Trezimides and tennimides: new imide-based macrocycles.
The reaction of isophthaloyl dichloride with 2-aminopyridine or 2-aminopyrimidine provides a facile entry into a new class of imide-based "3 + 3" macrocyclic trimer (trezimide), together with the known tetramer scaffold (tennimide). The trezimides can adopt two distinct asymmetric conformations in the solid state, isolated as (P) in (IO)3 (from 2-aminopyridine) and (R) in (26IO)3 (from 2-aminopyrimidine). The tennimide crystal structure (26IO)4 (from 2-aminopyrimidine) exhibits three discrete conformational states, highlighting subtle geometric changes with the tennimide channel (pore) open (o) and/or closed (c), as noted by three macrocycle conformations with their channel pores observed as cc/oc/oo. Macrocycle formation (though in competition with oligomer/polymer formation) relies on the o-pyr(im)idine N functionality and preorganized imide hinge (the "CO···CO" twist) together with the inherent flexibility of the isophthaloyl groups.
School of Chemical Sciences, Dublin City University, Dublin 9, Ireland.
Pavle
P
Mocilac
John F
JF
Gallagher
D000631:Aminopyridines / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007094:Imides / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D010795:Phthalic Acids / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry*; D011743:Pyrimidines / Q000138:chemical synthesis / Q000737:chemistry*
D000631:Aminopyridines; D007094:Imides; D047028:Macrocyclic Compounds; D010795:Phthalic Acids; D011108:Polymers; D011743:Pyrimidines; C012180:2-aminopyrimidine; C035659:isophthaloyl dichloride; C032439:alpha-aminopyridine