Fluoroalkylation of porphyrins: synthesis and reactions of beta-fluoroalkyltetraarylporphyrins.
Treatment of 5,10,15,20-tetraarylporphyrins (1) with perfluoroalkyl iodides (2) in the presence of Na(2)S(2)O(4)/NaHCO(3) in DMSO-CH(2)Cl(2) at 30-40 degrees C for several hours gives the corresponding 2-perfluoroalkylporphyrins (3). Nucleophilic attack on 3 with dimethyl malonate, diethyl malonate, malonitrile, or cyano acetate (Nu) anion results in the formation of (E)-3-Nu-2-perfuoroalkyl(methylenyl)chlorins. Electrophilic substitution on 3 with NBS or NO(2) affords regioselectively the corresponding 12(or 13)-bromo- and 12,13-dibromo- or nitroporphyrins.
College of Chemistry and Chemical Engineering, Hunan University, Changsha, 410082, China.
Li-Mei
LM
Jin
Zhuo
Z
Zeng
Can-Cheng
CC
Guo
Qing-Yun
QY
Chen