CN107556348A - Acryloyl acid esters compound and preparation method thereof - Google Patents
Acryloyl acid esters compound and preparation method thereof Download PDFInfo
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- CN107556348A CN107556348A CN201710938476.3A CN201710938476A CN107556348A CN 107556348 A CN107556348 A CN 107556348A CN 201710938476 A CN201710938476 A CN 201710938476A CN 107556348 A CN107556348 A CN 107556348A
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Abstract
The invention provides a kind of new compound, and it includes the ZE configurational isomers as shown in formula I and formula II.Present invention also offers the method for preparing two kinds of isomers：(1) dry Idesia polycarpa blade is taken, is crushed, is extracted with organic solvent a, filtering, extract medicinal extract is produced after concentration；(2) after dissolving medicinal extract with distilled water, organic solvent b extractions is added, semifinished product is produced after sloughing solvent；(3) above-mentioned semifinished product is taken, is dissolved in organic solvent c, is separated using high performance liquid chromatography, fragment is flowed out according to the chromatogram collection type I of computer real-time acquisition or the compound chromatographic peak of formula II, formula I or the compound of formula II are produced after sloughing solvent.Experiment results proved, the invention provides a kind of new Idesia polycarpa polyphenol, and the target compound of high-purity can be effectively isolated from the blade of Idesia polycarpa, avoid the waste of Idesia polycarpa blade.
Description
Technical field
The present invention relates to natural materials to extract field, and in particular to a kind of Idesia polycarpa extract and preparation method thereof.
Background technology
Idesia polycarpa (IdesiapolycarpaMaxim.var.vestitaDiels) is thorn hedge Ochnaceae, also referred to as strong wind
The deciduous tree plant of scarabaeidae (Flacourtiaceae) idesia category (Idesia).Idesia polycarpa is a change for idesia
Kind, the difference between idesia in existing forms, because blade back surface has close hair to be coated with, therefore the quilt in Plant Taxonomy
Referred to as Idesia polycarpa.At home, it is distributed mainly on the Qinling Mountains, on the south Huaihe River each province；Foreign countries be distributed mainly on Japan, Korea,
South Korea and Far-east Area of Russia.
At present, a variety of phenols components are isolated in extraction from Idesia polycarpa fruit for China and South Korea, are mainly had：Sugar
The leuco-compounds idescarpin of pulpous state, white powder idesin, white powder salirepin (salirepin), syrup
The idesin hydrogen sulfate of shape, white powder remove first laricin, brown syrup shape compound 2-
Hydroxyphenol-1-O- β-D-glucopyra-nosyl- (6 → 1)-α-L-rhamnopyranoside, faint yellow nothing are determined
Type powder idesin salicylate, and 6- (the oxymethyl) -2-hydroxyphenyl-O- β-D- of latest find
glucopyranosyl-(1→6)-β-D-glucopyrano side.These aldehydes matters have very strong oxidation resistance,
Free radical such as DPPH, ABTS, hydroxyl radical free radical can not only be suppressed, moreover it is possible to suppress lipid, lipoprotein peroxidating, have similar super
Superoxide dismutase can suppress the activity of superoxide anion.In addition, Idesia polycarpa polyphenol also has very strong reducing power
And metal chelation abilities, the generation of nitrite can be suppressed.Therefore, it is food, medicine and change that idesia polyphenol, which has exploitation,
The possibility of cosmetic.
But the seldom of Idesia polycarpa leaf composition research can not be entered to its potential value both at home and abroad at present
Row exploitation, annual a large amount of Idesia polycarpa blades are caused to be dropped.And have no extract 2- from Idesia polycarpa blade at present
((3,4,5- trihydroxies -6- (methylol) tetrahydrochysene -2H- pyrans -2- bases) oxo) phenyl 3- (4- hydroxy phenyls) acryloyl acid esters
The report of (i.e. compound shown in formula III).
The content of the invention
In order to solve the above problems, the invention provides one kind to extract compound shown in formula III from Idesia polycarpa blade
Method.
The invention provides compound shown in a kind of formula III：
Further, the compound of formula III also includes the ZE configurational isomers as shown in formula I and formula II：
The invention provides a kind of formula I or the method for formula II, it is characterised in that：Comprise the following steps：
(1) dry Idesia polycarpa blade is taken, is crushed, is extracted with organic solvent a, filtering, extract leaching is produced after concentration
Cream；
(2) after dissolving medicinal extract with distilled water, organic solvent b extractions is added, semifinished product is produced after sloughing solvent；
(3) above-mentioned semifinished product is taken, is dissolved in organic solvent c, is separated using high performance liquid chromatography, separation condition is such as
Under：
Chromatographic column：C18 posts or C8 posts,
Mobile phase：Water-organic solvent d, water and organic solvent d volume ratio are 30：70~55：45
Detection wavelength：300~350nm,
Column temperature：35~40 DEG C,
Flow velocity：4~5ml/min；
According to the chromatogram collection type I of computer real-time acquisition or the compound chromatographic peak of formula II outflow fragment, solvent is sloughed
After produce formula I or the compound of formula II.
