CN101880269B - Diterpene monomers and method for separating and preparing diterpene monomers from Clerodendron cyrtophyllum Turcz - Google Patents
Diterpene monomers and method for separating and preparing diterpene monomers from Clerodendron cyrtophyllum Turcz Download PDFInfo
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Abstract
The invention discloses four diterpene monomers and further a method for separating and preparing diterpene monomers from Clerodendron cyrtophyllum Turcz. The method comprises the following steps of: (1) placing the stem of Clerodendron cyrtophyllum Turcz which is taken as raw material in an ethanol solution, extracting the raw material in a reflux state and carrying out reduced pressure concentration on the obtained leach liquid; (2) extracting the obtained concentrated extracting solution with petroleum ether, obtaining a extracted aqueous phase at the lower layer after the obtained extractliquid is layered; (3) extracting the extracted aqueous phase with ethyl acetate, carrying out reduced pressure concentration on the obtained extracted liquid to obtain diterpene crude extract; (4) separating the diterpene crude extract by countercurrent chromatography; and (5) collecting the target components separated by countercurrent chromatography for reduced pressure concentration till the mass fraction of the solid substance is above 70%, then carrying out freeze drying to obtain powdered diterpene monomers. The diterpene monomers have the anti-tumor property.
Description
Technical field
The invention belongs to the light industry technical field, relate to the deep process technology of Chinese medicinal materials smalt, be specially and from smalt, separate preparation high purity diterpene monomer methods.
Background technology
From successive dynasties book on Chinese herbal medicine record and among the people cure the disease through examining; The Clerodendron various plants; Effects such as its tool is clearing heat and detoxicating, dispel rheumatism, promoting blood circulation to remove blood stasis, step-down, anti-inflammatory analgesic are usually used in diseases such as the high heat of treatment flu, rheumatic arthritis, wound, hypotensive, ulcer, furunculosis.Contain multiple terpene substances in the smalt of Zhejiang, existing research shows that natural diterpenes material has good anticancer, anti-inflammatory, effect such as anti-oxidant, and can be developed to is of value to the healthy medicine of people.
Have now and mainly adopt column chromatography and preparative high performance liquid chromatography about the separation of diterpene, its limitation is that inferior separating effect, preparation amount are few and workload is big.Secondly, difficulty is relatively used in column chromatography and preparative high performance liquid chromatography regeneration, separates the diterpene-kind compound that obtains, and is difficult to develop into the big stripping technique of preparation amount.
Summary of the invention
The technical problem that the present invention will solve provides a kind of preparation diterpene monomer methods of from smalt, separating with low cost, adopts this method can the highly purified diterpene monomer of more large batch of acquisition.
In order to solve the problems of the technologies described above, the present invention provides 4 kinds of diterpene monomers, and these 4 kinds of diterpene monomers are respectively diterpene monomer (I), diterpene monomer (II), diterpene monomer (III) and diterpene monomer (IV), and its structural formula respectively as follows;
The present invention also provides a kind of preparation diterpene monomer methods of from smalt, separating simultaneously, may further comprise the steps:
1), with the stem of smalt as raw material, above-mentioned raw materials is put into ethanolic soln under reflux state, extracts, the vat liquor concentrating under reduced pressure of gained; Get concentrated extracting solution;
2), concentrated extracting solution is used isopyknic petroleum ether extraction, after the layering of gained extraction liquid, must be positioned at water after the extraction of lower floor;
3), will extract the back water and use equal volume of ethyl acetate, gained extraction liquid concentrating under reduced pressure must the diterpene crude extract;
4), adopt the adverse current chromatogram method to separate the diterpene crude extract;
5), collect the adverse current chromatogram target components separated and carry out concentrating under reduced pressure, reach more than 70% until the solid quality mark, adopt lyophilize again, obtain Powdered diterpene monomer.
