CN108976191A - A kind of method of flavones in separation and Extraction Radix Ophiopogonis - Google Patents
A kind of method of flavones in separation and Extraction Radix Ophiopogonis Download PDFInfo
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- CN108976191A CN108976191A CN201810705657.6A CN201810705657A CN108976191A CN 108976191 A CN108976191 A CN 108976191A CN 201810705657 A CN201810705657 A CN 201810705657A CN 108976191 A CN108976191 A CN 108976191A
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- C07—ORGANIC CHEMISTRY
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
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- C07—ORGANIC CHEMISTRY
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- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
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Abstract
The invention discloses a kind of method of flavones in separation and Extraction Radix Ophiopogonis, this method is extracted by the reflux type of ethanol water and the separation of AB-8 macroporous resin column, and saponin(e, flavones and polysaccharide etc. are separated；Then by ether, sodium chloride, smashed metal organic framework compound HKUST-1 and the system cooperation of sodium bicarbonate combination, different flavones are separated, and passes through water-soluble product and is filtered to remove impurity, have the advantages that the different flavone compounds of separation.
Description
Technical field
The present invention relates to a kind of methods of flavones in separation and Extraction Radix Ophiopogonis.
Background technique
Flavonoids closes object and is also known as flavonoids, flavone and flavonoids, makes the major class compound for being widely present in nature,
As many as quantity can arrange first of natural phenoloid.Flavone compound in plant it is most of with sugar at glycosides, a part with
Aglycone forms exist.Flavone compound resists because of its antiactive oxygen free radical function, to adjustment effect, the anti-aging of lipid-metabolism
Fatigue effect, anticancer and antitumor action, reducing blood lipid and the effect of serum cholesterol-lowering, inhibit prostate at enhancing immunity function
Growth and hyperplasia, to endocrine adjustment effect, antibacterial bacteriostatic performance function, antiallergy anti-inflammatory effect, estrogen-like action, right
Therapeutic effect of the loose disease of sclerotin etc. is studied in the protective effect of kidney extensively.To need different Huangs convenient for research
Ketone carries out separation and Extraction.
Radix Ophiopogonis (scientific name: Ophiopogon japonicus (Linn.f.) Ker-Gawl.) Liliaceae Ophiopogon is perennial
Evergreen herbage.The main component of Radix Ophiopogonis is saponins, flavone compound and carbohydrate content.The flavone compound of Radix Ophiopogonis
There are mainly four types of, it is respectively compound I, compound II, compound III and compound IV.
Compound I, shown in formula I, for unformed white powder (methanol), FeCl3Chromogenic reaction is positive.[α]20 D-
2.6 ° of (c=0.85, CH3COOC2H5).Its1HNMR (400MHz, CDCl3) display 5 fatty proton signals: δ 4.52 (1H, dd, J
=11.2,4.8Hz), 4.22 (1H, dd, J=10.8,10.8Hz), 3.10 (1H, m), 3.01 (1H, dd, J=14.4,
5.2Hz), 2.86 (1H, dd, J=14.4,6.4Hz)；3 fragrant proton signals: δ 6.46 (1H, d, J=2.4Hz), 6.42 (1H,
Dd, J=8.4,2.4Hz), 6.94 (1H, dd, J=8.4)；2 hydroxyl hydrogen nuclear signals: δ 11.94 (1H, s), 6.62 (1H, s)；2
A aromatic ring methoxyl group proton signal δ 3.75 (3H, s), 3.85 (3H, s)；1 aromatic ring methyl hydrogen nuclear signal: δ 2.04 (3H, s).Change
Close object I's13CNMR (50MHz, CDCl3) show 3 fatty carbon, 12 aromatic ring carbon, 1 carbonyl carbon, 1 methyl carbon and 2
A methoxyl group carbon signal.Above data shows that compound I is Homoisoflavonoids class compound, data and document (Nguyen
THA, Tmm VS, Andrea P, et al.Homoisoflavonoids from Ophiopogon japonicus Ker-
Gawler.Phytochemistry, 2003,62:1153~1158) it is almost the same, determine that its planar structure is 5,7-
dihydroxy-6-methyl-8-methoxy-(2’-hydroxy-4’-methoxybenzyl)chrom-4-one。
Compound II is faint yellow unformed powder (methanol), FeCl as shown in Formula II3Chromogenic reaction is positive.[α
]20 D+ 3.8 ° of (c=1.0, CH3COCH3).Its1HNMR (400MHz, DMSO-d6) display 5 fatty proton signals: δ 4.24 (1H,
Dd, J=11.2,4.2Hz), 4.05 (1H, dd, J=11.2,8.4Hz), 2.95 (1H, m), 3.03 (1H, dd, J=13.6,
4.8Hz), 2.56 (1H, dd, J=13.6,9.6Hz)；3 fragrant proton signals: δ 6.80 (1H, d, J=1.6Hz), 6.69 (1H,
D, J=8.0Hz), 6.60 (1H, d, J=8.0Hz)；1 hydroxyl hydrogen nuclear signal: δ 12.49 (1H, s)；1 aromatic ring methoxyl group hydrogen
Nuclear signal δ 3.74 (3H, s) and 2 aromatic ring methyl hydrogen nuclear signals: δ 1.92 (3H, s), 1.90 (3H, s).Compound I's13CNMR (50MHz, DMSO-d6) show 3 fatty carbon, 12 aromatic ring carbon, 1 carbonyl carbon, 2 methyl carbon and 1 methoxy
Base carbon signal.Above data shows that compound II is Homoisoflavonoids class compound, data and document (Nguyen THA,
Tmm VS, Andrea P, et al.Homoisoflavonoids from Ophiopogon japonicus Ker-
Gawler.Phytochemistry, 2003,62:1153~1158) it is almost the same, determine that its planar structure is 5,7-
Dihydroxy-6,8-dimethyl-3- (3 '-methoxy-4 '-hydroxybenzyl) chrom-4-one.
