Crystalline forms of tyrosine kinase inhibitors and their salts
The invention relates to various polymorphic forms and amorphous form of sodium 4-((3-(4-cyclohexylpiperazin-1-yl)-6-oxo-6H-anthra[1,9-cd]isoxazol-5-yl)amino)benzate, including the polymorphic form A, mixtures of the polymorphs, process for the preparation thereof and the use thereof in a pharmaceutical composition containing thereof.
1. A crystalline polymorph of Compound I, sodium 4-((3-(4-cyclohexylpiperazin-1-yl)-6-oxo-6H-anthra[1,9-cd]isoxazol-5-yl)amino)benzoate, with the following structure:
having Form B, Form C, Form D, or Form E, wherein:
Form B is characterized as having an x-ray powder diffraction pattern exhibiting three or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.5±0.3, 17.8±0.3, 18.5±0.3, 19.6±0.3, 21.0±0.3, 21.7±0.3, 23.1±0.3, 25.0±0.3, 25.6±0.3, 28.4±0.3, 29.4±0.3, 30.2±0.3, and 31.6±0.3;
Form C is characterized as having an x-ray powder diffraction pattern exhibiting three or more peak positions at a degree two-theta selected from the group consisting of about: 9.0±0.3, 9.8±0.3, 10.2±0.3, 14.3±0.3, 15.9±0.3, 17.4±0.3, 18.2±0.3, 18.9±0.3, 19.2±0.3, 19.6±0.3, 20.2±0.3, 21.3±0.3, 22.1±0.3, 22.7±0.3, 24.7±0.3, 28.3±0.3, 28.9±0.3, 29.1±0.3, and 30.1±0.3;
Form D is characterized as having an x-ray powder diffraction pattern peak positions at a degree two-theta of about: 5.6±0.3, 26.0±0.3, and 26.7±0.3; and
Form E is characterized as having an x-ray powder diffraction pattern peak positions at a degree two-theta of about: 14.4±0.3, 20.0±0.3 and 23.5±0.3.
2. The crystalline polymorph of Compound I of claim 1 , having Form B.
3. The crystalline polymorph of Compound I having Form B of claim 2 , characterized as having an x-ray powder diffraction pattern exhibiting three or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.5±0.3, 17.8±0.3, 18.5±0.3, 19.6±0.3, 21.0±0.3, 21.7±0.3, and 23.1±0.3.
4. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits an x-ray powder diffraction pattern that is substantially similar to that of FIG. 11 .
5. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits a differential scanning calorimetry thermogram comprising an exotherm with an onset of about 106° C.
6. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits a differential scanning calorimetry thermogram comprising an exotherm with a peak of about 120° C.
7. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits a differential scanning calorimetry thermogram comprising an endotherm with an onset of about 225° C.
8. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits a differential scanning calorimetry thermogram comprising an endotherm with a peak of about 253° C.
9. The crystalline polymorph of Compound I having Form B of claim 2 , wherein the crystalline polymorph exhibits a differential scanning calorimetry thermogram that is substantially similar to FIG. 13 .
10. The crystalline polymorph of Compound I of claim 1 , having Form C.
11. The crystalline polymorph of Compound I having Form C of claim 10 , characterized as having an x-ray powder diffraction pattern exhibiting three or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.3±0.3, 17.4±0.3, 18.2±0.3, 18.9±0.3, 19.2±0.3, 22.1±0.3, 22.7±0.3, and 29.1±0.3.
12. The crystalline polymorph of Compound I having Form C of claim 10 , wherein the crystalline polymorph exhibits an x-ray powder diffraction pattern that is substantially similar to FIG. 14 .
13. The crystalline polymorph of Compound I of claim 1 , having Form D.
14. The crystalline polymorph of Compound I having Form D of claim 13 , wherein the crystalline polymorph is further characterized by having an x-ray powder diffraction pattern peak positions at a degree two-theta of about: 8.5±0.3, 14.9±0.3 and 17.0±0.3.
15. The crystalline polymorph of Compound I having Form D of claim 13 , wherein the crystalline polymorph exhibits an x-ray powder diffraction pattern substantially similar to that of FIG. 16 .
16. The crystalline polymorph of Compound I of claim 1 , having Form E.
17. The crystalline polymorph of Compound I having Form E of claim 16 , wherein the crystalline polymorph is further characterized by having an x-ray powder diffraction pattern peak positions at a degree two-theta of about: 5.6±0.3, 9.5±0.3 and 18.9±0.3.
18. The crystalline polymorph of Compound I having Form E of claim 16 , wherein the crystalline polymorph exhibits an x-ray powder diffraction pattern substantially the same as FIG. 17 .
