CN102743352A - Triamcinolone tablet and polymorphs and preparation method - Google Patents
Triamcinolone tablet and polymorphs and preparation method Download PDFInfo
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- CN102743352A CN102743352A CN2012102504969A CN201210250496A CN102743352A CN 102743352 A CN102743352 A CN 102743352A CN 2012102504969 A CN2012102504969 A CN 2012102504969A CN 201210250496 A CN201210250496 A CN 201210250496A CN 102743352 A CN102743352 A CN 102743352A
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Abstract
The invention discloses a triamcinolone tablet, a triamcinolone polymorphs and a preparation method. The triamcinolone tablet comprises a triamcinolone polymorphs 1 serving as active ingredients and one or more pharmaceutic adjuvants applicable to tablets, X-ray powder diffraction of the triamcinolone polymorphs 1 has characteristic peaks at diffraction angles 2theta=9.0 degrees, 15.6 degrees, 18.5 degrees and 21.7 degrees.
Description
Invention field:
The invention belongs to and relate to a kind of steroidal compounds, particularly new triamcinolone crystal formation and preparation method thereof and the application in preparation.
Background technology:
The triamcinolone sheet (CAS:124-94-7, Triamcinolone) its chemical structural formula is as follows:
Triamcinolone is a kind of middle glucocorticoid medicine of imitating, and has pharmacological actions such as antiinflammatory, immunosuppressant, antiallergic, shock.U.S. Pat 2789118; US 3021347 discloses the synthetic method of triamcinolone, document Investigations on the Polymorphism and Pseudopolymorphism of the Glucocorticoid Triamcinolone:New Findings for a Well-Known Drug (Viktor Suitchmezian .etc, CRYSTAL GROWTH & DESIGN; 2007 VOL.7; NO.1,69-74 is hereinafter to be referred as document 1) existing two yeast inoculation Anxis dragon crystal form A and B disclosed; And a kind of triamcinolone hydrate crystal forms; Wherein the A crystal formation is buied the existing crystal formation in the crude drug for it, and the B crystal formation is from alcohol, acetonitrile, halogenated hydrocarbons, N, dinethylformamide; Make in the solvent such as esters, ketone, and point out that the B crystal formation is a thermodynamically stable crystal formation under the room temperature.Wherein the peroral dosage form of triamcinolone mainly is a tablet, and commercially available Aristo-Pak has the Aristo-Pak (Tianjin Tianyao Pharmaceutical Co., Ltd., 4mg/ sheet) of trade name " A Saisong " at present.Yet in tablet formulation is produced; We find that adopting and no matter adopting the A crystal formation still is the triamcinolone crude drug of B crystal formation, when being used for tablet manufacturing, exist to be unfavorable for many drawbacks of producing; Bad like the raw material flowability; When mixing, need stir for a long time and just can reach the uniformity of dosage units requirement, seriously reduced the efficient of producing, improve the consumption of the energy, equipment with adjuvant; The less stable of the Aristo-Pak that makes in the tabletting process, because the mobile official post of triamcinolone raw material problems such as sticking, pitted skin, fracture occur when getting tabletting easily, makes lower or the like the problem of the yield rate of tablet.
Summary of the invention:
The crystal formation research work of medicine has become more and more important at present; The crystallization polymorphic that Chinese patent ZL200580026414.0 discloses specific medication usually is difficulty or ease, stability, dissolubility, the storage stability of medication preparation, a pharmacological important factor of judgment in preparation difficulty or ease and the body.
Surprising ground, we are in carrying out triamcinolone crystal formation research process, and we have found a kind of brand-new triamcinolone crystal formation 1; Investigate through stability test; Triamcinolone crystal formation 1 is compared with crystal form B with existing triamcinolone crystal form A, is convenient to more pulverize, and the flowability of pulverizing the micropowder that obtains is better; More easily and auxiliary materials and mixing, thus can improve the efficient and the yield rate of tablet manufacturing.Therefore this triamcinolone crystal formation 1 can become the new selection of triamcinolone preparation product.
