CN110386875A - A method of separating caffeoyl gluconic acid serial position isomers from evodia rutaecarpa - Google Patents
A method of separating caffeoyl gluconic acid serial position isomers from evodia rutaecarpa Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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Abstract
The method of the present invention provides a kind of from evodia rutaecarpa quick separating caffeoyl gluconic acid complete series position isomer; water refluxing extraction is carried out to evodia rutaecarpa; sample is quickly handled; prepare liquid phase separation and purifying; the method protected simultaneously using low temperature and anaerobic; 5 kinds of caffeoyl gluconic acid serial isomers have disposably been successfully separated, and have not needed secondarily purified, thus have had many advantages, such as that separative efficiency is high, save solvent and time, organic solvent expend less.
Description
Technical field
The invention belongs to the extraction of the effective component in plant component extraction, especially Chinese medicine, it is more particularly to from Wu Zhu
The method of complete series caffeoyl gluconic acid isomers is separated in cornel.
Background technique
Evodia rutaecarpa is rutaceae evodia rutaecarpa Euodia rutaecarpa (Juss.) Benth., Shi Hu Euodia
Rutaecarpa (Juss.) Benth.var.officinalis (Dode) Huang or thin hair evodia rutaecarpa Euodia
The drying almost ripe fruit of rutaecarpa (Juss.) Benth.var.bodinieri (Dode) Huang.It is more from ancient times to the present
In the Chinese medicine tradition ancient books of a classics, evodia rutaecarpa is all described as " toxic " or " slightly poisonous ".It is found in early-stage study, toxicity
Source may be caffeic acid and gluconic acid condensation product.It is therefore desirable to be separated to the series compound to do into one
Step research.Wherein, caffeic acid and gluconic acid condensation generate caffeoyl gluconic acid.Not according to the position of hydroxyl in gluconic acid
With (2-O-, 3-O-, 4-O-, 5-O- and 6-O-), there are 5 kinds of position isomers.At present only 6-O- it is trans--caffeoyl gluconic acid
(referred to as compound 5, structural formula is as follows) success is isolated from evodia rutaecarpa.
Reported 6-O- is trans--caffeoyl gluconic acid (compound 5) preparation method there are two types of:
(1) 11kg evodia rutaecarpa crushes, 4.4L95% alcohol reflux 1h, extracts 4 times, obtains alcohol extract 2.3kg.By alcohol extract point
It is scattered in 1.5L water, hydrochloric acid adjusts PH to 3, successively uses hexamethylene (3L, 4 times), after ethyl acetate (3L, 4 times) extraction, obtains Wu
Fruit of medicinal cornel water extract.
It is successively water-soluble with 10%, 30%, 60%, 95% ethyl alcohol using D101 macroreticular resin post separation evodia rutaecarpa water extract
Liquid elution, obtains 4 components.10% ethanol elution component uses silica gel column chromatography, is obtained using chloroform-methanol system gradient elution
48 components are obtained, merge into 3 components after the detection of TLC thin-layer chromatography, the 3rd component is placed in ethanol water later
It being precipitated, isolated 6-O- is trans--caffeoyl gluconic acid (compound 5).(Zhao,M.Y.；Yang,X.W.Two new
acylgluconic acids from the nearly ripe fruits of Evodia rutaecarpa.J.Asian
Nat.Prod.Res.2008,10,769–773.)
(2) twice, water extract is separated 3kg evodia rutaecarpa water refluxing extraction using D101 macroreticular resin, first with 95% ethyl alcohol
Impurity is eluted, is then eluted with 1% aqueous formic acid.Eluent is concentrated by evaporation to obtain crude extract 197g.40g runic object is taken, is used
Sephadex lh-20 post separation, successively obtains 1-22 component with methanol-water 90:10, and 100:0 elutes to obtain 23-38 component.