Further, in step (1), the organic solvent a includes methanol, ethanol and its aqueous solution；The hair leaf mountain paulownia
Son and organic solvent a w/v are 1:20~40g/ml；The extraction includes lixiviation process, percolation, circumfluence method, ultrasound
Ripple assisted extraction method.
Further, in step (2), the organic solvent b is selected from ethyl acetate, ether, isopropyl ether, dichloromethane, chlorine
It is imitative, ethyl acetate.
Further, in step (3), the organic solvent c includes methanol aqueous solution and acetonitrile solution.
Further, in step (3), the organic solvent d includes methanol, ethanol, acetonitrile, acetone；It is preferred that methanol, second
Nitrile.
Further, in step (3), when separating type I compound, the Detection wavelength is 319 ± 3nm；Separate type II is changed
During compound, the Detection wavelength is 312 ± 3nm.
The invention provides purposes of the above-claimed cpd in antimicrobial DP finish is prepared.
Further, the mushroom is candida albicans；Preferably, the mushroom is Candida albicans.
Experiment results proved, the invention provides a kind of new Idesia polycarpa polyphenol, and can be effectively from Mao Yeshan paulownias
The target compound of high-purity is isolated in the blade of son, avoids the waste of Idesia polycarpa blade.
Obviously, according to the above of the present invention, according to the ordinary technical knowledge and customary means of this area, do not departing from
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The embodiment of form by the following examples, the above of the present invention is remake further specifically
It is bright.But the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following example.It is all to be based on the above of the present invention
The technology realized belongs to the scope of the present invention.
Brief description of the drawings
Fig. 1 is the superelevation liquid chromatogram of type I compound of the present invention.
Fig. 2 is the superelevation liquid chromatogram of the compound of formula II.
Fig. 3 is the proton nmr spectra of type I compound of the present invention.
Fig. 4 is the carbon-13 nmr spectra of type I compound of the present invention.
Fig. 5 is the proton nmr spectra of the compound of formula II.
Fig. 6 is the carbon-13 nmr spectra of the compound of formula II.
Embodiment
The preparation of compound shown in embodiment 1, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 4000ml straight alcohols immersion 10min
Afterwards, 60min, filtering, after adding 4000ml straight alcohols into filter residue, with ultrasound are extracted with ultrasonic wave (180w, 40 DEG C, 59kHz)
Ripple (180w, 40 DEG C, 59kHz) extracts 60min, and filtering discards filter residue, and merging is extracted filtrate, concentrated with Rotary Evaporators twice
Filtrate obtains extract medicinal extract to sticky medicinal extract shape.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 20 times, so
After add isometric ethyl acetate and extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains slightly
Product 2.30g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C18 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Ladder
Spending program is：0~30min, A：40%, B：60%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram (Fig. 1) of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 50.5mg, through mass spectroscopy [M-] it is 417.1196, core
Magnetic hydrogen spectrum is shown in Fig. 3, and nuclear-magnetism carbon spectrum is shown in Fig. 4, (purity is 98.67% through UPLC analyses).
The preparation of compound shown in embodiment 2, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 70%V/V ethanol waters 3000ml
After soaking 10h, 30min is extracted with ultrasonic wave (180w, 40 DEG C, 5kHz), filtering, it is water-soluble that 70%V/V ethanol is added into filter residue
Liquid 3000ml, 30min is extracted with ultrasonic wave (180w, 40 DEG C, 59kHz), filtering, discards filter residue, filtrate is extracted in merging twice, is used
Rotary Evaporators concentrate filtrate to sticky medicinal extract shape, obtain extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 12 times, so
After add isometric ethyl acetate and extract 8 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains slightly
Product 2.44g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Gradient
Program is：0~30min, A：52%, B：48%；Flow velocity:4ml/min；Column temperature：35℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 45.8mg, through mass spectroscopy [M-] it is 417.1196, it is (pure
Degree is through UPLC analyses for 98.51%).
