Entry point into new trimeric and tetrameric imide-based macrocyclic esters derived from isophthaloyl dichloride and methyl 6-aminonicotinate
Mocilac, Pavle and Gallagher, John F. (2013) Entry point into new trimeric and tetrameric imide-based macrocyclic esters derived from isophthaloyl dichloride and methyl 6-aminonicotinate. Acta Crystallographica Section B: Structural Science, 69 (1). pp. 62-69. ISSN 1600-5740
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The one-step reaction of isophthaloyl dichloride with the 2-aminopyridine derivative (methyl 6-aminonicotinate) yields (i) a trimer-based macrocycle (EsIO)3 and (ii) a tetramer-based macrocycle (EsIO)4 in modest isolated synthetic yields (total of 25%), together with (iii) longer open-chain oligomers. The macrocyclisation relies on the semi-flexible imide hinge formed by reaction of the 2-amino(pyridine) functional group with two acyl chloride functional groups. The determining factors in macrocycle synthesis are (a) imide formation using the heteroaromatic ortho-N functionality; (b) the inherent ability of the imide to twist by 85-115 degrees from planarity (as measured by the CO...CO imide torsion angles and from computational calculations), thereby providing a hinge for macrocyclic ring closure or potentially (non)helical assembly in oligomer/polymer formation and (c) the conformational flexibility of the isophthaloyl group with meta-related carbonyl groups to twist and adopt either syn- or anti-conformations, although the syn-conformation is observed structurally for all isophthaloyl groups in both (EsIO)3 and (EsIO)4 macrocycles.
|Item Type:||Article (Published)|
|Additional Information:||Electronic Supplementary available at the following website
The idea to synthesise imide-based macrocycles stems from the original paper by Evans & Gale (2004) and our structural systematic studies of benzamides and carboxamides (Cryst. Eng. Comm. 2010, 2011) and Acta Crystallographica Section B68, 2012 together with some earlier research studies.
Evans, L.S. & Gale, P.A. (2004). Chem. Commun. 1286–1287.
Mocilac, P. (2012). PhD thesis. DCU, Ireland.
Mocilac, P., Tallon, M., Lough, A.J. & Gallagher, J.F. (2010). CrystEngComm, 12, 3080–3090.
Mocilac, P., Donnelly, K. & Gallagher, J.F. (2012). Acta Cryst. B68, 189–203.
|Uncontrolled Keywords:||macrocyclization; macrocycle synthesis|
|Subjects:||Physical Sciences > Organic chemistry|
Physical Sciences > Chemistry
Physical Sciences > Crystallography
|DCU Faculties and Centres:||DCU Faculties and Schools > Faculty of Science and Health > School of Chemical Sciences|
|Publisher:||Wiley-Blackwell (International Union of Crystallography)|
|Copyright Information:||© 2013 IUCR|
|Use License:||This item is licensed under a Creative Commons Attribution-NonCommercial-Share Alike 3.0 License. View License|
|Funders:||Dublin City University for research support., Programme for Research in Third Level Institutions (PRTLI) Cycle 4, European Regional Development, European Union Structural Funds Programme 2007–2013|
|Deposited On:||22 Jan 2013 11:53 by John Gallagher. Last Modified 22 Jan 2013 11:53|
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