Efficient Preparation of Monoadducts of [60]Fullerene and Anthracenes by Solution Chemistry and Their Thermolytic Decomposition in the Solid State

• Published in: Chemistry : a European journal Vol. 7; no. 15; pp. 3223 - 3235
• Main Authors: Kräutler, Bernhard, Müller, Thomas, Duarte-Ruiz, Alvaro
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag GmbH 03.08.2001; WILEY‐VCH Verlag GmbH; Wiley
• Subjects: Chemistry; Chemistry, Multidisciplinary; cycloaddition; Diels-Alder reactions; fullerenes; Physical Sciences; Science & Technology; solid-state reactions; topochemistry; BUCKMINSTERFULLERENE C-60; CARBON; fullerenes; ADDUCT; T-H; Diels-Alder reactions; cycloaddition; FULLERENE CHEMISTRY; CYCLOADDITIONS; DIRECTED REMOTE FUNCTIONALIZATION; topochemistry; CYCLOPENTADIENE; solid-state reactions; METAL-COMPLEXES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/1521-3765(20010803)7:15<3223::AID-CHEM3223>3.0.CO;2-B

The efficient preparation of monoadducts of [60]fullerene and seven anthracenes (anthracene, 1‐methylanthracene, 2‐methylanthracene, 9‐methylanthracene, 9,10‐dimethylanthracene, 2,3,6,7‐tetramethylanthracene, and 2,6‐di‐tert‐butylanthracene) by cycloaddition in solution is described. The seven mono‐adducts of [60]fullerene and the anthracenes were characterized spectroscopically and were obtained in good yields as crystalline solids. The monoadducts of [60]fullerene and anthracene, 1‐methylanthracene, 2‐methylanthracene and 9,10‐dimethylanthracene crystallized directly from the reaction mixture. The thermolytic decomposition at 180 °C of the crystalline monoadducts of [60]fullerene and anthracene, 1‐methylanthracene, 9‐methylanthracene and 9,10‐dimethylanthracene all gave rise to the specific formation of a roughly 1:1 mixture of [60]fullerene and the corresponding antipodal bisadducts (“trans‐1”‐bisadducts) of [60]fullerene and the anthracenes. In contrast, the crystalline monoadducts of [60]fullerene and the anthracene derivatives 2‐methylanthracene, 2,3,6,7‐tetramethylanthracene and 2,6‐di‐tert‐butylanthracene all decomposed to [60]fullerene and anthracenes (without detectable formation of bisadducts) upon heating in the solid state to temperatures of 180 to 240 °C. The formation of the antipodal bisadducts from thermolytic decomposition of crystalline samples of the monoadducts was rationalized by topochemical control. “Rare” antipodal bisadducts and [60]fullerene can be obtained with high selectivity and topochemical control by thermolysis in the solid state of some monoadducts of anthracenes and [60]fullerene. The preparative result of the solid‐state transformation of seven of the monoadducts (see scheme) was studied; these were efficiently prepared by cycloaddition at or below ambient temperature in solution.