ipso-Nitration of tert-butyl(n.2)metacyclophanes; through-space electronic interactions between two benzene rings
Article Abstract:
Selective introduction of 1-2 nitro groups by replacement, directly, of tert-butyl structures using the ipso aromatic nitration for the meta-bridge aromatics with two arene rings has been investigated. Through-space electronic interactions of two benzene rings, that is, face-to face overlapping with intra-annular interaction with the opposing benzene ring, which speeds the reaction, is of interest. The first sigma-complex intermediate is stabilized by the interaction in two forms. One tert-butyl group, only, is ipso-nitrated in mild reaction conditions because of deactivation of the second aromatic ring by the introduced nitro group. An example of the mild reaction conditions would be copper(II) nitrate in an acetic anhydride solution. The number of ipso-nitration at the tert-butyl groups of the compounds in question, syn- and anti-di-tert-butyl-dimethoxy(n.2)metacyclophanes, was much affected by the reactivity of the nitration reagent.
Publication Name: Canadian Journal of Chemistry
Subject: Chemistry
ISSN: 0008-4042
Year: 1998
User Contributions:
Comment about this article or add new information about this topic:
A comparative theoretical study of the electronic structure of some nickel(II) azides, thiocyanates, and isothiocyanates
Article Abstract:
A comparative theoretical study of conformation and molecular orbitals of some nickel(II) azides has been carried out. Thiocyanates and isothiocyanates were included. Basis sets used to find the optimum ground state for nickel included split valence with 6 d-Gaussians (SV6D), split valence and double zeta sets. The combination DZ-3F was found to give results most like the experimental values.
Publication Name: Canadian Journal of Chemistry
Subject: Chemistry
ISSN: 0008-4042
Year: 1998
User Contributions:
Comment about this article or add new information about this topic:
- Abstracts: State of the art and challenges of the ab initio theory of intermolecular interactions. Poly(aryleneethynylene)s: syntheses, properties, structures, and applications
- Abstracts: Preparation and spectroscopic investigations of mixed octahedral complexes and clusters. Self-assembling supramolecular complexes
- Abstracts: The electrophilic substitution reaction of the dithionitronium cation (SNS)+ with benzene. Extended lithium ion pair indicator scale in tetrahydrofuran
- Abstracts: The self-assembly of a layered material: metal-alkanethiolate bilayers. Remarkable kinetic stability of alpha-thiocarbamoyl substituted 4-methoxybenzyl cations
- Abstracts: On the influence of secondary structure on the alpha-C--H bond dissociation energy of proline residues in proteins: a theoretical study