CN109777843A - A kind of new method preparing quininic acid - Google Patents
A kind of new method preparing quininic acid Download PDFInfo
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- CN109777843A CN109777843A CN201910172792.3A CN201910172792A CN109777843A CN 109777843 A CN109777843 A CN 109777843A CN 201910172792 A CN201910172792 A CN 201910172792A CN 109777843 A CN109777843 A CN 109777843A
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Abstract
The invention discloses a kind of new methods for preparing quininic acid to extract specifically using gouge as raw material by solvent of polar solvent, then digests through tannase, most obtains afterwards through polystyrene type macroporous adsorbent resin column chromatography；Wherein, the polar solvent is water and the composition selected from one or more of methanol, ethyl alcohol and acetone, and the accounting of the water is >=20v/v%；Model D101, the Diaion HP-20 or AB-8 of the polystyrene type macroporous absorbent resin；In chromatography, eluant, eluent used is water and the composition selected from one or more of methanol, ethyl alcohol and acetone, and the accounting of the water is >=20v/v%.For the first time using gouge leaf as raw material, extracted, tannin enzyme hydrolysis, column chromatograph to obtain the quininic acid of quality stabilization, high yield pulp1, high-purity the present invention, not the preparation of only quininic acid provide it is new supply raw material, new utilization ways are also opened for gouge.
Description
Technical field
The present invention relates to a kind of preparation methods of quininic acid, and in particular to a kind of new method for preparing quininic acid.
Background technique
Quininic acid is the distinctive alicyclic ring organic acid of higher plant, is a kind of precursor of aromatic amino acid biosynthesis
Matter is prevalent in vascular plant, often coexists with shikimic acid in plant.Quininic acid structure is special, has multiple chiralitys
Center is material important in three-dimensional organic synthesis, as chiral raw material synthesis of natural product, the side such as prepare new polymeric material
Face is widely applied, and specific structure is shown below:
Gouge (Castanopsis tibetana Hance) is a kind of Fagaceae, cone platymiscium, and bark is thick, such as pine bark
Shape cracking, endothelium reddish tan are bordering on smooth.Ring porous wood, xylem only have thin wood radiaftive rays, and heart sapwood is clearly demarcated, heartwood bronzing,
Sapwood color is thin, and annual ring is clearly demarcated, material heavily fortified point weight, resistance to water-wet, suitable to make mine timber, beam, column, building and wood for furniture, belongs to cone class, is the Changjiang river
On the south more typical main timber tree species.Gouge fruit (hook chestnut) can be used for the treatment of dysentery.So far not yet discovery is from gouge
The relevant report of isolated quininic acid.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new method for preparing quininic acid, this method is with gouge for the first time
Raw material, the easy techniques such as extracted, tannin enzyme hydrolysis, column chromatography, obtains the quininic acid of quality stabilization, high yield pulp1, high-purity, is
The preparation of quininic acid provide it is new supply raw material, new utilization ways are also opened for gouge.
The new method of the present invention for preparing quininic acid is to be mentioned using gouge as raw material by solvent of polar solvent
It takes, extracting solution recycling design, gained residual solution is digested with tannase, and enzymolysis liquid is through polystyrene type large pore resin absorption column
It chromatographs and obtains；Wherein,
Composition of the polar solvent for water and selected from one or more of methanol, ethyl alcohol and acetone,
In, water ratio shared in polar solvent is >=20v/v%；
Model D101, the Diaion HP-20 or AB-8 of the polystyrene type macroporous absorbent resin；
When enzymolysis liquid is through polystyrene type macroporous adsorbent resin column chromatography, eluant, eluent used be water with selected from methanol,
The composition of one or more of ethyl alcohol and acetone, wherein water ratio shared in eluant, eluent is >=20v/v%.
