CN104327051A - Crystal form of fumarate of pyrrole derivative - Google Patents
Crystal form of fumarate of pyrrole derivative Download PDFInfo
- Publication number
- CN104327051A CN104327051A CN201410538331.0A CN201410538331A CN104327051A CN 104327051 A CN104327051 A CN 104327051A CN 201410538331 A CN201410538331 A CN 201410538331A CN 104327051 A CN104327051 A CN 104327051A
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- CN
- China
- Prior art keywords
- fluorophenyl
- pyrroles
- alkylsulfonyl
- pyridin
- base
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- 0 CNCc(cc1-c2c(CC=C)cccc2)c[n]1S(*1)(C1c1cnccc1)(O)=O Chemical compound CNCc(cc1-c2c(CC=C)cccc2)c[n]1S(*1)(C1c1cnccc1)(O)=O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention relates to a crystal form of fumarate of a pyrrole derivative, and concretely relates to a crystal form of 1-[5-(2-fluorophenyl)-1-(prindine-3-ylsulfonyl)-1H-pyrrol-3-yl]-N-methylmethamide monofumarate and a preparation method thereof. An X-ray powder diffraction spectrum represented by 2theta angle and the interplanar distance by performing Cu-Ka radiation on the crystal form, and is shown as figure 1. The crystal form is high in purity and good in stability, is applicable to preparation technological process and long-term storage, and also has superiority in industrialized production.
Description
Technical field
The present invention relates to a kind of crystallized form of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate and preparation method thereof.
Background technology
In research and development pharmaceutical composition, medicine is a kind of form be convenient to operation and process is very important, aborning, medicine can be provided with crystallized form pure to be as far as possible also very important.If a kind of active constituents of medicine can be obtained with stable crystalline form easily, then more satisfactory.Therefore, in production viable commercial and pharmaceutically acceptable medicinal compositions time, no matter which kind of may, medicine should be provided with a kind of sufficient crystallising and stable crystallized form as far as possible.
1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate is that the one of Takeda Pharmaceutical Company Limited's research and development is for gastric acid secretion inhibitor (research and development code name: TAK-438, popular name: vonoprazan fumaric acid), this medicine belongs to the new class inhibitor of the competitive sour retarding agent (P-CAB) of potassium ion (K+), have powerful, lasting gastric acid secretion restraining effect, simultaneously, in the final step of parietal cell gastric acid secretion, by suppressing K+ to H+, the keying action of K+-ATP enzyme (proton pump), to gastric acid secretion, also there is premature termination effect.
Its molecular formula is: C
17h
16fN
3o
2sC
4h
4o
4, molecular weight: 461.46, chemical structure is such as formula shown in I.
CN101300229A discloses 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate, but does not relate to its crystallized form.
Summary of the invention
The invention discloses a kind of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A and preparation method thereof.
Now content of the present invention is specifically described.
The invention provides a kind of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A; the X-ray powder diffraction charateristic avsorption band (2 θ) of this crystallized form and D value as follows, error is ± 0.2.
| Diffraction angle 2 θ (D value) | Diffraction angle 2 θ (D value) |
| 5.1(17.3) | 20.6(4.3) |
| 10.1(8.7) | 21.0(4.2) |
| 11.4(7.7) | 21.5(4.1) |
| 11.5(7.6) | 22.4(4.0) |
| 12.2(7.3) | 23.0(3.9) |
| 13.4(6.6) | 23.5(3.8) |
| 13.9(6.4) | 24.3(3.7) |
| 15.2(5.8) | 25.1(3.5) |
| 16.1(5.5) | 25.5(3.5) |
| 16.6(5.3) | 26.0(3.4) |
| 16.9(5.3) | 26.7(3.3) |
| 17.3(5.1) | 27.6(3.2) |
| 17.8(5.0) | 27.9(3.2) |
| 18.5(4.8) | 28.8(3.1) |
| 19.1(4.7) | 29.1(3.1) |
| 20.0(4.4) | 29.9(3.0) |
| 20.3(4.4) |
Powder X-ray analysis is usually used in the research of the structural confirmation of crystallized form, thermodynamic stability and other qualitative, quantitatives, is one of the most frequently used method of drugs crystallized form.