The preparation of compound shown in embodiment 3, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 20%V/V ethanol waters 4000ml
After soaking 48h, filtering, filter residue adds 20%V/V ethanol waters 4000ml immersion 24h, filtering, discards filter residue, merges twice
Filtrate is extracted, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, adds isometric ethyl acetate and extract 3 times, merge acetic acid second
Ester extraction phase, reduction vaporization slough ethyl acetate solvent, obtain semifinished product 2.97g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Gradient
Program is：0~30min, A：55%, B：45%；Flow velocity:4ml/min；Column temperature：35℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 37.1mg, through mass spectroscopy [M-] it is 417.1196, it is (pure
Degree is through UPLC analyses for 98.23%).
The preparation of compound shown in embodiment 4, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds pure methanol solution 2000ml immersions
After 5min, ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 60min, filter, filter residue surpasses after adding the pure methanol solvates of 2000ml
Sound wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 60min, filtering discard filter residue, and merging extracts filtrate, uses rotary evaporation twice
Instrument concentrates filtrate to sticky medicinal extract shape, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 8 times, then
Add isometric ethyl acetate to extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains rough
Product 2.98g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 50% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C18 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Ladder
Spending program is：0~30min, A：40%, B：60%；Flow velocity:5ml/min；Column temperature：35℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 47.6mg, through mass spectroscopy [M-] it is 417.1196, it is (pure
Degree is through UPLC analyses for 98.78%).
The preparation of compound shown in embodiment 5, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 60%V/V methanol aqueous solutions 2000ml
After soaking 10h, ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 20min, filtering, the filter residue addition volume integrals of 2000ml 60%
Ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 20min after number methanol aqueous solution, filtering discard filter residue, and merging is extracted twice
Filtrate, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 15 times, then
Add isometric ethyl acetate to extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains rough
Product 3.27g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 50% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Gradient
Program is：0~30min, A：45%, B：55%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 40.4mg, through mass spectroscopy [M-] it is 417.1196, it is (pure
Degree is through UPLC analyses for 98.34%).
The preparation of compound shown in embodiment 6, formula I
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 30%V/V methanol aqueous solutions 2000ml
After soaking 72h, filtering, filter residue adds the volume fraction methanol aqueous solutions of 2000ml 30% immersion 24h, filtering, discards filter residue, closes
And filtrate is extracted twice, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric ethyl acetate and extract 6 times, merge acetic acid
Ethyl ester extraction phase, reduction vaporization slough ethyl acetate solvent, obtain semifinished product 3.48g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 50% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Gradient
Program is：0~30min, A：50%, B：50%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：319nm.
4) type I compound chromatographic peak outflow fragment is collected according to the chromatogram of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, merge type I compound chromatogram
Peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine type I compound 35.7mg, through mass spectroscopy [M-] it is 417.1196, it is (pure
Degree is through UPLC analyses for 98.17%).
The preparation of compound shown in embodiment 7, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 4000ml straight alcohol solvent soakings
After 10min, ultrasonic wave (180w, 40 DEG C, 59kHz) ultrasonic extraction 60min, filtering, after filter residue adds 4000ml straight alcohol solvents
Ultrasonic wave (180w, 40 DEG C, 59kHz) ultrasonic extraction 60min, filtering, filter residue is discarded, filtrate is extracted in merging twice, is steamed with rotation
Send out instrument and concentrate filtrate to sticky medicinal extract shape, obtain extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 20 times, then
Add isometric ethyl acetate to extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains rough
Product 2.55g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C18 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Ladder
Spending program is：0~30min, A：55%, B：45%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram (Fig. 2) collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 79.5mg of formula II, through mass spectroscopy [M-] it is 417.1196,
Nucleus magnetic hydrogen spectrum is shown in Fig. 5, and nuclear-magnetism carbon spectrum is shown in Fig. 6, (purity is 98.67% through UPLC analyses).
The preparation of compound shown in embodiment 8, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 70%V/V ethanol waters 3000ml
After soaking 10h, ultrasonic wave (180w, 30 DEG C, 59kHz) ultrasonic extraction 30min, filtering, the filter residue addition volume integrals of 3000ml 70%
Ultrasonic wave (180w, 30 DEG C, 59kHz) ultrasonic extraction 30min after number ethanol water, filtering discard filter residue, and merging is extracted twice
Filtrate, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first adds isometric n-hexane extraction and remove depigmentaton 12 times, then
Add isometric ethyl acetate to extract 8 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains rough
Product 2.95g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Gradient
Program is：0~30min, A：50%, B：50%；Flow velocity:4ml/min；Column temperature：35℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 66.8mg of formula II, through mass spectroscopy [M-] it is 417.1196,
(purity is 98.55% through UPLC analyses).
