectra shows the ultraviolet absorption maximum of the compound in 203nm.
The preparation method of the compound of formula I, specifically includes following steps：
1) after dry Tibet Paeonia ludlowii root skin is taken to crush, 95% ethyl alcohol is added in, room temperature extracts for 24 hours, repeats to filter,
50 DEG C are concentrated under reduced pressure, and using ethyl acetate into extraction, extract liquor under the conditions of 50 DEG C are concentrated under reduced pressure, obtains dry powder A；
2) by dry powder A and polyamide in mass ratio 1:4~5 ratio mixing, utilizes the methanol-water that volumetric concentration is 20%
Solution affords component B；
3) it is 10 with petroleum ether and ethyl acetate volume ratio by component B silica gel mixed samples:1 mixed liquor elution, obtains group
Divide C；
4) component C is subjected to silica gel column chromatography, is 6 with petroleum ether and acetone volume ratio:1 mixed liquor elution, obtains group
Divide D；
5) component D is continued into gel column chromatography, is eluted with methanol, isolate and purify to obtain Formulas I monomeric compound.
The mass volume ratio of root skin and 95% ethyl alcohol is 1 in preparation method step (1) of the present invention:10.
Dry powder A and polyamide preferably in mass ratio 1 in preparation method step (2) of the present invention:4.2 ratio mixing.
The present invention also provides application of the compound of formula I as antifungal drug.
The drug can be processed into any pharmaceutically acceptable dosage form on demand, wherein more preferably dosage form is piece
Agent, capsule, granule, syrup, freeze drying powder injection or parenteral solution.It is prepared can be public by common those skilled in the art institute
Prepared by the processing method known, i.e., after active material compound of formula I is mixed with liquid flux or solid carrier, add filling
Agent, adhesive, wetting agent, disintegrant, sorbefacient, solvent, surfactant, flavouring agent, preservative, lubricant, sweet taste
One or more of agent or pigment.
Drug of the present invention can be used through dilution or directly before use by user.
Beneficial effects of the present invention are：The present invention extracts from the Paeonia ludlowii root skin of Tibet and isolates a kind of new chemical combination
Object, the extraction is easy, quick with separation method, efficient.The compound has antimycotic active function simultaneously, compared to Tibet
The pharmacological action of Paeonia ludlowii root skin more precisely, solves complex chemical composition in the Paeonia ludlowii root skin of Tibet, and quality is difficult to
The problem of control.
Specific embodiment
With reference to embodiment, the present invention is described further, as described below, is only the preferable implementation to the present invention
Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents be changed to the equivalent embodiment changed on an equal basis.It is every without departing from the present invention program content, according to the present invention
Any simple modification for being made to following embodiment of technical spirit or equivalent variations, all fall in protection scope of the present invention.
Embodiment 1
Dry Tibet Paeonia ludlowii root skin is taken, 10kg is accurately weighed after crushing, according to root skin and solvent 1:10(W/V)
Ratio add in 95% ethyl alcohol, room temperature is extracted for 24 hours, filtered, and in triplicate, 50 DEG C are concentrated under reduced pressure, and then use total extract
Ethyl acetate extracts, and extract liquor is concentrated under reduced pressure under the conditions of 50 DEG C, obtains the component dry powder A of 356g.
Dry powder A is weighed into 356g and mixes sample with 1.5kg polyamide, carries out medium pressure liquid chromatography, reverse phase column material is
MCI-Gel affords 51g component B using the methanol aqueous solution that volumetric concentration is 20%, with silica gel mixed sample, and carries out silica gel
Column chromatography, with volume ratio 10:After 1 petrol ether/ethyl acetate mixed liquor elution, repeat silica gel column chromatography, utilize volume
Than 6:1 petroleum ether/acetone mixture elution, continues gel column chromatography, methanol is isolated and purified as eluant, eluent after merging
To Formulas I monomeric compound 4mg.
