A New Synthetic Route to Heteroanthracenes

Abstract

In this report, we describe the synthesis of 2,3,4a,6,7,8a,9,10‐octaaza‐4,8‐dioxo‐3,4,4a,7,8,8a,9,9a,10,10a‐decahydroanthracene, an octaaza derivative of reduced anthracene, through the reaction of glyoxal bis(nitrosemicarbazone) with glyoxal bis(hydrazone) in aqueous medium at 70 °C as well as by the hydrolytic decomposition of glyoxal bis(nitrosemicarbazone) in aqueous medium at 70 °C in a one‐pot transformation. The structure of the resultant compound was confirmed by physicochemical analytical methods and X‐ray diffraction. We also obtained the first representative of the cyclic monohydrazone dimer 1,2,4,5,8,9,11,12‐octaazacyclotetradeca‐5,7,12,14‐tetraene‐3,10‐dione, which exists as lactam and lactim tautomers, through the reaction of glyoxal bis(nitrosemicarbazone) with glyoxal bis(hydrazone) in alkaline aqueous medium.

Synthesis of Nitro‐Octaaza Derivatives of Reduced Anthracene

“…The reported procedure was used to prepare 2,3,4a,6,7,8a,9,10‐octaaza‐4,8‐dioxo‐3,4,4a,7,8,8a,9,9a,10,10a‐decahydroanthracene ( 1 ).…”

“…This work was done using instruments provided by the Biysk Regional Center for Shared Use of Scientific Equipment of the SB RAS (IPCET SB RAS, Biysk). 1 H and 13 C NMR spectra were recorded with Bruker Avance III 500 MHz and Bruker AV-400 operating at 500.03 and 400.13 MHz for 1 H, at 125.73 and 100.61 MHz for 13 C, at 50.67 MHz for 15 N, and at 36.12 MHz for 14 N. [D 6 ]DMSO signals were used as the reference standard: δ = 2.50 ppm for residual protons in 1 H NMR ARTICLE spectra and δ = 39.51 ppm for 13 C NMR spectra. 14 N, 15 N NMR spectra were taken relative to formamide as the external standard (δ(N) = 112.5 ppm).…”

“…The reported procedure [1] was used to prepare 2,3,4a,6,7,8a,9,10-octaaza-4,8-dioxo-3,4,4a,7,8,8a,9,9a,10,10a-decahydroanthracene (1). www.zaac.wiley-vch.de nitric acid (10 mL, ρ = 1.5 g·cm 3 ) with vigorous stirring and cooling to -30°C.…”

“…The precipitated crystals of 6 (0.81 g, 45 %) were combined by filtration and dried at room temperature. 1 Supporting Information (see footnote on the first page of this article): IR spectra, 1 H and 13 C NMR spectra, UV-vis spectra, and DSC/TGA data for compounds 5Ϫ7.…”

Salt-Forming Ability of 2,3,4а,6,7,8а,9,10-Octaaza-4,8-Dioxo-3,4,4a,7,8,8а,9,9a,10,10а-Decahydroantracene

“…В этом аспекте представляет интерес недавно синтезированное соединение 2,3,4а,6,7,8а,9,10-октааза-4,8-диоксо-3,4,4a,7,8,8а,9,9a,10,10а-декагидроантрацен (соединение 1) полученный реакцией трициклизации бис(нитросемикарбазон)глиоксаля [4], и его аналог, содержащий в положениях 1 и 5 метильные радикалы [5].…”