Compound III, as shown in formula III, for faint yellow needle (ethyl acetate), FeCl3Chromogenic reaction is positive.[α
]20 D- 71.3 ° of (c=0.7, CH3COOC2H5).Its1HNMR (400MHz, CDCl3) display 5 fatty proton signals: δ 4.27 (1H,
Dd, J=11.4,4.0Hz), 4.11 (1H, dd, J=11.4,7.0Hz), 2.78 (1H, m), 3.17 (1H, dd, J=13.6,
4.2Hz), 2.69 (1H, dd, J=13.6,10.4Hz)；4 fragrant proton signals: δ 7.14 (2H, d, J=8.4), 6.85 (2H, d,
J=8.4)；2 hydroxyl hydrogen nuclear signals: δ 5.50 (1H, s), 12.38 (1H, s)；1 aromatic ring methoxyl group proton signal δ 3.79
(3H, s) and 2 aromatic ring methyl hydrogen nuclear signals: δ 2.02 (3H, s), 2.06 (3H, s).Compound III's13CNMR (50MHz,
CDCl3) show 3 fatty carbon, 12 aromatic ring carbon, 1 carbonyl carbon, 2 methyl carbon and 1 methoxyl group carbon signal.More than
Data show that compound III is Homoisoflavonoids class compound, data and document (Tada A, Kasa R, Saitoh T,
et al.Studies on the constituents of ophionogonis tuber V.Isolation of novel
class of homoisoflavonoids and determination of their structure(1).Chem.Pharm
Bull, 1980,28 (5): it is 1477) almost the same, determine that its planar structure is 5,7-dihydroxy-6,8-dimethyl-3-
(4’-methoxyzyl)-4-one(methylophiopogonanone B)。
Compound IV, as shown in formula IV, for faint yellow needle (ethyl acetate), FeCl3Chromogenic reaction is positive.[α]20 D-
34.0 ° of (c=0.96, CH3COOC2H5).Its1HNMR (400MHz, CDCl3) display 5 fatty proton signals: δ 4.29 (1H, dd,
J=11.2,4.4Hz), 4.13 (1H, dd, J=11.2,7.0Hz), 2.79 (1H, m), 3.15 (1H, dd, J=13.6,
4.4Hz), 2.68 (1H, dd, J=13.6,10.4Hz)；3 fragrant proton signals: δ 6.73 (1H, d, J=1.6Hz), 6.76 (1H,
D, J=8.0Hz), 6.68 (1H, dd, J=8.0,1.6Hz)；2 hydroxyl hydrogen nuclear signals: δ 12.36 (1H, s), 5.48 (1H, s)；
1 methylenedioxy group signal: δ 5.95 (2H, s) and 2 aromatic ring methyl hydrogen nuclear signals: δ 2.03 (3H, s), 2.07 (3H, s).
Compound III's13CNMR (50MHz, CDCl3) show 3 fatty carbon, 12 aromatic ring carbon, 1 carbonyl carbon and 2 methyl
Carbon signal.Above data shows that compound IV is Homoisoflavonoids class compound, data and document (Tada A, Kasa R,
Saitoh T, et al.Studies on the constituents of ophionogonis tuber V.Isolation
ofnovel class ofhomoisoflavonoids and determination oftheir structure(1)
.Chem.Pharm Bull, 1980,28 (5): it is 1477) almost the same, determine that its planar structure is 5,7-dihydroxy-6,8-
Dimethyl-3- (3 ', 4 '-methylenedioxybenzyl)-chroman-4-one (methyl ophiopogonanone
A)。
The prior art is separated Formulas I-IV in the form of post separation, develops another separate mode still and has and is more important
Meaning.
