Synthesis of a Polyphenol with a Mesoionic 6‐Oxo‐1,6‐dihydropyrimidin‐3‐ium‐4‐olate as Pendant Group and Its Photochemical Behavior

Tonami, Hiroyuki; Uyama, Hiroshi; Kobayashi, Shiro; Menges, Bernhard; Mittler, Silvia; Theis, Alexander; Ritter, Helmut

doi:10.1002/macp.200390076

Cited by 9 publications

(11 citation statements)

References 25 publications

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“…In 2013, Ramsden recognized two new classes employing a connectivity-matrix analysis supported by DFT calculations . The classification system is the basis to understanding the physical and chemical properties of mesomeric betaines, and this knowledge translates into interesting applications in materials chemistry, synthetic organic chemistry, and natural product chemistry . The distinct classes of mesomeric betaines (MB) also open access to distinct types of N-heterocyclic carbenes (NHCs).…”

Section: Introductionmentioning

confidence: 99%

Dipolar Bent and Linear Acetylenes Substituted by Cationic Quinolinium and Anionic Benzoates. Formation of Mesomeric Betaines

et al. 2016

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3-Ethynylquinoline was subjected to a Sonogashira-Hagihara reaction with methyl 2-, 3-, and 4-bromobenzoates, respectively, and then N-methylated to give 3-[((methoxycarbonyl)phenyl)ethynyl]-1-methylquinolinium salts (two X-ray analyses). On saponification of the 3- and 4-substituted benzoates, the mesomeric betaines 3- and 4-[(1-methylquinolinium-3-yl)ethynyl]benzoates were formed. By contrast, the 2-benzoate derivative gave either the corresponding (1-oxo-1H-isochromen-3-yl)quinolinium derivative or the mesomeric betaine 2-(1-methylquinolinium-3-yl)-1,3-dioxo-2,3-dihydro-1H-inden-2-ide depending on the reaction conditions. A DFT calculation predicts a transoid conformation of the acetylene bond in the intermediate 2-[(1-methylquinolinium-3-yl)ethynyl]benzoate which is due to a strong hydrogen bond between the carboxylate group and 2H of the quinolinium ring, in addition to a 1,5-interaction between the carboxylate group and the CC triple bond. The bond angles of the transoid CC triple bond were calculated to be 211.6° and -175.1° in vacuo. The corresponding linear triple bond is 50.4 kJ/mol less stable in vacuo according to the calculation, and the N-heterocyclic carbene quinoline-2-ylidene is not formed as a tautomer.

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Section: Introductionmentioning

confidence: 99%

Dipolar Bent and Linear Acetylenes Substituted by Cationic Quinolinium and Anionic Benzoates. Formation of Mesomeric Betaines

et al. 2016

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“…179.1 C 4 -N 11 1.476 C 12 -N 11 -C 4 121.3 N 3 -C 4 -N 11 -C 12 158.6 N 11 -C 12 1.352 N 11 -C 12 -C 13 122.0 C 13 -C 12 -N 11 -C 4 179.9 C 12 -C 13 1.370 C 12 -C 13 -C 14 120.3 N 11 -C 12 -C 13 -C 14 0.8 C 13 -C 14 1.421 C 13 -C 14 -C 15 116.0 C 12 -C 13 -C 14 -C 15 0.8 C 14 -C 15 1.419 C 14 -C 15 -C 16 120.6 C 13 -C 14 -C 15 -C 16 1.0 C 15 -C 16 1.370 C 15 -C 16 -N 11 121.7 C 14 -C 15 -C 16 -N 11 0.4 C 16 -N 11 1.354 C 16 -N 11 -C 12 119.3 C 15 -C 16 -N 11 -C 12 2.1 C 14 -N 21 1.352 C 15 -C 14 -N 21 122.1 C 16 -N 11 -C 12 -C 13 2.2 N 21 -C 22 1.455 C 14 -N 21 -C 22 120.3 C 15 -C 14 -N 21 -C 22 179.8 N 21 -C 23 1.455 C 14 -N 21 -C 23 120.1 C 25 -C 14 In addition, infrared and Raman spectra present different patterns, contrary to what was observed for UPC, whose spectra were rather similar. This fact can be due to an increase of the charge fluxes between the uracilyl and the pyridinium groups on going from the neutral betaine to the N3-protonated species.…”