In technical solution of the present invention, the yield of the model of the polystyrene type macroporous absorbent resin to products therefrom
And purity all has particularly important influence, the applicant's experiments have shown that, only when select model D101, Diaion HP-20
Or AB-8 polystyrene type macroporous absorbent resin when, could obtain high yield pulp1 (2.5~3.2%) and high-purity (93% or more,
HPLC analytic approach).
In technical solution of the present invention, specifically it can be using the leaf of gouge and/or branch and/or bark as raw material,
It is extracted again after preferably raw material is chopped up or is crushed.
In technical solution of the present invention, described is extracted as heating extraction, ultrasonic extraction or room temperature extraction, time of extraction
Number, additional amount, the time of extraction etc. of solvent can refer to existing conventional techniques when extracting every time.It is preferred that refluxing extraction is used, tool
Body, Extracting temperature is 40 DEG C of reflow temperature ranges to solvent, preferably 50 DEG C to solvent of reflow temperature range；Extraction time
It is 2~4 times, preferably 3 times；The additional amount of solvent is 3~12 times, preferably 6~10 times of raw material weight when extracting every time；Every time
The time of extraction is 2~3h, preferably 2.5h.
In technical solution of the present invention, the dosage of the tannase specifically can be 0.2~the 1.0 ‰ of raw material weight,
It is preferred that 0.5 ‰.Enzymatic hydrolysis usually carries out under the conditions of≤35 DEG C, and enzymolysis time is 1~4h.It is preferred that enzymatic hydrolysis is under the conditions of 20~30 DEG C
It carries out, enzymolysis time is preferably 2~4h at this time.
In technical solution of the present invention, in the composition of polar solvent, preferably ratio shared by water is 20~50v/
V%；In the composition of eluant, eluent, preferably ratio shared by water is 20~50v/v%.
When by polystyrene type macroporous adsorbent resin column chromatography on enzymolysis liquid, be first washed with water column to efflux it is colourless after again
It with eluent, is examined to know with thin-layer chromatography during elution and merges fraction, collect target fraction, it is dry after recycling design,
Obtain quininic acid.
Compared with prior art, the method for the invention is for the first time using gouge leaf as raw material, extracted, tannin enzyme hydrolysis,
The easy technique such as column chromatography, obtains quality stabilization, high yield pulp1 (2.5~3.3%), high-purity (93% or more, HPLC analytic approach)
Quininic acid, not the preparation of only quininic acid provide it is new supply raw material, new utilization ways are also opened for gouge.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
Embodiment 1
Fresh leaf raw material 1.0kg is bored in hook taking, is chopped up, and addition is equivalent to the ethanol/water solution of 8 times of raw material weights (wherein
Ethyl alcohol accounts for 60v/v%), 50 DEG C of heat preservations are extracted 2.5 hours, filtering；Filter residue adds ethanol/water solution (the wherein second of 8 times of raw material weights
Alcohol accounts for 60v/v%), 50 DEG C of heat preservations are extracted 2.5 hours, filtering；Filter residue adds ethanol/water solution (the wherein ethyl alcohol of 8 times of raw material weights
Account for 60v/v%), 50 DEG C of heat preservations are extracted 2.5 hours, and filtering merges 3 filtrates, obtain extracting solution, and extracting solution recycles mistake after ethyl alcohol
Remaining insoluble matter is filtered out, filtrate is collected；When filtrate is cooled to 25 DEG C, the addition enzyme hydrolysis of 0.5g tannin 3 hours is filtered, filter
Polystyrene type macroporous absorbent resin (D101) adsorbs on liquid, first with 3 times of column volume deionized waters, then with 4 times of column volumes
Ethanol/water solution (wherein ethyl alcohol accounts for 30v/v%) elution, 0.2 times of volume are a fraction, are determined by thin-layer chromatography and merge stream
Part, medicinal extract is concentrated under reduced pressure into amalgamation liquid, and medicinal extract is dried to obtain white solid 30.1g (content 96.3%).
