Studies towards the synthesis of isoflavonoids and fluorinated analogs

Submitted by Boris Flegr (boris@uerj.br) on 2021-01-07T19:03:42Z No. of bitstreams: 1 Josi Macillo Firmo Pires.pdf: 4309461 bytes, checksum: d1ac00cacebd1813b4af73f837b0c564 (MD5) Made available in DSpace on 2021-01-07T19:03:42Z (GMT). No. of bitstreams: 1 Josi Macillo Firmo Pires.pdf: 4309461 bytes, checksum: d1ac00cacebd1813b4af73f837b0c564 (MD5) Previous issue date: 2016-03-11 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior The work presented here has as main goals the preparation of isoflavanones and to study the synthesis of fluorinated analogs of isoflavanones, homo-isoflavanones and its carba-analogues. It is worth to mention that these fluorinated analogs were not previously reported in literature. Four isoflavanones were obteined with different pattern of substituitions at A and C rings, one of them was synthesized through the α-arylation reaction of 4-chromanone with bromo-2,4-dimethoxybenzene, while the others with substitution at the A-ring, prepared in three steps from resorcinol and phenylacetic acids. Global yields were about 70%. One α-aryl-α-tetralones were also obtained through the α-arylation reaction in good yield. The homoisoflavonoids were prepared by reacting chromanone and tetralones with p-methoxybenzaldehyde, under secondary amine and acid catalysis, respectively. The products were obtained in yields ranging from 60-95%. The fluorination reactions were tested by using two fluorinating agents, XtalFluor-M and DAST, and the substrates were the α-aryl-α-tetralone and the homoisoflavonoid derived from 6-methoxy-tetralone. The TLC analysis of the reactions indicated the consumption of the starting materials A dissertação aqui apresentada tem como focos principais a preparação de isoflavanonas e estudar a síntese de análogos fluorados de isoflavanonas, homo-isoflavanonas e carba-análogos. Cabe ressaltar que estes análogos fluorados não são descritos na literatura. Quatro isoflavanonas foram obtidas com variação no padrão de oxigenação dos anéis A e C, uma delas foi obtida pela reação de α-arilação da 4-cromanona com o bromo-2,4-dimetoxi-benzeno, sendo as outras isoflavanonas substituídas no anel A, preparadas em três etapas a partir do resorcinol e ácidos fenilacéticos. Os rendimentos globais de foram em torno de 70%. Uma α-aril-α-tetralonas também foi preparada pela reação de α-arilação, sendo obtidas em bom rendimento. Os homo-isoflavonóides foram preparados pela reação de cromanonas e tetralonas com p-metoxibenzaldeído, sob catálise de amina secundária e ácida, respectivamente, sendo obtidos os produtos em rendimentos variando entre 60-95%. Dois agentes de fluoração foram empregados nos testes para as reações de fluoração, XtalFluor-M e DAST, sendo empregados como substratos uma α-aril-tetralona e um homo-isoflavonóide derivados da 6-metoxi-tetralona. O monitoramento por CCF indicou o consumo dos materiais de partida