CN105017274A - Novel crystal forms of deoxypodophyllotoxin and preparation methods thereof - Google Patents
Novel crystal forms of deoxypodophyllotoxin and preparation methods thereof Download PDFInfo
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- CN105017274A CN105017274A CN201510510669.XA CN201510510669A CN105017274A CN 105017274 A CN105017274 A CN 105017274A CN 201510510669 A CN201510510669 A CN 201510510669A CN 105017274 A CN105017274 A CN 105017274A
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
The invention relates to two novel crystal forms of the alpha crystal form and the beta crystal form of deoxypodophyllotoxin and preparation methods thereof. The reflection angle 2theta of an X-ray powder diffraction pattern (a CuKalpha source, lambda=0.15406 nm) of the alpha crystal form of the deoxypodophyllotoxin has characteristic peaks at about 9.06 degrees, 12.59 degrees, 16.44 degrees, 17.54 degrees, 18.59 degrees, 20.59 degrees, 22.08 degrees, 23.90 degrees and 25.44 degrees; the reflection angle 2theta of an X-ray powder diffraction pattern (a CuKalpha source, lambda=0.15406 nm) of the beta crystal form of the deoxypodophyllotoxin has characteristic peaks at about 7.39 degrees, 8.98 degrees, 11.11 degrees, 12.51 degrees, 14.21 degrees, 14.74 degrees, 16.44 degrees, 17.47 degrees, 18.47 degrees, 19.62 degrees, 20.07 degrees, 21.11 degrees, 22.30 degrees, 23.03 degrees, 23.60 degrees, 24.05 degrees, 25.28 degrees, 26.46 degrees, 27.03 degrees, 27.47 degrees and 28.12 degrees. The two crystal forms both have the good stability, reproducibility and the better solubility, the preparation technology is simple, and the important value on drug application and scientific research of the deoxypodophyllotoxin is achieved.
Description
Technical field
The divisional application that the present invention is the applying date is on May 15th, 2014, application number is 201410206568.9, denomination of invention is the application for a patent for invention of " new crystal of Silicicolin and preparation method thereof ".
Background technology
Silicicolin (Deoxypodophyllotoxin, DPT), also known as Deoxypodophyllotoxin, chemistry 5R-5,8,8a by name, 9-tetrahydrochysene-5-(3,4,5-2,4,5-trimethoxyphenyl) furans (3 ', 4 ': 6,7) naphtho--[2,3-d] dioxa cyclenes-6 (5aH)-one between-1,3-, structural formula is as follows:
The compound that Silicicolin is a kind of extraction purification from lignin plant and obtains, its structure is close with lignan podophyllinic acid lactone structure, and there is very excellent biological activity, such as antitumor, anti-inflammatory, antiviral, the pharmacological action such as anti-platelet aggregation and antianaphylaxis.
As everyone knows, medicine is subject to the impact of various factors when crystallization, thus make in molecule or intermolecular bonding mode changes and causes the lattice arrangement of molecule or atom different, thus forming different crystalline structure, this same substance has two or more spatial disposition and unit cell parameters and the phenomenon forming multiple crystal formation is referred to as heteromorphism.Many crystalline drugs all ubiquity this kind of heteromorphism.The different crystal forms of same medicine may have remarkable difference in outward appearance, solubleness, fusing point, dissolution rate, biological effectiveness etc., thus have impact on the stability of medicine, bioavailability and curative effect, polymorph in pharmaceuticals phenomenon still affects one of important factor of drug quality and clinical efficacy.
Although there is the several preparation about Silicicolin and pharmaceutical activity research in prior art, the relevant crystal formation of Silicicolin has not yet been had to be seen in report up to now.The present inventor passes through research and the experimental exploring of lot of documents, the new crystal of two kinds of Silicicolins is being have developed after a large amount of creative works, i.e. alpha-crystal form and beta crystal, thus crystal formation kind having enriched Silicicolin and preparation method thereof, and be expected to play positive meaning improving in its medicine solution degree, dissolution rate, biological effectiveness etc.
