| Directed ortho Metalation (DoM) of the readily prepared N,N-diethyl naphthalene-1,8-dicarboxamide leads, after electrophilic quench, to 2- and 2,7-substituted N,N-diethyl naphthalene-1,8-dicarboxamide products as a function of the conditions. When the 2 and 2,7 substituents are halogens (N,N-diethyl-2-iodonaphthalene-1,8-dicarboxamide, N,N-diethyl-2,7-dibromonaphthalene-1,8-dicarboxamide, N,N-diethyl-2,7-diiodonaphthalene-1,8-dicarboxamide, Suzuki-Miyaura Pd-catalyzed cross coupling methodology was employed to form 2-aryl and 2,7-diaryl- N,N-diethyl naphthalene-1,8-dicarboxamides. Treatment of N,N-diethyl-2,7-diphenylnaphthalene-1,8-dicarboxamide leads to the mono fluorenone of N,N-diethyl-2,7-diphenylnaphthalene-1,8-dicarboxamide by a Directed remote Metalation (DreM) reaction. The scope and limitations of these methodologies are presented. Different ratios of 2- and 2,7-deuterated products are obtained as a function of conditions and these results are discussed. Rotational barriers of the C-Ar bond rotation have been determined for N,N-diethyl naphthalene-1,8-dicarboxamide using VT NMR. The X-ray structure of N,N-diethyl-2,7-bis(trimethylsilanyl)naphthalene-1,8-dicarboxamide is presented. |
