CN105801392B - A kind of extracting method of Paeonol - Google Patents
A kind of extracting method of Paeonol Download PDFInfo
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- CN105801392B CN105801392B CN201610230255.6A CN201610230255A CN105801392B CN 105801392 B CN105801392 B CN 105801392B CN 201610230255 A CN201610230255 A CN 201610230255A CN 105801392 B CN105801392 B CN 105801392B
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/84—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by azeotropic distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
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Abstract
The present invention provides a kind of extracting method of Paeonol, methods described is extracted using the heavy associated methods of steam distillation alkali soluble acid to Paeonol, using moutan bark, complete stool paniculate swallowwort or paniculate swallowwort root as raw material, raw material is crushed into the simultaneously laggard water-filling steam distillations of the h of water extraction 10 ~ 23, stop distillation when liquid quality to be distillated is 2.5 ~ 3 times of raw material, distillate cold filtration is obtained into product A, then the raw material after regulation steam distillation in flask and Liquid Residue pH to 12 ~ 14 carry out alkali soluble, pH value of solution to 5 ~ 7 progress acid are adjusted after alkali soluble to sink and through cold filtration, obtain product B.The inventive method can efficiently extract Paeonol, and recovery rate is up to 95.3%, obtained Paeonol high purity 98.8%, and the inventive method does not use organic solvent, environmental pollution is avoided, with more the feature of environmental protection.
Description
Technical field
The invention belongs to active component and application field are extracted in Chinese herbal medicine, and in particular to a kind of extraction side of Paeonol
Method.
Background technology
Paeonol is mainly from the root skin or Mo Luoke plant paniculate swallowworts dry root, herb of Ranunculaceae Chinese herbaceous peony platymiscium tree peony
It is middle to extract the active component separated.Have found a variety of medicinal efficacies of Paeonol, main pharmacological action have calmness, hypnosis,
Anti-oxidant, hypotensive, antibacterial, anti-inflammatory etc. act on, and Paeonol can be by the pigment reducing decoloration deposited in skin so that skin
Skin brightens, and is widely used in cosmetics, toothpaste, gargle, tooth powder.
There is following several the main extracting method of Paeonol in moutan bark or paniculate swallowwort:1st, organic solvent lixiviation process.Kang Ye
Refined, great life of business etc. exists《The process optimization of technology for extracting paeonol from cortex moutan with solvents》Middle proposition chloroform, carbon tetrachloride, acetone, ethanol, acetic acid second
The amount of ester extraction Paeonol reduces successively, and the amount of contained other impurity raises successively, wherein using carbon tetrachloride as solvent, 2 times
The total amount of extraction Paeonol accounts for the 96.9% of 3 extraction total amounts.2nd, steam distillation.Koryo is beautiful, red legend is beautiful, Luo Xiao is still living and in good health《Water
Steam distillation method extracts Paeonol technical study》In continuously collect 2 distillates, for the first time to slipping out liquid clarification, second after
Continuous to collect 30 min, the amount for collecting Paeonol altogether twice accounts for 88.1%;3、CO2Supercritical fluid extraction.Wang Lihong, Zhou Lili,
Lei Xue etc. exists《Supercritical CO2The technique for extracting Paeonol in paniculate swallowwort》Middle proposition is with supercritical CO2Paeonol is extracted, with ultraviolet
Spectrophotometry paeonol content, as a result show that extraction efficiency increases;Separately there are patent CN201410021621.8, the applying date
2014.01.17《One kind utilizes CO2The method that supercritical extraction technique extracts Paeonol》In also mention supercritical extraction method and carry
Take Paeonol.
