Maria Marinescu

Hydroacridines: part 29. 15N NMR chemical shifts of 9-substituted 1,2,3,4,5,6,7,8-octahydroacridines and their N-oxides-Taft, Swain-Lupton, and other types of linear correlations.

The 15N NMR chemical shifts of 1,2,3,4,5,6,7,8‐octahydroacridine, 12 of its 9‐substituted derivatives, and of the corresponding N‐oxides were measured and examined in terms of the 9‐substituent effects and the effects of N‐oxidation. For the 9‐substituent effects, good linear correlations were found with the Taft and Swain‐Lupton substituent constants, for both octahydroacridines and their N‐oxides. The 15N chemical shifts of both octahydroacridines and their N‐oxides also correlate well, linearly with the 13C chemical shifts of the para‐carbons in analogously substituted benzene derivatives.

Experimental and theoretical study of the interaction of 3-carboxy-5,6-benzocoumarin with some 1,2,3,4,5,6,7,8-octahydroacridines and the corresponding N-oxides

The interaction of 3-carboxy-5,6-benzocoumarin (BzCum) with 1,2,3,4,5,6,7,8-octahydroacridine (OHA), 9-amino-1,2,3,4,5,6,7,8-octahydroacridine (H(2)N-OHA) and the corresponding N-oxides (OHA-NO and H(2)N-OHA-NO) was studied by fluorescence (steady state, time resolved) and absorption spectroscopy. The analysis of the fluorescence data in terms of Stern-Volmer plots indicated a predominant dynamic quenching for OHA and OHA-NO, and a more complex process for H(2)N-OHA and H(2)N-OHA-NO. The dynamic process was assigned to a photoinduced electron transfer (PET) from the acridine derivatives to the excited state of BzCum. The application of the Rehm-Weller-Marcus theory leads to a good agreement with literature data and allows for the estimation of the solvent organization energy. The presence of the PET mechanism was also supported by DFT results. The absorption spectra evidence the formation of a ground state complex assigned to a hydrogen bond complex involving the carboxylic hydrogen of BzCum.

Hydroacridines: part 30. 1H and 13C NMR spectra of 9-substituted 1,2,3,4,5,6,7,8-octahydroacridines and of their N-oxides.

The 1H and 13C NMR chemical shifts of 1,2,3,4,5,6,7,8‐octahydroacridine, 12 of its 9‐substituted derivatives, and of the corresponding N‐oxides were determined, assigned, and discussed in terms of 9‐substituent effects and effects of N‐oxidation. A good linear correlation was found between the 13C chemical shifts of the aromatic carbons in octahydroacridines and those of respective carbons in the corresponding N‐oxides. Copyright

Thermal behavior of several stable hydrazyl free radicals and of their parent hydrazines

A thermal analysis study has been performed for the stable free radical 2,2-diphenyl-1-picrylhydrazyl and other ten free radical congeners, together with their corresponding parent hydrazines. Qualitative studies on the decomposition products showed that nitrogen dioxide plays a key role. A mechanistic decomposition pathway is also proposed.