The preparation of compound shown in embodiment 9, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 30%V/V ethanol waters 4000ml
After soaking 48h, filtering, filter residue adds 30%V/V ethanol waters 4000ml immersion 24h, filtering, discards filter residue, merges twice
Filtrate is extracted, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, isometric ethyl acetate that adds extracts 3 times, merges acetic acid second
Ester extraction phase, reduction vaporization slough ethyl acetate solvent, obtain semifinished product 3.08g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 30% methanol-water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Methanol；Gradient
Program is：0~30min, A：49%, B：51%；Flow velocity:4ml/min；Column temperature：35℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 60.1mg of formula II, through mass spectroscopy [M-] it is 417.1196,
(purity is 98.43% through UPLC analyses).
The preparation of compound shown in embodiment 10, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds the pure methanol alcoholic solvent immersions of 4000ml
After 5min, ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 60min, filter, filter residue surpasses after adding the pure methanol solvates of 4000ml
Sound wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 60min, filtering discard filter residue, and merging extracts filtrate, uses rotary evaporation twice
Instrument concentrates filtrate to sticky medicinal extract shape, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first isometric n-hexane extraction that adds removes depigmentaton 8 times, so
Add ethyl acetate in equal volume afterwards to extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains slightly
Product 2.87g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 50% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C18 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Ladder
Spending program is：0~30min, A：30%, B：70%；Flow velocity:5ml/min；Column temperature：35℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 78.2mg of formula II, through mass spectroscopy [M-] it is 417.1196,
(purity is 98.89% through UPLC analyses).
The preparation of compound shown in embodiment 11, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 60%V/V methanol aqueous solutions 2000ml
After soaking 10h, ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 20min, filtering, filter residue addition 60%V/V methanol aqueous solutions
Ultrasonic wave (180w, 35 DEG C, 40kHz) ultrasonic extraction 20min after 2000ml, filtering, filter residue being discarded, filtrate is extracted in merging twice,
Filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, first isometric n-hexane extraction that adds removes depigmentaton 15 times, so
Add ethyl acetate in equal volume afterwards to extract 10 times, combined ethyl acetate extraction phase, reduction vaporization sloughs ethyl acetate solvent, obtains slightly
Product 3.07g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 50% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Gradient
Program is：0~30min, A：50%, B：50%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 66.4mg of formula II, through mass spectroscopy [M-] it is 417.1196,
(purity is 98.27% through UPLC analyses).
The preparation of compound shown in embodiment 12, formula II
1) dry Idesia polycarpa blade 100g is taken, 60 mesh sieves are crossed after crushing, adds 30%V/V methanol aqueous solutions 2000ml
After soaking 72h, filtering, filter residue adds 2000ml 30%V/V methanol aqueous solutions immersion 24h, filtering, discards filter residue, merges twice
Filtrate is extracted, filtrate is concentrated to sticky medicinal extract shape with Rotary Evaporators, obtains extract medicinal extract.
2) extract medicinal extract is dissolved with 200ml distilled water, isometric ethyl acetate that adds extracts 6 times, merges acetic acid second
Ester extraction phase, reduction vaporization slough ethyl acetate solvent, obtain semifinished product 3.18g.
3) above-mentioned semifinished product 125mg is taken, is dissolved in 45% acetonitrile water, is separated using high performance liquid chromatography, chromatostrip
Part is：Chromatographic column filler：C8 bonded silica gel columns (250mm*30mm)；Mobile phase A is mutually：Water；Mobile phase B is mutually：Acetonitrile；Gradient
Program is：0~30min, A：55%, B：45%；Flow velocity:5ml/min；Column temperature：40℃；Detection wavelength：312nm.
4) fragment is flowed out according to the compound chromatographic peak of chromatogram collection type II of computer real-time acquisition.
5) by the method described in step 4), repeat preparation process 2) described in semifinished product, the chemical combination of combination type II looks for
Spectral peak flows out fragment, is concentrated under reduced pressure and sloughs solvent and must refine the compound 40.5mg of formula II, through mass spectroscopy [M-] it is 417.1196,
(purity is 98.05% through UPLC analyses).
Beneficial effects of the present invention are illustrated below by way of the mode of test example.
The biocidal property of test example 1, the compounds of this invention
1st, experimental method
Sample treatment：Distinguish dissolved compound I, II with DMSO, be configured to the mother liquor that concentration is 40000 μM, it is stand-by.