It is big using chloroform, carbon tetrachloride toxicity in solvent method in above-mentioned several extraction methods of Paeonol at present, pollution weight,
Be not suitable for industrialized production, although alcohol toxicity is weak, the efficiency extracted using ethanol is slightly lower, even if taking extract several times more
Method solves, it is also possible to the problem of causing the impurity level of extraction also accordingly to increase, and still use organic solvent, the feature of environmental protection
Difference.It is 88.1% only with recovery rate of the steam distillation through 2 extractions, and 30 min of second stage steam distillation
Extremely inefficient, energy consumption cost accordingly improves, and there is also some problems.And CO2Though supercritical extraction technique extraction can be by medicinal material
In organic matter more preferably bring out, but other organic impurity contents are also high, poor selectivity.
The content of the invention
For deficiencies of the prior art, the technical problem to be solved in the present invention is:How a kind of root bark of tree peony is provided
The extracting method of phenol, the Paeonol purity for obtaining its extraction efficiency height, extraction is high, and with the low spy of safety and environmental protection, cost
Point.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that:A kind of extracting method of Paeonol, including
Following steps:
1)Using moutan bark, complete stool paniculate swallowwort or paniculate swallowwort root as raw material, the raw material is crushed and is added to the water in 30 ~ 40
The h of soak extraction 10 ~ 23 at DEG C;Wherein, the mass volume ratio of the raw material and water is 1 g:6~10 mL;It is the moutan bark, complete
Strain paniculate swallowwort or paniculate swallowwort root are dry product;
2)Step 1)After the completion of immersion, leaching liquor and raw material are transferred in flask in the lump, put up steam distillation device,
Steam distillation is proceeded by, collects distillate, is stopped when the quality of the distillate is 2.5 ~ 3 times of the material quality
Distillation, is filtered after the distillate is cooled down into 24 ~ 30 h at 2 ~ 10 DEG C, is collected filter residue and is obtained steam distillation Paeonol product
A;
3)To step 2)Alkali, regulation pH value of solution to 12 ~ 14 are added in raw material and Liquid Residue after steam distillation in flask
After carrying out the h of alkali carries 2 ~ 3, alkali extract is filtered, collects filtrate, the pH to 5 ~ 7 of the filtrate is adjusted with acid, pH will be adjusted
Filtrate afterwards is filtered after cooling down 24 ~ 30 h at 2 ~ 10 DEG C, is collected filter residue and is obtained the heavy Paeonol product B of alkali soluble acid.
Compared with prior art, the present invention has the advantages that:
1st, the present invention in the prior art only with extraction by steam distillation root bark of tree peony phenol extraction gross efficiency it is not high, extraction
Rate is low, and the deficiencies of extraction cost is high, is damaged to environment be present using organic solvent method, proposes that one kind is steamed using water
Steam distillation and the heavy method for being combined extraction Paeonol of alkali soluble acid.The present invention first uses steam distillation to make Paeonol and water can be with
Form azeotropic mixture to distillate, when steam distillation efficiency declines, switch to alkali soluble acid heavy method and second extraction is carried out to Paeonol, lead to
Such extracting mode is crossed, ensures that cut and the Paeonol in residue can obtain further extraction and reclaim, Paeonol is also easier
Separated from other components.The inventive method is to the extraction efficiency of Paeonol compared to carrying only with steam distillation
Take efficiency to be greatly improved, 95.3% can be reached, extraction effect is good, obtained Paeonol purity 98.8%.
2nd, the inventive method is found by studying, can be with when being extracted using test parameters of the present invention to Paeonol
Make the Paeonol dissolution to large extent in moutan bark or paniculate swallowwort, recovery rate is up to 95.3%, and is steamed using vapor of the present invention
Evaporate-the heavy associated methods of alkali soluble acid are extracted, as steam distillation is carried out, the Determination of Paeonol not steamed significantly reduces, and
Because the fibr tissue of medicinal material adsorbs Paeonol, so that extraction efficiency reduces suddenly;And except the heavy principle of alkali soluble acid and water
Steam distillation is different outer, and the process of alkali soluble destroys fibr tissue, so that Paeonol is more easy to from dissolution inside medicinal material, further
Recovery rate is ensure that, and the present invention will not bring harmful effect to the property of Paeonol, the Paeonol for extracting to obtain is best in quality.
