scholarly journals A Semi-empirical Calculation of the Substituent Effects on the1H Chemical Shifts of 1-Substituted Naphthalenes

1977 ◽  
Vol 50 (4) ◽  
pp. 979-983 ◽  
Author(s):  
Jun Niwa
Keyword(s):  
Chemical Shifts ◽  
Substituent Effects ◽  
Semi Empirical

scholarly journals Effect of substituents on the 13C-NMR chemical shifts of 3-methylene-4-substituted-1, 4-pentadienes - Part I

2003 ◽  
Vol 68 (2) ◽  
pp. 67-76 ◽  
Author(s):  
Natasa Valentic ◽  
Zeljko Vitnik ◽  
Sergei Kozhushkov ◽  
Majere de ◽  
Gordana Uscumlic ◽  
...  
Keyword(s):  
Chemical Shifts ◽  
Substituent Effects ◽  
Heat Of Formation ◽  
Electronic Effects ◽  
Resonance Effects ◽  
Linear Free Energy ◽  
Energy Relationships ◽  
Consistent Picture ◽  
The One ◽  
Semi Empirical

The principles of linear free energy relationships were applied to the 13C substituent chemical shifts (SCS) of the carbon atoms in the unsaturated chain of 3-methylene-4-substituted-1,4-pentadienes. Correlations of the SCS with the substituent parameters of Swain and Lupton provide a mutually consistent picture of the electronic effects in these compounds. The pattern of the electronic effects can be fully rationalized by a model based on the direct transmission of substituent effects through-space (direct through-space field effects), and via conjugative interactions (resonance effects), or by substituent-induced polarization of the ?-system in the unsaturated chain (?-polarization effect). Semi-empirical MNDO-PM3 calculations suggest the s-cis conformation of 3-methylene-4-substituted-1,4-pentadienes as the one with minimal heat of formation.

Chemometric Analysis of Substituent Effects. VII. Inductive Effect as a Basic Substituent Effect. Isoeffect Substituent Constant

1995 ◽  
Vol 60 (8) ◽  
pp. 1316-1332 ◽  
Author(s):  
Oldřich Pytela ◽  
Aleš Halama
Keyword(s):  
Inductive Effect ◽  
Chemical Shifts ◽  
Quantitative Description ◽  
Substituent Effects ◽  
Intersection Point ◽  
Chemometric Analysis ◽  
Reaction Centre ◽  
Substituent Constant ◽  
Modified Method ◽  
Substituted Benzoic Acids

The paper deals with chemometric analysis of the inductive effect. The notion of inductive effect is discussed, and unambiguous definitions are given for the notions of triad: reaction centre-basic skeleton-substituent, and the therewith connected definitions of inductive effect. For a quantitative description of inductive effect 7 types of chemical models were selected including noncyclic compounds, cyclic, and bicyclic compounds, derivatives of quinuclidine, 3-substituted benzoic acids, sulfonamides and pyridines. Altogether 139 sets of experimental data from literature have been used including altogether 1 294 points (9.3 points per set, 5 points at least) reflecting substituent effects of 34 substituents. It has been found that for a standard model the dissociation of substituted bicycloalkanecarboxylic acids only is satisfactory, all the other models reflecting also the mesomeric effects to variable extent (up to 10%). A distinctly different substitution behaviour was observed with 19F and 13C NMR chemical shifts of 4-substituted 1-fluoro- or 1-methylbicyclo[2.2.2]octanes. The earlier suggested model of substituent effects based on different way of transmission of substituent effects (3 classes) has been used for separating the inductive and mesomeric effects: it is mathematically presented as a set of straight lines with the intersection point at the so-called isoeffect substituent constant. Using the modified method of conjugated deviations a chemometric scale has been created for the inductive effect which agrees very well with the conventional scales given in literature; the only differences were observed for F and CH=O substituents (which are overestimated and underestimated, respectively, in literature). In the context given the inductive effect appears as a fundamental quantity forming a basis for quantitative description of other effects transferred by electrons.

Nuclear Magnetic Resonance Chemical Shifts of some Monosubstituted Isothiazoles

1975 ◽  
Vol 53 (4) ◽  
pp. 596-603 ◽  
Author(s):  
Roderick E. Wasylishen ◽  
Thomas R. Clem ◽  
Edwin D. Becker
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Charge Densities ◽  
Monosubstituted Benzenes ◽  
Proton Chemical Shifts ◽  
Nuclear Magnetic

Carbon-13 and proton chemical shifts have been measured for several monosubstituted isothiazoles. Substituent effects upon these chemical shifts are compared with those observed for monosubstituted benzenes, pyridines, and thiophenes. In general the observed substituent effects in the isothiazoles and thiophenes closely parallel one another. Correlations between the observed carbon-13 Chemical shifts and CNDO/2 calculated charge densities are examined.

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