It is prepared by culture medium：After Candida albicans is activated, picking colony, it is dissolved in sterilized water, it is 0.5 wheat to be diluted to concentration
Family name dilutes 10 times with MHB culture mediums again than turbid concentration using preceding.
Bacteriostatic experiment：
Sample DMSO mother liquors are diluted to 1600 μM with MHB culture mediums, takes 200 μ L to add in 96 orifice plates, is entered with culture medium
Row doubling dilution, it is 100 μ L per hole herb liquid volume.Each extract final concentration of 800,400,200,100,50,25 μM.It is positive
Control uses hydrochloric acid Itraconazole, the g/mL of concentration range 128,64,32,16,8,4, μ.In concentration highest decoction hole, DMSO
Concentration is 2%, and doubling dilution is also carried out as medicine group as solvent control.The white added after the dilution of 100 μ L culture mediums
Candida albicans dilution, 37 DEG C of culture 24h, inhibition is determined according to culture medium muddiness degree.The edge of 96 orifice plates adds 200 μ L
Aqua sterilisa, prevent middle experiment boreliquid from volatilizing.Culture medium blank control and medicine blank control are set simultaneously, to observe culture
Whether base has pollution and staphylococcus aureus normal growth situation.Experiment is in triplicate.
2nd, experimental result
Inhibiting rate of the various concentrations type I compound of table 1 to Candida albicans
Inhibiting rate of the compound of 2 various concentrations formula of table II to Candida albicans
Test result indicates that type I compound of the present invention and the compound of formula II under various concentrations to Candida albicans
Growth has certain inhibitory action.Two compounds reach maximum when concentration is 800 μM to Candida albicans inhibiting rate, respectively
For 40.53% and 29.76%.
In summary, the present invention isolated compound completely newly from Idesia polycarpa blade, expands Mao Yeshan
The utilization rate of seeds of a tung oil tree blade；And these compounds have Candida albicans excellent inhibitory action, can be used for preparing antibacterial
Class medicine；The preparation method of the compounds of this invention, have step is easy, reaction condition is gentle, energy consumption is low, efficiency high, cost are low,
The advantages that green, the application being especially suitable in industry.
Claims (10)
1. compound shown in formula III：
2. compound according to claim 1, it is characterised in that：The compound also includes as shown in formula I and formula II
ZE configurational isomers：
3. a kind of method of formula I or the compound of formula II, it is characterised in that：Comprise the following steps：
(1) dry Idesia polycarpa blade is taken, is crushed, is extracted with organic solvent a, filtering, extract medicinal extract is produced after concentration；
(2) after dissolving medicinal extract with distilled water, organic solvent b extractions is added, semifinished product is produced after sloughing solvent；
(3) above-mentioned semifinished product is taken, is dissolved in organic solvent c, is separated using high performance liquid chromatography, separation condition is as follows：
Chromatographic column：C18 posts or C8 posts,
Mobile phase：Water-organic solvent d, water and organic solvent d volume ratio are 30：70~55：45
Detection wavelength：300~350nm,
Column temperature：35~40 DEG C,
Flow velocity：4~5ml/min；
According to the chromatogram collection type I of computer real-time acquisition or the compound chromatographic peak of formula II outflow fragment, slough after solvent i.e.
Obtain formula I or the compound of formula II.
4. according to the method for claim 3, it is characterised in that：In step (1), the organic solvent a includes methanol, ethanol
And its aqueous solution；The Idesia polycarpa and organic solvent a w/v are 1:20~40g/ml；The extraction includes leaching
Go out method, percolation, circumfluence method, ultrasonic assistant extraction method.
5. according to the method described in any one of claim 3 or 4, it is characterised in that：In step (2), the organic solvent b choosings
From ethyl acetate, ether, isopropyl ether, dichloromethane, chloroform, ethyl acetate.
6. according to the method described in claim 3-5 any one, it is characterised in that：In step (3), organic solvent c includes first
Alcohol solution and acetonitrile solution.
7. according to the method described in claim 3-6 any one, it is characterised in that：In step (3), the organic solvent d bags
Include methanol, ethanol, acetonitrile, acetone；It is preferred that methanol, acetonitrile.
8. according to the method described in claim 3-7 any one, it is characterised in that：In step (3), when separating type I compound,
The Detection wavelength is 319 ± 3nm；During II compound of separate type, the Detection wavelength is 312 ± 3nm.
9. purposes of the compound described in claim 1 or 2 in antimicrobial DP finish is prepared.
10. purposes according to claim 9, it is characterised in that：The mushroom is candida albicans；Preferably, the mushroom is
Candida albicans.
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