10-Dimethylamino Derivatives of Benzo[h]quinoline and Benzo[h]quinazolines: Fluorescent Proton Sponge Analogues with Opposed peri-NMe2/–N Groups. How to Distinguish between Proton Sponges and Pseudo-Proton Sponges

• Published in: Journal of organic chemistry 2016-07, Vol.81 (13), p.5574-5587
• Main Authors: Pozharskii, Alexander F, Ozeryanskii, Valery A, Mikshiev, Vladimir Y, Antonov, Alexander S, Chernyshev, Anatoly V, Metelitsa, Anatoly V, Borodkin, Gennady S, Fedik, Nikita S, Dyablo, Olga V
• Format: Article
• Language: English
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/acs.joc.6b00917

For the first time, 10-dimethylamino derivatives of benzo­[h]­quinoline 6 and benzo­[h]­quinazoline 7a–e as mixed analogues of archetypal 1,8-bis­(dimethylamino)­naphthalene (“proton sponge”) 1 and quino­[7,8-h]­quinoline 2a have been examined. Similar to 1 and 2, compounds 6 and 7 display rather high basicity, forming chelated monocations. At the same time, unexpected specifics of the protonated NMe2/N systems consist of a strong shift of the NH proton to the 10-NMe2 group, contrary to the “aniline–pyridine” basicity rule. In case of 4H + , a rapid migration (in the NMR time scale) of the NH proton between two nitrogen atoms along the N–H···N hydrogen bond was registered at room temperature and frozen below −30 °C with the proton fixed on the NMe2 group. Two different approaches for classification of strong neutral nitrogen organic bases as proton sponges (kinetically inert compounds) or pseudo-proton sponges (kinetically active) are discussed. On this basis, benzoquinoline 6 was identified as staying closer to pseudo-proton sponges while 7a–e to proton sponges due to the presence in their molecules of bulky substituents in the pyrimidine ring. Other remarkable peculiarities of 6 and 7 are their yellow color and luminescence in the visible region distinguishing them from colorless 1 and 2a.