Section: Infrared and Raman Spectramentioning

confidence: 99%

Vibrational spectra and quantum chemical calculations of uracilyl–pyridinium mesomeric betaine

Schmidt¹,

Lindner²,

Casado³

et al. 2007

J Raman Spectroscopy

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Modified nucleobases (MNs) are promising molecules with potential application in non-linear optic (NLO) and drug design against a wide number of diseases. In the present paper we report studies on a cross-conjugated mesomeric betaine, which can act as a MN, formed by the covalent union of a 4-dimethylamino pyridinium and a uracilyl groups. The molecule thus formed must be presented by a dipolar canonical formulae in which positive and negative charges are delocalized within separated moieties. Quantum chemistry density functional theory (DFT) calculations, at the B3PW91/6-31G * * level, and Fourier transform (FT) infrared and Raman spectra of this molecule and its N-deuterated derivative were performed. The calculated structural properties over the ground state optimized structure evidenced a strong separation between the two conjugated systems. Comparison with previous results obtained for the cationic species indicated that N-protonation clearly affects the degree of conjugation. Assignments of the FT-IR and FT-Raman spectra were supported by the DFT wavenumbers, intensities and normal modes, which also evidenced the separation of the two conjugated systems. Significant deviations were found for the stretching force constants of the inter-ring and the uracilyl skeletal bonds when comparing this molecule with its N-protonated species.

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“…12 The chemical, physical, and biological consequences of these three types of conjugation have been surveyed recently. 13 Conjugated mesomeric betaines such as pyridinium-olates and isoquinolinium-3-olates 14 as well as cross-conjugated systems such as pyrimidinium-olates 15 are interesting as photosensitive moieties of polymeric materials, as polarities, refractive indices and densities of such materials change on irradiation. Spiropyrans which undergo ring-cleavage to zwitterionic species 16 found interest as photochromic materials.…”

Section: Introductionmentioning

confidence: 99%

Studies on photocatalytically active materials containing structure elements of a pyridinium alkaloid from Punica granatum

et al. 2007

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The alkaloid punicin from Punica granatum, N-(29,59-dihydroxyphenyl)pyridinium chloride, forms heterocyclic mesomeric betaines and radicals, which were examined by ESR measurements and DFT calculations, in aqueous solution. By reaction of poly(4-vinylpyridine) with p-benzoquinone under two different reaction conditions, polymeric structures with punicin constituents were prepared and characterized. The ESR signals of these polymers were calculated and discussed. The 4,49-bipyridine derivative of these polymers was prepared starting from Merrifield resin which was subsequently reacted with 4,49-bipyridine and p-benzoquinone, or, alternatively, with N-(20-50-dihydroxyphenyl)-4-(49-pyridine)pyridinium chloride. The properties of these new materials in reversible photocatalytic processes via radical species were examined. Therefore, solutions or suspensions were irradiated in water in the presence of proflavinium as a sensitizer, and EDTA as a sacrificial donor under an inert atomsphere. Oxygen (air) recovers the starting materials by formation of hydroxide ions which were determined by pH measurements.

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Synthesis of a Polyphenol with a Mesoionic 6‐Oxo‐1,6‐dihydropyrimidin‐3‐ium‐4‐olate as Pendant Group and Its Photochemical Behavior

Cited by 9 publications

References 25 publications

Dipolar Bent and Linear Acetylenes Substituted by Cationic Quinolinium and Anionic Benzoates. Formation of Mesomeric Betaines

Dipolar Bent and Linear Acetylenes Substituted by Cationic Quinolinium and Anionic Benzoates. Formation of Mesomeric Betaines

Vibrational spectra and quantum chemical calculations of uracilyl–pyridinium mesomeric betaine

Studies on photocatalytically active materials containing structure elements of a pyridinium alkaloid from Punica granatum

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