Superacid mediated hydroxyalkylation reaction of 1,2,3‐indanetrione: a theoretical study |
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Authors: | Daniel Romero Nieto Mikhail G Zolotukhin Lioudmila Fomina Serguei Fomine |
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Institution: | Instituto de Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico, Apartado Postal 70‐360, CU, Coyoacan, Mexico DF 04510, México |
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Abstract: | Energies of mono‐ and multiprotonation for 1,2,3‐indanetrione and ninhydrin in triflic acid (TFSA) media were estimated at PBE0/aug‐cc‐pvtz//6‐31+G** level of theory. The reactivity of formed intermediates in the reaction of aromatic electrophilic substitution has been studied at the same level of theory. It appears that the basicity of carbonyl groups in 1,2,3‐indanetrione is extremely low due to mutual influences of carbonyl groups. Carbonyl 2 is the least basic but the most reactive in accordance with experiment. Calculations demonstrated that monoprotonated intermediates are the principal reactive species in the reaction of hydroxyalkylation of 1,2,3‐indanetrione in TFSA. A new isomerization mechanism of 2,2‐diaryl‐1,3‐indanediones to 3‐(diarylmethylene)isobenzofuranones in TFSA media has been proposed. Copyright © 2010 John Wiley & Sons, Ltd. |
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Keywords: | hydroxyalkylation PBE0 protonation superacid |
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