Summary of the invention
The crystal formation of the present inventor to Silicicolin conducts in-depth research, and after having paid a large amount of creative work, thus prepares two kinds of new crystal of Silicicolin: alpha-crystal form and beta crystal, and then completes the present invention.
Specifically, technical scheme of the present invention and content relate to the content of two aspects,
First aspect, technical scheme of the present invention and content relate to two kinds of crystal formations of Silicicolin: alpha-crystal form and beta crystal.
Silicicolin alpha-crystal form of the present invention, this crystal formation uses CuK α radiation, the X-ray powder diffraction represented with 2 θ angles has diffraction peak at 9.06 °, 12.59 °, 16.44 °, 17.54 °, 18.59 °, 20.59 °, 22.08 °, 23.90 ° and 25.44 ° of places, sees Fig. 1.
Silicicolin beta crystal of the present invention, this crystal formation uses CuK α radiation, the X-ray powder diffraction represented with 2 θ angles has diffraction peak at 7.39 °, 8.98 °, 11.11 °, 12.51 °, 14.21 °, 14.74 °, 16.44 °, 17.47 °, 18.47 °, 19.62 °, 20.07 °, 21.11 °, 22.30 °, 23.03 °, 23.60 °, 24.05 °, 25.28 °, 26.46 °, 27.03 °, 27.47 ° and 28.12 ° of places, sees Fig. 2.
In the new crystal of Silicicolin of the present invention, the value at all above-mentioned 2 θ angles has allowed certain reasonably limit of error, and its limit of error is ± 0.2 °.
Second aspect, technical scheme of the present invention and content relate to a kind of alpha-crystal form of Silicicolin and the preparation method of beta crystal.
The preparation method of Silicicolin alpha-crystal form of the present invention, its concrete grammar comprises: be dissolved in by Silicicolin in organic solvent, be stirred to dissolve completely and form solution, then vacuum rotary steam concentrates, except desolventizing is to crystallize out, finally constant pressure and dry under infrared lamp, obtains Silicicolin alpha-crystal form after not needing grinding.
In the preparation method of Silicicolin alpha-crystal form of the present invention, described organic solvent is the mixed solvent of methylene dichloride and hexanaphthene, and the volume ratio of the two is 1:1-1:2, such as, can be 1:1,1:1.5 or 1:2, is preferably 1:2.
In the preparation method of Silicicolin alpha-crystal form of the present invention, the mass volume ratio of Silicicolin and solvent is 5-10mg/ml, its implication is dissolve 5-10mg Silicicolin in every ml solvent, such as can be 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg/ml or 10mg/ml, be preferably 10mg/ml.
In the preparation method of Silicicolin alpha-crystal form of the present invention, the temperature of vacuum rotary steam is 25-60 DEG C, such as, can be 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C, is preferably 30-50 DEG C.
In the preparation method of Silicicolin alpha-crystal form of the present invention, the time of infrared lamp constant pressure and dry is 4-12h, such as, can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
The preparation method of Silicicolin beta crystal of the present invention, its concrete grammar comprises: be dissolved in by Silicicolin in organic solvent, be stirred to dissolve completely and form solution, then slowly volatilize under being placed in low temperature crystallization, decompress filter is except desolventizing, constant pressure and dry under infrared lamp, obtains Silicicolin beta crystal after not needing grinding.
In the preparation method of Silicicolin beta crystal of the present invention, described organic solvent is chloroform, and recrystallization temperature is 0-10 DEG C, is preferably 5 DEG C.
In the preparation method of Silicicolin beta crystal of the present invention, the mass volume ratio 5-10mg/ml of Silicicolin and solvent, its implication is dissolve 5-10mg Silicicolin in every ml solvent, such as can be 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg/ml or 10mg/ml, preferred 10mg/ml.
In the preparation method of Silicicolin beta crystal of the present invention, the time of infrared lamp constant pressure and dry is 4-12h, such as, can be 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.