The present invention also provides the crystallization preparation method of above-mentioned triamcinolone crystal formation 1.The method for preparing of this triamcinolone crystal formation 1 is stable and can repeat, more easy for industrialized.
The triamcinolone crystal formation that provides 1 usefulness X-ray powder diffraction of the present invention is measured; Its X-ray powder diffraction has been located characteristic peak the angle of diffraction 2 θ=9.0 °, 15.6 °, 18.5 °, 21.7 °, and its relative diffracted intensity is respectively its detailed spectrogram such as Fig. 3 in fact to shown in Figure 6.Said term " in fact " is to be understood that to the diffracted intensity of the characteristic peak different trace to some extent along with crystal preparing technology, sample installation method and gauge change, also should be within the scope of the invention.In addition, the difference of instrument and other factors possibly influence the angle of diffraction 2 θ values, so the above-mentioned angle of diffraction 2 θ values that characteristic peak arranged can be in variation in the existing value ± 0.2 °.
The present invention also provides a kind of method for preparing of triamcinolone of said crystal formation 1 following:
Triamcinolone is dissolved in the organic solvent 1 entirely, slowly adds the dissolved agent, treat that deposition is separated out after, filter, obtain triamcinolone crystal formation 1.
Said organic solvent 1 is 5-10:1 with the envelope-bulk to weight ratio of triamcinolone
Said organic solvent 1 is selected from the mixed solvent of one or more lower alcohols and ether solvent; The volume ratio of said lower alcohol and ether solvent is 1:1-10.Said lower alcohol is the monohydric alcohol of C1-~ C4.
Said ether solvent is selected from ether, oxolane (THF), dioxane;
Said lower alcohol is selected from methanol, ethanol;
Said organic solvent 1 is the mixed solvent that constitutes of methanol and oxolane most preferably.
Said dissolved agent is selected from the hydro carbons solvent, one or more in preferred normal hexane, the cyclohexane extraction.The volume of said dissolved agent is 5-10 a times of organic solvent 1
The present invention also provides the application of triamcinolone crystal formation 1 in the medicine of preparation treatment people or mammalian diseases.
The present invention also provides a kind of Aristo-Pak, and the triamcinolone crystal formation 1 that contains as active component is applicable to the pharmaceutic adjuvant of tablet with one or more.
Described pharmaceutic adjuvant is selected from lactose monohydrate, starch, sucrose, dextrin, polyvinylpyrrolidone K30, Polyethylene Glycol, cross-linking sodium carboxymethyl cellulose, magnesium stearate.
The kind of the said pharmaceutic adjuvant that is applicable to tablet and consumption can be selected for use and add according to the adjuvant commonly used of disclosed tablet among " pharmaceutics " (Cui Fude, 2003 November the 5th edition).
Can find out that from test example 1 triamcinolone crystal provided by the invention is under the same conditions pulverized than triamcinolone of the prior art more easily, therefore when being used to prepare the micronized pharmaceutical preparation of various needs, have potential advantage.And show in test example 2; The flowability of triamcinolone crystallization micropowder provided by the invention will be apparently higher than the triamcinolone micropowder of commercially available same particle size; Explain that the present invention provides the triamcinolone crystallization mobile better after processing micropowder; More easily in the adjuvant mix homogeneously, thereby improve the quality of the pharmaceutical preparations, reduce the preparation cost.The test of the tablet formulation of test example 3 shows, adopting invention that the triamcinolone crystallization is provided is that the tablet content uniformity of raw material will be higher than that to adopt commercially available triamcinolone be the tablet of raw material.Explain that triamcinolone crystallization provided by the invention compares with existing triamcinolone and have significant advantage when being used for preparation.
Used powder diffraction instrument is a Rigaku D/max-2500 powder diffractometer among the present invention, Japanese Company products of science.