9-38 component (35g) uses ODS pillar layer separation, is successively eluted with 10%, 15%, 20%, 30%, 40%, 50% methanol,
76 components are obtained, wherein 12-36 component is washed using preparation liquid phase, -0.1% formic acid of methanol (23%-30%, 30min) gradient
It is de-, purifies and separates obtain 6-O- it is trans--caffeoyl gluconic acid (compound 5).(He,Y.；Li,J.；Wu,H.H.；Chai,X.；
Yang,J.；Wang,Y.F.；Zhang,P.；Zhu,Y.；Gao,X.M.A new caffeoylgluconic acid
derivative from the nearly ripe fruits of Evodia
rutaecarpa.Nat.Prod.Res.2015,29,1243–1248.)
Above-mentioned two prior arts be only capable of separation 6-O- it is trans--caffeoyl gluconic acid (compound 5), and evodia rutaecarpa extract
Afterwards, extract uses large size D101 macroporous resin column chromatography rough segmentation, is then combined with flow point, and then further purifying obtains.It is whole
A process is cumbersome, consuming time is long, consumption quantity of solvent is big, can not isolate compound 1 to 4.Structural formula is as follows:
The article reported success delivered recently by the present inventor be successfully separated above compound 1 to 5 (Liang Wang,
et al.Four new caffeoylgluconic acid positional isomers from the fruits of
Evodia rutaecarpa.Journal of Asian Natural Products Research.2019.06).It is based on
The high speed adverse current chromatogram separation of aqueous two-phase dicyandiamide solution (i.e. ethyl alcohol-n-butanol-ammonium sulfate dicyandiamide solution), preparation liquid-phase pure
Change, while being protected using low temperature and anaerobic, establishes the inverse of 5 kinds of serial isomers (compound 1-5) of caffeoyl gluconic acid
Flow chromatography separation method, but it is relative complex to remain on that there are operating procedures, needs the deficiencies of secondarily purified.
Summary of the invention
It is completed the present invention is based on the deficiencies in the prior art.The present invention provides one kind quick separating complete series from evodia rutaecarpa
The method of caffeoyl gluconic acid position isomer, using evodia rutaecarpa water refluxing extraction, sample is quickly handled, and prepares liquid phase separation
And purifying, while the method protected using low temperature and anaerobic, the series compound can be made to keep stablizing, separative efficiency is high, saves
Solvent and time, organic solvent expend less, and caffeoyl gluconic acid complete series isomers has successfully been prepared.
It is characterized by comprising following steps:
1) evodia rutaecarpa is crushed and carries out refluxing extraction, methanol is added after extracting solution concentration, is filtered after ultrasonic treatment；
These, it is preferred to which the water of refluxing extraction mentions, or repeats to extract 1-3 times, add after extracting solution concentration by 1:3-5
Enter methanol, ultrasonic treatment condition is 35kHz ultrasound 25-40min, and filtering is filtered using filter paper, is still more preferably repeated 3 times.
2) dry to filtrate recycling design solid；
3) it is dissolved with methanol, is collected by centrifugation precipitating, dry solid powder；
Preferably, concrete operations are dissolved with 4-10% methanol, methanol are added by 1:8-10 volume ratio, centrifugal condition is
4000rpm, 10min collect precipitating, dry selection rotary evaporated to dryness.
4) liquid chromatogram separation is carried out to above-mentioned sample, wherein -3% formic acid water of mobile phase acetonitrile (A), gradient elution: 0-
26min, 7%A；26-27min, 7%-9%A；27-40min 9%A；
Wherein, respectively respectively at 13.07-14.70min, preferred 13.58-13.88min；16.36-17.92min excellent
The 16.80-17.24min of choosing；19.76-21.67min preferred 20.26-20.86min；25.57-27.52min preferably
26.10-26.88min；30.31-33.04min, preferred 30.81-32.22min collect flow point obtain compound 1,2,3,
4,5 liquid chromatography purification liquid.
The compound 1:2-O- trans- caffeoyl gluconic acid, is changed the trans- caffeoyl gluconic acid of compound 2:3-O-
It is trans- to close the trans- caffeoyl gluconic acid of object 3:4-O-, the trans- caffeoyl gluconic acid of compound 4:5-O-, compound 5:6-O-
Caffeoyl gluconic acid.Structure is as follows:
Wherein preferably specific condition is: flow velocity 10mL/min, column temperature are room temperature.