Summary of the invention
The object of the present invention is to provide a kind of methods of flavones in separation and Extraction Radix Ophiopogonis, have and separate different flavonoids
The advantages of object.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of method of flavones in separation and Extraction Radix Ophiopogonis, comprising the following steps:
(1) dry Radix Ophiopogonis is taken, crushes and crosses 50~100 meshes, be put into reflux unit；The first second is added into reflux unit
Alcohol solution is heated to flowing back, and reacts 2~3hr, obtains extracting solution；The mass ratio of dry Radix Ophiopogonis and the first ethanol water is 1: 8
~10, the content of ethyl alcohol is 75~90wt% in the first ethanol water；
(2) it takes the extracting solution of step (1) to be filtered with 0.45~0.22 μm of organic filter film, obtains filtrate and filter residue, take filter
Liquid is dried in vacuo at 30~35 DEG C and eliminates solvent, adds water that the sample being precipitated is made to dissolve and use water constant volume, as test liquid；Initially
1kg: 1~2L of ratio of the volume of the quality and test liquid after constant volume for the dry Radix Ophiopogonis being added；
(3) by AB-8 macroporous resin column on the test liquid of step (2), after loading adsorbs 1.0~1.5hr, with the first distillation
Water elution, collects eluent and loading efflux merges into efflux A；Macroreticular resin uses the ammonium hydroxide of 0.08~0.12mol/l again
It is eluted, collects efflux B；Macroreticular resin is rinsed with after-fractionating water to neutrality again, then is eluted with the second ethanol water,
Collect efflux C；The content of ethyl alcohol is 45~60wt% in second ethanol water；Test liquid, the first distilled water, ammonium hydroxide,
The volume ratio of two distilled water and the second ethanol water is 1: 4~5: 4~5: 4~5: 4~5；
(4) it takes the eluate B of step (3), 0.5~1.0mol/l hydrochloric acid is added and is adjusted to neutrality, it will AB-8 macropore thereon
Resin column is eluted with third distilled water, then is eluted with third ethanol water, collects eluent and vacuum is dry at 30~35 DEG C
It is dry to eliminate solvent, obtain Radix Ophiopogonis general flavone powder；The content of ethyl alcohol is 75~90wt% in third ethanol water；Eluate B,
The volume ratio of third distilled water and third ethanol water is 1: 2~3: 2~3；
(5) the Radix Ophiopogonis general flavone powder of step (4) is taken to add in reaction flask, into reaction flask be added ether, sodium chloride and
Smashed metal organic framework compound HKUST-1,30~40min of ultrasonic disperse at 25~28 DEG C, with 0.45~0.22 μ
The filtering of m organic filter film, obtains the first filtrate and the first filter residue；Radix Ophiopogonis general flavone powder, ether, sodium chloride and smashed gold
The mass ratio for belonging to organic frame compound HKUST-1 is 1: 3~4: 0.01~0.02: 0.05~0.06；
(6) the first filter residue for taking step (5), vacuum drying eliminates solvent at 30~35 DEG C, adds in reaction flask, to anti-
It answers and ether, sodium chloride and smashed metal organic framework compound HKUST-1, the ultrasonic disperse at 30~32 DEG C is added in bottle
30~40min is filtered with 0.45~0.22 μm of organic filter film, obtains the second filtrate and the second filter residue；First filter residue, ether,
The mass ratio of sodium chloride and smashed metal organic framework compound HKUST-1 be 1: 6~8: 0.06~0.07: 0.15~
0.18；
(7) the second filter residue for taking step (6), vacuum drying eliminates solvent at 30~35 DEG C, adds in reaction flask, to anti-
It answers and ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 is added in bottle, in 34~35 DEG C
30~40min of lower ultrasonic disperse is filtered with 0.45~0.22 μm of organic filter film, obtains third filtrate and third filter residue；Second
Filter residue, ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 mass ratio be 1: 4~5:
0.05~0.06: 0.05~0.06: 0.08~0.10；
(8) the third filter residue for taking step (7), vacuum drying eliminates solvent at 30~35 DEG C, adds in reaction flask, to anti-
It answers and ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 is added in bottle, in 25~
30~40min of ultrasonic disperse at 26 DEG C is filtered with 0.45~0.22 μm of organic filter film, obtains the 4th filtrate and the 4th filter residue；
Third filter residue, ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 mass ratio
It is 1: 3~4: 0.03~0.04: 0.05~0.06: 0.06~0.08；
(9) the first filtrate of step (5), the second filtrate of step (6), the third filtrate of step (7) and step are taken respectively
(8) the 4th filtrate, vacuum drying eliminates solvent at 30~35 DEG C respectively, and water and the ultrasonic disperse at 15~35 DEG C is added,
Filtrate is filtered to take respectively, filtrate is dried in vacuo at 30~35 DEG C eliminates solvent respectively, is respectively obtained and the first filtrate, second
Filtrate, third filtrate, the one-to-one product I of the 4th filtrate, product I I, product I II and product I V.