Description of drawings:
Fig. 1 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of control Example 1
Fig. 2 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of control Example 2
Fig. 3 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of embodiment 1
Fig. 4 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of embodiment 2
Fig. 5 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of embodiment 3
Fig. 6 is the X-ray powder diffraction spectrogram of the triamcinolone that makes of embodiment 4
The specific embodiment: the X-ray powder diffraction test of carrying out in the embodiment of the invention, adopt X ray wavelength X=1.540598
Control Example 1, commercially available triamcinolone available from Tianjin Tianyao Pharmaceutical Co., Ltd., through the X-ray powder diffraction test, records spectrogram such as Fig. 1, and is identical with document 1 record A crystal formation
Control Example 2 is got commercially available triamcinolone, according to disclosed method in the document 1, at normal temperatures, in the 1-butanols, fully stirs, and filters, and drying is carried out the test of X-ray powder diffraction with the product that obtains, and it is identical with document 1 record B crystal formation to record spectrogram such as Fig. 2.
Embodiment 1
Get in the mixed solvent that the 1g triamcinolone is dissolved in 7mL butanols: oxolane=1:3 (volume ratio), slowly be added dropwise to the 50ml cyclohexane extraction with 30min, slowly cooling is cooled to 0 ℃ when dripping cyclohexane extraction.Keep 0 ℃ of insulated and stirred 1h, will separate out crystallization filtration, drying, carry out X-ray powder diffraction and measure.X-ray powder diffraction is measured, and records characteristic peak positions and be 2 θ=9.0 °, 15.6 °, 18.6 °, 21.7 ° spectrograms are as shown in Figure 3.
Embodiment 2
Get in the mixed solvent that the 1g triamcinolone is dissolved in 7mL ethanol: oxolane=1:1 (volume ratio),, slowly be added dropwise to the 50ml normal hexane, slowly cooling is cooled to 0 ℃ when dripping cyclohexane extraction.Keep 0 ℃ of insulated and stirred 2h, will separate out crystallization filtration, drying, carry out X-ray powder diffraction and measure.X-ray powder diffraction is measured, and records characteristic peak positions and be 2 θ=8.9 °, 15.6 °, 18.6 °, 21.8 ° spectrograms are as shown in Figure 4.
Embodiment 3
Get in the mixed solvent that the 1g triamcinolone is dissolved in 8mL propanol: dioxane=1:8 (volume ratio),, slowly be added dropwise to the 60ml normal hexane, slowly cooling is cooled to 0 ℃ when dripping cyclohexane extraction.Keep 0 ℃ of insulated and stirred 3h, will separate out crystallization filtration, drying, carry out X-ray powder diffraction and measure.X-ray powder diffraction is measured, and records characteristic peak positions and be 2 θ=9.0 °, 15.5 °, 18.6 °, 21.7 ° spectrograms are as shown in Figure 5.
Embodiment 4
Get in the mixed solvent that the 1g triamcinolone is dissolved in 9mL methanol: ether=1:10 (volume ratio), slowly be added dropwise to the 90ml cyclohexane extraction, slowly cooling is cooled to 0 ℃ when dripping cyclohexane extraction.Keep 0 ℃ of insulated and stirred 1h, will separate out crystallization filtration, drying, carry out X-ray powder diffraction and measure.X-ray powder diffraction is measured, and records characteristic peak positions and be 2 θ=9.0 °, 15.6 °, 18.7 °, 21.7 ° spectrograms are as shown in Figure 6.
Test example 1 is pulverized experiment
Experimental facilities: WLFM-P-85 type jet mill Beijing Wei Ling Hu Xin Mechanical Equipment Co., Ltd produces
Grain diameter measurement instrument: Easysizer20 laser particle analyzer, Zhuhai OMEC Technology Co., Ltd.
Sample divides into groups:
The A group is commercially available triamcinolone (control Example 1) 500g, is equally divided into ten pulverizing, feed size 80-100 order, the particle diameter D of ten pulverizing
90Carry out again average;
The B group is the made triamcinolone crystal 5 of control Example 2 methods 00g, is equally divided into ten pulverizing, feed size 80-100 order, the particle diameter D of ten pulverizing
90Carry out again average.
C1 ~ C4 group is respectively made each 500g of triamcinolone crystal of embodiment 1-5 method, is equally divided into ten pulverizing separately, feed size 80-100 order, the particle diameter D of ten pulverizing
90Carry out again average.
