Reactions of Perylene with Aryne Intermediates

Diels–Alder Cycloaddition to the Bay Region of Perylene and Its Derivatives as an Attractive Strategy for PAH Core Expansion: Theoretical and Practical Aspects

“…Recently, a new variant of the above-described benzyne-generation method was reported. First, a diazonium salt is synthesized, and then it is subjected to a reaction with KF and 18-Crown-6 to generate benzyne [ 168 ]. Thus-generated 50 undergoes in situ cycloaddition to 1 , and naphtho[ ghi ]perylene ( 51 ) is formed in 77% yield.…”

“… Cycloaddition of benzyne to the perylene bay region: synthesis of naphtho[ ghi ]perylene [ 167 , 168 , 169 ]. Reagents and conditions: (a) benzenediazonium 2-carboxylate, DCM/THF (4 v /1 v ), rfx, 3.5 h, Y = 66%; (b) NBu 4 F trihydrate (TBAF), 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (benzyne precursor), PhMe, rfx, 2.5 h, Y = 45%; and (c) phthalic anhydride (benzyne precursor), high-temperature flow system (up to 1000 °C), Y = 4.8%.…”

“…Cycloaddition of 2,3-naphthyne and 9,10-anthryne to the perylene bisimide bay region [132]. Reagents and conditions: (a) 160 °C, 48 h, PhCN, KF, Y = 54% (166); 54% (167); trace (168); and 36% (169).…”

“…bay region [167,168]. Reagents and conditions: (a) isoamyl nitrite, DCM + THF, rfx, 8 h; Y = not reported.…”

“…In our opinion, it may be the result of MW application and significant local overheating of the reaction mixture, which has been well documented for reactions characterized by various mechanisms [136]. In a U.S. patent, the authors also described the cycloaddition of benzyne (generated from anthranilic acid (183) and isoamyl nitrite) to 29, resulting in the formation of 184 (Scheme 44) [167,168]. Moreover, we observed that the generation of arynes using systems containing KF (in THF) was not efficient, in contrast to the reaction with the unsubstituted perylene core (see Section 2.10).…”