title: Synthesis, structures, and solid state self-assemblies of formyl and acetyl substituted triptycenes and their derivatives.
abstract: Starting from triptycene, 2-, (2,6- or 2,7-)di-, and (2,6,14- or 2,7,14-)triformyl or acetyl substituted triptycenes were selectively synthesized. The derivatization of the formyl or acetyl substituted triptycenes was then investigated. Consequently, it was found that the formyl-substituted triptycenes could be transformed into cyano substituted triptycene derivatives by the aldoxime formation and dehydration. Acetoxyl- and acetamino-substituted triptycenes were synthesized by Baeyer-Villiger oxidation of acetyl-substituted triptycenes and Beckmann rearrangement of acetyl-oxime triptycenes, respectively. Deacetylation of triacetaminotriptycene provided an alternative way to the synthesis of triaminotriptycene. In addition, 2-ethynyltriptycene could be conveniently synthesized by Corey-Fuchs reaction of 2-formyltriptycene, and 1,3,5-tritriptycenebenzene was obtained in high yield by the dehydration cyclotrimerization of 2-acetyltriptycene. The different functionalized triptycene derivatives and their regioisomers were well characterized by the FT-IR, (1)H NMR, (13)C NMR, MS spectra, and single crystal X-ray analyses. Moreover, it was also found that 2,6,14-triacetaminotriptycene with the three amide groups paralleled to their connected aromatic rings could self-assemble into a 2D layer with porous structure, and further 3D microporous architecture by the hydrogen-bond network in the solid state.
authors.affiliation: Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
authors.forename: Peng-Fei
authors.initials: PF
authors.lastname: Li
authors.forename: Chuan-Feng
authors.initials: CF
authors.lastname: Chen
mesh_terms: D000873:Anthracenes / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000873:Anthracenes; C520712:triptycene