Experimental and theoretical investigation of the unusual substituent effect of the vinyl group

Reynolds, William F.; Modro, Tomasz A.; Mezey, Paul G.; Skorupowa, Eugenia; Maron, Antonina

doi:10.1139/v80-066

Cited by 9 publications

(8 citation statements)

References 5 publications

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“…However, a+ for the p-vinyl and p-thiol groups are scarcely known. In the case of nitration of /J-substituted styrene, a+ for the p-vinyl group was determined as -0.18 25 . a+ for the p-thiol substituent has been reported as 0.019, 26 based on rates of solvolysis of cumyl chlorides.…”

Section: Relative Rates Of Adduct Formationmentioning

confidence: 99%

Polyaddition of Dithiol Compounds to Divinyl Compounds: The Kinetics of the Model Addition Reaction of Thiophenols to Styrenes

Kobayashi

Obata

Aoshima

et al. 1990

Polym J

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ABSTRACT:The addition reaction mechanism of thiophenol with styrene was studied as a model of the polyaddition of 1,4-benzenedithiol to 1,4-divinylbenzene. The addition reaction of thiophenol to styrene occurred without a side reaction and an adduct of the anti-Markownikoff's structure (SCH 2CH 2 ) was quantitatively obtained. The kinetic study shows that the rate-determining step of the addition reaction is the chain transfer reaction between thiophenol and P-phenylthiostyryl radical. The substituent effect of the chain transfer reaction was determined on various thiophenols and styrenes. Fairly good linear correlation was obtained for the Hammett plot of logk" to u+ on both monomers (p(k1r(St))= -0.60, p(k,,(TP)}= +0.64). These results are discussed in detail by comparing with polyaddition.

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Section: Relative Rates Of Adduct Formationmentioning

confidence: 99%

Polyaddition of Dithiol Compounds to Divinyl Compounds: The Kinetics of the Model Addition Reaction of Thiophenols to Styrenes

Kobayashi

Obata

Aoshima

et al. 1990

Polym J

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“…Some of the early studies on intramolecular interactions, without explicit use of similarity measures, have focussed on the interpretation and the evaluation of the dominant energy components influencing reactivities in various molecules, involving, for example, aromatic hydrocarbons. [55][56][57][58][59] However, as advancement of quantum chemistry computational methodologies, as well as interpretative approaches have progressed, more precise and more detailed studies have become possible. One of the most recent related developments 60 involves electron density shape analysis of both complete molecules and individual molecular fragments, providing a new approach for the analysis of various components of the interactions within molecules.…”

Section: Introductionmentioning

confidence: 99%

Substituent effects and local molecular shape correlations

Antal

Mezey

2014

Phys. Chem. Chem. Phys.

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Using a detailed electron density shape analysis methodology, a new method is proposed for studying the main components of substituent effects in a series of disubstituted benzenes, in correlation with their activating and deactivating characteristics as observed by the induced shape changes of a local electron density cloud. The numerical measures obtained for the extent of shape changes can be correlated with known and with some unexpected effects of various substituents. The insight obtained from the shape analysis provides a theoretical, electron density based justification for some well-known trends, but it also provides new explanations for some of the unexpected features of these substituent effects.

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“…The way different substituents influence global molecular properties, their reactivities in some typical reactions, as well as local properties in some different, neighboring regions of the molecule, have been the topic of the early studies in physical organic chemistry. [1][2][3][4][5][6][7][8][9][10][11] How similar or different effects various substituents may produce have been initially investigated primarily by experimental techniques. On the other hand, among the early theoretical studies on the relevant aspects of molecular similarity, the works based on the original quantum similarity approach of Carbo has played a central role.…”

Section: Introductionmentioning

confidence: 99%

Electron density shape analysis of a family of through-space and through-bond interactions

Antal

Warburton

Mezey

2014

Phys. Chem. Chem. Phys.

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A family of styrene derivatives has been used to study the effects of through-space and through-bond interactions on the local and global shapes of electron densities of complete molecules and a set of substituents on their central rings. Shape analysis methods which have been used extensively in the past for the study of molecular property-molecular shape correlations have shown that in these molecules a complementary role is played by the through-space and through-bond interactions. For each specific example, the dominance of either one of the two interactions can be identified and interpreted in terms of local shapes and the typical reactivities of the various substituents. Three levels of quantum chemical computational methods have been applied for these structures, including the B3LYP/cc-pVTZ level of density functional methodology, and the essential conclusions are the same for all three levels. The general approach is suggested as a tool for the identification of specific interaction types which are able to modify molecular electron densities. By separately influencing the through-space and through-bond components using polar groups and groups capable of conjugation, some fine-tuning of the overall effects becomes possible. The method described may contribute to an improved understanding and control of molecular properties involving complex interactions with a possible role in the emerging field of molecular design.

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Experimental and theoretical investigation of the unusual substituent effect of the vinyl group

Cited by 9 publications

References 5 publications

Polyaddition of Dithiol Compounds to Divinyl Compounds: The Kinetics of the Model Addition Reaction of Thiophenols to Styrenes

Polyaddition of Dithiol Compounds to Divinyl Compounds: The Kinetics of the Model Addition Reaction of Thiophenols to Styrenes

Substituent effects and local molecular shape correlations

Electron density shape analysis of a family of through-space and through-bond interactions

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