The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X = H), nitroperbenzoates (X = para-, meta-, ortho-NO2), and methoxyperbenzoates (X = para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions c...

a distinctive and general feature of gas-phase aromatic substitution, occurs only in those cases where the electrophile fulfils certain requirements. Paramount among the latter seem to be the presence of H atoms carrying a substantial fraction of the positive charge, capable of establishing localized H bonds with the unshared electrons of the substituent, as well as a suitable geometry of the c...

We report the synthesis of a series of hydrophilic butadiyne-linked conjugated zinc porphyrin dimers, designed as photodynamic therapy (PDT) agents. These porphyrin dimers exhibit exceptionally high two-photon absorption cross sections (delta(max) approximately 8,000-17,000 GM) and red-shifted linear absorption spectra (lambda(max) approximately 700-800 nm) making them ideal candidates for one-...

A synthetic strategy based on reactions of cyclic imine oxides, namely 2H-imidazole 1-oxides, with thiophenols mediated by acetyl chloride was successfully applied as a convenient tool to obtain series novel azaheterocyclic molecules, including water-soluble hydrochloride forms. Optimized reaction conditions found herein for the nucleophilic substitution hydrogen (SNH) in non-aromatic substrate...

Addition of amine nucleophiles to acetonitrile solutions of the OsIV anilido complex TpOs(NHPh)Cl2 (1) [Tp = hydrotris(1-pyrazolyl)borate] gives products with derivatized anilido ligands, i.e., TpOs[NH-p-C6H4(N(CH2)5)]Cl2 (2) from piperidine and TpOs[NH-p-C6H4N(CH2)4]Cl2 (3) from pyrrolidine. These materials are formed in approximately 30% yield under anaerobic conditions, together with approxi...

Highly optically enriched, protected, nitrogenated heterocycles with different ring sizes have been synthesized by a very efficient methodology consisting of the asymmetric transfer hydrogenation of N-(tert-butylsulfinyl)haloimines followed by treatment with a base to promote an intramolecular nucleophilic substitution process. N-protected aziridines, pyrrolidines, piperidines, and azepanes bea...

A simple method for the synthesis of new bio-based silane coupling agents (SCAs) with a terpene aromatic core by functionalization cheap, natural eugenol and its sulfur derivatives using hydrosilylation C=C bonds HSi(OEt)3, followed nucleophilic substitution reactions OH/SH groups is presented. The obtained alkoxysilanes possess different polymer-reactive functionalities (alkenyl, epoxide, thii...