Synthesis and spectroscopic characterization of 1,2,3-triazole tethered quinoline-ferrocene conjugates

U ovom radu je opisana sinteza novih konjugata kinolina i ferocena premoštenih 1,2,3-triazolnim prstenom te njihova strukturna karakterizacija 1HNMR i UV/Vis spektroskopijom. Skraup-ovim reakcijama potpomognutim mikrovalovima su pripravljeni hidroksiderivati kinolina 1 i 2 koji su nadalje prevedeni s odgovarajućim terminalnim alkinil-halogenidima u O-alkilirane derivate kinolina 4, 5 i 7. Mikrovalovima potpomognutom klik reakcijom O-alikiniranih derivata kinolina (4, 5 i 7) s azidoferocenom sintetizirani su hibridi kinolina i ferocena premošteni 1,2,3-triazolom (8-10 i 13). Konjugati kinolina i različito supstituiranih arila premošteni 1,2,3-triazolom (14-19) su pripravljeni mikrovalovima potpomognutim klik reakcijama uz bakrov katalizator. Paladijem kataliziranom Sonogashira-inom reakcijom unakrsnog povezivanja 4-klorkinolina (11) s etinilferocenom i o-metoksifenilacetilenom sintetizirani su 4-alkinilni derivati kinolina 20 i 21. Reakcijom kloriranja 4-hidroksi-2-metilkinolina je pripravljen spoj 22 koji je preveden u 4-azido-2-metilkinolin (23). Klik reakcijom 4-azidokinolina 23 s etinilferocenom pripravljen je 1,2,3-triazolni hibrid kinolina i ferocena 24. Klorkinolinski derivati 25 i 26 su pripravljeni Conrad-Limpach-ovom reakcijom o-i m-kloranilina s etil-acetoacetatom. Kinolinil-ferocenoat 27 je priređen reakcijom esterifikacije ferocen karboksilne kiseline i 8-hidroksikinolina. Strukturna karakterizacija novosintetiziranih spojeva provedena je 1H NMR i UV/Vis spektroskopijom.This paper describes the synthesis of new quinoline and ferrocene conjugates and their structural characterization by 1HNMR and UV/VIS spectroscopy. Hydroxyquinoline derivatives 1 i 2 were prepared by microwave-assisted Skraup reaction, which were further converted with an appropriate terminal alkynyl halides to the O-alkinylated quinoline derivatives 4, 5 and 7. Quinoline and azidoferrocene hybrids (8-10 and 13) bridged with 1,2,3-triazole were prepared by click reaction of O-alkylated derivatives (4, 5 and 7) and azidoferrocene assisted by microwave irradiation in the presence of Cu catalyst. Furthermore, conjugates of quinoline and substituted aryles (14-19) bridged with 1,2,3-triazole ring were also prepared by microwave assisted click reaction. The palladium catalyzed cross-coupling Sonogashira reaction of 4-chloroquinoline (11) with ethynylferrocene and 1-ethynyl-2-methoxybenzene gave 4-alkinylated quinoline derivatives 20 and 21. Chlorination reaction of 4-hydroxy-2-methylquinoline gave compound 22 which is converted to 4-azido-2-methylquinoline (23). Click reaction of 4-azidoquinoline 23 with ethynylferrocene afforded 1,2,3-triazole hybrid of quinoline and ferrocene 24. Chloroquinoline derivatives 25 and 26 were prepared by Conrad-Limpach reaction of o- and m-chloroaniline and ethyl acetoacetate. Quinoline-ferrocenoate 27 was prepared by esterification reaction of ferrocene carboxylic acid and 8-hydroxyquinoline. Structural characterization of novel compounds was performed using 1H NMR i UV/Vis spectroscopy