Journal of Organic Chemistry
Journal of Organic Chemistry
5 years ago

Photoinduced Intramolecular Bifurcate Hydrogen Bond: Unusual Mutual Influence of the Components

Photoinduced Intramolecular Bifurcate Hydrogen Bond: Unusual Mutual Influence of the Components
Mark V. Sigalov, Irina V. Sterkhova, Bagrat A. Shainyan
A series of 7-hydroxy-2-methylidene-2,3-dihydro-1H-inden-1-ones with 2-pyrrolyl (3), 4-dimethylaminophenyl (4), 4-nitrophenyl (5), and carboxyl group (6) as substituents at the exocyclic double bond was synthesized in the form of the E-isomers (4–6) or predominantly as the Z-isomer (3) which in solution is converted to the E-isomer. The synthesized compounds and their model analogues were studied by NMR spectroscopy, X-ray analysis, and MP2 theoretical calculations. The E-isomers having intramolecular O–H···O═C hydrogen bond are converted by UV irradiation to the Z-isomers having bifurcated O–H···O···H–X hydrogen bond. Unexpected shortening (and, thus, strengthening) of the O–H···O═C component of the bifurcated hydrogen bond upon the formation of the C═O···H–X hydrogen bond was found experimentally, proved theoretically (MP2), and explained by a roundabout interaction of the H-donor (HX) and H-acceptor (C═O) via the system of conjugated bonds.

Publisher URL: http://dx.doi.org/10.1021/acs.joc.7b01589

DOI: 10.1021/acs.joc.7b01589

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