Preferably 4) anaerobic described in step be by nitrogen protection, low-temperature protection refers in 0-8 DEG C, preferably 0-6 DEG C, most
Under preferably 4 DEG C of environment.
And concrete operations are as follows: receiving flask connection vacuum and connect skirt and pre- inflated with nitrogen, set in ice-water bath, vacuum connects skirt
It is sealed with rubber stopper, rubber stopper passes through the PTFE inlet tube of 1 internal diameter 1mm, and the vacuum orifice that vacuum connects skirt, which connects, fills part nitrogen
The balloon of gas prevents the reception pressure in the bottle excessive.The row of the trickle of preparation liquid phase is controlled by a 7725i six-way valve
Enter the switching between waste liquid and anaerobic reception.
Optionally, further, further include following step:
5) anaerobic and low-temperature protection are combined, sample is dried: sample solution under anaerobic, is preferably protected with nitrogen
Under shield, and it is dried in the environment of being lower than 25 DEG C.
Preferably, (preferably 20 DEG C) water-bath rotary evaporated to dryness 15 to 23 DEG C under sample solution nitrogen protection, then
5mL/min nitrogen purges 30min to completely remove remaining moisture and formic acid, nitrogen charging hermetic seal cryo-conservation.
The present invention is the method for the quick separating complete series caffeoyl gluconic acid position isomer from evodia rutaecarpa, relative to
For existing method, have operating procedure simple, separative efficiency height, saving solvent and time, organic solvent consuming are few, separate pure
The advantages that higher is spent, the complete series isomers for especially industrially applying to purification caffeoyl gluconic acid on a large scale is applicable in.
Detailed description of the invention
Fig. 1 evodia rutaecarpa sample preparation liquid chromatogram.
Fig. 2 compound 1-5HPLC figure.
Wherein: (A) is the crude samples of liquid phase separation before purification here；
(B) purity 94.66% of compound 1；
(C) purity 94.49% of compound 2；
(D) purity 91.68% of compound 3；
(E) purity 93.15% of compound 4；
(F) purity 93.20% of compound 5.
Specific embodiment
According to following embodiments, the present invention is described further, but is not construed as limiting the invention.
Embodiment 1
1, sample extraction method
1kg evodia rutaecarpa crushes, and 10 times of amount water reflux 1h are extracted 2 times, extracting solution is concentrated into 1L, and 3L methanol, 35kHz is added
Ultrasonic 30min, filter paper filtering.2L methanol, 35kHz ultrasonic extraction is added in filter residue, and filtering is repeated 3 times.Merging filtrate, rotation are steamed
Recycling design is sent out to doing, obtains solid 85.1g.It is completely dissolved with 5% methanol 200mL.
Methanol 1800mL is added by 1:9 volume ratio, 4000rpm is centrifuged 10min, discards supernatant liquid, and collection is precipitated to 100mL
In flask, rotary evaporated to dryness obtains light tan solid powder sample 6.41g.
HPLC analysis is carried out to the sample, wherein the condition of HPLC are as follows: chromatographic column Thermo Syncronis C18
(250mm × 4.6mm, 5 μm)；0.3% phosphoric acid water of mobile phase (A)-acetonitrile (B), gradient elution: 0~25min, 4%~6.5%
B；25~32min, 6.5%B；32~37min, 6.5%~8%B；37~52min, 8%B；52~70min, 8%~100%
B；30 DEG C of column temperature；Volume flow 1.0mL/min；Detection wavelength 325nm.The ultraviolet spectra of target compound is examined by the DAD of HPLC
Survey device all-wave length mode detection.Testing result is shown in Fig. 1.
2, liquid phase separation purifies
Appropriate (about 10mL) 3% aqueous formic acid is dissolved in above-mentioned acquisition light tan solid powder 1g sample, ultrasonic dissolution,
Cross 0.45 μm of filtering with microporous membrane.Its condition is as follows: chromatographic column SHIMADZU Shim-Pack PRC-ODS, mobile phase acetonitrile
(A) -3% formic acid water, gradient elution: 0-26min, 7%A；26-27min, 7%-9%A；27-40min 9%A.Flow velocity 10mL/
Min, sample volume 1mL, column temperature are room temperature.