Further preferably are as follows: calcium oxide, Radix Ophiopogonis general flavone powder, ether, sodium chloride, crushing are also added in step (5)
The mass ratio of metal organic framework compound HKUST-1 and calcium oxide afterwards are 1: 3~4: 0.01~0.02: 0.05~0.06:
0.005~0.008；
Calcium oxide, the first filter residue, ether, sodium chloride, smashed metal organic frame chemical combination are also added in step (6)
Object HKUST-1 and the mass ratio of calcium oxide are 1: 6~8: 0.06~0.07: 0.15~0.18: 0.005~0.008；
Calcium oxide is also added in step (7), the second filter residue, ether, sodium chloride, sodium bicarbonate, smashed metal have
Machine frame compound HKUST-1 and the mass ratio of calcium oxide are 1: 4~5: 0.05~0.06: 0.05~0.06: 0.08~0.10:
0.005~0.008；
Calcium oxide, third filter residue, ethyl acetate, sodium chloride, sodium bicarbonate, smashed gold are also added in step (8)
The mass ratio for belonging to organic frame compound HKUST-1 and calcium oxide is 1: 3~4: 0.03~0.04: 0.05~0.06: 0.06~
0.08: 0.005~0.008.
In conclusion the invention has the following advantages: can be by the similar multiple flavone compounds of structure in Radix Ophiopogonis
It separates, isolated flavones purity is high, yield are high, and process simplicity is easy to control.
Specific embodiment
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art
Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this
All by the protection of Patent Law in the protection scope of invention.
Embodiment 1: a kind of method of flavones in separation and Extraction Radix Ophiopogonis, comprising the following steps:
(1) dry Radix Ophiopogonis is taken, crushes and crosses 50 meshes, be put into reflux unit；The first ethanol water is added into reflux unit
Solution is heated to flowing back, and reacts 3hr, obtains extracting solution；The mass ratio of dry Radix Ophiopogonis and the first ethanol water is 1: 8, the first second
The content of ethyl alcohol is 90wt% in alcohol solution；
(2) it takes the extracting solution of step (1) to be filtered with 0.45 μm of organic filter film, obtains filtrate and filter residue, take filtrate 30
Vacuum drying eliminates solvent at DEG C, adds water that the sample being precipitated is made to dissolve and use water constant volume, as test liquid；The dry wheat being initially added
Ratio 1kg: 1L of the volume of the quality and test liquid after constant volume in winter；
(3) it by AB-8 macroporous resin column on the test liquid of step (2), after loading adsorbs 1.0hr, is washed with the first distillation
It is de-, it collects eluent and loading efflux merges into efflux A；Macroreticular resin is eluted with the ammonium hydroxide of 0.08mol/l again, is received
Collect efflux B；Macroreticular resin is rinsed with after-fractionating water to neutrality again, then is eluted with the second ethanol water, and efflux is collected
C；The content of ethyl alcohol is 45wt% in second ethanol water；Test liquid, the first distilled water, ammonium hydroxide, after-fractionating water and second
The volume ratio of ethanol water is 1: 4: 4: 4: 4；
(4) it takes the eluate B of step (3), 0.5mol/l hydrochloric acid is added and is adjusted to neutrality, it will AB-8 macroreticular resin thereon
Column, with third distilled water elute, then with third ethanol water elute, collect eluent and at 30 DEG C be dried in vacuo eliminate it is molten
Agent obtains Radix Ophiopogonis general flavone powder；The content of ethyl alcohol is 75wt% in third ethanol water；Eluate B, third distilled water and
The volume ratio of third ethanol water is 1: 2: 2；
(5) the Radix Ophiopogonis general flavone powder of step (4) is taken to add in reaction flask, into reaction flask be added ether, sodium chloride and
Smashed metal organic framework compound HKUST-1, the ultrasonic disperse 40min at 25 DEG C, with 0.45 μm of organic filter film mistake
Filter, obtains the first filtrate and the first filter residue；Radix Ophiopogonis general flavone powder, ether, sodium chloride and smashed metal organic frame
The mass ratio for closing object HKUST-1 is 1: 3: 0.01: 0.05；
(6) the first filter residue for taking step (5), vacuum drying eliminates solvent at 30 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride and smashed metal organic framework compound HKUST-1, the ultrasonic disperse 40min at 30 DEG C are used
0.45 μm of organic filter film filtering, obtains the second filtrate and the second filter residue；First filter residue, ether, sodium chloride and smashed gold
The mass ratio for belonging to organic frame compound HKUST-1 is 1: 6: 0.06: 0.15；
(7) the second filter residue for taking step (6), vacuum drying eliminates solvent at 30 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1, the ultrasound point at 34 DEG C
40min is dissipated, is filtered with 0.45 μm of organic filter film, obtains third filtrate and third filter residue；Second filter residue, ether, sodium chloride, carbon
The mass ratio of sour hydrogen sodium and smashed metal organic framework compound HKUST-1 are 1: 4: 0.05: 0.05: 0.08；
(8) the third filter residue for taking step (7), vacuum drying eliminates solvent at 30 DEG C, adds in reaction flask, to reaction flask
Interior addition ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 surpass at 25 DEG C
Sound disperses 40min, is filtered with 0.45 μm of organic filter film, obtains the 4th filtrate and the 4th filter residue；Third filter residue, ethyl acetate,
The mass ratio of sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 is 1: 3: 0.03: 0.05:
0.06；
(9) the first filtrate of step (5), the second filtrate of step (6), the third filtrate of step (7) and step are taken respectively
(8) the 4th filtrate, vacuum drying eliminates solvent at 30 DEG C respectively, and water and the ultrasonic disperse at 15 DEG C is added, filters respectively
Filtrate is taken, filtrate is dried in vacuo at 30 DEG C eliminates solvent respectively, respectively obtains and is filtered with the first filtrate, the second filtrate, third
Liquid, the one-to-one product I of the 4th filtrate, product I I, product I II and product I V.
