Sinteza nekih anuliranih derivata pirazolopirido (ili pirano) pirimidina, pirazolopiridina i piranopirazola

The bifunctional pyrazolopyridine (2) and pyrano-pyrazole (3) derivatives were prepared by the reaction of 2-(2,4-dinitrophenyl)-5-methyl-2,4-dihydro-3H-pyrazol-3-one (1) with p-methoxybenzaldehyde, malononitrile in the presence of ammonium acetate or piperidine, respectively. Compound 2 was used as the key intermediate to prepare the pyrazolo-pyrido-pyrimidine derivatives through its reaction with formic acid, formamide-formic acid-DMF, ammonium thiocyanate or reaction with triethyl orthoformate followed by cyclization with hydrazine hydrate. Reaction of 3 with triethyl orthoformate followed by cyclization with hydrazine hydrate gave the pyrazolo-pyrano-pyrimidine derivative 11. Reaction of ethyl-3-oxo-2-[2-phenyl-diazenyl]butanoate and ethyl 2-[2-(4-chlorophenyl)diazenyl]-3-oxobutanoate with 1 to give the pyrazolone derivatives 13a and 13b was also considered.Bifunkcionalni derivati pirazolopiridina (2) i piranopirazola (3) pripravljeni su reakcijom 2-(2,4-dinitrofenil)-5-metil-2,4-dihidro-3H-pirazol-3-ona (1) s p-metoksibenzaldehidom, malononitrilom u prisutnosti amonijevog acetata ili piperidina. Iz spoja 2 su pripravljeni derivati pirazolopiridopirimidina reakcijom s mravljom kiselinom, smjesom formamida-mravlje kiseline-DMF, amonijevim tiocijanatom ili s trietil ortoformatom, te naknadnom ciklizacijom s hidrazin hidratom. Reakcija spoja 3 s trietil ortoformatom te cillizacijom s hidrazin hidratom dobiveni su derivati pirazolo-pirano-pirimidina (11). Reakcijom etil-3-okso-2-[2-fenil-diazenil]butanoata i etil 2-[2-(4-klorfenil)diazenil]-3-oksobutanoata sa spojem 1 sintetizirani su derivati pirazolona 13a i 13b