Effects on Reactivity

Effect on Reactivity. Long-range interactions of cyclopropyl groups with carbonium ion centres have been reviewed. 

Haywood-Farmer, Chem. Rev., 1974, 74, 315 see also A. T. Bottini and J. E. Christensen, Tetrahedron, 

The delocalized cation (785) is formed transiently on dissolving thujan-3-ol in strong acid but no evidence for cyclopropyl participation was found in the solvolysis of the tosylate (786).  

Results of the thermal decomposition of the tosylhydrazone salt (787), which affords a complex mixture of hydrocarbons, indicate significant homoconjugative interaction between the p-orbital of the bivalent carbene generated and the symmetric Walsh orbital of the cyclopropane.  

The Z- and -isomers of the bromomethylenecyclopropane (788) solvolyse at approximately the same rate and give the same ratio of products via a stabilized cyclopropylidenecarbinyl cation (789). 

Effect on Reactivity Much of the work on cyclopropane participation continues to utilize bridged and caged compounds where steric relationships are rigorously defined.  

Solvolysis studies of l-(4-cyclopropylphenyl)-l-arylethyl chlorides show a modest rate increase over the l-(4-isopropylphenyl) counterparts, due to electron release by the distal cyclopropane.  

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Pairwise hydrophobic interactions can be used to alter the reactivity of organic molecules in water. For instance, the rate of hydrolysis reactions may be influenced significantly by the presence of hydrophobic cosolutes. The effect on reactivity has been analysed by comparirg the interactions between initial state and cosolute with those between transition state and cosolute. ... 

Regarding the substituent effect on reactivity of groups in positions 4 and 5 there is little information in the literature. The reactivity of halogen in position 5 seems to be increased when an amino group is present in position 2. Substitution products are easily obtained using neutral nucleophiles such as thiourea, thiophenols, and mercaptans (52-59). 

Reactions such as catalytic hydrogenation that take place at the less hindered side of a reactant are common m organic chemistry and are examples of steric effects on reactivity Previously we saw steric effects on structure and stability m the case of CIS and trans stereoisomers and m the preference for equatorial substituents on cyclo hexane rings... 

In Chapter 4, we will discuss the relative importance of inductive effects and field effects on reactivity. Generally, field effects appear to be the dominant mechanism for the transmission of electrostatic effects of polar bonds to other parts of a molecule. 

Ipso substitution, in which the electrophile attacks a position already carrying a substituent, is relatively rare in electrophilic aromatic substitution and was not explicitly covered in Section 10.2 in the discussion of substituent effects on reactivity and selectivity Using qualitative MO cOTicepts, discuss the effect of the following types of substituents on the energy of the transition state for ipso substitution. 

Both the language of valence bond theory and of molecular orbital theory are used in discussing structural effects on reactivity and mechanism. Our intent is to illustrate both approaches to interpretation. A decade has passed since the publication of the Third Edition. That decade has seen significant developments in areas covered by the text. Perhaps most noteworthy has been the application of computational methods to a much wider range of problems of structure and mechanism. We have updated the description of computational methods and have included examples throughout the text of application of computational methods to specific reactions. 

Robert Filler, The Pentafluorophenyl Croup Effects on Reactivity of Organic Compounds... 

Next we turn to the magnitudes of the p constants. Evidently if p = 0, there is no substituent effect on reactivity. Moreover because p = -I-1.000 by definition for the aqueous ionization of benzoic acids, we have a scale calibration of sorts. Wiberg gives examples of p as a measure of the extent of charge development in the transition state. McLennan" has pointed out that p values must first be adjusted for the transmission factor before they can be taken as measures of charge devel-... 

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... 

Some of these model-dependent quantities were formulated as measures of a particular phenomenon, such as electron-pair donor ability but many of them have been proposed as empirical measures of solvent polarity, with the goal, or hope, that they may embody a useful blend of solvent properties that quantitatively accounts for the solvent effect on reactivity. This section describes many, although not all, of these empirical measures. Reichardt has reviewed this subject. 

In addition to sodium, other metals have found application for the Wurtz coupling reaction, e.g. zinc, iron, copper, lithium, magnesium. The use of ultrasound can have positive effect on reactivity as well as rate and yield of this two-phase reaction aryl halides can then even undergo an aryl-aryl coupling reaction to yield biaryls. ... 

Besides the electrostatic potential effect on reactivity, functionalized polyelectrolytes have a variety of interesting features worthy of study. If a polyelectrolyte is covalently modified with highly hydrophobic functional groups, it provides an unusual opportunity to study the chemical reactions of normally otherwise water insoluble functional groups in aqueous solution. Furthermore, a structural organization via hydrophobic interactions may occur in aqueous solution [25 — 31], which is of general scientific importance and is worth studying for its own sake. 

The effects of solvent on radical copolymerization are mentioned in a number of reviews.69 72 97,98 For copolymerizations involving monomers that arc ionizablc or form hydrogen bonds (AM, MAM, HEA, HEMA, MAA, etc.) solvent effects on reactivity ratios can be dramatic. Some data for MAA-MMA copolymerization are shown in Table 8.4.w... 

Studies on the reactions of small model radicals with monomers provide indirect support but do not prove the bootstrap effect.111 Krstina et ahL i showed that the reactivities of MMA and MAN model radicals towards MMA, S and VAc were independent of solvent. However, small but significant solvent effects on reactivity ratios are reported for MMA/VAc111 and MMA S 7 copolymerizations. For the model systems, where there is no polymer coil to solvate, there should be no bootstrap effect and reactivities are determined by the global monomer ratio [Ma0]/[Mb0].1j1... 

There are also reports of template effects on reactivity ratios in copolymerization. For example, Polowinski20S has reported that both kinetics and reactivity ratios in MMA-MAA copolymerization in benzene arc affected by the presence of a PVA template. 

Most of the chemical reactions presented in this book have been studied in homogeneous solutions. This chapter presents a conceptual and theoretical framework for these processes. Some of the matters involve principles, such as diffusion-controlled rates and applications of TST to questions of solvent effects on reactivity. Others have practical components as well, especially those dealing with salt effects and kinetic isotope effects. 

Diazocarbonyl compounds are especially useful in these reactions because of their ease of formation, relative stability, and controlled reactivity in catalytic reactions [ 1,11 ]. As outlined in Scheme 1, a wide diversity of methodologies are available for this synthesis, with access dependent on the nature of Z. Vinyl- and aryldiazoacetates are accessible by other pathways [2]. The order of reactivity toward diazo decomposition has diazoketones and diazoacetates much more reactive than diazoacetoacetates or diazomalonates. However, the influence of electronic effects on reactivities is more pronounced with phenyl- and vinyl-diazoacetates than with diazoacetoacetates and, especially, diazoacetates [12]. 

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