As the improvement that from smalt, separates preparation diterpene monomer methods of the present invention, step 4) is:
A, preparation solvent systems I and solvent systems II, solvent systems I are according to sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 3: 6 volume ratio is formed, and solvent systems II is according to sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 5: 5 volume ratio is formed; Solvent systems I leaves standstill after fully shaking up, respectively solvent systems I go up mutually with solvent systems I under mutually; Solvent systems II leaves standstill after fully shaking up, respectively solvent systems II go up mutually with solvent systems II under mutually;
B, with the chromatographic column of injecting counter current chromatograph on the solvent systems I mutually;
C, solvent systems I is gone up mutually and solvent systems I mixes the back as solvent according to 1: 1 volume ratio down, the diterpene crude extract of step 3) gained is dissolved in the said solvent, get adverse current chromatogram sample separation solution;
D, unlatching counter current chromatograph, select following any one injection mode for use:
Inject adverse current chromatogram sample separation solution earlier, inject the moving phase (following phase) of solvent systems I then; Perhaps inject the moving phase of solvent systems I earlier, the adverse current chromatogram sample separation of reinjecting after balance solution;
Then, detect the adverse current chromatogram effluent, change moving phase (following phase) gradient elution of solvent systems II after waiting preceding two peaks to come out into, collect target components according to the color atlas of gained with the ultraviolet-visible detector.
As the further improvement that from smalt, separates preparation diterpene monomer methods of the present invention: counter current chromatograph is high-speed counter-current chromatograph HSCCC or low speed counter current chromatograph SRCCC.
As the further improvement that from smalt, separates preparation diterpene monomer methods of the present invention: adopting massfraction in the step 1) is that 70%～80% ethanolic soln extracts, and extracts altogether 3 times, extracts 2.5～3.5 hours at every turn; The mass volume ratio of raw material and used ethanolic soln is during each the extraction: 1g/5ml.
As the further improvement that from smalt, separates preparation diterpene monomer methods of the present invention: extraction times step 2) is 2 times, and the extraction times of said step 3) is 2 times.
As the further improvement that from smalt, separates preparation diterpene monomer methods of the present invention: the concentrating under reduced pressure condition in step 1) and the step 3) is: vacuum tightness is lower than 0.09Mpa, and temperature is 50～60 ℃; Concentrating under reduced pressure condition in the step 5) is: vacuum tightness is lower than 0.05Mpa, and temperature is 40～50 ℃.
As the further improvement that from smalt, separates preparation diterpene monomer methods of the present invention: the lyophilize condition in the step 5) is: vacuum tightness is lower than 30Pa, and temperature is-35～-30 ℃.
In method for separating and preparing of the present invention; With the counter current chromatograph is that separating device separates the diterpene monomer in the crude extract; Its solvent systems is formed by being in liquid sherwood oil, ETHYLE ACETATE, first alcohol and water under the normal temperature and pressure, on the phase that fixes mutually, time do moving phase mutually.
Advantage of the present invention is: good separating effect, efficient are high, and the purity of diterpene monomer product reaches more than 95%, and diterpene monomer preparation cost is far below prior art, are a kind of economy, from the smalt of Zhejiang, separate preparation high purity diterpene monomer methods efficiently.
Diterpene monomer (I), diterpene monomer (II), diterpene monomer (III) and diterpene monomer (IV) all have antineoplastic characteristic, and their usage and consumption are: oral 5mg/kg (body weight).
Description of drawings
Do further explain below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is a process flow sheet of the present invention.
Fig. 2 is the HSCCC-D400 separating spectrum of embodiment 1.
Fig. 3 is the HSCCC-D1200 separating spectrum of embodiment 2.
Fig. 4 is the HSCCC-D3500 separating spectrum of embodiment 3.
Embodiment
1), the stem with exsiccant Zhejiang smalt is ground into powder as raw material; It is that 75% ethanolic soln extracts under 75 ℃ reflux temperature that above-mentioned raw materials is put into massfraction (mass concentration); Extract altogether 3 times; Each condition of extracting is all following: the mass volume ratio of raw material and used ethanolic soln is: 1g/5ml, extraction time is 2.5～3.5 hours.