Embodiment 2: a kind of method of flavones in separation and Extraction Radix Ophiopogonis, comprising the following steps:
(1) dry Radix Ophiopogonis is taken, crush and is sieved with 100 mesh sieve, is put into reflux unit；The first ethanol water is added into reflux unit
Solution is heated to flowing back, and reacts 2hr, obtains extracting solution；The mass ratio of dry Radix Ophiopogonis and the first ethanol water is 1: 10, first
The content of ethyl alcohol is 75wt% in ethanol water；
(2) it takes the extracting solution of step (1) to be filtered with 0.22 μm of organic filter film, obtains filtrate and filter residue, take filtrate 35
Vacuum drying eliminates solvent at DEG C, adds water that the sample being precipitated is made to dissolve and use water constant volume, as test liquid；The dry wheat being initially added
Ratio 1kg: 2L of the volume of the quality and test liquid after constant volume in winter；
(3) it by AB-8 macroporous resin column on the test liquid of step (2), after loading adsorbs 1.5hr, is washed with the first distillation
It is de-, it collects eluent and loading efflux merges into efflux A；Macroreticular resin is eluted with the ammonium hydroxide of 0.12mol/l again, is received
Collect efflux B；Macroreticular resin is rinsed with after-fractionating water to neutrality again, then is eluted with the second ethanol water, and efflux is collected
C；The content of ethyl alcohol is 60wt% in second ethanol water；Test liquid, the first distilled water, ammonium hydroxide, after-fractionating water and second
The volume ratio of ethanol water is 1: 5: 5:5: 5；
(4) it takes the eluate B of step (3), 0.5~1.0mol/l hydrochloric acid is added and is adjusted to neutrality, it will AB-8 macropore thereon
Resin column is eluted with third distilled water, then is eluted with third ethanol water, collects eluent and vacuum is dry at 30~35 DEG C
It is dry to eliminate solvent, obtain Radix Ophiopogonis general flavone powder；The content of ethyl alcohol is 90wt% in third ethanol water；Eluate B, third
The volume ratio of distilled water and third ethanol water is 1: 3: 3；
(5) the Radix Ophiopogonis general flavone powder of step (4) is taken to add in reaction flask, into reaction flask be added ether, sodium chloride and
Smashed metal organic framework compound HKUST-1, the ultrasonic disperse 30min at 28 DEG C, with 0.22 μm of organic filter film mistake
Filter, obtains the first filtrate and the first filter residue；Radix Ophiopogonis general flavone powder, ether, sodium chloride and smashed metal organic frame
The mass ratio for closing object HKUST-1 is 1: 4: 0.02: 0.06；
(6) the first filter residue for taking step (5), vacuum drying eliminates solvent at 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride and smashed metal organic framework compound HKUST-1, the ultrasonic disperse 30min at 32 DEG C are used
0.22 μm of organic filter film filtering, obtains the second filtrate and the second filter residue；First filter residue, ether, sodium chloride and smashed gold
The mass ratio for belonging to organic frame compound HKUST-1 is 1: 8: 0.07: 0.18；
(7) the second filter residue for taking step (6), vacuum drying eliminates solvent at 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1, the ultrasound point at 35 DEG C
30min is dissipated, is filtered with 0.22 μm of organic filter film, obtains third filtrate and third filter residue；Second filter residue, ether, sodium chloride, carbon
The mass ratio of sour hydrogen sodium and smashed metal organic framework compound HKUST-1 are 1: 5: 0.06: 0.06: 0.10；
(8) the third filter residue for taking step (7), vacuum drying eliminates solvent at 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 surpass at 26 DEG C
Sound disperses 30min, is filtered with 0.22 μm of organic filter film, obtains the 4th filtrate and the 4th filter residue；Third filter residue, ethyl acetate,
The mass ratio of sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 is 1: 4: 0.04: 0.06:
0.08；
(9) the first filtrate of step (5), the second filtrate of step (6), the third filtrate of step (7) and step are taken respectively
(8) the 4th filtrate, vacuum drying eliminates solvent at 35 DEG C respectively, and water and the ultrasonic disperse at 35 DEG C is added, filters respectively
Filtrate is taken, filtrate is dried in vacuo at 35 DEG C eliminates solvent respectively, respectively obtains and is filtered with the first filtrate, the second filtrate, third
Liquid, the one-to-one product I of the 4th filtrate, product I I, product I II and product I V.
