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Опубликовано 2013-01-18 Опубликовано на SciPeople2013-07-28 18:18:50 ЖурналInorganic Chemistry

“Synthesis and investigation of regioselectively functionalized novel Corroles.”
Pruthviraj Mohite / Pruthviraj Mohite
UV, NMR, Crystallographic structure, Maldi Tof etc.
Аннотация The research work portrays a concise account on, Amination reaction on copper aryl corrole. The first step of this work is related to the modification of a synthetic protocol for preparation of the β-substituted nitrocorroles. In the second step this β-substituted nitrocorroles were reacted with 4-amino-4H-1,2, 4-triazole to give β-amino-β-nitro derivatives. This is the first successful example of vicarious nucleophilic substitution. The second part presents our study on regioselectively nitration of different meso-triarylcorroles and chloroiron-triarylcorroles, with electron-releasing and electron-withdrawing meso substitutions by two different methods. In all of them substitution took place selectively in only the directly joined pyrrole rings of macrocycle.This was proven by a combination of Xray crystallography of various products and detailed analysis of their NMR spectra. In the third part we discovered the new meso functionalized iron and copper alkyl corroles. The chloroiron complex of alkyl corrole gives nitrosyl iron 5,10,15-nitro corrolato as a unique reaction product. The conformation of this compound was done by NMR, where as the crystallographic structure shows the axial methoxy group by nucleophilic substitutation of nitrosyl ligand. In the case of copper alkyl corrole regioselectelyl Cu-5-nitro alkyl corrole was obtained which was characterized at lower temperature by NMR.We also demonstrated the role of palladium carbon and sodium borohydride to reduce the nitro group and rearomatization of nitro-isocorrole first time. We examined the scope of bromination reaction on silver, free base and isocorrole which can be useful platform for the extension of π-conjugation to form C-C and carbon hetero atom bond. In conclusion we developed new synthetic methods to discover novel compounds.
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