We have developed a procedure for the direct synthesis of 2-arylazulenes. The 2-arylazulenes are formed in moderate to excellent yields by [8+2] cycloaddition of 2H-cyclohepta[b]furan-2-one derivatives with aryl-substituted silyl enol ethers.

Tetrathiafulvalene (TTF) derivatives with 2-azulenyl substituents 5-11 were prepared by the palladium-catalyzed direct arylation reaction of 2-chloroazulenes with TTF in good yield. Photophysical properties of these compounds were investigated by UV-vis spectroscopy and theoretical calculations. Redox behavior of the novel azulene-substituted TTFs was examined by using cyclic voltammetry and differential pulse voltammetry, which revealed their multistep electrochemical oxidation and/or reduction properties. Moreover, these TTF derivatives showed significant spectral change in the visible region under the redox conditions.

The nucleophilic aromatic substitution (SNAr) reaction of diethyl 6-bromoazulene-1,3-dicarboxylate (1) with a variety of amines afforded the corresponding 6-aminoazulene derivatives 2a–2j in good-to-excellent yields. 6-Aminoazulene derivatives 3a–3f without the 1,3-diethoxycarbonyl functions were obtained by the deesterification of 2a–2f with 100% H3PO4. The reactivity of 6-aminoazulenes toward the bromination, SNAr, and palladium-catalyzed cross-coupling reactions was also clarified. 6-Arylazoazulenes 13a–13c were also prepared via the SNAr reaction of 1 with arylhydrazines, followed by oxidation with Pb­(OAc)4 in the presence of N2H4. The structural, optical, and electrochemical properties of the 6-amino- and 6-arylazoazulenes were revealed by single-crystal X-ray structure analysis, UV/vis spectroscopy, voltammetry analysis, spectroelectrochemistry, and theoretical calculations.