The vat liquor that merges 3 extraction gained carries out concentrating under reduced pressure (vacuum tightness is lower than 0.09Mpa, temperature is 50～60 ℃), is removed until ethanol, gets concentrated extracting solution;
2), concentrated extracting solution is used isopyknic petroleum ether extraction, extraction times is 2 times, merges the extraction liquid layering of 2 extraction gained, must be positioned at water after the extraction of lower floor;
3), will extract the back water and use equal volume of ethyl acetate, extraction times is 2 times, merges the extraction liquid concentrating under reduced pressure (vacuum tightness is lower than 0.09Mpa, and temperature is 50～60 ℃) that extracts gained for 2 times, must the diterpene crude extract; Detect through HPLC, diterpene content accounts for 30% in this diterpene crude extract.
4), adopt the adverse current chromatogram method to separate the diterpene crude extract, specifically carry out as follows successively:
A, preparation solvent systems I and solvent systems II.
Solvent systems I is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 3: 6 volume ratio is formed; Promptly measure sherwood oil 250ml, ETHYLE ACETATE 250ml, methyl alcohol 150ml and water 300ml respectively and place the 1000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems I go up mutually with solvent systems I under mutually.
Solvent systems II is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 5: 5 volume ratio is formed; Promptly measure sherwood oil 250ml, ETHYLE ACETATE 250ml, methyl alcohol 250ml, water 250ml respectively and place the 1000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems II go up mutually with solvent systems II under mutually.
B, solvent systems I is gone up phase 400ml injects counter current chromatograph (HSCCC-D400 high-speed counter-current chromatograph) with the flow velocity of 20ml/min chromatographic column;
C, with volume ratio be 1: 1 solvent systems I go up mutually with solvent systems I under (be respectively 10ml) mutually and mix the back as solvent (20ml), the 1.0g diterpene crude extract of step 3) gained is dissolved in the said solvent, get adverse current chromatogram sample separation solution;
D, open counter current chromatograph to 800 commentaries on classics/min, pump into adverse current chromatogram sample separation solution with the flow velocity of 1.0ml/min; After treating that sample introduction finishes; Inject the moving phase (phase under the solvent systems I of solvent systems I again with the flow velocity of 2.0ml/min; 400ml) the diterpene component in the wash-out post at 254nm detection adverse current chromatogram effluent, changes moving phase (the following phase of solvent systems II with the ultraviolet-visible detector after waiting preceding two peaks to come out into; 400ml) gradient elution is collected target components according to the color atlas of gained.
That is, when 220-280ml, collecting gained is diterpene monomer (I) component; When 300-380ml, collecting gained is diterpene monomer (II) component; When 500-550ml, collecting gained is diterpene monomer (III) component; When 580-660ml, collecting gained is diterpene monomer (IV) component.
5), diterpene monomer (I) component, diterpene monomer (II) component, diterpene monomer (III) component and diterpene monomer (IV) component are carried out following concentrating under reduced pressure and lyophilize respectively:
Elder generation's concentrating under reduced pressure (vacuum tightness is lower than 0.05Mpa, and temperature is 40～50 ℃) reaches more than 70% until solid concentration, adopts lyophilize (vacuum tightness is lower than 30Pa, and temperature is-30～-35 ℃) again;
At last, obtain diterpene monomer (I) 15.9mg, diterpene monomer (II) 15.5mg, diterpene monomer (III) 24.1mg, diterpene monomer (IV) 19.4mg respectively.
Detect through the HPLC method, purity is all more than 95%.
What the structural formula of diterpene monomer (I), diterpene monomer (II), diterpene monomer (III) and diterpene monomer (IV) was corresponding respectively is with following formula I, formula II, formula III, formula IV.