Embodiment 3: a kind of method of flavones in separation and Extraction Radix Ophiopogonis, difference from example 1 is that, step (5)
In also be added with calcium oxide, Radix Ophiopogonis general flavone powder, ether, sodium chloride, smashed metal organic framework compound HKUST-1
Mass ratio with calcium oxide is 1: 3: 0.01: 0.05: 0.005；In step (6) also be added with calcium oxide, the first filter residue, ether,
The mass ratio of sodium chloride, smashed metal organic framework compound HKUST-1 and calcium oxide is 1: 6: 0.06: 0.15:
0.005；Calcium oxide is also added in step (7), the second filter residue, ether, sodium chloride, sodium bicarbonate, smashed metal are organic
Frame compound HKUST-1 and the mass ratio of calcium oxide are 1: 4: 0.05: 0.05: 0.08: 0.005；Step is also added in (8)
Calcium oxide, third filter residue, ethyl acetate, sodium chloride, sodium bicarbonate, smashed metal organic framework compound HKUST-1 and
The mass ratio of calcium oxide is 1: 3: 0.03: 0.05: 0.06: 0.005.
Embodiment 4: a kind of method of flavones in separation and Extraction Radix Ophiopogonis, with embodiment 2 the difference is that, step (5)
In also be added with calcium oxide, Radix Ophiopogonis general flavone powder, ether, sodium chloride, smashed metal organic framework compound HKUST-1
Mass ratio with calcium oxide is 1: 4: 0.02: 0.06: 0.008；In step (6) also be added with calcium oxide, the first filter residue, ether,
The mass ratio of sodium chloride, smashed metal organic framework compound HKUST-1 and calcium oxide is 1: 8: 0.07: 0.18:
0.008；Calcium oxide is also added in step (7), the second filter residue, ether, sodium chloride, sodium bicarbonate, smashed metal are organic
Frame compound HKUST-1 and the mass ratio of calcium oxide are 1: 5: 0.06: 0.06: 0.10: 0.008；Step is also added in (8)
Calcium oxide, third filter residue, ethyl acetate, sodium chloride, sodium bicarbonate, smashed metal organic framework compound HKUST-1 and
The mass ratio of calcium oxide is 1: 4: 0.04: 0.06: 0.08: 0.008.
Performance characterization
1, purity test
Test method: HPLC method.Using Japanese Shimadzu LC-10Avp high performance liquid chromatograph, attached UV detector.Chromatography
Column be enlightening horse C18:250mm × 4.6mm, 5 μm.Mobile phase is acetonitrile and water, gradient elution: 1-15min:17% acetonitrile；15-
17min:17% acetonitrile becomes 30%；17-40min: 30% acetonitrile is kept；40-42min:30% acetonitrile becomes 17%.Flow velocity is
1ml/min, sampling volume are 10 μ l, and Detection wavelength 260nm, temperature is 30 DEG C.Data are calculated using normalization method.
Test result is as shown in table 1.Table 1 shows that the compound I-IV in embodiment 1-4 is preferably separated, product
Purity is higher.
1 purity test of table
2, yield is tested
Yield=product quality/material quality × 100%, wherein product quality, which can directly adopt, weighs the mode of product and obtains
It arrives, and material quality=content × dry Radix Ophiopogonis, content can be tested and are calculated according to HPLC.HPLC content data uses at 5 points
Calibration curve method calculates.
Test result is as shown in table 2.Table 2 shows, the compound I-IV high income in embodiment 1-4.
The test of 2 yield of table
The specific implementation of the invention is not to be limited to these illustrations for the above content, and technology belonging to the present invention is led
For the those of ordinary skill in domain, without departing from the inventive concept of the premise, a number of simple deductions or replacements can also be made,
It all shall be regarded as belonging to present invention scope of patent protection determined by the appended claims.