3rd, the present invention make it that the dissolution of Paeonol is more abundant using ultrasonic auxiliary extraction method, and auxiliary using ultrasonic wave
Help extraction to be advantageous to shorten extraction time, improve extraction efficiency, be more suitable in the high-volume extraction of Paeonol, more accelerate
It is prompt.
4th, the inventive method is higher only with the method extraction efficiency of steam distillation compared with prior art, and energy consumption is lower;
When carrying out root bark of tree peony phenol extraction using organic solvent in the prior art, because Paeonol is soluble in organic solvent, thus it is organic removing
During solvent part Paeonol can be made to be removed with organic solvent, reduce the recovery rate of Paeonol, and the present invention uses water
As solvent, because Paeonol in cold water it is insoluble, so organic solvent extracting method compared with prior art, the present invention further subtracts
Lack the loss of Paeonol in a solvent, ensure that the recovery rate of Paeonol.As fully visible, the present invention extracts compared with prior art
Method cost is lower, with more environment friendly, meets the demand for development of recycling economy, and recovery rate is higher, the obtained root bark of tree peony
Phenol finished product purity is high, therefore has more replicability, and application prospect is good.
Brief description of the drawings
Fig. 1 is steam distillation Paeonol product A of the present invention HPLC spectrograms;
Fig. 2 is the heavy Paeonol product B of alkali soluble of the present invention acid HPLC spectrograms.
Embodiment
The present invention is described in further detail with reference to specific embodiment and Figure of description.The implementation case with
Implemented under premised on the technology of the present invention, now provide detailed embodiment and specific operating process, to illustrate the present invention
It is creative, but protection scope of the present invention is not limited to following embodiment.
PH regulation is carried out in following embodiments using 2 mol/L hydrochloric acid solution and 1 mol/L sodium hydroxide solution.
A kind of extracting method of 1 Paeonol of embodiment, comprises the following steps:
1)Moutan bark dry product is broken into powder, powder is in canescence, crosses 10#Sieve(Particle diameter is less than 2 mm), as raw material;
The g of Tree peony Bark 25.0 accurately is weighed, is placed in 250 mL round-bottomed flasks, 150 mL distilled water is added and carries out warm leaching, when temperature is soaked
Between be 19 h, in order that material is more dissolved in distilled water in moutan bark, ultrasonic cleaning instrument is placed on after immersion(100
KHz、50 W)Middle ultrasonic 20 min.
2)Step 1)After the completion of immersion, leaching liquor and raw material are transferred in flask in the lump, put up steam distillation device,
Proceed by steam distillation, collect distillate, the muddy degree of distillate is decreased obviously in pipe to be condensed, and the raw material is with evaporating
The mass volume ratio for going out liquid is 1:Stop distillation when 2.5, weigh the quality of distillate between 63.5 ~ 64.5g(Distillate quality
It is 2.5 ~ 2.6 times of Tree peony Bark material quality), by the distillate in refrigerator(4~6℃)Filter, obtain after cooling down 24 h
The filter residue arrived is steam distillation product A;
3)While hot with glass bar while stirring to step 2)Added in raw material and Liquid Residue after steam distillation in flask
NaOH solution, regulation pH value of solution to 13 carry out the h of alkali carries 2, are cooled to room temperature, are filtered under diminished pressure, and remove moutan bark residue and insoluble
Material, filtrate is collected, the pH to 5 of the filtrate is adjusted with hydrochloric acid, is cooled to room temperature, is filtered after 24 h are cooled down at 4 ~ 6 DEG C, collected
Filter residue, filter residue is washed with cold water, obtain the heavy product B of alkali soluble acid(It is faint yellow);
4)Collection step 3)The filter residue being filtrated to get to alkali extract, 30 mL distilled water are added into the filter residue(The filter
The mass volume ratio of slag and water is 3 g:2 mL)Filtered after immersion 2h, remove root bark of tree peony residue and insoluble substance, collect and adjust
The pH of filtrate to 5, it is cooled to room temperature, and is filtered after cooling down 24h in 4 ~ 6 DEG C, collects filter residue and obtain Paeonol product C, micro cold water
Washed product C, weighing weight are 0.0251 g.
