A One Step Synthesis of Boronated meso-Tetraphenylporphyrins

Abstract

5,10,15,porphyrin and their metal complexes were used for a one stage synthesis of boronated porphyrins with elevated boron content (~30-35%). The reaction of amino groups in para position of porphyrin phenyl rings with carborane triflates, epoxides and isocyanates smoothly led to carboranylsubstituted secondary amines, amino alcohols and amides potentially applicable in anticancer boron neutron capture therapy (BNCT). 5-(4-Aminophenyl)-10,15,20-triphenylporphyrin was used as a model compound in reactions with above mentioned functionally substituted carboranes. boron neutron capture therapy (BNCT). 3 J нн = 12.5 Hz), 2.00 (4Н, dd, СНН-С-carborane, 2 J нн = 16.0 Hz, 3 J нн = 7.9 Hz), 1.50 (4Н, dd, СНН-С-carborane, 2 J нн = 16.1 Hz, 3 J нн = 3.5 Hz).Pd complex of 5,10,15,20-tetra[p-2-hydroxy-3-(1'-ophenylcarboran-2'-yl)propyl]aminophenylporphyrin, 21. Yield 130 mg (84.5%). Found: C 56.71, H 5.87, B 22.45, N 6.05 %. C 88 H 112 B 40 N 8 O 4 Pd requires C 56.08, H 5.99, B 22.94, N 5.95 %. m/z (MALDI): 1886 [M + ]. IR (hexachloro-1,3-butadiene) ν max cm -1 : 3338 (ОН, NH), 2585 (ВН). UV-vis (CHCl 3 ) λ max nm (lg ε): 428 (4.90), 535 (3.76), 610 (3.30). 1 Н NMR (CDCl 3 ) δ ppm: 9.48 (8Н, s, pyrrole-H), 8.67 (4Н, s, NH), m, Ph), 3.64 -3.79 (4Н, m, СН), 2.55 (4Н, br.s, ОН), 2.31 (4Н, dd, СНН-N, 2 J нн = 13.5 Hz, 3 J нн = 3.9 Hz), 2.16 (4Н, dd, СНН-N, 2 J нн = 13.5 Hz, 3 J нн = 11.4 Hz), 2.11 (4Н, dd, СНН-С-carborane, 2 J нн = 14.6 Hz, 3 J нн = 6.9 Hz), 1.63 (4Н, dd, СНН-С-carborane, 2 J нн = 14.6 Hz, 3 J нн = 4.0 Hz).

Synthesis of Sulfonamide Derivatives of Carboranyl Porphyrins Based on 5-(4-Aminophenyl)-10,15,20-triphenylporphyrin and Mercapto Carboranes

“…[14,15] Conjugates of porphyrins with carboranes are potential agents for use in PDT and BNCT. To continue our ongoing efforts on porphyrin functionalization, [16] we present herein the synthesis of sulphonamide substituted boronated porphyrins based on reactions of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin with mercapto carboranes. The sulfonamide functional groups can be found in a variety of drugs which show broad spectrum of pharmacological activity such as antitumor, [17,18] anti-HIV, [19] antitubercular, [20] antimicrobial, [21] antileukemic, [22] anticonvulsant and analgesic.…”

Synthesis and antitumor activity of novel tetrakis[4-(closo-carboranylthio)tetrafluorophenyl]porphyrins

“…11 B NMR spectra were run on a Bruker Avance 400 instrument (working frequencies of 400.13 and 161.98 MHz, respectively) 19. F NMR spectra were recorded with a BrukerScheme 2 M = Cu (8, 13); Zn (9, 14); Pd (10, 15); R´ =…”