Estudios de la reacción de los aminales (2R,7R,11S,16S)- y (2S,7R,11S,16R)-1,8,10,17- tetrazapentaciclo[8.8.1.1.8,170.2,7011,16]eicosano con nucleófilos y electrófilos
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Quiroga Daza, Diego Enrique
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Los aminales cíclicos (2R,7R,11S,16S)- y (2S,7R,11S,16R)-1,8,10,17-tetrazapentaciclo [8.8.1.1.8,170.2,7011,16]eicosano (VII y VIII), sintetizados por reacción entre formaldehído y trans- y cis-1,2-diaminociclohexano respectivamente, son moléculas con características estructurales que determinan su reactividad química tales como la presencia de anillos de ciclohexano con isomería trans o cis de la diamina de partida y grupos aminálicos con comportamiento tanto nucleofílico como electrofílico. En esta Tesis Doctoral, fue llevado a cabo el estudio comparativo de la reactividad química de VII y VIII frente a nucleófilos (como fenoles p-sustituídos, benzotriazol, amoniaco y sales de amonio), y electrófilos (ion nitrosonio y sales de diazonio), identificando diferencias en las condiciones, tiempos de reacción y porcentajes de rendimiento de los productos de interés, los cuales fueron caracterizados por técnicas espectroscópicas. De acuerdo a estos resultados, la estabilidad relativa y la potencial reactividad de estos aminales son afectadas por la influencia de la estereoquímica y las interacciones estereoelectrónicas que estabilizan estos aminales cíclicos.
Abstract. The cyclic aminals (2R,7R,11S,16S)- and (2S,7R,11S,16R)-1,8,10,17-tetraazapentacyclo [8.8.1.1.8,170.2,7011,16]icosane (VII and VIII) were synthesized by reaction between formaldehyde and trans- or cis-1,2-diaminocyclohexane pure diastereoisomers respectively. Considering the presence of cyclohexane rings with trans or cis isomerism in the diamine precursor and aminalic groups with both nucleophilic and electrophilic behavior, the structural characteristics of each aminal establish their chemical reactivity. In this Doctoral Thesis, a comparative investigation of the chemical reactivity of VII and VIII against nucleophiles (as p-substituted phenols, 4-chloroxylenol, benzotriazole, ammonia and ammonium salts), and electrophiles (nitrosonium and diazonium salts) were performed to identify some differences according the optimal reaction conditions, times of reaction and the yields of the products, which differ in the 1,2-diamine absolute configuration. According these results, the relative stability and the potential reactivity of these aminals depend on the stereochemical configuration and stereoelectronic interactions in each aminal, which are responsible of the cyclic system stability.
Abstract. The cyclic aminals (2R,7R,11S,16S)- and (2S,7R,11S,16R)-1,8,10,17-tetraazapentacyclo [8.8.1.1.8,170.2,7011,16]icosane (VII and VIII) were synthesized by reaction between formaldehyde and trans- or cis-1,2-diaminocyclohexane pure diastereoisomers respectively. Considering the presence of cyclohexane rings with trans or cis isomerism in the diamine precursor and aminalic groups with both nucleophilic and electrophilic behavior, the structural characteristics of each aminal establish their chemical reactivity. In this Doctoral Thesis, a comparative investigation of the chemical reactivity of VII and VIII against nucleophiles (as p-substituted phenols, 4-chloroxylenol, benzotriazole, ammonia and ammonium salts), and electrophiles (nitrosonium and diazonium salts) were performed to identify some differences according the optimal reaction conditions, times of reaction and the yields of the products, which differ in the 1,2-diamine absolute configuration. According these results, the relative stability and the potential reactivity of these aminals depend on the stereochemical configuration and stereoelectronic interactions in each aminal, which are responsible of the cyclic system stability.