Topology steric effects

The Topological Steric Effect Index (TSEI) was proposed to describe the steric effects of substituents in terms ofthe relative specific volume ofthe reaction center screened by the atoms... 

Then, the topological steric effect index TSEI for an alkyl substituent, ignoring hydrogen atoms, is defined as... 

The topological steric effect index TSEIx for a substituent containing any heteroatom X is analogously calculated as... 

TSEI = Topological Steric Effect Index steric descriptors (O Taft steric constant)... 

The steric constant Es and related quantities do not constitute the only approach to the study of steric effects on reactivity. Steric strain energy calculations and topological indices are more recent approaches. Qualitative concepts have been... 

According to the orbital phase theory, the Gloss s diradical 62 is predicted to have a triplet ground state due to the same orbital-phase topology as the TM (2). In derivatives of 62, electronic and steric effects of various substituents as well as ring strains in the cyclic diradicals have successfully been applied to modulate the... 

From topological methods. This method is best restricted to steric effect and polarizability parameters. 

Simple branching equation (SB) A topological method for describing steric effects which takes into account the order of branching by using as parameters the number of atoms other than H that are bonded to the i-th atoms of the substituent. 

Other approaches to expressing topological differences include treating the problem of directionality of steric effects by the direct expedient of modeling a substituent and calculating its extension in five orthogonal directions (e.g., the minimal steric difference method, [289]). Other approaches [111-115,290-295]... 

Lipophilicity in particular, as reflected in partition coefficients between aqueous and non-aqueous media most commonly water (or aqueous buffer) and Z-octanol,has received much attention [105,141,152,153,176,199,232,233]. Logic )W for the octanol-water system has been shown to be approximately additive and constitutive, and hence, schemes for its a priori calculation from molecular structure have been devised using either substituent tt values or substructural fragment constants [289, 299]. The approximate nature of any partition coefficient has been frequently emphasized and, indeed, some of the structural features that cause unreliability have been identified and accommodated. Other complications such as steric effects, conformational effects, and substitution at the active positions of hetero-aromatic rings have been observed but cannot as yet be accounted for completely and systematically. Theoretical statistical and topological methods to approach some of these problems have been reported [116-119,175,289,300]. The observations of linear relationships among partition coefficients between water and various organic solvents have been extended and qualified to include other dose-response relationships [120-122,160,161,299-302]. 

The origin of stereofacial selectivity in electrophilic additions to methylene-cyclohexanes (2) and 5-methylene-l,3-dioxane (3) has been elucidated experimentally (Table 2) and theoretically. Ab initio calculations suggest that two electronic factors contribute to the experimentally observed axial stereoselectivity for polarizable electrophiles (in epoxidation and diimide reduction) the spatial anisotropy of the HOMO (common to both molecules) and the anisotropy in the electrostatic potential field (in the case of methylenedioxane). The anisotropy of the HOMO arises from the important topological difference between the contributions made to the HOMO by the periplanar p C-H a-bonds and opposing p C—O or C—C cr-bonds. In contrast, catalytic reduction proceeds with equatorial face selectivity for both the cyclohexane and the dioxane systems and appears to be governed largely by steric effects. ... 

The difficulty can be avoided by the use of topological methods which represent steric effects as the result of contributions of all atoms other than H in the group Various topological methods have been proposed. The discussion here will be restricted to the branching equations (A 8.o). The simple branching (SB) equation is defined by... 

From topological algorithms . This method is best restricted to steric effects and polarizability parameters. The nature of topological parameters has been described. They are composite parameters and result from a count of structural features. ... 

ClogP This method developed by Leo and Hansch presents some similarities with the method of Rekker, since the log P of a molecule is calculated by adding lipophUicity values attributed to multiatomic fragments and numerous corrections factors which take into account not only geometrical and topological effects but also electronic and steric effects (Equation 5.3) [39-41]. 

Log P and MR are considered thermodynamic descriptors, pR a combined thermodynamic and electronic index, and a an electronic property index, E is designed to account for steric effects. Corrections for non-additivity, based upon the chemical bonding topology, have been suggested and used. These include proximity, bond type, ring, and group shape correction features. (8-10)... 

Quantitative structure-activity relationships represent an attempt to correlate activities with structural descriptors of compounds. These physicochemical descriptors, which include hydrophobicity, topology, electronic properties, and steric effects, are determined empirically or, more recently, by computational methods. The success of a QSAR method depends on two factors the training dataset obtained by testing a group of chemicals and the descriptors obtained from some easily measurable or calculable property of the chemicals. 

To cast some light on the relative importance of steric effects on the positional reactivities of benzenoid hydrocarbons, correlations of experimental a values of phenanthrene (4), tetrahelicene (5), pentahelicene (<5), and hexahelicene (7) with purely topological reactivity indices (Huckel cation localization energy, Dewar reactivity number and Herndon structure count ratio) have been studied [59],... 

Quantitative structure-activity relationship (QSAR) (Hansch and Klein, 1986 Hansch and Leo, 1995) represents an attempt to correlate structural descriptors of compounds with activities. The physicochemical descriptors include numerical parameters to account for electronic properties, steric effect, topology, and hydrophobicity of analogous compounds. In its simplest form, the biochemical activities are correlated to the numerical substituent descriptors of analogous compounds tested by a linear equation such as... 

The area per surfactant molecule at the hydrophobic-hydrophilic interface -the head-group area - is prescribed by the temperature, water content, steric effects and ionic concentration for ionic surfactants. Assume for now that the area per each surfactant "block" making up the assembly is set a priori. This assumption implies that the surface to volume ratio of the mixture (assumed to be homogeneous) is set by the concentration of the surfactant. So the interfacial topology is predetermined by this global constraint, the surface to volume ratio. 

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