Novel and Convenient Synthesis of 2, 7-Dialkyl-1, 8-dihydro-as-indacenes

Faúndez, Rodrigo; Castillo, Francisco; Preite, Marcelo; Schott, Eduardo; Zarate, Ximena; Manriquez, Juan Manuel; Molins, Elies; Morales-Verdejo, Cesar; Chavez, Ivonne

Keywords: as-indacene, regiospecific cycloeliminations, polycyclic bridge ligands

Abstract

A novel and convenient synthetic route towards dialkyl as-indacenes was achieved by alkylation of malonic esters with o-xylylene dibromide, to give the corresponding tetraester, and related diacid. The alkyl groups on the central benzene ring induce intramolecular, regiospecific cycloeliminations leading selectively to the diketones, the precursors of the corresponding 1,8-dihydro-as-indacenes. The structure of the 2,7-dimethyl-1,8-dihydro-as-indacene was determined by X-ray diffraction. The compound 2,7-diethyl-1,8-dihydro-as-indacene was characterized by means of 1H NMR, 13C NMR, FT-IR, UV/Vis measurements, electrochemistry, and elemental analysis. On the other hand, quantum chemical computations based on DFT methods were carried out to get insight into the molecular and electronic structures of the studied ligands. TDDFT approach was employed to calculate the vertical excitations and characterize the nature the UV/Vis absorption bands present in the experiments showing a very good agreement between experimental and calculated values. Finally, the reactivity of the compounds was assessed using the chemical potential (μ), chemical hardness (η), and electrophilicity (ω). Also, the electron-donating (ω–), electron-accepting (ω+), and the net electrophilicity powers (ω±) indexes were studied.

Más información

Título de la Revista: SYNTHESIS-STUTTGART
Volumen: 51
Editorial: Georg Thieme Verlag
Fecha de publicación: 2019
Página de inicio: 441
Página final: 449
Idioma: inglés
URL: https://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-0037-1610631
DOI:

https://doi.org/10.1055/s-0037-1610631

Notas: WOS, ISI