By calculating, after the extraction of two steps, it is 0.3493 g to obtain Paeonol gross weight, accounts for root bark of tree peony powder gross weight
1.40%, recovery rate is high.Paeonol obtained by further calculating steam distillation accounts for the 67.9% of extraction total amount;Second step extracted amount accounts for
The 25.4% of total amount is extracted, Paeonol obtained by first two steps accounts for the 93.3% of total extracted amount, and the 3rd step obtains the 6.7% of gross weight.Thus may be used
See, can extract the Paeonol in full moutan bark substantially using the method for two steps extraction of the invention, extraction efficiency is high.
The impurity that may contain during extracting Paeonol to steam distillation is analyzed.Take 0.2-0.3 mL water
Steam distillation distillate, add ethyl acetate+petroleum ether(Volume ratio 1:5)Mixed solution shakes, after static layering, with hair
Tubule draws a small amount of upper organic phase solution and carries out thin-layer chromatographic analysis(TLC), silica gel thin-layer plate, with ethyl acetate+petroleum ether
(Volume ratio 1:5)For solvent, expansion, dry, 254 nm inspect spot under uv lamps, analyze the results of 2 parallel determinations with
The TLC results of reference substance Paeonol, as a result show the R of distillate principal spotfIt is worth for 0.64, the principal spot Rf values of distillate sample
It is consistent with reference substance, illustrate that composition is Paeonol in the distillate of steam distillation.
HPLC analyses are carried out to steam distillation product A purity, take a small amount of steam distillation product A in cillin bottle,
Being dissolved with 2 mL methanol, the solution after dissolving takes 20 μ L to be injected into chromatographic column after 0.45 μm of organic phase filter membrane filters,
With efficient liquid phase chromatographic analysis [chromatographic condition:ODS posts(4.6×250 mm, Ø 5 µm);Methanol+H2O(Volume ratio 80:20)
For mobile phase, the mL/min of flow rate of mobile phase 1.0;UV-detector, Detection wavelength are 274 nm].Sample chromatogram figure such as Fig. 1 institutes
Show, as seen from Figure 1 retention time(t)Peak within 5 min is because molten caused by solvent and the mobile phase mismatch of sample
Agent peak, the min of t=49.7 peak are Paeonol, and the min of t=26.4 peak is the impurity peaks contained in extract, and analysis chart 1 is visible,
Impurity content is few in steam distillation product A of the present invention, and purity is high.
Take a small amount of heavy product B of alkali soluble acid to be dissolved with methanol, take a small amount of solution to carry out TLC tlc analysis [acetic acid with capillary
Ethyl ester+petroleum ether(Volume ratio 1:5)For solvent], as a result show that the heavy product B of alkali soluble acid is Paeonol, only containing micro miscellaneous
Matter, purity are high.Product B heavy to alkali soluble acid carries out HPLC analyses, as a result as shown in Fig. 2 as seen from Figure 2 only in retention time
(Between 5-15 min)There is trace impurity peak(Because the stronger other components soluble in water of polarity are extracted), do not occur
Other impurities peak, show that the heavy product B of alkali soluble acid purity is high, impurity content is few.
A kind of extracting method of 2 Paeonol of embodiment, comprises the following steps:
1)Complete stool paniculate swallowwort dry product is broken into powder, crosses 10#Sieve(Particle diameter is less than 2 mm), as raw material;Accurately weigh
The g of complete stool paniculate swallowwort powder 25.0, is placed in 250 mL round-bottomed flasks, adds 250 mL distilled water and carries out warm leaching, and the temperature leaching time is
15 h, in order that material is more dissolved in aqueous solvent in complete stool paniculate swallowwort, ultrasonic cleaning instrument is placed on after immersion(100
KHz、50 W)Middle ultrasonic 10 min.