Pulverization conditions: pulverize air-flow 1.0Mpa
Charging rate 0.5kg/h
Above-mentioned A group and B group sample are carried out comminution by gas stream according to above-mentioned pulverization conditions respectively, the product granularity that obtains is seen the following form
| Group | A | B | C1 | C2 | C3 | C4 |
| Average D90/ μ m | 100.5 | 53.1 | 31.1 | 32.3 | 30.5 | 29.8 |
Mensuration and the bulk testing of 2 angle of reposes of test example
The preparation of test specimen: test specimen is divided into seven groups of A, B, C1-C4, and the grouping situation is identical with test example 1
Adopt the jet mill in the test example 1 to pulverize respectively, the powder D90 that all groupings obtain is between 100 ~ 102 μ m.
Adopt fixedly conical bottom method.The chassis is the culture dish of diameter 7cm, and two glass funnels are overlapping up and down, is fixed on the iron stand, and following hopper outlet and chassis distance are 5.0cm.Slowly add from upper funnel, sample is deposited on the chassis through the buffering of two funnels gradually, form cone, till obtaining the highest cone.Measure the high H of cone, every kind of sample measured three times, averages, and is calculated as follows angle of repose:
α=arctg（H/R）
Wherein, α is angle of repose, and R is the chassis radius
Angle of repose, data saw the following form:
| Group | A | B | C1 | C2 | C3 | C4 |
| Angle of repose | 42.6° | 35.1° | 28.1° | 29.0° | 28.5° | 27.9° |
Test example 3, tablet formulation embodiment feeds intake according to 10000
Mixing apparatus: WCH-10 trough type mixing machine
Feed intake to prepare 10000, the above-mentioned adjuvant pulverize separately of the recipe quantity except that polyvinylpyrrolidone, Polyethylene Glycol, magnesium stearate crosses 100 mesh sieves; Mix with the triamcinolone micropowder that makes according to test example 2 methods; Adopt the WCH-10 trough type mixing machine during mixing, rotating speed 12rpm adds fluidized bed pelletizer behind the mixing 10min; Start fluid bed; The aqueous solution that polyvinylpyrrolidone, the Polyethylene Glycol of recipe quantity is made into 20% (in the gross weight of above-mentioned two kinds of adjuvants) is spraying and carry out drying and granulating through the mode of heated fluidized bed continuously on fluid bed, and the magnesium stearate with recipe quantity of granulating when finishing sucks fluidized bed pelletizer and fully mixes, and the granule that obtains is carried out tabletting obtain 10000 of triamcinolone sheets; Sheet heavily is 120mg, triamcinolone 4mg/ sheet
Adopt A in the test example 2, B, C1 ~ C4 group to make the triamcinolone micropowder and prepare tablet respectively.Obtain tablet A, B, C1 ~ C4
Uniformity of dosage units detects
Content analysis method:
The triamcinolone assay is analyzed with HPLC:
The chromatographic condition position of HPLC: chromatographic column octadecylsilane chemically bonded silica
Mobile phase methanol-water (95:5)
Detect wavelength 243nm
The perfect damage of outward appearance from tablet A and tablet B respectively, smooth in appearance, each 10 in the uniform tablet of color and luster, according to the uniformity of dosage units inspection technique detection level uniformity in 2005 editions appendix 75-76 of Chinese Pharmacopoeia page or leaf,
Measuring every respectively is 100 relative amount X with labelled amount (4mg/ sheet); Ask its meansigma methods
and standard deviation S; And the absolute value A of the difference of labelled amount and average; Calculate A+1.80S, the result sees the following form
| Group | A | B | C1 | C2 | C3 | C4 |
| A+1.80S | 18.5 | 15.3 | 5.1 | 5.5 | 5.3 | 5.3 |
Wherein the tablet content uniformity of all groups all meets the pharmacopeia regulation; But the uniformity of dosage units of tablet C1-C4 is better than tablet A and tablet B; Under equal conditions preparation is described, triamcinolone crystallization provided by the invention realizes uniformity of dosage units preferably easily because flowability is better.