Diterpene monomer (I):
reddish?needles；m.p.240-243℃；[α]
25+78.2°(c?0.05，MeOH)；UVλ
max；254，298，370，430nm；ESIMS?obsd?m/z?339[M-H]
-；
Diterpene monomer (II):
reddish?needles；m.p.317-319℃；[α]
25-50.8°(c?0.05，MeOH)；UVλ
max：201，227，243，297nm；ESIMS?obsd?m/z?337[M-H]
-；
Diterpene monomer (III):
reddish?needles；m.p.201-204℃；[α]
25+26.8°(c?0.05，MeOH)；UVλ
max：268，290，334，380nm；ESIMS?obsd?m/z?341[M-H]
-
Diterpene monomer (IV):
reddish?needles；m.p.290-292℃；[α]
25-11.0°(c?0.05，MeOH)；UVλ
max：268，290，330，380nm；ESIMS?obsd?m/z?343[M-H]
-
Step 1)～step 3) is with embodiment 1.
4), adopt the adverse current chromatogram method to separate the diterpene crude extract, specifically carry out as follows successively:
A, preparation solvent systems I and solvent systems II.
Solvent systems I is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 3: 6 volume ratio is formed; Promptly measure sherwood oil 1000ml, ETHYLE ACETATE 1000ml, methyl alcohol 600ml, water 1200ml respectively and place the 5000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems I go up mutually with solvent systems I under mutually.
Solvent systems II is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 5: 5 volume ratio is formed; Promptly measure sherwood oil 1000ml, ETHYLE ACETATE 1000ml, methyl alcohol 1000ml, water 1000ml respectively and place the 5000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems II go up mutually with solvent systems II under mutually.
B, solvent systems I is gone up phase 1200ml injects counter current chromatograph (HSCCC-D1200 high-speed counter-current chromatograph) with the flow velocity of 20ml/min chromatographic column;
C, be that the upper and lower phase (promptly being respectively 25ml) of 1: 1 solvent systems I is mixed the back as solvent (50ml), the 5.0g diterpene crude extract of step 3) gained dissolved in the said solvent volume ratio, adverse current chromatogram sample separation solution;
D, open counter current chromatograph to 800 commentaries on classics/min, pump into adverse current chromatogram sample separation solution with the flow velocity of 2.0ml/min; After treating that sample introduction finishes; Inject the moving phase I (phase under the solvent systems I of solvent systems I again with the flow velocity of 5.0ml/min; 1500ml) the diterpene component in the wash-out post at 254nm detection adverse current chromatogram effluent, changes moving phase (the following phase of solvent systems II with the ultraviolet-visible detector after waiting preceding two peaks to come out into; 1500ml) gradient elution is collected target components according to the color atlas of gained.
That is, when 850-1000ml, collecting gained is diterpene monomer (I) component; When 1200-1450ml, collecting gained is diterpene monomer (II) component; When 1850-2250ml, collecting gained is diterpene monomer (III) component; When 2400-2800ml, collecting gained is diterpene monomer (IV) component.
5), diterpene monomer (I) component, diterpene monomer (II) component, diterpene monomer (III) component and diterpene monomer (IV) component are equal to concentrating under reduced pressure and the lyophilize of embodiment 1 respectively:
At last, obtain diterpene monomer (I) 45.6mg respectively, diterpene monomer (II) 46.6mg, diterpene monomer (III) 80.0mg, diterpene monomer (IV) 70.4mg.
Detect through the HPLC method, purity is all more than 95%.
The structural formula of diterpene monomer (I), diterpene monomer (II), diterpene monomer (III), diterpene monomer (IV) is the same.
Step 1)～step 3) is with embodiment 1.
4), adopt the adverse current chromatogram method to separate the diterpene crude extract, specifically carry out as follows successively:
A, preparation solvent systems I and solvent systems II.
Solvent systems I is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 3: 6 volume ratio is formed; Promptly measure respectively and measure sherwood oil 2500ml, ETHYLE ACETATE 2500ml, methyl alcohol 1500ml, water 3000ml respectively and place the 10000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems I go up mutually with solvent systems I under mutually.