2)Step 1)After the completion of immersion, leaching liquor and raw material are transferred in flask in the lump, put up steam distillation device,
Proceed by steam distillation, the muddy degree of distillate is decreased obviously in pipe to be condensed, and distillate quality is complete stool paniculate swallowwort
Stop distillation at 2.5 times of powder stock quality, by the distillate in refrigerator(4~6℃)Filter, obtain after cooling down 24 h
Filter residue be steam distillation product A;
3)While hot with glass bar while stirring to step 2)Added in raw material and Liquid Residue after steam distillation in flask
NaOH solution, regulation pH value of solution to 13 carry out the h of alkali carries 2.5, be cooled to room temperature, be filtered under diminished pressure, remove complete stool paniculate swallowwort residue and
Insoluble substance, filtrate is collected, the pH to 5 of the filtrate is adjusted with hydrochloric acid, is cooled to room temperature, mistake after 24 h is cooled down at 4 ~ 6 DEG C
Filter, filter residue is collected, filter residue is washed with cold water, obtain the heavy product B of alkali soluble acid(It is faint yellow);
4)Collection step 3)The filter residue being filtrated to get to alkali extract, 30 mL distilled water are added into the filter residue(The filter
The mass volume ratio of slag and water is 6 g:5 mL)Filtered after immersion 2.5h, remove complete stool paniculate swallowwort residue and insoluble substance, received
Collect and adjust the pH to 5 of filtrate, be cooled to room temperature, and filtered after cooling down 24h in 4 ~ 6 DEG C, collect filter residue and obtain Paeonol product C.
By calculating, after the extraction of two steps, it is 0.3407g to obtain Paeonol gross weight, accounts for complete stool paniculate swallowwort powder gross weight
1.36%, recovery rate is high.Paeonol obtained by further calculating steam distillation accounts for the 65.2% of extraction total amount;Second step extracted amount
The 22.6% of extraction total amount is accounted for, Paeonol obtained by first two steps accounts for the 87.8% of total extracted amount, and the 3rd step obtains the 12.2% of gross weight.
A kind of extracting method of 3 Paeonol of embodiment, comprises the following steps:
1)Paniculate swallowwort root dry product is broken into powder, crosses 10#Sieve(Particle diameter is less than 2 mm), as raw material;It is accurate to weigh Xu
The long g of minister in ancient times's root powder 25.0, is placed in 250 mL round-bottomed flasks, adds 200 mL distilled water and carries out warm leaching, the temperature leaching time is 10
H, in order that material is more dissolved in aqueous solvent in paniculate swallowwort root, ultrasonic cleaning instrument is placed on after immersion(100 KHz、50
W)Middle ultrasonic 30 min.
2)Step 1)After the completion of immersion, leaching liquor and raw material are transferred in flask in the lump, put up steam distillation device,
Proceed by steam distillation, the muddy degree of distillate is decreased obviously in pipe to be condensed, and distillate quality is paniculate swallowwort root powder
Stop distillation at 3 times of powder stock quality, by the distillate in refrigerator(4~6℃)Filtered after cooling down 24 h, obtained filter
Slag is steam distillation product A;
3)While hot with glass bar while stirring to step 2)Added in raw material and Liquid Residue after steam distillation in flask
NaOH solution, regulation pH value of solution to 13 carry out alkali carries 3h, are cooled to room temperature, are filtered under diminished pressure, and remove paniculate swallowwort root residue and insoluble
Property material, collect filtrate, the pH to 5 of the filtrate adjusted with hydrochloric acid, be cooled to room temperature, filtered after 24 h are cooled down at 4 ~ 6 DEG C, receive
Collect filter residue, filter residue is washed with cold water, obtain the heavy product B of alkali soluble acid(It is faint yellow);
4)Collection step 3)The filter residue being filtrated to get to alkali extract, 30mL distilled water is added into the filter residue(The filter
The mass volume ratio of slag and water is 7 g:5 mL)Filtered after immersion 3h, remove paniculate swallowwort root residue and insoluble substance, collected simultaneously
The pH to 5 of filtrate is adjusted, is cooled to room temperature, and is filtered after cooling down 24h in 4 ~ 6 DEG C, filter residue is collected and obtains Paeonol product C.
