Synthesis of chlorin e6 amide derivatives

Novel pH-Independent Amphiphilic Chlorophyll a Derivatives with Oligoethyleneglycol Substituents as a Hydrophilic Part: Synthesis and Hydrophilicity Estimation

“…[22][23][24][25][26] In the IR spectra of chlorin e 6 derivatives 22-32 the 13(1)-keto group absorption band about 1700 cm -1 is absent and absorption bands of amide groups ("amide-I» in the region of 1640-1650 cm -1 and «amide-II» in the region 1530-1550 cm -1 ) are present. The singlet of the proton in position 13(2) at 6.25-6.35 ppm is absent and the signals of protons of the methylene group which is formed by opening exocycle (AB multiplet system at 5-6 ppm region) as well as the methylamide group proton signals (broad quartet or unresolved multiplet of NH proton and doublet of the methyl moiety) are observed in the 1 Н NMR spectra of compounds 22-32.…”

“…The same activating agent was also used by us to synthesize 13(2) ethers and methylpheophorbides 6-10 with the di-, tri-, tetra-, penta-and hexaethylene glycol fragments: it is known that the ester group exocycle methylpheophorbide has a relatively high chemical activity and, therefore, can undergo a trans-esterification reaction. [33][34][35][36] Synthesis of chlorin e 6 derivatives with oligoethylene glycol substituents at position 15 (22)(23)(24)(25)(26) was carried out by the action of methylamine on phorbin derivatives 6-10. Chlorin e 6 derivatives with oligoethylene glycol substituents at position 17 (27)(28)(29) were obtained by the same way (the phorbin derivatives 11-13 exo ring recovering by the action of methylamine).…”

“…[15][16][17][18] And the influence of the structure of these compounds on the hydrophilicity was not studied systematically. Here we report the synthesis of several phorbines (6)(7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21) and chlorins (22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32) with di-, tri-, tetra-, penta-and hexaethylene glycol substituents using methyl pheophorbide a (1) and its derivatives (2)(3)(4)(5) as an initial material (Scheme 1). The influence of the oligoethylene glycol chain length, its position at the macrocycle periphery and the structure of macrocycle on the hydrophilicity of compounds obtained was estimated using their mobility on the reverse phase HPLC data.…”

Erythrocytes Membrane Photodestruction Sensitized Chlorophyll a Derivatives: Some Structure-Activity Regularities

“…[48,49,[58][59][60] 13-Amide derivatives 30 (Scheme 2) and 34 (Scheme 6) were obtained by the same way. [59] The insertion of additional ethanolamine fragments (compounds 32, 33) was carried out using corresponding ester groups amidation of 13-amide (24) (Scheme 5).…”

“…methyl-13(1)-desoxopyropheophorbide a (15) [55] were obtained according to literature procedures. Methyl-13(1)-hydroxy-13(1)desoxo-pheophorbide a (18), [57] chlorin e 6 13(1)-N-(2-hydroxyethyl)amide-15(3),17(3)-dimethyl ester (24), [58] chlorin e 6 13(1)-morpholinylamide-15(3),17(3)-dimethyl ester (25), [58] rodin g 7 13(1)-N,N-dimethylamide-15(3),17(3)-dimethyl ester (34), [59] chlorin e 6 13(1),17(3)-N,N'-(2-hydroxyethyl)diamide-15(3),17(3)-dimethyl ester (32), [60] and chlorin e 6 13(1),15(2),17(3)-N,N',N''-(2-hydroxyethyl)triamide (33) [60] were also obtained according to the known procedures.…”