Thermal, X-ray Structural, and Dissolution Characteristics of Solid Forms Derived from the Anticancer Agents 2-Methoxyestradiol and 2-Methoxyestradiol-3,17-O,O-Bis-Sulfamate

J Pharm Sci. 2015 Oct;104(10):3418-25. doi: 10.1002/jps.24545. Epub 2015 Jun 12.

Abstract

The aim of the study was to generate alternative solid forms of 2-methoxyestradiol (2ME) and its sulfamoylated derivative 2-methoxyestradiol-3,17-O,O-bis-sulfamate (2MES), both of which are potent anticancer agents with no significant history of solid-state investigation. Screening for polymorphs and solvates by a variety of procedures yielded four distinct species: a crystalline form of 2ME, an amorphous form of 2ME, a chloroform solvate 2ME·(CHCl3 )2 , and the hemihydrate of the bis-sulfamate, 2MES·(H2 O)0.5 . Hydrogen-bonded assembly of 2ME molecules into layers in both crystalline 2ME and its chloroform solvate was established using single-crystal X-ray diffraction. This technique also revealed disorder of the sulfamate group at position 17 in both molecules comprising the asymmetric unit in the crystal of 2MES·(H2 O)0.5 . The thermal stabilities of the crystalline phases were recorded using hot-stage microscopy, thermogravimetry, and differential scanning calorimetry, and the results were reconciled with the crystal structures. Aqueous dissolution rates measured at 37°C generally decreased in the order 2MES·(H2 O)0.5 > 2ME(amorphous) > 2ME(crystalline).

Keywords: 2-methoxyestradiol; 2-methoxyestradiol-3,17-O,O-bis-sulfamate; crystal structure; crystallization; dissolution; hydrates/solvates; polymorphism; thermal analysis.

MeSH terms

  • 2-Methoxyestradiol
  • Antineoplastic Agents, Hormonal / chemistry*
  • Chloroform
  • Estradiol / analogs & derivatives*
  • Estradiol / chemistry
  • Hydrogen Bonding
  • Models, Molecular
  • Solubility
  • Solvents
  • Thermogravimetry
  • X-Ray Diffraction

Substances

  • 2-methoxyestradiol-3,17-bis-O,O-sulfamate
  • Antineoplastic Agents, Hormonal
  • Solvents
  • Estradiol
  • 2-Methoxyestradiol
  • Chloroform