Reference substituent selection

Instead of the definition in Eq. (7-82), the selectivity is often written as log k,). Another way to consider a selectivity-reactivity relationship is to compare the relative effects of a series of substituents on a pair of reactions. This is what is done when Hammett plots are made for a pair of reactions and their p values are compared. The slope of an LEER is a function of the sensitivity of the process being correlated to structural or solvent changes. Thus, in a family of closely related LFERs, the one with the steepest slope is the most selective, and the one with the smallest slope is the least selective.Moreover, the intercept (or some arbitrarily selected abscissa value, usually log fco for fhe reference substituent) should be a measure of reactivity in each reaction series. Thus, a correlation should exist between the slopes (selectivity) and intercepts (reactivity) of a family of related LFERs. It has been suggested that the slopes and intercepts should be linearly related, but the conditions required for linearity are seldom met, and it is instead common to find only a rough correlation, indicative of normal selectivity-reactivity behavior. The Br nsted slopes, p, for the halogenation of a series of carbonyl compounds catalyzed by carboxylate ions show a smooth but nonlinear correlation with log... 

The independence of tt on the molecular system endows it with the characteristic of a substituent constant. This property is a direct consequence of the first approximation, namely that it reflects only the different solvation of substituent X compared to a reference substituent H. The validity of this approximation can be tested by obtaining tt from different molecular systems. It is well known (112) that irx values derived from aromatic systems differ from those derived from aliphatic systems tt The following table presents a few selected examples (112j>T ... 

Mager [414 — 416] introduced the term reduced Free Wilson model for this modification and proposed the use of stepwise regression analysis to derive the equation some more examples of this approach have been published [417, 544, 545]. However, one should bear in mind that the significance of a certain group contribution not only depends on its confidence interval but also on the selection of the reference substituents [390, 391, 410]. 

We must now select a reference substituent. For this purpose we choose the hypothetical group AV for which... 

In unsaturated molecules electronic effects can be transmitted by mesomerism as well as by inductive effects. As with the latter, the mesomeric properties of a group are described by reference to hydrogen. Groups which release electrons to the unsaturated residue of the molecule are said to exert a +Af effect, whereas groups which attract electrons are said to exert a —Af effect. In aromatic structures the important feature of an M-substituent is that it influences the 0- and p-positions selectively. 

The following table lists the benzofuroxan derivatives, with their melting points, which the authors have been able to find in the published literature. No attempt has been made to provide an exhaustive reference list those quoted are intended to be selected for their preparative usefulness. Substituents in parentheses indicate that a ring CH group, rather than a H atom, is replaced. Additional references (144-149) not cited earlier in the text are to be found at the foot of this page. 

Effects of various substituents on 13C chemical shifts can be found in textbooks (2-5,11) or reviews concerned with applications of l3C NMR spectroscopy to specific classes of chemical compounds (16-24,142). Therefore, this section is limited to recent information about effects of less common substituents and to reference data for various carbo- and heterocyclic molecules. It is not the author s intention to present a comprehensive survey rather, a number of typical examples have been selected. The reader may use this section as an entry into the original papers and the references cited therein. 

A Mukaiyama-type aldol reaction of silyl ketene thioacetal (48) with an aldehyde with large and small a-substituents (e.g. Ph and Me), catalysed by boron trifluoride etherate, gives mainly the iyn-isomer (49), i.e. Cram selectivity. For the example given, changing R from SiBu Me2 to Si(Pr )3 raises the syn preference considerably, which the authors refer to as the triisopropylsilyl effect. Even when the and R groups are as similar as ethyl and methyl, a syn. anti ratio of 5.4 was achieved using the triisopropylsilyl ketene thioacetal. 

These monomers produce a single disyndiotactic polymer characterized by alternating erythro and threo relationships between adjacent substituents, 18 or 19. In such a polymer it is not possible—unless one turns to selective isotopic labeling—to determine whether the erythro and threo relationship refers to the substituents A and B of the same monomer unit or to those of two successive monomeric units. 

The second group of saturated 5(47/)-oxazolones used as intermediates for polymer synthesis are the 2,2 -bis(oxazolones) with 2,2 -bis[4,4-dimethyl-5(47/)-oxazolone] 329 being the simplest member of the series (Fig. 7.33). These compounds, are prepared by cyclization of the corresponding bis(amino acids) and give a wide variety of polymers after ring opening with diamines, dialcohols or other nucleophiles. The physical chemical properties of these polymers depend on the nature of the substituents and the size of the chain. Some selected references describe representative examples. 

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