122379-60-6Relevant articles and documents
Comprehensive studies on dual excitation behavior of double proton versus charge transfer in 4-(N-substituted amino)-1H-pyrrolo[2,3-b]pyridines
Cheng, Chung-Chih,Chang, Chen-Pin,Yu, Wei-Shan,Hung, Fa-Tsai,Liu, Yun-I,Wu, Guo-Ray,Chou, Pi-Tai
, p. 1459 - 1471 (2003)
Comprehensive spectroscopic and dynamical studies on the dual excitation behavior of proton vs charge transfer for 4-(dimethylamino)-1H-pyrrolo[2,3-b]pyridine (DPP) and its related derivatives are reported. In cyclohexane, DPP dimer and/or dual hydrogen-bonded complex are formed with association constants Ka as high as ～4.2 × 103 and 5.2 × 104 M-1 (e.g., the DPP/acetic acid complex) at 298 K, respectively, which upon electronic excitation undergo ultrafast rate (?6.7 × 1010 s-1) of double-proton transfer, resulting in a unique tautomer emission. Dual fluorescence was observed in polar, aprotic solvents, in which the large Stokes shifted emission band originates from the charge-transfer species incorporating a dimethylamine and pyridine ring as electron donor and acceptor, respectively. Detailed solvent-polarity and temperature-dependent studies in combination with theoretical approaches have been performed to determine the excited-state charge-transfer properties such as dipole moment, orbital configuration, etc. Supplementary support for the dual charge/proton-transfer behavior was provided by the comparative spectroscopy and dynamics of various DPP-related derivatives. Further time-resolved measurements conclude that dual emissions share a common Franck-Condon excited state but undergo two independent relaxation channels. In protic solvents, such as ethanol, following fast solvent relaxation dynamics, the excited charge-transfer state further undergoes a solvent (i.e. alcohol) assisted proton-transfer reaction. The charge versus proton-transfer emission can be distinguished via the temporal spectral evolution. The results demonstrate DPP to be a unique model among 7-azaindole analogues in which the interplay between charge and proton-transfer reactions is operative in the excited state.
The Synthesis of 5-Azaindoles by Substitution-Rearrangement of 7-Azaindoles upon Treatment with Certain Primary Amines
Girgis, Nabih S.,Larson, Steven B.,Robins, Roland K.,Cottam, Howard B.
, p. 317 - 325 (2007/10/02)
Certain 4-substituted 1H-pyrrolopyridines (7-azaindoles) undergo a nucleophilic substitution-rearrangement upon treatment with various primary amines at elevated temperatures to yield N-1-substituted 4-amino-1H-pyrrolopyridines (5-azaindoles).Treatment of the same 7-azaindoles with secondary amines under the same reaction conditions led to simple nucleophilic substitution products.