Solvent systems II is by sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 5: 5 volume ratio is formed; Promptly measure sherwood oil 2500ml, ETHYLE ACETATE 2500ml, methyl alcohol 2500ml, water 2500ml respectively and place the 10000ml separating funnel; Fully shake up the back standing demix, thus respectively solvent systems II go up mutually with solvent systems II under mutually.
B, solvent systems I is gone up phase 3500ml injects counter current chromatograph (HSCCC-D3500 high-speed counter-current chromatograph) with the flow velocity of 20ml/min chromatographic column;
C, be that 1: 1 solvent systems I upper and lower phase (promptly being respectively 100ml) is mixed the back as solvent (200ml), the 50.0g diterpene crude extract of step 3) gained dissolved in the said solvent volume ratio, adverse current chromatogram sample separation solution;
D, open counter current chromatograph to 600 commentaries on classics/min, pump into adverse current chromatogram sample separation solution with the flow velocity of 4.0ml/min; After treating that sample introduction finishes; Flow velocity with 8.0ml/min injects solvent systems I moving phase (phase under the solvent systems I again; 4500ml) the diterpene component in the wash-out post at 254nm detection adverse current chromatogram effluent, changes the moving phase (phase under the solvent systems II of solvent systems II with the ultraviolet-visible detector after waiting preceding two peaks to come out into; 4500ml) gradient elution is collected target components according to the color atlas of gained.
That is, when 2800-3200ml, collecting gained is diterpene monomer (I) component; When 3400-4200ml, collecting gained is diterpene monomer (II) component; When 5500-6400ml, collecting gained is diterpene monomer (III) component; Ml when 7000-8000, collecting gained is diterpene monomer (IV) component.
5), diterpene monomer (I) component, diterpene monomer (II) component, diterpene monomer (III) component and diterpene monomer (IV) component are equal to concentrating under reduced pressure and the lyophilize of embodiment 1 respectively:
At last, obtain diterpene monomer (I) 300.0mg respectively, diterpene monomer (II) 400.0mg, diterpene monomer (III) 356.0mg, diterpene monomer (IV) 545.0mg.
Detect through HPLC, purity is all more than 90%.
The structural formula of diterpene monomer (I), diterpene monomer (II), diterpene monomer (III), diterpene monomer (IV) is the same.
Tumor cell in vitro propagation inhibition test: the tumour cell in vegetative period of taking the logarithm, adjustment concentration of cell suspension (50000～100000/milliliter), every hole 100 μ l cell suspension inoculations are in 96 porocyte culture plates; Blank group, cell control group and 6 concentration (1.56,3.12 are established in administration (100 μ l/ hole) behind the inoculation 24h respectively; 6.25; 12.5,25,50 μ mol/L) and tried drug group.Every hole adds 100 μ l MTT (1mg/ml after continuing to cultivate 72h; With the dissolving of DMEM nutrient solution); Hatch 4h for 37 ℃; Discard and add 150 μ l acidifying Virahols (containing 0.04mol/L HCl) in each hole behind the liquid, lucifuge placement 30min, ELIASA mensuration 570nm place absorbancy; Calculating receives the proliferation inhibition rate of reagent thing to tumour cell, and is tried the half-inhibition concentration (IC of thing to tumor cell proliferation (72h) with NDST (the New Drug Statistical Treatment) computed in software that professor Sun Ruiyuan writes
50).Specifically as shown in table 1.
