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ISSN 1998-9539

Diazotization of 5-(4`-Aminophenyl)-10,15,20-tris(4`-sulfophenyl)porphine in Water. Synthesis of Conjugate with H-Acid

Dmitriy A. Ivanov,a Vladimir B. Sheinin,а@ Alexey V. Lyubimtsev,b Olga M. Kulikova,a and Oscar I. Koifmana,b
aG.A. Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia
bIvanovo State University of Chemistry and Technology, 153000 Ivanovo, Russia
@Corresponding author E-mail: vbs@isc-ras.ru
 
Water-soluble 5-(4`-aminophenyl)-10,15,20-tris(4`-sulfophenyl)porphin was obtained by three-stage synthesis from tetraphenylporphyrin under conditions of supramolecular control of regioselectivity of nitration and sulfonation reactions. In acidic medium (pH≈2) the trianion H2P(PhNH2)(PhSO3-)3 is protonated at the porphyrin platform and the amino group to form the aqua complex of the zwitterion [H4P2+(PhNH3)(PhSO3H)(PhSO3-)2](H2O)2, which is self-assembled into porphyrin nanotubes (PNTs), the outer surface of which is covered with positively charged groups -PhNH3+, and the inner electroneutral groups -PhSO3H. By the action of nitrous acid, stable diazotized PNTs were obtained. Supramolecular self-assembly inhibits the azo coupling reaction of H4P2+(PhN2+)(PhSO3H)(PhSO3-)2 tectons with H-acid in an acidic medium. H-Conjugate was obtained by azo coupling in an alkaline medium (pH≈10), where diazotized PNTs are destroyed with formation of the diazocompound H2P(PhN2+)(PhSO3-)3. The resulting product was characterized by 1H NMR, MS MALDI-TOF and UV-Vis spectra. 
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