Abstract
The X-ray crystal structures of C,C,N-triaryl-substituted imine compounds, which have methoxy or hydroxy group adjacent to the imino moiety, are reported and discussed in comparison with those of the precursor ketone compounds, 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene and 1-(4-chlorobenzoyl)-2-hydroxy-7-methoxynaphthalene. In crystals, three aromatic rings in a molecule of the methyl ether-retained imine compound are positioned almost perpendicularly to each other by giving non-coplanar spatial organization of the single molecular structure [dihedral angles: 85.32(18)° for C-linked phenyl ring and naphthalene ring; 79.27(17)° for N-linked phenyl ring and naphthalene ring; 84.78(17)° for C-linked phenyl ring and N-linked phenyl ring]. Spatial organization of the analogous methyl ether-cleaved imine compound has essentially same topology [dihedral angles 80.39(6)° for the C-linked phenyl ring and naphthalene ring; 82.35(6)° for the N-linked phenyl ring and naphthalene ring; 87.09(7)° for C- and N-linked phenyl rings]. These structural features of triarylimines apparently differ from those of the precursor ketones. Two aromatic rings in the methyl ether-cleaved ketone compound make smaller dihedral angle [58.10(6)°] by intramolecular hydrogen bond between ketonic carbonyl group and hydroxy group [2.5573(16) A] than that of the methyl ether-retained ketone [72.06(7)°]. In molecular packing, the methyl ether-retained imine forms tubular molecular alignments composed of R—S dimeric molecular pairs, whereas the methyl ether-retained ketone affords consecutively stacks of one configurated molecules.
Highlights
Non-coplanarly accumulated aromatic-rings compounds, e.g., biphenyls and binaphthyls, have been demonstrated as unique building blocks in construction for many functional materials such as molecular catalysis and functional polymers [1,2,3,4,5,6,7,8,9,10,11,12]
The authors have reported specific and characteristic electrophilic aromatic aroylation of naphthalene derivatives, i.e., two aroyl groups are regioselectively and effectively introduced at the 1,8-positions of the naphthalene ring accompanying with simultaneously proceeding retroaroylation behavior [17,18]
C,C,N-triarylimines were prepared by TiCl4—1,4-diazabicyclo [2.2.2] octane (DABCO)-mediated imination
Summary
Non-coplanarly accumulated aromatic-rings compounds, e.g., biphenyls and binaphthyls, have been demonstrated as unique building blocks in construction for many functional materials such as molecular catalysis and functional polymers [1,2,3,4,5,6,7,8,9,10,11,12]. Minute spatial structural characterization of these compounds [13,14,15,16] has attracted attention of the chemists in the wide-range of organic molecular science and polymer materials fields. As one of the protocols to estimate such interactions, the authors have been investigating synthesis and X-ray crystal structure analysis of congested spatial organization of aromatic rings accumulating molecules. The 1-aroylated naphthalenes, which correspond to the intermediates in the diaroylation, are obtained by choice of acidic mediator
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