2 monomeric compound Structural Identification of embodiment
1) wave spectrum is tested
Isolated compound, liquid chromatogram progress purity detecting, if without UV absorption, analyzes liquid phase color by analysis
Spectrum can not detect, and carry out TLC detections.And corresponding deuterated solvent is chosen according to monomeric compound polarity and is dissolved, it is examined using NMR
It surveys, tetramethylsilane (TMS) is used as internal standard.Noval chemical compound needs KBr tablettings to carry out function contained in IR authenticating compound structures
Group's species；Meanwhile appropriate compound is taken, UV detections are carried out with the dissolving of corresponding polar solvent, determine that there is purple in compound structure
Functional group's species of outer absorption.Compound molecular weight is speculated according to ESI-MS, compound is determined according further to HR-ESI-MS
Molecular weight, molecular formula and degree of unsaturation.
2) sugared configuration is definite
With reference to sour water solution thin layer chromatography, suitable compound is weighed, methanol dissolving is configured to the solution of 1mg/mL, uses
Capillary point sample on silica gel plate, and being invested in the closed developing tank equipped with the concentrated sulfuric acid, 60 DEG C of water-bath 30min, after take
Go out with hair-dryer be blown to solvent wave to the greatest extent, on silica gel plate blank space point D-Glucose, D- celerys sugar, D- xylose standard product, by chloroform/
Methanol (7:3, v/v) mixed solution water saturation takes the chloroform/methanol solution after 9mL water saturations, adds the ice of 1mL
Acetic acid is unfolded after mixing as solvent, is sprayed with the butanol solution of phthalic acid aniline, in 105 DEG C of heating
10min develops the color.
The configuration of aniline-phthalic acid color developing agent：It accurately weighs aniline 0.93g and phthalic acid 1.66g is dissolved in
The water saturated n-butanols of 100mL.
3) result and analysis
Colorless oil.By ESI-MS compose ([M-H]-m/z 195) and HR-ESI-MS spectrum ([M-H]-m/z,
195.0655calcd for C10H11O4,195.0663) the molecular formula C10H12O4 of the compound, degree of unsaturation, are determined
For 5.IR spectrums (KBr tablettings) give hydroxyl (3419cm-1), carbonyl (1671cm-1) and aromatic rings (1592,1516,1464,
1428cm-1) signal.Ultraviolet spectra shows the ultraviolet absorption maximum of the compound in 203nm.
There is 1 methoxyl group hydrogen signal δ H 3.91 (s, 3H, H-10), 1 methyl hydrogen signal 1.40 (d, J in 1H-NMR spectrums
=7.2Hz, 3H, H-9), 3 aromatic signal δ H 7.56 (d, J=8.4Hz, 1H, H-2), δ H 6.86 (dd, J=1.8,
8.4Hz, 1H, H-4) and δ H 7.57 (d, J=1.8Hz, 1H, H-5).It can according to the chemical shift of these three hydrogen and coupling constant
Substitute by 1,3,6- tri- of the phenyl ring in the presence of pushing-out structure.In 13C-NMR spectrums, 10 carbon signals are given altogether, with reference to
DEPT is composed and 1H-NMR composes to obtain：1 carbonyl, 1 methine δ C 70.00 (d, C-8), 1 company oxygen methyl δ C 56.50 (q,
C-10), 1 methyl δ C22.28 (q, C-9).According to C-1, C-3 chemical shifts may infer that C-1, C-3 are optionally substituted by a hydroxyl group.
1H-1H COSY spectrograms prompt the presence for having 2 segments：a：-CHCH-；b：-CHCH3-.
Analysis HMBC is composed and is combined its hydrogen spectrum, carbon modal data, δ H 1.40 (d, J=7.2Hz, 3H, H-9) and δ C 202.02
(s, C-7), δ C 70.00 (d, C-8) are related, and δ H5.18 (q, J=7.2Hz, 1H, H-8) and δ C 202.02 (s, C-7) are related,
Show that C-6, C-8 are connected by C-7；δ H 3.91 (s, 3H, H-10) and δ C 149.37 (s, C-3) are related, show C-3, C-10
It is connected by oxygen；δ H 7.56 (d, J=8.4Hz, 1H, H-2) are related with δ C 153.79 (s, C-1), δ C 149.37 (s, C-3),
δ H 6.86 (dd, J=1.8,8.4Hz, 1H, H-4) are related with δ C 149.37 (s, C-3), δ C 125.15 (d, C-5), further
It is that 1,3,6- tri- substitutes to illustrate the phenyl ring in compound.The compound has similar structure, difference compared with Paeonol
It is that C-8 has connected a hydroxyl and methyl.Therefore finally determine that the compound structure is
It is retrieved by Sc ifinder, does not find relevant report, show that this compound for noval chemical compound, is named as 2- hydroxyl -1- (2-
Hydroxyl -4- methoxyphenyls) propane -1- ketone (2-hydroxy-1- (2-hydroxy-4-methoxyphenyl) propan-1-
one).Nuclear magnetic data is shown in Table 1.