The preparation method of Silicicolin beta crystal of the present invention, its concrete grammar also comprises: on the basis of the Silicicolin alpha-crystal form obtained, and gained alpha-crystal form is done further fully grinding, can prepare beta crystal.
The preparation method of Silicicolin beta crystal of the present invention, its concrete grammar also comprises: in the preparation method of Silicicolin alpha-crystal form, described mixed solvent methylene dichloride and hexanaphthene are replaced with chloroform and the hexanaphthene of respective volume ratio, can beta crystal be prepared.
Compared with prior art, beneficial effect of the present invention is:
1, the present inventor's Late Cambrian new crystal of Silicicolin, it successfully prepares alpha-crystal form and the beta crystal of Silicicolin by the suitable selection of recrystallisation solvent, crystallization mode etc.;
2, solid Silicicolin only need be dissolved in organic solvent by technical scheme of the present invention, is realized, have simple to operate by processing modes such as concentrated by rotary evaporation dryings, without the need to specific installation, and advantage with low cost;
3, the stable crystal form, the favorable reproducibility that prepare of technical solution of the present invention, and solubility property is more excellent.
Accompanying drawing explanation
Fig. 1 is the alpha-crystal form x-ray diffraction pattern of the Silicicolin of the embodiment of the present invention.
Fig. 2 is the beta crystal x-ray diffraction pattern of the Silicicolin of the embodiment of the present invention.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Embodiment 1
Silicicolin is added in eggplant-shape bottle, add the methylene dichloride of volume ratio 1:1 and the mixed solvent of hexanaphthene, wherein the mass volume ratio of Silicicolin and mixed solvent is 10mg/ml, be stirred to dissolve completely and form solution, then at 40 DEG C, vacuum rotary steam concentrates, except desolventizing is to crystallize out, and finally constant pressure and dry 6h under infrared lamp, obtain crystalline powder, do not need to grind the alpha-crystal form obtaining Silicicolin.
Embodiment 2
Silicicolin is added in eggplant-shape bottle, add the methylene dichloride of volume ratio 1:2 and the mixed solvent of hexanaphthene, wherein the mass volume ratio of Silicicolin and mixed solvent is 10mg/ml, be stirred to dissolve completely and form solution, then concentrate at 40 DEG C of vacuum rotary steams, except desolventizing is to crystallize out, finally constant pressure and dry 8h under infrared lamp, obtain crystalline powder, do not need to grind the alpha-crystal form obtaining Silicicolin.
Embodiment 3
Silicicolin is added in eggplant-shape bottle, add chloroform, wherein the mass volume ratio of Silicicolin and chloroform is 10mg/ml, be stirred to dissolve completely and form solution, then 5 DEG C of refrigerator and cooled are placed in but, slow crystallize out, finally constant pressure and dry 12h under infrared lamp after a couple of days, obtain crystalline powder, do not need to grind the beta crystal obtaining Silicicolin.
Embodiment 4
Silicicolin is added in eggplant-shape bottle, add the methylene dichloride of volume ratio 1:2 and the mixed solvent of hexanaphthene, wherein the mass volume ratio of Silicicolin and mixed solvent is 10mg/ml, be stirred to dissolve completely and form solution, then concentrate at 40 DEG C of vacuum rotary steams, except desolventizing is to crystallize out, finally constant pressure and dry 8h under infrared lamp, obtains crystalline powder.This powder is fully ground, obtains the beta crystal of Silicicolin.
Embodiment 5
Silicicolin is added in eggplant-shape bottle, add the chloroform of volume ratio 1:1 and the mixed solvent of hexanaphthene, wherein the mass volume ratio of Silicicolin and mixed solvent is 10mg/ml, be stirred to dissolve completely and form solution, then concentrate at 40 DEG C of vacuum rotary steams, except desolventizing is to crystallize out, finally constant pressure and dry 10h under infrared lamp, obtain crystalline powder, do not need to grind the beta crystal obtaining Silicicolin.
