Perylene derivatives are of interest as components of molecular electronics and nonlinear optics devices, in particular, as fluorophores emitting in the near-IR range. In organic synthesis, perylene and its derivatives most often act as dienes in Diels - Alder reactions with some dienophiles. We investigated a Diels-Alder reaction of perylene (diene) with 1,2-dehydrobenzene and 4,5-dimethoxy-1,2-dehydrobenzene (dienophiles). These arуnes were generated by two methods. The first method is based on the use of diazonium salts of anthranilic acid, stabilized by the presence of para-dodecyl-substituted benzenesulfonic acid. The action of KF as a base in the presence of 18-crown-6 in toluene upon heating leads to a soft generation of the corresponding aryne intermediates in situ. The second method is based on the generation of arynes directly from the corresponding substituted anthranilic acids by the action of isoamyl nitrite in toluene upon heating. Reaction products were isolated in up to 77% yields. A detailed study of both methods for the aryne generation has demonstrated that the yield of the reaction products, namely naphtho[1,2,3,4-ghi]perylene and 10,11-dimethoxynaphto[1,2,3,4-ghi]perylene, are strongly depend on the aryne generation pathway. So, when the arynes were generated from the stabilized diazonium salts, higher yields of the reaction products are observed. The nature of aryne intermediate is also determines its reactivity in reaction with perylene. In particular, it was found that in the case of the use of difluoro-substituted and benzoannulated arynes, such as 4,5-difluoro-1,2-dehydrobenzene and 2,3dehydronaphthalene, generated by both methods, the expected reaction was not observed, and exclusively perylene in an unchanged form was isolated from the reaction mixture. The composition and structure of the obtained naphtha-[1,2,3,4-ghi]perylenes were confirmed using 1H NMR spectroscopy, mass-spectrometry and elemental analysis. Thus, the 1H NMR spectra of the reaction products contains signals of the protons of perylene residue, signals of protons of the corresponding annulated aryne residues in a form of characteristic multiplets in the region corresponding to the resonance of aromatic protons, as well as signals of protons of two methoxy groups (in the case of 4,5-dimethoxy-1,2-dehydrobenzene).