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Unusual open chain quinolinyl peroxol and its alcohol counterpart obtained through a modified Skraup–Doebner–Von Miller quinoline synthesis: theoretical studies and complete 1 H‐ and 13 C‐NMR assignments
Author(s) -
Fotie Jean,
Kemami Wangun Hilaire V.,
Dreux Katelyn,
Sommerfeld Thomas,
Pittman Jacob
Publication year - 2012
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.3791
Subject(s) - chemistry , quinoline , dimer , nmr spectra database , proton nmr , alkoxy group , dissociation (chemistry) , chemical shift , carbon 13 nmr , computational chemistry , stereochemistry , spectral line , organic chemistry , alkyl , physics , astronomy
Because of their extreme instability, it is generally difficult to synthesize and fully characterize open chain peroxides, also known as peroxols. In our attempt to investigate the mechanism of the Skraup–Doebner–Von Miller quinoline synthesis, we were able to obtain an unusual open chain peroxy‐quinoline, namely, 4‐(8‐ethoxy‐2,3‐dihydro‐ 1H ‐cyclopenta[ c ]quinolin‐4‐yl)butane‐1‐peroxol (1), and its alcohol counterpart, namely 4‐(8‐ethoxy‐2,3‐dihydro‐ 1H ‐cyclopenta[ c ]quinolin‐4‐yl)butan‐1‐ol (2) obtained as a side product during the same reaction. Although structurally similar, these two compounds appeared to display some very distinct physical and spectroscopic characteristics. This work reports detailed NMR studies and full 1 H and 13 C NMR assignments for these two compounds. These assignments are based upon the analysis of the NMR spectra of these compounds including 1 H, 13 C, COSY, gHSQC and gHMBC. The effect of the peroxide functional group on the chemical shift of neighboring carbons and protons was also investigated by comparing the NMR data of these two compounds. Furthermore, the effects of potential hydrogen bondings in 1, 2, and possible 1–1 dimer, 2–2 dimer and in prototypical model systems, as well as the stability of these compounds, were investigated computationally. The computed dissociation energies and NMR data support the interpretation of the experimental data. Copyright © 2012 John Wiley & Sons, Ltd.