To gained white solid carry out Structural Identification (by MS,1H-NMR and13The spectroscopys such as C-NMR data authentication), and will
As a result it is compared with literature values.
LCIT-TOF-MS:m/z 191.0756 (M-H) (calculated value C7H12O6,192.0634)。
1H-NMR(500MHz,acetone-d6)δ:2.14-2.28(4H,m,H-2a,H-2b,H-6a,H-6b),3.68
(1H, dd, J=2.9,8.3Hz, H-4), 4.16 (1H, m, H-3), 4.24 (1H, m, H-5).
13C-NMR(125MHz,acetone-d6) δ: 37.1 (C-2), 39.9 (C-6), 68.3 (C-5), 71.3 (C-4),
71.0 (C-3), 75.4 (C-1), 167.6 (C-7).
Above-mentioned MS,1H-NMR and13C-NMR data and document report are almost the same, therefore are accredited as quininic acid, and structure is as follows:
Purity test: HPLC analytic approach [chromatographic column: Cosmosil 5C is used18AR II (4.6 × 250mm, 5 μm)；Column
Temperature: 35 DEG C；Mobile phase: CH3CN-50mM H3PO4, 0~39 minute 4-30%CH3CN；Flow velocity: 0.8mL/min；Detection wavelength:
209nm] detection the present embodiment obtained by white solid purity, as the result is shown gained white solid quininic acid purity be 96.3%.
Comparative example 1
Embodiment 1 is repeated, the difference is that replacing D101 macroreticular resin with D102 macroreticular resin.Finally obtain white solid
20.3g。
To white solid obtained by this comparative example through MS same as Example 1,1H-NMR and13The spectroscopys data such as C-NMR mirror
It is fixed, it is determined as quininic acid.
Purity detecting is carried out through method same as Example 1 to white solid obtained by this comparative example, determines that purity is
87.7%.
Comparative example 2
Embodiment 1 is repeated, the difference is that replacing D101 macroreticular resin with ADS-8 macroreticular resin.Finally obtain white solid
24.6g。
To white solid obtained by this comparative example through MS same as Example 1,1H-NMR and13The spectroscopys data such as C-NMR mirror
It is fixed, it is determined as quininic acid.
Purity detecting is carried out through method same as Example 1 to white solid obtained by this comparative example, determines that purity is
86.2%.
Embodiment 2
Fresh leaf raw material 1.0kg is bored in hook taking, is chopped up, and the water for being equivalent to 6 times of raw material weights is added, and 80 DEG C of heat preservations extract 3
Hour, filtering；Filter residue adds the water of 6 times of raw material weights, and 70 DEG C of heat preservations are extracted 3 hours, filtering；Filter residue adds the water of 8 times of raw material weights,
70 DEG C of heat preservations are extracted 2 hours, and filtering merges 3 filtrates, are obtained extracting solution, are filtered to remove after extracting solution recycling ethyl alcohol remaining
Insoluble matter collects filtrate；When filtrate is cooled to 30 DEG C, the addition enzyme hydrolysis of 0.5g tannin 3 hours is filtered, polystyrene on filtrate
Type macroporous absorbent resin (D101) absorption, first with 3 times of column volume deionized waters, then with the ethanol/water solution of 4 times of column volumes
(wherein ethyl alcohol accounts for 80v/v%) elution, 0.2 times of volume are a fraction, are determined by thin-layer chromatography and merge fraction, amalgamation liquid is through subtracting
Pressure is condensed into medicinal extract, and medicinal extract is through being dried to obtain quininic acid 28.6g (purity 97.5%) (to the structure and Purity of products therefrom
With embodiment 1, similarly hereinafter).
Embodiment 3
Embodiment 1 is repeated, unlike:
It 1) is ethanol/water solution for the polar solvent of extraction (wherein ethyl alcohol accounts for 80v/v%)；
2) additional amount of tannase is 0.6g；
3) the polystyrene type macroreticular resin used in is Diaion HP-20.