In the present invention, the precision of 2 θ values is ± 0.2, and therefore above-mentioned got value has certain reasonably limit of error, and its limit of error is ± 0.2; The most typical charateristic avsorption band of this crystallized form A is 5.1 and 10.1 for (2 θ), and the strongest charateristic avsorption band (2 θ) is 15.2.
1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate sample X-ray diffraction spectrogram is sharp-pointed diffraction peak, and sample is crystal form, sees Fig. 1.
The differential thermal analysis curve display of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate sample, its fusing point is about 203 DEG C, sees Fig. 2.
The invention discloses the preparation method of a kind of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A.1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A, obtains according to following route:
Compound II per: 5-(2-fluorophenyl)-pyrroles-3-formaldehyde
Compound III: pyridine-3-SULPHURYL CHLORIDE
Compound IV: 5-(2-fluorophenyl)-1-(pyridine-3-alkylsulfonyl)-1H-pyrroles-3-formaldehyde
Compound V:1-[5-(2-fluorophenyl)-1-(pyridine-3-alkylsulfonyl)-1H-pyrroles-3-base]-N-methyl methylamine
Compound I: 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate
The invention still further relates to the preparation method of a kind of described crystallized form A, described method comprises the steps:
1) by 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate, or 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine and fumaric acid are distinguished heating for dissolving in appropriate organic solvent, cooling, crystallization, described organic solvent be selected from carbonatoms be less than or equal to 3 alcohols, ketone, ester class any one or a few mixed solvent; Or the mixed solvent of they and water;
2) filtering for crystallizing washing, dry.
Described organic solvent can be selected from methyl alcohol, ethanol, Virahol, isopropylcarbinol, tertiary amyl alcohol, acetone, butanone, ethyl acetate, isopropyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, isopropyl ether, methyl tertiary butyl ether, methylcyclopentyl ether, acetonitrile, N, dinethylformamide, N,N-dimethylacetamide; .
Crystallized form A purity is high, good stability, is applicable to preparation technical process and standing storage, industrial production also has superiority.
Accompanying drawing explanation
Fig. 1 illustrates the X-ray powder diffraction figure (XRPD) of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A;
Fig. 2 illustrates the differential thermal analysis curve (DSC) of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate crystallized form A.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described further, makes professional and technical personnel in the field understand the present invention better.Embodiment is only indicative, never means that it limits the scope of the invention by any way.
Test testing tool used
1, DSC spectrum
INSTRUMENT MODEL: Mettler Toledo DSC 1Staree System
Sweep gas: nitrogen
Temperature rise rate: 10.0oC/min
Temperature range: 40-200 DEG C
2, x-ray diffraction pattern
INSTRUMENT MODEL: Bruker D8Focus X-ray powder diffractometer
Ray: monochromatic Cu-Ka ray (l=1.5406)
Scan mode: q/2q, sweep limit: 2-40o
Voltage: 40KV, electric current: 40mA
Embodiment 1
The preparation method with A crystal formation pyrrole derivative maleate is shown in lower detailed description.
The synthesis of step 1:5-(2-fluorophenyl)-1-(pyridine-3-alkylsulfonyl)-1H-pyrroles-3-formaldehyde
Be dissolved in tetrahydrofuran (THF) (50ml) by Compound II per (260mg), add 60%NaH, stirring at normal temperature reacts 30 minutes.Add 15-crown ether-5 (1.5g) again, stirring at room temperature reacts 1 hour, add pyridine-3-SULPHURYL CHLORIDE again, stirring at room temperature is reacted 2 little tracking up to thin-layer chromatography and is reacted completely, and then in reaction system, adds 20mL saturated brine, extract by ethyl acetate (100mL × 2), merge organic phase, wash organic phase with saturated brine 50ml, appropriate anhydrous sodium sulfate drying, filter, filtrate reduced in volume obtains crude Compound IV (200mg) and directly casts single step reaction.