Claims (10)
1. Aristo-Pak; The triamcinolone crystal formation 1 that contains as active component is applicable to the pharmaceutic adjuvant of tablet with one or more; It is characterized in that the X-ray powder diffraction of described triamcinolone crystal formation 1 has been located characteristic peak the angle of diffraction 2 θ=9.0 °, 15.6 °, 18.5 °, 21.7 °.
2. tablet as claimed in claim 1, characteristic are the preferred lactose monohydrate of said pharmaceutic adjuvant, starch, sucrose, dextrin, polyvinylpyrrolidone K30, Polyethylene Glycol, cross-linking sodium carboxymethyl cellulose, magnesium stearate.
3. triamcinolone crystal formation 1, the X-ray powder diffraction of the said crystal formation 1 of its characteristic has been located characteristic peak the angle of diffraction 2 θ=9.0 °, 15.6 °, 18.5 °, 21.7 °.
4. the method for preparing of a triamcinolone crystal formation 1; It is characterized in that: triamcinolone is dissolved in the organic solvent 1 entirely, slowly adds the dissolved agent, treat the deposition separate out after; Filter; Obtain triamcinolone crystal formation 1, said organic solvent 1 is selected from the mixed solvent of one or more lower alcohols and ether solvent, and said dissolved agent is selected from the hydro carbons solvent.
5. method for preparing as claimed in claim 4 is characterized in that the said organic solvent 1 and the envelope-bulk to weight ratio of triamcinolone are 5-10:1.
6. method for preparing as claimed in claim 4, the volume that it is characterized in that said dissolved agent are 5-10 times of organic solvent 1.
7. method for preparing as claimed in claim 4, the volume ratio that it is characterized in that said lower alcohol and ether solvent is 1:1-10, said ether solvent is selected from ether, oxolane (THF), dioxane; Said lower alcohol is selected from methanol, ethanol.
8. method for preparing as claimed in claim 7 is characterized in that the most preferably mixed solvent that constitutes of methanol and oxolane of described organic solvent 1.
9. like the arbitrary described method for preparing of claim 4-8, it is characterized in that said hydro carbons solvent is selected from one or more in cyclohexane extraction, the normal hexane.
10. the application of triamcinolone crystal formation 1 as claimed in claim 3 in the medicine of preparation treatment people or mammalian diseases.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2789118A (en) * | 1956-03-30 | 1957-04-16 | American Cyanamid Co | 16-alpha oxy-belta1, 4-pregnadienes |
| US3021347A (en) * | 1959-10-13 | 1962-02-13 | American Cyanamid Co | Process for hydrolyzing 16, 17 steroid acetonides |
-
2012
- 2012-07-19 CN CN201210250496.9A patent/CN102743352B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2789118A (en) * | 1956-03-30 | 1957-04-16 | American Cyanamid Co | 16-alpha oxy-belta1, 4-pregnadienes |
| US3021347A (en) * | 1959-10-13 | 1962-02-13 | American Cyanamid Co | Process for hydrolyzing 16, 17 steroid acetonides |
Non-Patent Citations (1)
| Title |
|---|
| SUITCHMEZIAN,ET AL: "Investigations on the Polymorphism and Pseudopolymorphism of the Glucocorticoid Triamcinolone: New Findings for a Well-Known Drug", 《CRYSTAL GROWTH & DESIGN》, vol. 7, no. 1, 13 December 2006 (2006-12-13), pages 69 - 74 * |
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Application publication date: 20121024 Assignee: Tianjin Tianyao Pharmaceutical Co., Ltd. Assignor: Tianjin Jinyao Group Co., Ltd. Contract record no.: 2015120000007 Denomination of invention: Triamcinolone tablet and polymorphs and preparation method Granted publication date: 20140611 License type: Exclusive License Record date: 20150309 |
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Application publication date: 20121024 Assignee: TIANJIN TIANYAO PHARMACEUTICAL Co.,Ltd. Assignor: TIANJIN JINYAO GROUP Co.,Ltd. Contract record no.: X2020120000004 Denomination of invention: Triamcinolone tablets, crystal forms and preparation methods Granted publication date: 20140611 License type: Exclusive License Record date: 20200728 |
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