Embodiment 6
Silicicolin is added in eggplant-shape bottle, add the chloroform of volume ratio 1:2 and the mixed solvent of hexanaphthene, wherein the mass volume ratio of Silicicolin and mixed solvent is 10mg/ml, be stirred to dissolve completely and form solution, then concentrate at 40 DEG C of vacuum rotary steams, except desolventizing is to crystallize out, finally constant pressure and dry 8h under infrared lamp, obtain crystalline powder, do not need to grind the beta crystal obtaining Silicicolin.
Embodiment 7-10
Except changing the temperature of vacuum rotary steam, implement embodiment 7-10 respectively in the mode identical with embodiment 1-2, the corresponding relation of embodiment and experimental result is as shown in table 1 below.
Table 1
Embodiment 11-12
Except the subcooled temperature of change, implement embodiment 11-12 respectively in the mode identical with embodiment 3, the corresponding relation of embodiment and experimental result is as shown in table 2 below.
Table 2
Embodiment 13-18
Except being replaced by except 5mg/ml by the mass volume ratio of Silicicolin and solvent, implement embodiment 13-18 respectively in the mode identical with embodiment 1-6, the corresponding relation of embodiment and experimental result is as shown in table 3 below.
Table 3
The sign of crystal and test
1, the new crystal of the preparation-obtained Silicicolin of XRD testing example 1-18 is adopted, i.e. alpha-crystal form and beta crystal.
XRD instrument parameter is: INSTRUMENT MODEL: Bruker D8diffractometer, and the mensuration of 2 θ values uses CuK α light source, and λ=0.15406nm, precision is ± 0.2 °.
Interpretation of result: the X-ray powder diffractogram of two kinds of crystal formations is see attached Fig. 1 and 2.Can obviously be found out by figure, all there is many obvious difference in these two kinds of crystal formation diffraction peak numbers and position, it confirms the two kinds of different crystal forms obtaining crystal prepared by different testing method of the present invention and really belong to Silicicolin apparently, and it has different crystalline structure.
2, the alpha-crystal form of solvability testing research embodiment of the present invention 1-18 and the solubility property difference of beta crystal and Silicicolin solid material is adopted.Found by the contrast test of solubility experiment, the new crystal of the Silicicolin prepared by the present invention, namely alpha-crystal form and beta crystal all compare Silicicolin solid material show better, water-soluble faster, it has the advantage that dissolving is rapid, solution is homogeneous, stable, this is conducive to dissolution rate and the biological effectiveness of improving medicine, of great advantage in the practical application of biomedicine field to it.
In sum, the present inventor is by a large amount of experimental exploring and processing condition (as crystallization condition, crystallization mode etc.) screening, successfully research has prepared two kinds of different crystal forms of Silicicolin first, i.e. alpha-crystal form and beta crystal, and provide the preparation method of two kinds of crystal formations, its method has simple to operate, without the need to specific installation, and advantage with low cost.Two kinds of crystal form X RD characterization parameter difference are obvious, and all possess excellent stability and circulation ratio, and improve it as solubleness during medicine, also can produce more excellent effect to its aspect such as dissolution rate and biological effectiveness simultaneously.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (5)
1. the beta crystal of the Silicicolin that a structural formula is following, it is characterized in that: this crystal formation uses CuK α radiation, the X-ray powder diffraction represented with 2 θ angles has diffraction peak at 7.39 °, 8.98 °, 11.11 °, 12.51 °, 14.21 °, 14.74 °, 16.44 °, 17.47 °, 18.47 °, 19.62 °, 20.07 °, 21.11 °, 22.30 °, 23.03 °, 23.60 °, 24.05 °, 25.28 °, 26.46 °, 27.03 °, 27.47 ° and 28.12 ° of places, wherein the limit of error at 2 θ angles is ± 0.2 °
2. the preparation method of a beta crystal as claimed in claim 1, it is characterized in that: Silicicolin is dissolved in organic solvent, be stirred to dissolve completely and form solution, then slowly volatilize under being placed in low temperature crystallization, decompress filter is except desolventizing, constant pressure and dry under infrared lamp, obtains Silicicolin beta crystal after not needing grinding.