Claims (2)
1. a kind of method of flavones in separation and Extraction Radix Ophiopogonis, which comprises the following steps:
(1) dry Radix Ophiopogonis is taken, crushes and crosses 50 ~ 100 meshes, be put into reflux unit；The first ethanol water is added into reflux unit
Solution is heated to flowing back, and reacts 2 ~ 3hr, obtains extracting solution；The mass ratio of dry Radix Ophiopogonis and the first ethanol water is 1:8 ~ 10,
The content of ethyl alcohol is 75 ~ 90wt% in first ethanol water；
(2) it takes the extracting solution of step (1) to be filtered with 0.45 ~ 0.22 μm of organic filter film, obtains filtrate and filter residue, take filtrate 30
Vacuum drying eliminates solvent at ~ 35 DEG C, adds water that the sample being precipitated is made to dissolve and use water constant volume, as test liquid；It is initially added
Ratio 1kg:1 ~ 2L of the volume of the quality and test liquid after constant volume of dry Radix Ophiopogonis；
(3) it by AB-8 macroporous resin column on the test liquid of step (2), after loading adsorbs 1.0 ~ 1.5hr, is washed with the first distillation
It is de-, it collects eluent and loading efflux merges into efflux A；Macroreticular resin is washed with the ammonium hydroxide of 0.08 ~ 0.12mol/l again
It is de-, collect efflux B；Macroreticular resin is rinsed with after-fractionating water to neutrality again, then is eluted with the second ethanol water, and stream is collected
Liquid C out；The content of ethyl alcohol is 45 ~ 60wt% in second ethanol water；Test liquid, the first distilled water, ammonium hydroxide, after-fractionating water
Volume ratio with the second ethanol water is 1:4 ~ 5:4 ~ 5:4 ~ 5:4 ~ 5；
(4) it takes the eluate B of step (3), 0.5 ~ 1.0mol/l hydrochloric acid is added and is adjusted to neutrality, it will AB-8 macroreticular resin thereon
Column is eluted with third distilled water, then is eluted with third ethanol water, is collected eluent and is dried in vacuo at 30 ~ 35 DEG C and removes
Solvent to the greatest extent, obtains Radix Ophiopogonis general flavone powder；The content of ethyl alcohol is 75 ~ 90wt% in third ethanol water；Eluate B, third are steamed
Distilled water and the volume ratio of third ethanol water are 1:2 ~ 3:2 ~ 3；
(5) it takes the Radix Ophiopogonis general flavone powder of step (4) to add in reaction flask, ether, sodium chloride and crushing is added into reaction flask
Metal organic framework compound HKUST-1 afterwards, 30 ~ 40min of ultrasonic disperse at 25 ~ 28 DEG C, with 0.45 ~ 0.22 μm of organic mistake
Membrane filtration obtains the first filtrate and the first filter residue；Radix Ophiopogonis general flavone powder, ether, sodium chloride and smashed metal are organic
The mass ratio of frame compound HKUST-1 is 1:3 ~ 4:0.01 ~ 0.02:0.05 ~ 0.06；
(6) the first filter residue for taking step (5), vacuum drying eliminates solvent at 30 ~ 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride and smashed metal organic framework compound HKUST-1, at 30 ~ 32 DEG C ultrasonic disperse 30 ~
40min is filtered with 0.45 ~ 0.22 μm of organic filter film, obtains the second filtrate and the second filter residue；First filter residue, ether, sodium chloride
Mass ratio with smashed metal organic framework compound HKUST-1 is 1:6 ~ 8:0.06 ~ 0.07:0.15 ~ 0.18；
(7) the second filter residue for taking step (6), vacuum drying eliminates solvent at 30 ~ 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1, it is ultrasonic at 34 ~ 35 DEG C
Disperse 30 ~ 40min, is filtered with 0.45 ~ 0.22 μm of organic filter film, obtain third filtrate and third filter residue；Second filter residue, second
Ether, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 mass ratio be 1:4 ~ 5:0.05 ~
0.06:0.05~0.06:0.08~0.10；
(8) the third filter residue for taking step (7), vacuum drying eliminates solvent at 30 ~ 35 DEG C, adds in reaction flask, to reaction flask
Interior addition ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1, at 25 ~ 26 DEG C
30 ~ 40min of ultrasonic disperse is filtered with 0.45 ~ 0.22 μm of organic filter film, obtains the 4th filtrate and the 4th filter residue；Third filter residue,
Ethyl acetate, sodium chloride, sodium bicarbonate and smashed metal organic framework compound HKUST-1 mass ratio be 1:3 ~ 4:
0.03~0.04:0.05~0.06:0.06~0.08；
(9) the first filtrate of step (5), the second filtrate of step (6), the third filtrate of step (7) and step (8) are taken respectively
4th filtrate, vacuum drying eliminates solvent at 30 ~ 35 DEG C respectively, and water and the ultrasonic disperse at 15 ~ 35 DEG C is added, filters respectively
Filtrate is taken, filtrate is dried in vacuo at 30 ~ 35 DEG C eliminates solvent respectively, is respectively obtained and the first filtrate, the second filtrate, third
Filtrate, the one-to-one product I of the 4th filtrate, product I I, product I II and product I V.