72 hours toxic limit medium doses of table 1, HL-60andA549 cell. (μ mol/L)
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (7)
1.2 plant the diterpene monomer, it is characterized in that: said 2 kinds of diterpene monomers are respectively diterpene monomer (III) and diterpene monomer (IV), its structural formula respectively as follows;
2. one kind is separated preparation 2 kinds of diterpene monomer methods as claimed in claim 1 from smalt, it is characterized in that may further comprise the steps:
1), with the stem of smalt as raw material, above-mentioned raw materials is put into ethanolic soln under reflux state, extracts, the vat liquor concentrating under reduced pressure of gained; Get concentrated extracting solution;
2), concentrated extracting solution is used isopyknic petroleum ether extraction, after the layering of gained extraction liquid, must be positioned at water after the extraction of lower floor;
3), will extract the back water and use equal volume of ethyl acetate, gained extraction liquid concentrating under reduced pressure must the diterpene crude extract;
4), adopt the adverse current chromatogram method to separate the diterpene crude extract; Be following steps:
A, preparation solvent systems I and solvent systems II; Said solvent systems I is according to sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 3: 6 volume ratio is formed, and said solvent systems II is according to sherwood oil: ETHYLE ACETATE: methyl alcohol: water=5: 5: 5: 5 volume ratio is formed; Solvent systems I leaves standstill after fully shaking up, respectively solvent systems I go up mutually with solvent systems I under mutually; Solvent systems II leaves standstill after fully shaking up, respectively solvent systems II go up mutually with solvent systems II under mutually;
B, with the chromatographic column of injecting counter current chromatograph on the solvent systems I mutually;
C, solvent systems I is gone up mutually and solvent systems I mixes the back as solvent according to 1: 1 volume ratio down, the diterpene crude extract of step 3) gained is dissolved in the said solvent, get adverse current chromatogram sample separation solution;
D, unlatching counter current chromatograph, select following any one injection mode for use:
Inject adverse current chromatogram sample separation solution earlier, inject the following phase of solvent systems I then; Perhaps inject the following phase of solvent systems I earlier, the adverse current chromatogram sample separation of reinjecting after balance solution;
Then, detect the adverse current chromatogram effluent, change the following phase gradient wash-out of solvent systems II after waiting preceding two peaks to come out into, collect target components according to the color atlas of gained with the ultraviolet-visible detector;
5), collect the adverse current chromatogram target components separated and carry out concentrating under reduced pressure, reach more than 70% until the solid quality mark, adopt lyophilize again, obtain Powdered diterpene monomer, said diterpene monomer is diterpene monomer (III) and diterpene monomer (IV).
3. the preparation diterpene monomer methods of from smalt, separating according to claim 2, it is characterized in that: said counter current chromatograph is high-speed counter-current chromatograph HSCCC or low speed counter current chromatograph SRCCC.
4. the preparation diterpene monomer methods of from smalt, separating according to claim 3 is characterized in that: adopting massfraction in the said step 1) is that 70%～80% ethanolic soln extracts, and extracts altogether 3 times, extracts 2.5～3.5 hours at every turn; The mass volume ratio of raw material and used ethanolic soln is during each the extraction: 1g/5ml.
5. the preparation diterpene monomer methods of from smalt, separating according to claim 4, it is characterized in that: extraction times said step 2) is 2 times, the extraction times of said step 3) is 2 times.
6. the preparation diterpene monomer methods of from smalt, separating according to claim 5, it is characterized in that: the concentrating under reduced pressure condition in said step 1) and the step 3) is: vacuum tightness is lower than 0.09Mpa, and temperature is 50～60 ℃; Concentrating under reduced pressure condition in the step 5) is: vacuum tightness is lower than 0.05Mpa, and temperature is 40～50 ℃.
7. the preparation diterpene monomer methods of from smalt, separating according to claim 6, it is characterized in that: the lyophilize condition in the said step 5) is: vacuum tightness is lower than 30Pa, and temperature is-35～-30 ℃.
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| CN113336634B (en) * | 2021-04-26 | 2022-07-29 | 杭州师范大学 | 17(15 → 16) -methyl abietane type diterpene compound, preparation method, pharmaceutical composition and application |
| CN113307785B (en) * | 2021-04-26 | 2022-09-23 | 杭州师范大学 | Abietane diterpenoid compound with anti-tumor effect, preparation method, pharmaceutical composition and application |
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