SYNTHESES AND PRELIMINARY IN-VIVO PHOTODYNAMIC EFFICACY OF BENZOPORPHYRIN DERIVATIVES FROM PHYLLOERYTHRIN AND RHODOPORPHYRIN-XV METHYL-ESTERS AND ASPARTYL AMIDES

Citation
Rk. Pandey et al., SYNTHESES AND PRELIMINARY IN-VIVO PHOTODYNAMIC EFFICACY OF BENZOPORPHYRIN DERIVATIVES FROM PHYLLOERYTHRIN AND RHODOPORPHYRIN-XV METHYL-ESTERS AND ASPARTYL AMIDES, Tetrahedron, 52(15), 1996, pp. 5349-5362
Citations number
24
Categorie Soggetti
Chemistry Inorganic & Nuclear
Journal title
ISSN journal
00404020
Volume
52
Issue
15
Year of publication
1996
Pages
5349 - 5362
Database
ISI
SICI code
0040-4020(1996)52:15<5349:SAPIPE>2.0.ZU;2-6
Abstract
Efficient approaches to the synthesis of methyl esters and aspartyl am ides of so-called ring 'A'-benzoporphyrin derivatives from rhodoporphy rin XV dimethyl ester 10 and 3-vinylphylloerythrin methyl ester 22 are reported. The benzo-rings in the products are obtained by way of Diel s-Alder [4+2] cyclizations which employ : a dieneophile and the vinyl and 2,3-double bonds in the starting materials as the diene. In the 3- vinylphylloerythrin series, the presence of the 13(1)-keto-group in ri ng E inhibits the Diels-Alder reaction with dimethyl acetylenedicarbox ylate, but with more reactive dienophiles, such as tetracyanoethylene, the Diels-Alder adduct was isolated in modest yield. Protection of th e 13(1)-keto- group as a ketal or thioketal afforded the intermediate benzoporphyrin adducts, which were rearranged to trans- and cis- isome rs on reacting with triethylamine and 1,8-diazabiclo[5,4,0]undec-7-ene , respectively, Among the sensitizers tested so far, the benzoporphyri n derivative (cis- isomer) obtained from rhodoporphyrin XV di-tert- bu tyl aspartate showed the best in vivo photosensitizing activity in DBA /2 mice transplanted with SMT/F tumors. Copyright (C) 1996 Elsevier Sc ience Ltd