The synthesis of step 2:1-[5-(2-fluorophenyl)-1-(pyridine-3-alkylsulfonyl)-1H-pyrroles-3-base]-N-methyl methylamine
Brown raffinate compound IV (200mg) obtained in the previous step is dissolved in 30mL methanol solution, adds 27%-33% methylamine solution, stirring reaction 1.5 hours.Add sodium borohydride (68mg), stirring reaction 20 minutes, add the 1mol/L HCl aqueous solution to acid, be stirred to thin-layer chromatography tracking and react completely.In reaction solution, add saturated sodium bicarbonate solution to system is faint alkalescence, and with ethyl acetate (100mL × 2) extraction, merge organic phase, saturated brine (50mL) washs, anhydrous Na
2sO
4drying, filters, concentrated, obtains crude product (208mg, yellow oil), productive rate: 100%.
The synthesis of step 3:1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate
The compound V obtained by back is dissolved in 20mL ethyl acetate, and the fumaric acid getting massfraction equivalent is dissolved in 2ml methyl alcohol.Drop in the ethyl acetate solution of compound V under stirring, stirring at room temperature 30 minutes.Be warming up to 55-65 degree again to reflux one hour, be cooled to room temperature and filter, obtain the cold ethyl acetate 10ml of off-white color solid and wash, vacuum-drying obtains the crystallization of 170mg Compound I, total recovery about 20%.The X-ray diffraction spectrogram of this crystallized sample is shown in Fig. 1.DSC spectrogram is shown in Fig. 2, and this crystal formation is defined as A crystal formation.
Above content is only general embodiment of the present invention, and for those of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, this description should not be construed as limitation of the present invention.
Claims (5)
1. the crystallized form of 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate, it is characterized in that: use Cu-Ka radiation, obtain the X-ray powder diffraction represented with 2 θ angles and spacing, described crystallization has X-ray powder diffraction as shown in Figure 1, wherein about 5.1 (17.3), 10.1 (8.7), 11.4 (7.7), 11.5 (7.6), 12.2 (7.3), 13.4 (6.6), 13.9 (6.4), 15.2 (5.8), 16.1 (5.5), 16.6 (5.3), 16.9 (5.3) 17.3 (5.1), 17.8 (5.0), 18.5 (4.8), 19.1 (4.7), 20.0 (4.4), 20.3 (4.4), 20.6 (4.3), 21.0 (4.2), 21.5 (4.1), 22.4 (4.0), 23.0 (3.9), 23.5 (3.8), 24.3 (3.7), 25.1 (3.5), 25.5 (3.5) 26.0 (3.4), 26.7 (3.3), 27.6 (3.2), 27.9 (3.2), 28.8 (3.1), 29.1 (3.1), characteristic peak is had with 29.9 (3.0) places.
2. prepare a method for the crystallized form of 1-as claimed in claim 1 [5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate, described method comprises the steps:
1) by 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate, or 1-[5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine and fumaric acid are distinguished heating for dissolving in appropriate organic solvent, cooling, crystallization, described organic solvent be selected from carbonatoms be less than or equal to 5 alcohols, ketone, ester class, ethers, small molecules amides any one or a few mixed solvent; Or the mixed solvent of they and water;
2) filtering for crystallizing washing, dry.
3. preparation method according to claim 2, it is characterized in that in step 1) described in organic solvent be methyl alcohol, ethanol, Virahol, isopropylcarbinol, tertiary amyl alcohol, acetone, butanone, ethyl acetate, isopropyl acetate, tetrahydrofuran (THF), 2-methyltetrahydrofuran, isopropyl ether, methyl tertiary butyl ether, methylcyclopentyl ether, acetonitrile, N, dinethylformamide, N,N-dimethylacetamide.
4. a pharmaceutical composition, it contains the crystallized form of 1-according to claim 1 [5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate and pharmaceutically acceptable carrier.