The hydrogen spectrum and carbon modal data (MeOH) of 1 compound Frp50 of table
3 antifungal activity of embodiment measures
Microsporum gypseum is a kind of filamentous fungi that can cause shallow-layer dermatophytosis, can result in ringworm of the body, jock itch,
Onychomycosis, favus of the scalp etc. are clinical common superficial part pathomycetes.Effect of the medicinal plant in terms of skin disease is treated in recent years receives
Concern, it is one important to seek and treat dermopathic drug using the active ingredient design novel non-toxic in natural medicinal plant
Research direction.Minimal inhibitory concentration (Minimum inhibitory concentration, MIC) is to weigh antibacterials to live
Property size important indicator, using test tube medicine base method, not only can easily interpretation MIC value, but also easy to be economic, easily grasp
Make.
What this laboratory reference Clinical Laboratory Standard association (CLSI) was recommended《The micro broth dilution method of filamentous fungi
Drug sensitivity test scheme》(M38-A2) activity of isolated monomeric compound is studied.
1. test monomeric compound
The isolated compound of formula I of embodiment 1.
2. test strain
Microsporum gypseum bacterial strain is purchased from Chinese Academy of Medical Sciences's Nanjing Hospital of Skin Diseases.
3. test apparatus
4. test reagent
5. the preparation of culture medium
Aseptically, fresh modified form 1640 (containing L-Glutamine not carbonate containing) culture medium 1000mL is taken,
Medium's PH Value is adjusted to 7.0 by the 3- for being 0.165mol/L with concentration (N- morpholinyls)-propane sulfonic acid buffer solution, then with 0.22 μm
Filtering with microporous membrane degerming and dispense, 4 DEG C save backup.
6. the preparation of bacteria suspension
Aseptically, eugonic Microsporum gypseum test tube slant is taken to add in sterile saline, with connecing
Kind ring gently scrapes the Filamentous culture of media surface, launches in the mortar for done aseptic process and grinds, uses hemocytometer
Number plate counts, and the concentration of bacteria suspension is adjusted to 0.5 × 10 with 1640 fluid nutrient mediums of improvement3-2×103CFU/mL is spare.
7. test method
The preparation of drug sensitive plate
Accurately weigh the monomeric compound of certain mass and griseofulvin tablet powder respectively, add in certain volume DMSO and
Content is less than 1%, is configured to the storing solution of 0.8mg/mL, and storing solution then is pressed 1 with 1640 fluid nutrient mediums after improvement：25
It is diluted to 2 times of final concentrations, i.e. 32 μ g/mL.The liquid for the 32g/mL that 200 μ L have prepared is taken to add in 96 orifice plates respectively with pipettor
The 1st hole per a line；2-11 holes are separately added into 1640 fluid nutrient mediums after 100 μ L improvement；It is taken with pipettor from the 1st hole
100 μ L liquids inject the 2nd hole, are diluted to the 10th hole, and the 100 μ L liquid rejects that will be taken from the 10th hole for 2 times successively, finally obtain
1-10 holes liquor strength is respectively 32 μ g/mL, 16 μ g/mL, 8 μ g/mL, 4 μ g/mL, 2 μ g/mL, 1 μ g/mL, 0.5 μ g/mL, and 0.25
μ g/mL, 0.125 μ g/mL, 0.0625 μ g/mL, ten gradient concentrations；Then 1-11 holes are separately added into 100 μ L bacteria suspensions, the 11st hole
As growth control, the 12nd hole adds in 1640 fluid nutrient medium of improvement of 200 μ L as blank control；Each sample sets three weights
Multiple, each sample sets growth control and blank control.
