Síntese de derivados triazólicos do Bis-eugenol e do SRPIN340
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2025-02-28
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Universidade Federal de Viçosa
Resumo
No presente trabalho, descreve-se a síntese de derivados 1,2,3-triazólicos do bis- eugenol (3a–3e) e a preparação da 2-(4-(((4-fluorobenzil)oximetil)-1H-1,2,3-triazol-1- il)-5-(trifluorometil)anilina (7). Os derivados do bis-eugenol foram obtidos em três etapas. Inicialmente, procedeu-se à síntese do bis-eugenol (1) por meio do acoplamento oxidativo do eugenol na presença de ferricianeto de potássio, resultando em um rendimento de 65%. Em seguida, o bis-eugenol (1) foi submetido a uma reação de alquilação com brometo de propargila, originando o derivado bis- propargilado (2) com 73% de rendimento. Na terceira e última etapa, a reação de cicloadição 1,3-dipolar entre um alcino terminal e uma azida orgânica catalisada por cobre(I) (CuAAC) entre o composto (2) e diferentes azidas fenílicas levou à obtenção de cinco derivados (3a–3e) com rendimentos variando de 57% a 81%. Estes compostos foram purificados por cromatografia em coluna de sílica gel e caracterizados por espectroscopia de ressonância magnética nuclear (RMN de 1H e 13C). Para a síntese da anilina (7), foi necessário, inicialmente, o preparo dos intermediários 1-azido-2-nitro-4-(trifluorometil)benzeno (4) e do alquino terminal 1- fluoro-4-((prop-2-in-1-iloxi)metil)benzeno (5). O composto (4) foi obtido com um rendimento de 85% por meio de uma reação de substituição nucleofílica aromática entre 1-fluoro-2-nitro-4-(trifluorometil)benzeno e azida de sódio. A alquilação do álcool 4-fluorobenzílico com brometo de propargila, empregando catálise por transferência de fase, resultou no composto (5) com um rendimento de 84%. A reação CuAAC entre (4) e (5) levou à obtenção do derivado 1,2,3-triazólico (6) com um rendimento de 83%. Na etapa final, a redução do grupo nitro de (6) com cloreto de estanho(II) originou a anilina (7) com um rendimento de 93%. Os compostos (4–7) foram purificados por cromatografia em coluna de sílica gel e caracterizados por espectroscopia de RMN. A síntese desses compostos foi realizada no contexto de uma subsequente avaliação de suas atividades fungicidas e antiparasitárias. Palavras-chave: Bis-eugenol; Eugenol; SRPIN340; Química “Click”; Triazóis; Síntese Orgânica
In the present work, the synthesis of 1,2,3-triazolic derivatives of bis-eugenol (3a–3e) and the preparation of 2-(4-(((4-fluorobenzyl)oxymethyl)-1H-1,2,3-triazol-1-yl)-5- (trifluoromethyl)aniline (7) are described. The bis-eugenol derivatives were obtained in three steps. Initially, bis-eugenol (1) was synthesized via the oxidative coupling of eugenol in the presence of potassium ferricyanide, yielding 65%. Next, bis-eugenol (1) was subjected to an alkylation reaction with propargyl bromide, resulting in the bis-propargyl derivative (2) with a yield of 73%. In the third and final step, the 1,3- dipolar cycloaddition reaction between a terminal alkyne and an organic azide, catalyzed by copper(I) (CuAAC), between compound (2) and various phenyl azides led to the formation of five derivatives (3a–3e) with yields ranging from 57% to 81%. These compounds were purified by silica gel column chromatography and characterized by nuclear magnetic resonance spectroscopy (1H and 13C NMR). For the synthesis of aniline (7), it was initially necessary to prepare the intermediates 1- azido-2-nitro-4-(trifluoromethyl)benzene (4) and the terminal alkyne 1-fluoro-4-((prop- 2-in-1-yloxy)methyl)benzene (5). Compound (4) was obtained with a yield of 85% through an aromatic nucleophilic substitution reaction between 1-fluoro-2-nitro-4- (trifluoromethyl)benzene and sodium azide. The alkylation of 4-fluorobenzyl alcohol with propargyl bromide, using phase-transfer catalysis, resulted in compound (5) with a yield of 84%. The CuAAC reaction between (4) and (5) led to the formation of the 1,2,3-triazolic derivative (6) with a yield of 83%. In the final step, the reduction of the nitro group of (6) with tin(II) chloride yielded aniline (7) with a yield of 93%. Compounds (4–7) were purified by silica gel column chromatography and characterized by NMR spectroscopy. The synthesis of these compounds was carried out in the context of a subsequent evaluation of their fungicide and antiparasitic activities. Keywords: Bis-eugenol; Eugenol; SRPIN340; “Click” Chemistry; Triazoles; Organic Synthesis
In the present work, the synthesis of 1,2,3-triazolic derivatives of bis-eugenol (3a–3e) and the preparation of 2-(4-(((4-fluorobenzyl)oxymethyl)-1H-1,2,3-triazol-1-yl)-5- (trifluoromethyl)aniline (7) are described. The bis-eugenol derivatives were obtained in three steps. Initially, bis-eugenol (1) was synthesized via the oxidative coupling of eugenol in the presence of potassium ferricyanide, yielding 65%. Next, bis-eugenol (1) was subjected to an alkylation reaction with propargyl bromide, resulting in the bis-propargyl derivative (2) with a yield of 73%. In the third and final step, the 1,3- dipolar cycloaddition reaction between a terminal alkyne and an organic azide, catalyzed by copper(I) (CuAAC), between compound (2) and various phenyl azides led to the formation of five derivatives (3a–3e) with yields ranging from 57% to 81%. These compounds were purified by silica gel column chromatography and characterized by nuclear magnetic resonance spectroscopy (1H and 13C NMR). For the synthesis of aniline (7), it was initially necessary to prepare the intermediates 1- azido-2-nitro-4-(trifluoromethyl)benzene (4) and the terminal alkyne 1-fluoro-4-((prop- 2-in-1-yloxy)methyl)benzene (5). Compound (4) was obtained with a yield of 85% through an aromatic nucleophilic substitution reaction between 1-fluoro-2-nitro-4- (trifluoromethyl)benzene and sodium azide. The alkylation of 4-fluorobenzyl alcohol with propargyl bromide, using phase-transfer catalysis, resulted in compound (5) with a yield of 84%. The CuAAC reaction between (4) and (5) led to the formation of the 1,2,3-triazolic derivative (6) with a yield of 83%. In the final step, the reduction of the nitro group of (6) with tin(II) chloride yielded aniline (7) with a yield of 93%. Compounds (4–7) were purified by silica gel column chromatography and characterized by NMR spectroscopy. The synthesis of these compounds was carried out in the context of a subsequent evaluation of their fungicide and antiparasitic activities. Keywords: Bis-eugenol; Eugenol; SRPIN340; “Click” Chemistry; Triazoles; Organic Synthesis
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Anilina - Síntese, Eugenol - Síntese
Citação
MOIZÉS, Bianca Fernandes. Síntese de derivados triazólicos do Bis-eugenol e do SRPIN340. 2025. 80 f. Dissertação (Mestrado em Agroquímica) - Universidade Federal de Viçosa, Viçosa. 2025.