5. the purposes of the crystallized form of 1-according to claim 1 [5-(2-fluorophenyl)-1-(pyridin-3-yl alkylsulfonyl)-1H-pyrroles-3 base]-N-methyl methylamine list fumarate in the medicine of the anti-gastric acid secretion of preparation.
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| CN105315258A (en) * | 2015-05-16 | 2016-02-10 | 南京海纳医药科技有限公司 | Vonoprazan fumarate polycrystalline forms and preparation method thereof |
| CN105440019A (en) * | 2015-12-17 | 2016-03-30 | 昆明贵研药业有限公司 | Preparation method of drug for treating gastric acid related diseases |
| CN106317020A (en) * | 2016-08-03 | 2017-01-11 | 宜昌人福药业有限责任公司 | Crystal form alpha of vonoprazan fumarate and the preparation method thereof |
| CN106604916A (en) * | 2014-11-12 | 2017-04-26 | 江苏豪森药业集团有限公司 | Crystal form of potassium-competitive acid blockers and preparation method therefor |
| CN107778286A (en) * | 2016-08-25 | 2018-03-09 | 成都弘达药业有限公司 | A kind of synthesis technique of Vonoprazan fumarate |
| CN110272409A (en) * | 2019-03-11 | 2019-09-24 | 南京百迪尔生物医药有限公司 | The new method of one-step synthesis method Wo Nuolazan |
| CN110396080A (en) * | 2018-04-24 | 2019-11-01 | 广东东阳光药业有限公司 | A kind of preparation method of Vonoprazan fumarate metabolin and its deuterated object |
| CN115232107A (en) * | 2022-07-29 | 2022-10-25 | 南京唯创远医药科技有限公司 | Preparation method of high-purity Voranolan fumarate |
| CN107778286B (en) * | 2016-08-25 | 2024-05-10 | 四川弘远药业有限公司 | Synthesis process of voronoi fumarate |
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2014
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| CN106604916A (en) * | 2014-11-12 | 2017-04-26 | 江苏豪森药业集团有限公司 | Crystal form of potassium-competitive acid blockers and preparation method therefor |
| US20180282300A1 (en) * | 2014-11-12 | 2018-10-04 | Jiangsu Hansoh Pharmaceutical Group Co., Ltd. | Crystal form of a potassium-competitive acid blocker and preparation method thereof |
| US10538506B2 (en) * | 2014-11-12 | 2020-01-21 | Jiangsu Hansoh Pharmaceutical Group Co., Ltd. | Crystal form of a potassium-competitive acid blocker and preparation method thereof |
| CN105315258A (en) * | 2015-05-16 | 2016-02-10 | 南京海纳医药科技有限公司 | Vonoprazan fumarate polycrystalline forms and preparation method thereof |
| CN105440019A (en) * | 2015-12-17 | 2016-03-30 | 昆明贵研药业有限公司 | Preparation method of drug for treating gastric acid related diseases |
| CN106317020A (en) * | 2016-08-03 | 2017-01-11 | 宜昌人福药业有限责任公司 | Crystal form alpha of vonoprazan fumarate and the preparation method thereof |
| CN107778286A (en) * | 2016-08-25 | 2018-03-09 | 成都弘达药业有限公司 | A kind of synthesis technique of Vonoprazan fumarate |
| CN107778286B (en) * | 2016-08-25 | 2024-05-10 | 四川弘远药业有限公司 | Synthesis process of voronoi fumarate |
| CN110396080A (en) * | 2018-04-24 | 2019-11-01 | 广东东阳光药业有限公司 | A kind of preparation method of Vonoprazan fumarate metabolin and its deuterated object |
| CN110396080B (en) * | 2018-04-24 | 2022-07-08 | 广东东阳光药业有限公司 | Vonoprazan fumarate metabolite and preparation method of deutero metabolite thereof |
| CN110272409A (en) * | 2019-03-11 | 2019-09-24 | 南京百迪尔生物医药有限公司 | The new method of one-step synthesis method Wo Nuolazan |
| CN115232107A (en) * | 2022-07-29 | 2022-10-25 | 南京唯创远医药科技有限公司 | Preparation method of high-purity Voranolan fumarate |
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