1-Amino-4,5-8-naphthalenetricarboxylic acid-1,8-lactam-4,5-imide-containing macrocycles:: synthesis, molecular modelling and polymerization

Novel macrocycles containing 1-amino-4,5-8-naphthalenetricarboxylic acid-1,8-lactam-4,5-imide and 1,4,5-8-naphthalenetetracarboxylic bisimide fragments were synthesized by the high-temperature pseudo-high-dilution acylation of the corresponding diols with isophthaloyl chloride, 4,4'-and 2,2'-dichlorocarbonyl biphenyls with up to 60% yield. An important side-reaction that impedes cyclization was found to be the reaction of diol OH groups with HCl during the acetylation. The ring strain in synthesized macrocyles and model cycles was estimated using the isodesmic reaction approach at the B3LYP/6-311+G(d,p)//HF/3-21G level of theory. Lactamimide-containing macrocycles were found to be more strained than bisimide-containing macrocycles. The ring-opening polymerization (ROP) of synthesized macrocycles in the molten state shows that the driving force of this process is the strain release on ring-opening. The ROP of lactamimide-containing macrocycles was found to be an efficient way to obtain lactamimide-containing polymers, which are otherwise difficult to synthesize. (C) 2003 Society of Chemical Industry.