Highly conjugated architectures and labile reaction intermediates from coupling between 10π electron-deficient heteroaromatics and sym-trihydroxy- or triamino-benzene derivatives.

The C-C coupling reaction between neutral aromatic carbon nucleophiles such as 1,3,5-triamino- and 1,3,5-trihydroxy-benzene derivatives and 7-chloro-4,6-dinitrobenzofuroxan (Cl-DNBF) or 7-chloro-4,6-dinitrobenzofurazan (Cl-DNBZ) gave in high yield the corresponding conjugated structures, which are of potential interest in the materials field. When chlorine is absent on the electrophile, as in 4,6-dinitrobenzofurazan (DNBZ), the reaction with 1,3,5-triaminobenzene derivatives produces Wheland-Meisenheimer (WM) zwitterionic intermediates, intercepted and fully characterized via NMR at low temperature, whereas stable Meisenheimer complexes (M) were isolated in the reaction of phloroglucinol with 1,3,5-trimethoxybenzene. The latter also gave exclusively M complexes when reacted with 4,6-dinitrobenzofuroxan (DNBF), or 4,6-dinitrotetrazolopyridine (DNTP). The detection of WM or M intermediates can be rationalized by invoking the substituent stabilization ability of the positive charge in WM intermediates, on going from neutral carbon nucleophiles 1,3,5-triaminobenzenes to 1,3,5-trihydroxybenzene derivatives. Furthermore, variable-temperature NMR experiments on the M intermediates gave insights into the rotational barrier about the newly formed C-C bond.

New azo-decorated N-pyrrolidinylthiazoles: synthesis, properties and an unexpected remote substituent effect transmission.

New 5-azo substituted thiazole derivatives have been obtained, under mild conditions and in good yields, by the reaction between 2-N-pyrrolidinylthiazole and a series of aryldiazonium salts bearing, mainly in the para position, groups with different electronic effects. The NMR spectra of the products show broad signals of the methylene groups in the alpha position to the pyrrolidinyl nitrogen, suggesting a hindered rotation around the C2-N bond, of which a double bond character was also evidenced by X-ray diffraction analyses. The free energies of activation for the rotational processes have been obtained from (1)H NMR experiments and computer simulations at different temperatures and provided good correlation with the σ constants of the substituents on the 'remote' benzene ring. This represents an unexpected and peculiar result since the restricted rotation around the C2-N bond was shown to be influenced by a substituent situated very far away. 2,4-Di-N-pyrrolidinylthiazole showed a much greater reactivity than 2-N-pyrrolidinylthiazole with aryldiazonium salts.

Synthesis and antimicrobial activity of novel structural hybrids of benzofuroxan and benzothiazole derivatives.

New compounds containing both benzofuroxan and benzothiazole scaffolds were synthesized through electrophile/nucleophile combination of nitrobenzofuroxan derivatives and 2-mercapto- or 2-aminobenzothiazole derivatives and their biological effect on the natural strain Vibrio genus and different bacterial lux-biosensors was studied. Among all the compounds synthesized, that obtained from 2-mercaptobenzothiazole and 7-chloro-4,6-dinitrobenzofuroxan was toxic for bacterial cells, and also able to activated the 1st type Quorum Sensing system. The reaction between 7-chloro-4,6-dinitrobenzofuroxan and 2-aminobenzothiazole derivatives gave two products, one bearing the benzofuroxan moiety linked to the exocyclic amino nitrogen, and the second derived from the attack of two molecules of electrophile to both the nitrogen atoms of the benzothiazole reagent. Their relative ratio is modifiable by tuning the reagents ratio and the reaction time.

Ring closure of azo compounds to 1,2-annulated benzimidazole derivatives and further evidence of reversibility of the azo-coupling reaction.

The reaction between 1,3,5-tris(N,N-dialkylamino)benzene derivatives and 2 equiv of p-substituted benzenediazonium salts gives dicationic species which collapse to new benzimidazole derivatives with expulsion of p-substituted anilines. The presence of electron-withdrawing groups on the benzenediazo moiety of the dicationic species plays a key role in this unexpected ring closure reaction. The observed chemical behavior has been rationalized in terms of the already reported reversibility of azo coupling reactions and provided further evidence for it.