Finally obtain quininic acid 33.3g (purity 94.8%%).
Embodiment 4
Embodiment 1 is repeated, unlike:
1) raw material is broken gouge bark, and the polar solvent for extraction is that (wherein methanol accounts for methanol/water solution
60v/v%)；
2) additional amount of tannase is 1.0g；
3) the polystyrene type macroreticular resin used in is AB-8.
Finally obtain quininic acid 34.1g (purity 93.4%).
Embodiment 5
Embodiment 1 is repeated, unlike:
1) raw material is broken gouge branch, and the polar solvent for extraction is that (wherein acetone accounts for acetone/water solution
50v/v%)；
2) additional amount of tannase is 0.6g, and enzymatic hydrolysis carries out under the conditions of 35 DEG C, and enzymolysis time is 2 hours；
3) in elution, the ethyl alcohol of 30v/v% is replaced with the aqueous acetone solution of 50v/v%.
Finally obtain quininic acid 29.8g (purity 96.6%).
Embodiment 6
Embodiment 1 is repeated, unlike:
It 1) is methanol/water solution for the polar solvent of extraction (wherein methanol accounts for 70v/v%)；
2) additional amount of tannase is 0.2g, and enzymatic hydrolysis carries out at 20 °C, and enzymolysis time is 4 hours；
3) the polystyrene type macroreticular resin used in is Diaion HP-20, in elution, with 70v/v%'s
Methanol aqueous solution replaces the ethyl alcohol of 30v/v%.
Finally obtain quininic acid 32.6g (purity 95.0%).
Embodiment 7
Fresh leaf raw material 1.0kg is bored in hook taking, is chopped up, and addition is equivalent to the ethanol/water solution of 10 times of raw material weights (wherein
Ethyl alcohol accounts for 30v/v%), ultrasonic extraction 1 hour (power 250W, supersonic frequency 40kHz) at room temperature, filtering；Filter residue adds 5
The ethanol/water solution (wherein ethyl alcohol accounts for 30v/v%) of times raw material weight, at room temperature ultrasonic extraction 1 hour (power 250W,
Supersonic frequency is 40kHz), filtering merges 2 filtrates, obtains extracting solution, be filtered to remove after extracting solution recycling ethyl alcohol it is remaining not
Molten object collects filtrate；When filtrate is cooled to 30 DEG C, the addition enzyme hydrolysis of 0.5g tannin 3 hours is filtered, polystyrene type on filtrate
Macroporous absorbent resin (Diaion HP-20) absorption, first with 3 times of column volume deionized waters, then with the ethanol/water of 4 times of column volumes
Solution (wherein ethyl alcohol accounts for 30v/v%) elution, 0.2 times of column volume are a fraction, are determined by thin-layer chromatography and merge fraction, merged
Liquid is concentrated under reduced pressure through 50 DEG C or less into medicinal extract, and medicinal extract is dried to obtain quinine acid compound 31.1g (purity 95.6%).
Embodiment described above is merely a preferred embodiment of the present invention, and is not limited the spirit and scope of the present invention
It is fixed, although embodiment is described in detail in the present invention, within the spirit and principles in the present invention, to foregoing embodiments
Various changes can be made for documented technical solution, improves and replaces on an equal basis etc., all belongs to the scope of protection of the present invention.
Claims (7)
1. a kind of new method for preparing quininic acid, it is characterised in that: using gouge as raw material, mentioned by solvent of polar solvent
It takes, extracting solution recycling design, gained residual solution is digested with tannase, and enzymolysis liquid is through polystyrene type large pore resin absorption column
It chromatographs and obtains；Wherein,
The polar solvent is water and the composition selected from one or more of methanol, ethyl alcohol and acetone, wherein water
Shared ratio is >=20v/v% in polar solvent；
Model D101, the Diaion HP-20 or AB-8 of the polystyrene type macroporous absorbent resin；
When enzymolysis liquid is through polystyrene type macroporous adsorbent resin column chromatography, eluant, eluent used is water and is selected from methanol, ethyl alcohol
With the composition of one or more of acetone, wherein water ratio shared in eluant, eluent is >=20v/v%.
