synthesis of new pyrazole and pyrimidine steroidal derivatives新吡唑并嘧啶的合成甾族的衍生品.pdf

Molecules 2003, 8, 444-452 molecules ISSN 1420-3049 Synthesis of New Pyrazole and Pyrimidine Steroidal Derivatives Daniel G. Rivera 1, Klaus Peseke 2,*, Isabel Jomarrón 1, Alina Montero 3, Reinaldo Molina 3 and 1 Francisco Coll 1 Centro de Investigaciones de Producto Naturales, Facultad de Quimica, Universidad de La Habana, Zapata y G, Vedado, 10400 Habana, Cuba 2 Fachbereich Chemie der Universität Rostock, D-18051 Rostock, Germany 3 Centro Bioactivos Quimicos, Universidad Central de Las Villas, Santa Clara, Cuba * Author to whom the correspondence should be addressed; Fax +49-381-498-6410, E-mail: klaus.peseke@chemie.uni-rostock.de; http://www.fb-chemie.uni-rostock.de/organik/peseke/index.html Received: 16 April 2003; in revised form 8 May 2003 / Accepted: 9 May 2003 / Published: 31 May 2003 __________________________________________________________________________________ Abstract: The synthesis of steroidal heterocycles containing the pyrazole and pyrimidine ring fused to the 16,17-position of the steroid nucleus is reported. Androstenolone acetate (1) reacted with carbon disulfide, iodomethane and sodium hydride to furnish 3β- acetoxy-16-[bis(methylthio)methylene]-5-androst-5-en-17-one (2). The reactions of 2 with hydrazine hydrate and methylhydrazine afforded the 5’-methylthio- pyrazolo[4’,3’:16,17]androst-5-en-3β-ols 3a and 3b, respectively. Treatment of 2 with amidinium, guanidinium, and isothiuronium salts in the presence of sodium methoxide yielded the 6’-methoxy- pyrimido[5’,4’:16,1