Search results for "Intramolecular force"
showing 10 items of 599 documents
Comparative theoretical study of transition structures, barrier heights, and reaction energies for the intramolecular tautomerization in acetaldehyde…
1998
The transition structures associated with the possible intramolecular tautomerization for acetaldehyde/vinyl alcohol and acetaldimine/vinylamine systems as models of keto/enol and imine/enamine interconversion processes, respectively, were characterized. The relative stabilities of the tautomers and the associated barrier heights were calculated. Ab initio analytical gradients and second derivatives at the HF level of theory and 3-21G, 6-31G, 6-31G**, 6-31++G**, and 6-311++G** basis-set, DFT (BP86/6-311++G** and BLYP/6-311++G**), and semiempirical (AM1 and PM3) procedures were used to identify the stationary points. Correlation effects were estimated using the perturbational approach at MP2…
1993
In a new theoretical approach the separation of a pair of chain molecules (measured thermodynamically by the second osmotic virial coefficient A2) is treated as a two-step process: In the first step the molecules are detached from each other by the addition of solvent—keeping their dimensions constant—and in the second step the now isolated coils are allowed to relax into their equilibrium dimensions. For the description of the second step, in which only segments belonging to one molecule take part, an intra-molecular interaction parameter is introduced on the basis of the intrinsic viscosity. The present two-parameter approach yields A2 = A + σ M−(1−a) for the dependence of A2 on the molec…
New insights in chemical reactivity from quantum chemical topology.
2021
International audience; Based on the quantum chemical topology of the modified electron localization function ELFx, an efficient and robust mechanistic methodology designed to identify the favorable reaction pathway between two reactants is proposed. We first recall and reshape how the supermolecular interaction energy can be evaluated from only three distinct terms, namely the intermolecular coulomb energy, the intermolecular exchange‐correlation energy and the intramolecular energies of reactants. Thereafter, we show that the reactivity between the reactants is driven by the first‐order variation in the coulomb intermolecular energy defined in terms of the response to changes in the numbe…
Competing factors on the frequency separation between the OH stretching modes in water
2015
Abstract Recent simulations demonstrated that the inhomogeneous broadening as observed in the vibrational spectra of liquid water at ambient conditions can be viewed as a large vibrational splitting of symmetric and asymmetric OH stretching modes, due to the asymmetry of the local hydrogen-bonding network [J. Phys. Chem. Lett., 2013, 4(19), pp 3245–3250]. In this work, we show that the finite temperature and the liquid phase do not only modulate the local hydrogen-bonding asymmetry of water molecules, but also the intramolecular coupling strength. These two factors compete together in the determination of the overall magnitude of the frequency separation between the two OH stretching modes …
Macrocyclic hexaureas: synthesis, conformation, and anion binding.
2009
Varied flexibility: Cyclic oligoureas are formed by using anions as templates. Linking of six xanthene and/or diphenyl ether fragments by urea groups leads to the formation of five macrocyclic compounds with a 48-membered ring with variable flexibility (see picture). Their interaction with anions shows a strong influence of acetate and chloride ions on the cyclization from four precursor molecules. Five macrocylic compounds XXXXXX, XXDXXD, XDXDXD, XDDXDD, and DDDDDD with 48-membered rings, in which six xanthene and/or diphenyl ether fragments are linked through six urea (-NH-C(O)-NH-) groups, have been synthesized. In the cyclization step, a linear diamine was allowed to react with the appr…
Cyclic tetraureas with variable flexibility--synthesis, crystal structures and properties.
2008
Macrocyclic molecules containing several amide or urea functions may serve as anion receptors. We describe the synthesis of 32-membered macrocycles, in which four rigid xanthene units (X) and/or diphenyl ether units (D) as flexible analogues are linked via urea groups. All six possible combinations of these units (XXXX, XXXD, XXDD, XDXD, XDDD and DDDD) were synthesized and two examples were characterised by single-crystal X-ray analyses (DDDD and two structures for XXXD). Both macrocycles showed distinct differences in their overall conformation and consequently in their hydrogen-bonding pattern. Hydrogen-bonded solvent molecules are found for both compounds and intramolecular hydrogen bond…
Competitive and Selective Csp3Br versus Csp2Br Bond Activation in Palladium-Catalysed Suzuki Cross-Coupling: An Experimental and Theoretical Study …
2010
Phosphine ligands have been demonstrated to have an effect on reactivity and selectivity in the competitive intramolecular palladium-catalysed Suzuki-Miyaura coupling of dibromo sulfoxide 1a possessing two different hybridised electrophilic carbons. It was found that the bromine bond to the sp(3)-hybridised carbon is selectively replaced in the presence of unhindered phosphines such as PPh(3) or xantphos. The use of hindered phosphine ligands such as P(o-tol)(3) and P(1-naphthyl)(3) reversed the selectivity, conducting the cross-coupling at the Csp(2)-Br. Identical trends were observed in external competition experiments carried out with bromomethyl sulfoxide and different substituted bromo…
On the high resolution spectroscopy and intramolecular potential function of SO2
2009
Abstract Two weak stretching bands, ν 1 + 3 ν 3 and 3 ν 1 + ν 3 , of the sulfur dioxide molecule have been recorded at high resolution and analyzed for the first time with using a Fourier transform Bruker IFS-120 HR interferometer. About 1000 transitions with J max . = 51, K a max . = 16 , and 900 transitions with J max . = 53, K a max . = 16 have been assigned to the bands ν 1 + 3 ν 3 and 3 ν 1 + ν 3 , respectively. Analysis of the recorded spectra was made using the model of isolated vibrational states. Parameters obtained from the fit reproduce the initial experimental ro-vibrational energies with the rms deviation of 0.0006 and 0.0012 cm −1 for the bands, 3 ν 1 + ν 3 and ν 1 …
Asymmetric synthesis of functionalized tetrahydrofluorenones via an NHC-catalyzed homoenolate Michael addition
2018
The first example of an N-heterocyclic carbene-catalyzed asymmetric desymmetrization of enal-tethered cyclohexadienones via an intramolecular homoenolate Michael addition/esterification reaction is described. This new protocol offers a direct entry to various functionalized tetrahydrofluorenones with three contiguous stereocenters in high yields, good diastereoselectivities and excellent enantioselectivities.
Selective derivatisation of resorcarenes: 1. The regioselective formation of tetra-benzoxazine derivatives
1997
Abstract Four 5,6-benzo-1,3-oxazine rings are formed by the condensation of resorcarenes with various aliphatic or aromatic primary amines and formaldehyde. From four possible regioisomers only the C4 symmetrical compound is isolated in yields of up to 90%. Semiempirical calculations confirm its relative stability, which is due to the possible formation of four intramolecular OH…O hydrogen bonds. The regioselectivity of the reaction is further established for two examples by single crystal X-ray analysis. A solvent molecule is included in the extended cavity.