19. A pharmaceutical composition, comprising a crystalline polymorph of Compound I of claim 1 , or a combination thereof, and one or more pharmaceutically acceptable excipients.
20. The pharmaceutical composition of claim 19 , further comprising an amorphous form of Compound I, sodium 4-((3-(4-cyclohexylpiperazin-1-yl)-6-oxo-6H-anthra[1,9-cd]isoxazol-5-yl)amino)benzoate, with the following structure:
21. The pharmaceutical composition of claim 19 , wherein said composition is in a form of a solid or semi-solid dosage form.
22. The pharmaceutical composition of claim 21 , wherein the dosage form comprises one or more of a tablet, hard capsule, soft capsule, powder, suppository, and gel.
23. The pharmaceutical composition of claim 21 , wherein the dosage form comprises one or more of an injectable form, a transdermal patch, a sprayable form, and an implantable depot.
24. The crystalline polymorph of Compound I having Form B of claim 2 , further characterized by having an x-ray powder diffraction pattern exhibiting five or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.5±0.3, 17.8±0.3, 18.5±0.3, 19.6±0.3, 21.0±0.3, 21.7±0.3, 23.1±0.3, 25.0±0.3, 25.6±0.3, 28.4±0.3, 29.4±0.3, 30.2±0.3, and 31.6±0.3.
25. The crystalline polymorph of Compound I having Form B of claim 2 , further characterized by having an x-ray powder diffraction pattern exhibiting seven or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.5±0.3, 17.8±0.3, 18.5±0.3, 19.6±0.3, 21.0±0.3, 21.7±0.3, 23.1±0.3, 25.0±0.3, 25.6±0.3, 28.4±0.3, 29.4±0.3, 30.2±0.3, and 31.6±0.3.
26. The crystalline polymorph of Compound I having Form B of claim 2 , further characterized by having an x-ray powder diffraction pattern exhibiting ten or more peak positions at a degree two-theta selected from the group consisting of about: 9.8±0.3, 10.2±0.3, 14.5±0.3, 17.8±0.3, 18.5±0.3, 19.6±0.3, 21.0±0.3, 21.7±0.3, 23.1±0.3, 25.0±0.3, 25.6±0.3, 28.4±0.3, 29.4±0.3, 30.2±0.3, and 31.6±0.3.
27. The crystalline polymorph of Compound I having Form C of claim 10 , further characterized by having an x-ray powder diffraction pattern exhibiting five or more peak positions at a degree two-theta selected from the group consisting of about: 9.0±0.3, 9.8±0.3, 10.2±0.3, 14.3±0.3, 15.9±0.3, 17.4±0.3, 18.2±0.3, 18.9±0.3, 19.2±0.3, 19.6±0.3, 20.2±0.3, 21.3±0.3, 22.1±0.3, 22.7±0.3, 24.7±0.3, 28.3±0.3, 28.9±0.3, 29.1±0.3, and 30.1±0.3.
28. The crystalline polymorph of Compound I having Form C of claim 10 , further characterized by having an x-ray powder diffraction pattern exhibiting seven or more peak positions at a degree two-theta selected from the group consisting of about: 9.0±0.3, 9.8±0.3, 10.2±0.3, 14.3±0.3, 15.9±0.3, 17.4±0.3, 18.2±0.3, 18.9±0.3, 19.2±0.3, 19.6±0.3, 20.2±0.3, 21.3±0.3, 22.1±0.3, 22.7±0.3, 24.7±0.3, 28.3±0.3, 28.9±0.3, 29.1±0.3, and 30.1±0.3.
29. The crystalline polymorph of Compound I having Form C of claim 10 , further characterized by having an x-ray powder diffraction pattern exhibiting ten or more peak positions at a degree two-theta selected from the group consisting of about: 9.0±0.3, 9.8±0.3, 10.2±0.3, 14.3±0.3, 15.9±0.3, 17.4±0.3, 18.2±0.3, 18.9±0.3, 19.2±0.3, 19.6±0.3, 20.2±0.3, 21.3±0.3, 22.1±0.3, 22.7±0.3, 24.7±0.3, 28.3±0.3, 28.9±0.3, 29.1±0.3, and 30.1±0.3.
30. The pharmaceutical composition of claim 19 , comprising a crystalline polymorph of Compound I having Form B.
31. The pharmaceutical composition of claim 19 , comprising a crystalline polymorph of Compound I having Form C.
32. The pharmaceutical composition of claim 19 , comprising a crystalline polymorph of Compound I having Form D.
33. The pharmaceutical composition of claim 19 , comprising a crystalline polymorph of Compound I having Form E.