1,2,3,4,5 retention time of compound be respectively 13.552min, 16.815min, 20.233min, 25.951min,
31.160min accordingly respectively at 13.58-13.88min；16.80-17.24min；20.26-20.86min；26.10-
26.88min；30.81-32.22min collects flow point, that is, respectively obtains the sample solution of compound 1 to 5.Flow velocity 10mL/min,
Sample volume 1mL, column temperature are room temperature.It receives flask connection vacuum and connects skirt and pre- inflated with nitrogen, set in ice-water bath, vacuum connects skirt use
Rubber stopper sealing, rubber stopper pass through the PTFE inlet tube of 1 internal diameter 1mm, and the vacuum orifice that vacuum connects skirt, which connects, fills part nitrogen
Balloon, prevent receive the pressure in the bottle it is excessive.Being discharged into for the trickle of preparation liquid phase is controlled by a 7725i six-way valve
Switching between waste liquid and anaerobic reception.Corresponding compound is received respectively according to above-mentioned each the retention time of the compound.
3, dry
The each sample solution obtained in above-mentioned step 2 20 DEG C of water-bath rotary evaporated to dryness under nitrogen protection, rear 5mL/min
Nitrogen purges 30min to completely remove remaining moisture and formic acid, and inflated with nitrogen is sealed in -20 DEG C of refrigerators and saves.
Wherein HPLC chromatogram is as shown in Fig. 2, wherein A indicates that crude samples, B indicate that compound 1, C indicate compound 1, D table
Show that compound 3, E indicate that compound 4, F indicate compound 5.
Using HPLC area normalization method, purity testing is carried out, the results showed that the compound 1-5 purity point that this experiment obtains
Not Wei compound 1-5 purity is respectively 94.52%, 95.07%, 93.95%, 91.49% and 90.94%.
4, the qualification result of compound 1-5
Using UV, MS,1H NMR,13C NMR, HMBC, HHCOSY, HSQC, DEPT135 have carried out general survey to structure.
Qualification result is as follows:
The trans- caffeoyl gluconic acid of compound 1:2-O- (2-O-trans-caffeoylgluconic acid),1H
NMR(400MHz,D2O): being shown in Table 1.13C NMR(100MHz,D2O): being shown in Table 2.
The trans- caffeoyl gluconic acid of compound 2:3-O- (3-O-trans-caffeoylgluconic acid),1H
NMR(400MHz,D2O): being shown in Table 1.13C NMR(100MHz,D2O): being shown in Table 2.
The trans- caffeoyl gluconic acid of compound 3:4-O- (4-O-trans-caffeoylgluconic acid),1H
NMR(400MHz,D2O): being shown in Table 1.13C NMR(100MHz,D2O): being shown in Table 2.
The trans- caffeoyl gluconic acid of compound 4:5-O- (5-O-trans-caffeoylgluconic acid),1H
NMR(400MHz,D2O): being shown in Table 1.13C NMR(100MHz,D2O): being shown in Table 2.
The trans- caffeoyl gluconic acid of compound 5:6-O- (6-O-trans-caffeoylgluconic acid),1H
NMR(400MHz,D2O): being shown in Table 1.13C NMR(100MHz,D2O): being shown in Table 2.
Compound 1-5 in 1 heavy water of table1H NMR data
Compound 1-5 in 2 heavy water of table13C NMR data
* interchangeable.
