S_N^H‐ and S_N^ipso‐Arylamination of 1,3,7‐Triazapyrenes

Abstract

The ability of the oxidative arylamination process to derivatize electron‐deficient 1,3,7‐triazapyrenes has been investigated. These triazapyrenes react with a wide range of sodium aryl(hetaryl) amides to give access to the corresponding 6‐aryl(hetaryl)amino‐1,3,7‐triazapyrenes in moderate to good yields. The reaction of 6,8‐dialkoxy‐1,3,7‐triazapyrene with sodium arylamides gives rise to 6,8‐bis(arylamino)‐1,3,7‐triazapyrenes or 6‐methoxy‐8‐arylamino‐1,3,7‐triazapyrenes, depending on the reaction conditions.

Ureas as a New Nucleophilic Reagents for SNAr Amination and Carbamoyl Amination Reactions in 1,3,7‐Triazapyrene Series

“…The obvious reason for this is the low nucleophilicity of the reagent. As in the cases of aryl amination and amidation reactions, in order to increase its nucleophilicity, we generated further urea anion by action of sodium hydride in anhydrous DMSO.…”

“…The obvious reason for this is the low nucleophilicity of the reagent. As in the cases of aryl amination [8] and amidation [9] reactions, in order to increase its nucleophilicity, we generated further urea anion by action of sodium hydride in anhydrous DMSO. It is known that DMSO is a versatile and powerful solvent that provides maximum nucleophilicity of anionic nucleophiles due to the absence of the solvate shell.…”

“…Unusual examples of the relative nucleofugality are described for 7‐bromo‐6‐methoxy‐5,8‐quinolinedione and 4‐chloro‐8‐methoxy‐5‐nitroquinoline , because in these compounds, the methoxy group rather than halogen atoms was subjected to substitution by the amino group. Previously, we have shown the possibility to replace the alkoxy groups in 1,3,7‐triazapyrene ring by aryl amino and acyl amino groups . Note that peri ‐annelated azines including 1,3,7‐triazapyrene are now of practical interest for electronic applications, especially as organic light‐emitting diodes .…”

“…CH 3 ),4.14 (s, 3H, OCH 3 ),7.38 (d, J = 9.0 Hz, 1H, H-4),7.47 (d, J = 9.2 Hz, 1H, H-10),8.03 (br. s, 2H, NH 2 ),8.35 (d, J = 9.0 Hz, 1H, H-5),8.65 (d, J = 9.2 Hz, 1H, H-9);13 C NMR (DMSO-d 6 ): δ 26.6, 54.0, 102.9, 103.3, 115.3, 118.5, 119.4, 130.7, 131.1, 131.4, 155.7, 155.9, 157.5, 160.9, 166.4. HRMS (ESI): calculated for C 15 H 13 N 4 O 265.1089; found 265.1100 [M + H] + .…”

Ureas as new nucleophilic reagents for SNH amination and carbamoyl amination reactions in the 1,3,7-triazapyrene series

“…The obvious reason for this is the low nucleophilicity of the reagent. As in the cases of aryl amination 27 and amidation 28 reactions, in order to increase its nucleophilicity we generated a urea anion by the action of sodium hydride in anhydrous dimethyl sulfoxide. It is known that DMSO is a versatile and powerful solvent which provides maximum nucleophilicity of an anionic nucleophiles due to the absence of the solvate shell.…”