Formation of Perylenes by Oxidative Dimerization of Naphthalenes Bearing Radical Sources

Abstract

The introduction of phenol groups at the 1,8‐positions of naphthalene allowed its one‐pot oxidative dimerization and subsequent oxidative cyclization to the perylene structures under mild conditions and upon addition of iron (III) chloride. Examination using various derivatives and DFT calculations revealed that these reactions are initiated by the oxidation of the phenol moiety to generate a radical cation, which is supplied as a radical source for the reactions. The delocalization of the spin density from the radical cation of the introduced phenol groups to the naphthalene ring is proposed to be responsible for the intermolecular oxidative homo‐coupling reactions at the peri‐positions of the naphthalene and the subsequent oxidative cyclization at the 8,8’‐positions of the 1,1’‐binaphthyl derivative.

On-Surface Synthesis and Characterization of Super-nonazethrene

“…The synthesis of 2 started with the treatment of 1,5-dibromo-2,6-dimethylnaphthalene (3) 31 with n-BuLi and CuCl 2 at −78 °C, which provided the dimer 5,5′-dibromo-2,2′,6,6′-tetramethyl-1,1′-binaphthalene (4) in good yield. 32 In a next step, 2,2′-(2,2′,6,6′-tetramethyl-[1,1′-binaphthalene]-5,5′-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (5) was obtained under Suzuki−Miyaura conditions in quantitative yield using [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloride as the catalyst, potassium acetate as the base, and bis(pinacolato)diboron ((Bpin) 2 ) as the borylation reagent. 33 Finally, anthracene substituents were introduced to 5 through the Suzuki reaction, leading to the formation of 2 in 39% yield under the catalysis of tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3 ) and bis[(2-diphenylphosphino)phenyl] ether (DPEPhos).…”

“…To synthesize 1 , we designed the precursor 9,9′-(2,2′,6,6′-tetramethyl-[1,1′-binaphthalene]-5,5′-diyl)­dianthracene ( 2 ), which undergoes thermally induced cyclo­dehydrogenation and oxidative cyclization of methyl groups on a metal surface (Scheme ). The synthesis of 2 started with the treatment of 1,5-dibromo-2,6-dimethyl­naphthalene ( 3 ) with n -BuLi and CuCl 2 at −78 °C, which provided the dimer 5,5′-dibromo-2,2′,6,6′-tetramethyl-1,1′-binaphthalene ( 4 ) in good yield . In a next step, 2,2′-(2,2′,6,6′-tetramethyl-[1,1′-binaphthalene]-5,5′-diyl)­bis­(4,4,5,5-tetramethyl-1,3,2-dioxaborolane) ( 5 ) was obtained under Suzuki–Miyaura conditions in quantitative yield using [1,1′-bis­(diphenyl­phosphino)­ferrocene]­dichloro­palladium­(II) dichloride as the catalyst, potassium acetate as the base, and bis­(pinacolato)­diboron ((Bpin) 2 ) as the borylation reagent .…”

High‐Energy Proton‐Beam‐Induced Polymerization/Oxygenation of Hydroxynaphthalenes on Meteorites and Nitrogen Transfer from Urea: Modeling Insoluble Organic Matter?

“…The formation of benzofuran and benzopyran rings in hydroxynaphthalene dimers was previously reported as ac onsequence of intramolecular radical-mediated oxidative coupling in the biosynthetic melaninp athway. [36] Conversely,d imer 10 a wasi nvolved in a cascade of successive CÀCr adical-coupling and oxidation processest oy ield al arge panel of polyoxygenated perylene derivatives, including perylene-3,10-diol (13), [37] perylene-3,10-dione (14), [38] perylene-1,2,6-triol (16), [39] bis-perylene-3,4,9,10-tetraone (17) [40] and 2,4,9-trihydroxy perylene-3,10-dione( 18). [41] Perylen-3-ol (15), [42] ap roduct of deoxygenation of one of the naphthalene rings, was also detected in appreciable yield, probablyd ue to the occurrence of ad isproportionation process [43] ( Table 1).…”

Synergistic effects of side-functionalization and aza-substitution on the charge transport and optical properties of perylene-based organic materials: a DFT study

“…The modelled OSCs are categorized into four groups. The experimentally synthesized P1 (4,4 0 -(perylene-3,10diyl)bis(2,6-di-tert-butylphenol)) and P2 (4,4 0 ,4 00 ,4 0 0 0 -(perylene-3,4,9,10-tetrayl)tetrakis(2,6-di-tert-butylphenol)) by Hirao et al 38 are listed in Group-1. Group-2 (a, b and c as shown in Scheme 1) consists of six newly designed perylene-based compounds, namely, P3:4,4 0 -(perylene-3,10-diyl)bis(2-methylthiophene), P4:4,4 0 ,4 00 ,4 0 0 0 -(perylene-3,4,9,10-tetrayl)tetrakis(2-methylthiophene), P5:4,4 0 -(perylene-3,10-diyl)bis(2-methyl-1,3-thiazole), P6:4,4 0 ,4 00 ,4 0 0 0 -(perylene-3,4,9,10-tetrayl)tetrakis(2-methyl-1,3-thiazole), P7:4,4 0 -(perylene-3,10-diyl)bis(2-methylimidazole) and P8:4,4 0 ,4 00 ,4 0 0 0 -(perylene-3,4,9,10-tetrayl)tetrakis(2-methylimidazole).…”