39799-77-4Relevant articles and documents
High-Field NMR Spectroscopy Reveals Aromaticity-Modulated Hydrogen Bonding in Heterocycles
Kakeshpour, Tayeb,Bailey, John P.,Jenner, Madison R.,Howell, Darya E.,Staples, Richard J.,Holmes, Daniel,Wu, Judy I.,Jackson, James E.
, p. 9842 - 9846 (2017)
From DNA base pairs to drug–receptor binding, hydrogen (H-)bonding and aromaticity are common features of heterocycles. Herein, the interplay of these bonding aspects is explored. H-bond strength modulation due to enhancement or disruption of aromaticity of heterocycles is experimentally revealed by comparing homodimer H-bond energies of aromatic heterocycles with analogs that have the same H-bonding moieties but lack cyclic π-conjugation. NMR studies of dimerization in C6D6 find aromaticity-modulated H-bonding (AMHB) energy effects of approximately ±30 %, depending on whether they enhance or weaken aromatic delocalization. The attendant ring current perturbations expected from such modulation are confirmed by chemical shift changes in both observed ring C?H and calculated nucleus-independent sites. In silico modeling confirms that AMHB effects outweigh those of hybridization or dipole–dipole interaction.
Photochemistry of N-(pyrimidin-2-one-4-yl)pyridinium derivatives. The ring contraction of pyrimidinone into imidazolinone
Wenska,Skalski,Paszyc,Gdaniec
, p. 2178 - 2184 (2007/10/03)
Photochemical reactions (λ > 300 nm) of N-(1-methylpyrimidin-2-one)- and N-(1,5-dimethyl-pyrimidin-2-one)pyridinium chlorides were studied in deoxygenated aqueous solution at various pH's. Only the former compound was found to be reactive under these conditions to give pyrimidine ring contraction photoproducts 1-methyl-4-imidazolin-2-one and 1-methyl-4-imidazolin-2-one-5-carboxyaldehyde, with pH-dependent chemical yields. The photochemical pyrimidine ring contraction reaction does not occur for other photochemically reactive pyrimidin-2-ones bearing 3-methylimidazolium-1,1,2,4-triazol-1-yl, or imidazol-1-yl as substituents at the C-4 position. The suggested mechanism of the reaction involves the addition of water to the pyrimidinone part of the N-(1-methylpyrimidin-2-one)pyridinium salt in the excited triplet state as the primary photochemical step. Addition of alcohol to the pyridinium ring was found to be the major reaction under irradiation of N-(1-methylpyrimidin-2-one-4-yl)pyridinium chloride in methanol.
AN IMPROVED SYNTHESIS OF 1-ALKYL-4-IMIDAZOLIN-2-ONES
Wong, Ooi,Tsuzuki, Noriko,Richardson, Mark,Rytting, Howard,Konishi, Ryoji,Higuchi, Takeru
, p. 3153 - 3158 (2007/10/02)
Two 1-alkyl-4-imidazolin-2-ones were prepared by acid-catalysed cyclization of N-(2,2-dialkoxyethyl)-N-alkylureas with improved yields of over 90 percent.The amount of HCl used in the reaction and the proper isolation procedure are the important factors in obtaining the high yields.