2. the new method according to claim 1 for preparing quininic acid, it is characterised in that: it is described be extracted as heating extraction,
Ultrasonic extraction or room temperature extraction.
3. the new method according to claim 1 for preparing quininic acid, it is characterised in that: the dosage of the tannase is raw material
The 0.2 of weight~1.0 ‰.
4. the new method according to claim 1 for preparing quininic acid, it is characterised in that: enzymatic hydrolysis under the conditions of≤35 DEG C into
Row, enzymolysis time are 1~4h.
5. the new method according to any one of claims 1 to 4 for preparing quininic acid, it is characterised in that: be specifically with hook
The leaf and/or branch and/or bark of cone are raw material.
6. the new method according to any one of claims 1 to 4 for preparing quininic acid, it is characterised in that: the polarity is molten
In the composition of agent, ratio shared by water is 20~50v/v%.
7. the new method according to any one of claims 1 to 4 for preparing quininic acid, it is characterised in that: the eluant, eluent
Composition in, ratio shared by water be 20~50v/v%.
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| CN201910172792.3A CN109777843B (en) | 2019-03-07 | 2019-03-07 | Method for preparing quinic acid |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086575A (en) * | 1998-09-16 | 2000-03-28 | Mitsui Chemicals Inc | Production of quinic acid and quinic ester |
| CN101343225A (en) * | 2008-08-26 | 2009-01-14 | 施树云 | Preparation method for high-purity di-coffee mesitoyl quinine acid compounds |
| WO2011071056A1 (en) * | 2009-12-09 | 2011-06-16 | 花王株式会社 | Method for producing purified tea extract |
| JP2012183079A (en) * | 2012-07-03 | 2012-09-27 | Kao Corp | Method for producing non-polymer catechin-containing purified green tea extract |
| CN102766140A (en) * | 2012-08-14 | 2012-11-07 | 玉溪市维和生物技术有限责任公司 | Process for separating and preparing quinine sulfate from peruvian bark |
-
2019
- 2019-03-07 CN CN201910172792.3A patent/CN109777843B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086575A (en) * | 1998-09-16 | 2000-03-28 | Mitsui Chemicals Inc | Production of quinic acid and quinic ester |
| CN101343225A (en) * | 2008-08-26 | 2009-01-14 | 施树云 | Preparation method for high-purity di-coffee mesitoyl quinine acid compounds |
| WO2011071056A1 (en) * | 2009-12-09 | 2011-06-16 | 花王株式会社 | Method for producing purified tea extract |
| JP2012183079A (en) * | 2012-07-03 | 2012-09-27 | Kao Corp | Method for producing non-polymer catechin-containing purified green tea extract |
| CN102766140A (en) * | 2012-08-14 | 2012-11-07 | 玉溪市维和生物技术有限责任公司 | Process for separating and preparing quinine sulfate from peruvian bark |
Non-Patent Citations (4)
| Title |
|---|
| TINOTENDA SHOKO等: "Anti-aging potential of extracts from Sclerocarya birrea (A. Rich.) Hochst and its chemical profiling by UPLC-Q-TOF-MS", 《BMC COMPLEMENTARY AND ALTERNATIVE MEDICINE》 * |
| YA-FENG WANG等: "Three new compounds from the leaves of Castanopsis tibetana Hance", 《NATURAL PRODUCT RESEARCH》 * |
| 刘小兰: "青霉高单宁酶活性菌株选育及酶法转化没食子酸及奎尼酸研究", 《万方学位论文数据库》 * |
| 王亚凤等: "钩锥化学成分研究(Ⅰ)", 《中药材》 * |
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