Claims (9)
1. a kind of method of the quick separating caffeoyl gluconic acid from evodia rutaecarpa, characterized by the following steps:
1) evodia rutaecarpa is crushed and carries out refluxing extraction, methanol is added after extracting solution concentration, is filtered after ultrasonic treatment；
2) to filtrate recycling design, dry solid；
3) it is dissolved with methanol, is collected by centrifugation precipitating, dry solid powder；
4) liquid chromatogram separation is carried out to above-mentioned sample, wherein -3% formic acid water of mobile phase acetonitrile (A), gradient elution: 0-26min,
7%A；26-27min, 7%-9% A；27-40min 9% A；
Wherein, respectively at respectively at 13.07-14.70 min, preferred 13.58-13.88 min；16.36-17.92 min, excellent
The 16.80-17.24 min of choosing；19.76-21.67 min, preferred 20.26-20.86 min；25.57-27.52 min, excellent
The 26.10-26.88 min of choosing；30.31-33.04 min, it is to obtain compound that preferred 30.81-32.22 min, which collects flow point,
1,2,3,4,5 liquid chromatography purification liquid；
The compound 1:2-OTrans- caffeoyl gluconic acid, compound 2:3-OTrans- caffeoyl gluconic acid, chemical combination
The trans- caffeoyl gluconic acid of object 3:4-O-, the trans- caffeoyl gluconic acid of compound 4:5-O-, compound 5:6-O- are trans-
Caffeoyl gluconic acid；
Optionally, further, further include following step:
5) sample solution is dried in the environment of being lower than 25 DEG C under anaerobic.
2. the method as described in claim 1, it is characterised in that:
Wherein, in the 1) step, the refluxing extraction is that water mentions, and further repeats to extract 1-3 time, by 1 after extracting solution concentration:
Methanol is added in 3-5；Ultrasonic treatment condition is 35 kHz ultrasound 25-40 min；Filtering is filtered using filter paper, is preferably repeated 3 times.
3. the method for claim 1, wherein 2) and/or the 3) in step the, the drying is that rotary evaporation recycling is molten
Agent is to dry.
4. being dissolved using 4-10% methanol, the method for claim 1, wherein in the 3) step by 1:8-10 volume ratio
Methanol is added, centrifugal condition is 3500 to 4500 rpm, collects precipitating, dry selection rotary evaporated to dryness.
5. the method as described in claim 1, wherein 4) to be that low-temperature protection refers to by nitrogen protection be in anaerobic described in step
0-8 DEG C, preferably 0-6 DEG C, under most preferably 4 DEG C of environment.
6. the method as described in claim 1, wherein 4) step, the anaerobic and low-temperature protection refer to through nitrogen protection, connect
Bottle is received to be placed in ice-water bath.
7. method as claimed in claim 6, wherein anaerobic and the concrete operations of low-temperature protection are as follows: flask will be received and connected very
Sky connects skirt and pre- inflated with nitrogen, sets in ice-water bath, and vacuum connects skirt and sealed with rubber stopper, and rubber stopper passes through a PTFE feed liquor
Pipe, the vacuum orifice that vacuum connects skirt connect the balloon for filling part nitrogen, and the efflux of preparation liquid phase is controlled by six-way valve
The switching of body being discharged between waste liquid and anaerobic reception.
8. the method as described in claim 1, wherein 5) step concrete operations be: sample solution 15- under nitrogen protection
Then 23 DEG C of water-bath rotary evaporated to dryness are purged with nitrogen to completely remove remaining moisture and formic acid, nitrogen charging hermetic seal low temperature
It saves.
9. method according to claim 8, wherein 5) step concrete operations be: in 20 DEG C of water-baths under sample solution nitrogen protection
Rotary evaporated to dryness, then 5 mL/min nitrogen purge 30 min to completely remove remaining moisture and formic acid, nitrogen charging hermetic seal
It is saved in -20 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112972354A (en) * | 2021-02-26 | 2021-06-18 | 广东梵蜜琳生物科技有限公司 | Skin care composition and application thereof in cosmetics |
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2019
- 2019-08-22 CN CN201910776485.6A patent/CN110386875A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| HE,Y.等: "A new caffeoylgluconic acid derivative from the nearly ripe fruits of Evodia rutaecarpa", 《NATURAL PRODUCT RESEARCH》 * |
| LIANG WANG等: "Four new caffeoylgluconic acid positional isomers from the fruits of Evodia rutaecarpa", 《JOURNAL OF ASIAN NATURAL PRODUCTS RESEARCH》 * |
| ZHAO,M.Y.等: "Two new acylgluconic acids from the nearly ripe fruits of Evodia rutaecarpa", 《J.ASIAN NAT.PROD.RES.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112972354A (en) * | 2021-02-26 | 2021-06-18 | 广东梵蜜琳生物科技有限公司 | Skin care composition and application thereof in cosmetics |
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Application publication date: 20191029 |