By calculating, after the extraction of two steps, it is 0.3391g to obtain Paeonol gross weight, accounts for paniculate swallowwort root powder gross weight
1.35%, recovery rate is high.Paeonol obtained by further calculating steam distillation accounts for the 67.2% of extraction total amount;Second step extracted amount accounts for
The 24.5% of total amount is extracted, Paeonol obtained by first two steps accounts for the 91.7% of total extracted amount, and the 3rd step obtains the 8.3% of gross weight.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although with reference to compared with
The present invention is described in detail good embodiment, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent substitution, and without departing from the objective and scope of technical solution of the present invention, it all should cover at this
Among the right of invention.
Claims (6)
1. a kind of extracting method of Paeonol, it is characterised in that comprise the following steps:
1)Using moutan bark, complete stool paniculate swallowwort or paniculate swallowwort root as raw material, the raw material is crushed and is added to the water at 30 ~ 40 DEG C
After the h of soak extraction 10 ~ 23;10 ~ 30min is ultrasonically treated under 100 ~ 120 KHz, 50 ~ 80W;Wherein, the raw material and water
Mass volume ratio be 1 g:6~10 mL;
2)Step 1)After the completion of immersion, leaching liquor and raw material are transferred in flask in the lump, put up steam distillation device, is started
Steam distillation is carried out, collects distillate, stops steaming when the quality of the distillate is 2.5 ~ 3 times of the material quality
Evaporate, filtered after the distillate is cooled down into 24 ~ 30 h at 2 ~ 10 DEG C, collect filter residue and obtain steam distillation Paeonol product A;
3)To step 2)Alkali is added in raw material and Liquid Residue after steam distillation in flask, regulation pH value of solution to 12 ~ 14 is carried out
After the h of alkali carries 2 ~ 3, alkali extract is filtered, collects filtrate, the pH to 5 ~ 7 of the filtrate is adjusted with acid, after regulation pH
Filtrate is filtered after cooling down 24 ~ 30 h at 2 ~ 10 DEG C, is collected filter residue and is obtained the heavy Paeonol product B of alkali soluble acid;
4)Collection step 3)The residue obtained after being filtered to alkali extract, add after water soaks 2 ~ 5 h and filter into the residue, receive
Collect and adjust the pH to 5 ~ 7 of filtrate, filtered after the filtrate after regulation pH is cooled down into 24 ~ 30h at 2 ~ 10 DEG C, collect filter residue and obtain
Paeonol product C;Wherein, the mass volume ratio of the residue and water is 1g:0.6~1mL.
2. the extracting method of Paeonol according to claim 1, it is characterised in that step 1)It is middle that the raw material is crushed to 10
~ 12 mesh.
3. the extracting method of Paeonol according to claim 1, it is characterised in that step 1)Described in the matter of raw material and water
Amount volume ratio is 1 g:6 mL.
4. the extracting method of Paeonol according to claim 1, it is characterised in that in 100 KHz, 50 W ultrasound condition
20 min of lower supersound process.
5. the extracting method of Paeonol according to claim 1, it is characterised in that step 3)The middle pH value of solution that adjusts is to 13 progress
Alkali carries.
6. the extracting method of Paeonol according to claim 1, it is characterised in that step 3)It is middle to adjust the filtrate with acid
It is heavy that acid is carried out after pH to 5.
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