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

Abstract

15,porphine 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 H 2 P(PhNH 2 )(PhSO 3 -) 3 is protonated at the porphyrin platform and the amino group to form the aqua complex of the zwitterion [H 4 P 2+ (PhNH 3 )(PhSO 3 H)(PhSO 3 -) 2 ](H 2 O) 2 , which is self-assembled into porphyrin nanotubes (PNTs), the outer surface of which is covered with positively charged groups -PhNH 3 + , and the inner surface with electroneutral groups -PhSO 3 H. By the action of nitrous acid, stable diazotized PNTs were obtained. Supramolecular self-assembly inhibits the azo coupling reaction of H 4 P 2+ (PhN 2 + )(PhSO 3 H) (PhSO 3 -) 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 H 2 P(PhN 2

Molecular Structure Features and Acid-Base Ionization of the 5-(4`-Aminophenyl)-10,15,20-tris(4`-sulfophenyl)porphine Conjugate with H-acid in Water

“…H-Conjugate was synthesized by azo coupling of diazonium cation of 5-(4'-aminophenyl)-10,15,20-tris(4'-sulfonatophenyl)porphine and 1-amino-8-naphtholate-3,6-disulfonate (H-acid) in alkaline medium, isolated and characterized by UV-Vis, 1 Н NMR, MS-MALDI-TOF spectra in water as described in. [1] 5,10,15,20-(Tetraphenyl)porphine, 99 %, PorphyChem; H-acid (1-amino-8-naphtholate-3,6-disulfonate disodium salt), 99 %, Xian Health Biochem Technology Co., Ltd.; trifluoroacetic acid, 99 %, Panreac; sodium nitrate, reagent grade, JSC "Lenreaktiv"; aqueous ammonia 26 %, analytic grade, LLC "Sigma-Tech"; n-hexane, reagent grade, JSC "Lenreaktiv"; dichloromethane, reagent grade, LLC "Himmed"; hydrochloric acid 38 %, reagent grade, JSC "Lenreaktiv"; tin dihydrochloride, reagent grade, JSC "Lenreaktiv"; chloroform, reagent grade, LLC "Himmed"; sulfuric acid 95.6 %, reagent grade, CJSC "Vekton"; n-butanol, analytic grade, CJSC "Ekos-1"; sodium hydroxide, analytic grade, CJSC "Kaustic"; chitosan, Sigma Aldrich, 82 % degree of deacetylation; ε-polylysine, pure, Amtech Biotech Co., Ltd.…”

“…Aqua-complex (H 2 O) 2 [H 4 P ++ ] formation is the reason of synchronous diprotonation of H 2 P in H-conjugate with close values of step constants lgK b1 = 5.31 ± 0.01 [1] and lgK B2 = 4.88 ± 0.01, [1] corresponds to the equations (1) and (4). As follows from equation 4 3 , the half-sum (lgK b1 + lgK B2 ) is 5.06 ± 0.02.…”

“…Особенности молекулярного строения и кислотноосновная ионизация коньюгата 5 -(4`-аминофенил) -10,15,20 -трис(4`сульфофенил)порфина с Ашкислотой в воде В. Б. Шейнин, a@ Д. А. Иванов, a О. М. Куликова, a О. И. porphine diazonium cation with 1-amino-8-naphtholate-3,6-disulfonate in alkaline media leads to H-conjugate formation, [1] and its thermodynamically stable form (one of possible four, Figure 1S) is the hydrazone trans-tautomer with 1,2-quinoid structure of H-unit (Figure 1). H-Conjugate molecule is a porphyrin with multilayer system of substituents, which is convenient to consider as a "Russian doll" as the molecular structure becomes more complicated in the series (1)-H 2 P→(2)-H 2 P(Ph) 4 →(3)-H 2 P(PhNH 2 ) (PhSO 3 -) 3 →(4)-H-conjugate.…”

“…[15] In general, porphyrin J-aggregates assembly is monitored by characteristic narrow J-bands, strongly shifted to the red region relative to the initial Soret and Q1-bands of the corresponding monomers. [1,14] The most characteristic is the Soret band shift to 490 nm (Figure 8(a)).…”