3. preparation method as claimed in claim 2, it is characterized in that: described organic solvent is chloroform, recrystallization temperature is 0-10 DEG C, and the mass volume ratio of Silicicolin and solvent is 5-10mg/ml, and the time of infrared lamp constant pressure and dry is 4-12h.
4. a preparation method for beta crystal as claimed in claim 1, is characterized in that: on the basis of the Silicicolin alpha-crystal form obtained, and is done fully to grind further by gained alpha-crystal form, can prepare beta crystal.
5. the preparation method of a beta crystal as claimed in claim 1, it is characterized in that: Silicicolin is dissolved in organic solvent, be stirred to dissolve completely and form solution, then vacuum rotary steam concentrates, except desolventizing is to crystallize out, finally constant pressure and dry under infrared lamp, obtains Silicicolin beta crystal after not needing grinding, wherein said organic solvent is the mixed solvent of chloroform and hexanaphthene, and the volume ratio of the two is 1:1-1:2.
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| CN201410206568.9A CN103965209B (en) | 2014-05-15 | 2014-05-15 | Crystal formation of deoxypodophyllotoxin and preparation method thereof |
| CN201510510669.XA CN105017274B (en) | 2014-05-15 | 2014-05-15 | Crystal forms of deoxypodophyllotoxin and preparation methods thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997035557A1 (en) * | 1996-03-22 | 1997-10-02 | Kao Corporation | External skin-care composition |
| KR20090119123A (en) * | 2008-05-15 | 2009-11-19 | 건국대학교 산학협력단 | Use in anti-cancer agent of deoxypodophyllotoxin |
| CN101805348A (en) * | 2010-04-09 | 2010-08-18 | 北京市药品检验所 | Method for preparing desoxy-podophyllotoxin |
| CN102633808A (en) * | 2012-05-03 | 2012-08-15 | 浙江尖峰药业有限公司 | Manufacturing method for deoxypodophyllotoxin |
| CN103421016A (en) * | 2013-08-19 | 2013-12-04 | 南京标科生物科技有限公司 | Anthricin preparation method |
-
2014
- 2014-05-15 CN CN201410206568.9A patent/CN103965209B/en active Active
- 2014-05-15 CN CN201510510669.XA patent/CN105017274B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997035557A1 (en) * | 1996-03-22 | 1997-10-02 | Kao Corporation | External skin-care composition |
| KR20090119123A (en) * | 2008-05-15 | 2009-11-19 | 건국대학교 산학협력단 | Use in anti-cancer agent of deoxypodophyllotoxin |
| CN101805348A (en) * | 2010-04-09 | 2010-08-18 | 北京市药品检验所 | Method for preparing desoxy-podophyllotoxin |
| CN102633808A (en) * | 2012-05-03 | 2012-08-15 | 浙江尖峰药业有限公司 | Manufacturing method for deoxypodophyllotoxin |
| CN103421016A (en) * | 2013-08-19 | 2013-12-04 | 南京标科生物科技有限公司 | Anthricin preparation method |
Non-Patent Citations (2)
| Title |
|---|
| CHANGQI ZHAO 等: "New Lignan Glycosides from Chinese Medicinal Plant, Sinopodophillum emodi", 《CHEM. PHARM. BULL.》 * |
| GEORGE R. PETTIT 等: "Antineoplastic Agents. 522. Hernandia peltata (Malaysia) and Hernandia nymphaeifolia (Republic of Maldives)", 《J. NAT. PROD.》 * |
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| CN105017274B (en) | 2017-01-18 |
| CN103965209A (en) | 2014-08-06 |
| CN103965209B (en) | 2016-09-07 |
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