Ispitivanje reakcija građenja acetala pomoću trifenilfosfina i ugljen-tetrahlorida i oksidativnim aminovanjem metil-ketona pomoću joda i amina

Abstract

The aim of this doctoral dissertation was the development of a new method for the synthesis of acetals using a combination of reagents PPh3 and CCl4, directly from aldehydes and stoichiometric amounts of alcohol, under neutral conditions. This reagent combination was also used for the synthesis of tetrahydrofuranyl acetals of structurally different alcohols, using autoxidized tetrahydrofuran. In the second part, a facile one-step oxidative introduction of three nitrogen atoms onto arylmethyl ketones was developed yielding α-iminoamidines, a functionality completely unknown to chemistry. Depending on the fine-tuning of the reaction conditions, reaction workup, or simple subsequent transformations, this synthetic approach led to other nitrogen-containing compounds thus greatly broadening the structural diversity introduced in this way. A physico-chemical characterization of the products revealed that α-iminoamidines display biologically important properties such as a tunable combination of basicity and lipophilicity, and a possibility to be further diversified in a stereochemical manner via axial stereoisomerism. All synthesized products (acetals and α-iminoamidines) were fully spectrally (1D and 2D NMR, IR and MS) characterized, and their NMR spectra were assigned through the analysis of 1D and 2D NMR spectra. The spectrum assignment of the synthesized diastereomeric acetals and α-iminoamidines was performed directly from the mixture by spin simulation, that is, by generating the spectrum of the mixture by summing the simulated 1H NMR spectra of the individual diastereomers, and comparing it with the recorded spectra. In cases where it is necessary, spin simulation was also used for the assignment of spectra of other products. A detailed analysis of the NMR spectra of the prepared α-iminoamidines was conducted to investigate the presence of slow conformational processes and chemical exchanges.