Antibacterial result judgement
The drug sensitive plate for being inoculated with bacteria suspension is placed in 28 (± 1) DEG C constant incubators and is cultivated, is taken out after 7 days, singulation
The drug concentration that object inhibits growth to the MIC value of the strain for 100% is closed, that is, visually observes clarification or has no growth.
8. result
In order to find monomer resistant to Microsporum gypseum in the Paeonia ludlowii root skin ethyl acetate layer of Tibet
Compound, we, which utilize to have carried out from the isolated new monomeric compound of ethyl acetate layer component, resists Microsporum gypseum
Property experiment, result of the test measure learns that the isolated compound of formula I of embodiment 1 is 1 μ to the MIC value of Microsporum gypseum
G/mL compared with 0.5 μ g/mL of reference substance griseofulvin MIC, illustrates that the compound has Microsporum gypseum certain suppression
It makes and uses.
Claims (2)
1. a kind of preparation method of compound, it is characterised in that comprise the following steps：
1) after dry Tibet Paeonia ludlowii root skin is taken to crush, 95% ethyl alcohol is added in, room temperature extracts for 24 hours, repeats to filter, 50 DEG C
It is concentrated under reduced pressure, using ethyl acetate into extraction, extract liquor under the conditions of 50 DEG C is concentrated under reduced pressure, obtains dry powder A；
2) by dry powder A and polyamide in mass ratio 1:4~5 ratio mixing, carries out medium pressure liquid chromatography, reverse phase column material
For MCI-Gel, component B is afforded using the methanol aqueous solution that volumetric concentration is 20%；
3) by component B silica gel mixed samples, and silica gel column chromatography is carried out, is 10 with petroleum ether and ethyl acetate volume ratio:1 mixing
Liquid elutes, and obtains component C；
4) component C is subjected to silica gel column chromatography, is 6 with petroleum ether and acetone volume ratio:1 mixed liquor elution, obtains component D；
5) component D is continued into gel column chromatography, is eluted with methanol, isolate and purify to obtain Formulas I monomeric compound；
The structural formula of the monomeric compound is shown in formula I：
2. preparation method according to claim 1, it is characterised in that：Dry powder A and polyamide in mass ratio 1 in step (2):
4.2 ratio mixing.
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|---|---|---|---|---|
| JP2005015472A (en) * | 2003-06-02 | 2005-01-20 | Nippon Menaade Keshohin Kk | Melanin expression-enhancer |
| CN103787859A (en) * | 2014-01-17 | 2014-05-14 | 宣城市百草植物工贸有限公司 | Method for extracting paeonol by use of CO2 supercritical extraction technology |
| CN103784428A (en) * | 2013-10-11 | 2014-05-14 | 广东省农业科学院动物卫生研究所 | Application of paeonol in preparing medicine for resisting eimeria tenella |
| CN103804166A (en) * | 2014-01-17 | 2014-05-21 | 宣城市百草植物工贸有限公司 | Method for extracting active ingredient paeonol from coxtex moutan |
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2015
- 2015-12-02 CN CN201510875204.4A patent/CN105439843B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015472A (en) * | 2003-06-02 | 2005-01-20 | Nippon Menaade Keshohin Kk | Melanin expression-enhancer |
| CN103784428A (en) * | 2013-10-11 | 2014-05-14 | 广东省农业科学院动物卫生研究所 | Application of paeonol in preparing medicine for resisting eimeria tenella |
| CN103787859A (en) * | 2014-01-17 | 2014-05-14 | 宣城市百草植物工贸有限公司 | Method for extracting paeonol by use of CO2 supercritical extraction technology |
| CN103804166A (en) * | 2014-01-17 | 2014-05-21 | 宣城市百草植物工贸有限公司 | Method for extracting active ingredient paeonol from coxtex moutan |
Non-Patent Citations (1)
| Title |
|---|
| 丹皮酚、丹皮酚衍生物及其结构类似物的生物活性研究;于曙光;《中国博士学位论文全文数据库 医药卫生科技辑》;20131115;第E057-19，第9-13，19页 * |
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