2. the method for flavones in a kind of separation and Extraction Radix Ophiopogonis according to claim 1, which is characterized in that in step (5) also
Added with calcium oxide, Radix Ophiopogonis general flavone powder, ether, sodium chloride, smashed metal organic framework compound HKUST-1 and oxygen
The mass ratio for changing calcium is 1:3 ~ 4:0.01 ~ 0.02:0.05 ~ 0.06:0.005 ~ 0.008；Calcium oxide is also added in step (6),
First filter residue, ether, sodium chloride, smashed metal organic framework compound HKUST-1 and calcium oxide mass ratio be 1:6 ~
8:0.06~0.07:0.15~0.18:0.005~0.008；Calcium oxide, the second filter residue, ether, chlorination are also added in step (7)
Sodium, sodium bicarbonate, smashed metal organic framework compound HKUST-1 and calcium oxide mass ratio be 1:4 ~ 5:0.05 ~
0.06:0.05~0.06:0.08~0.10:0.005~0.008；Calcium oxide, third filter residue, acetic acid second are also added in step (8)
Ester, sodium chloride, sodium bicarbonate, smashed metal organic framework compound HKUST-1 and calcium oxide mass ratio be 1:3 ~ 4:
0.03~0.04:0.05~0.06:0.06~0.08:0.005~0.008。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109709223A (en) * | 2018-12-28 | 2019-05-03 | 杭州师范大学 | The extraction detection method of saponin(e active component in a kind of folium panacis japonici cum caule |
| CN111875571A (en) * | 2020-07-23 | 2020-11-03 | 长沙理工大学 | Method for extracting soybean isoflavone from soy sauce residues |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127042A (en) * | 2011-01-26 | 2011-07-20 | 浙江大学 | Homoisoflavonoid compounds and preparation method and use thereof |
| CN102406833A (en) * | 2010-12-01 | 2012-04-11 | 成都中医药大学 | Comprehensive extraction and utilization technology for creeping liriope |
| CN105367531A (en) * | 2015-11-30 | 2016-03-02 | 浙江科技学院 | Method for separating two homoisoflavonoids in fibrous roots of ophiopogon japonicusby adopting recycling high-speed counter-current chromatography |
| CN107880278A (en) * | 2017-12-07 | 2018-04-06 | 宁波诺丁汉新材料研究院有限公司 | A kind of porous level metal-organic framework material HKUST 1 preparation method |
| CN108129467A (en) * | 2017-11-30 | 2018-06-08 | 浙江科技学院 | A kind of HSCCC-DPPH is combined online activity analysis and the method for detaching Radix Ophiopogonis homoisoflavone |
-
2018
- 2018-07-01 CN CN201810705657.6A patent/CN108976191A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102406833A (en) * | 2010-12-01 | 2012-04-11 | 成都中医药大学 | Comprehensive extraction and utilization technology for creeping liriope |
| CN102127042A (en) * | 2011-01-26 | 2011-07-20 | 浙江大学 | Homoisoflavonoid compounds and preparation method and use thereof |
| CN105367531A (en) * | 2015-11-30 | 2016-03-02 | 浙江科技学院 | Method for separating two homoisoflavonoids in fibrous roots of ophiopogon japonicusby adopting recycling high-speed counter-current chromatography |
| CN108129467A (en) * | 2017-11-30 | 2018-06-08 | 浙江科技学院 | A kind of HSCCC-DPPH is combined online activity analysis and the method for detaching Radix Ophiopogonis homoisoflavone |
| CN107880278A (en) * | 2017-12-07 | 2018-04-06 | 宁波诺丁汉新材料研究院有限公司 | A kind of porous level metal-organic framework material HKUST 1 preparation method |
Non-Patent Citations (1)
| Title |
|---|
| LIN YINING等: "Characterization of homoisoflavonoids in different cultivation regions of Ophiopogon japonicus and related antioxidant activity", 《JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109709223A (en) * | 2018-12-28 | 2019-05-03 | 杭州师范大学 | The extraction detection method of saponin(e active component in a kind of folium panacis japonici cum caule |
| CN109709223B (en) * | 2018-12-28 | 2021-07-20 | 杭州师范大学 | Extraction and detection method of saponin active ingredients in ginseng leaves |
| CN111875571A (en) * | 2020-07-23 | 2020-11-03 | 长沙理工大学 | Method for extracting soybean isoflavone from soy sauce residues |
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