Electron donating substituent effect

The effect of substituents on the rate of the reaction catalysed by different metal ions has also been studied Correlation with resulted in perfectly linear Hammett plots. Now the p-values for the four Lewis-acids are of comparable magnitude and do not follow the Irving-Williams order. Note tlrat the substituents have opposing effects on complexation, which is favoured by electron donating substituents, and reactivity, which is increased by electron withdrawirg substituents. The effect on the reactivity is clearly more pronounced than the effect on the complexation equilibrium. 

Radicals are particularly strongly stabilized when both an electron-attracting and an electron-donating substituent are present at the radical site. This has been called mero-stabilization" or " capto-dative stabilization. This type of stabilization results from mutual reinforcement of the two substituent effects. Scheme 12.3 gives some information on the stability of this type of radical. 

For the uncatalyzed reactions the calculations showed that the ortho approaches were favored over the meta, and the endo selectivity was the energetic most favorable reaction paths for most of the electron-donating substituents studied [29]. The endo-ortho reaction path is under FMO control and the substituent effect on the regios-electivity was explained for by a dominant interaction between LUMOdiene id HOMOdienophUe- The ortho reaction path was investigated with BH3 as the Lewis acid and it was calculated that the presence of Lewis acid decreases the activation... 

Feng et al. [3] have studied the structural effect of acetanilide on the AAM polymerization either in water-for-mamide [3], water-acetonitrile [4], and water-DMF [26] mixed solution using Ce(IV) ion-acetanilide and its substituted derivatives as the initiator. The results showed that an electron donating substituent on the phenyl group would enhance the Rp, while an electron withdrawing group would decrease it, as shown in Table 1 [26]. 

Inductive and resonance effects account for the directing effects of substituents as well as for their activating or deactivating effects. Take alkyl groups, for instance, which have an electron-donating inductive effect and are ortho and para directors. The results of toluene nitration are shown in Figure 16.13. 

The traditional means of assessment of the sensitivity of radical reactions to polar factors and establishing the electrophilicity or nucleophilieity of radicals is by way of a Hammett op correlation. Thus, the reactions of radicals with substituted styrene derivatives have been examined to demonstrate that simple alkyl radicals have nucleophilic character38,39 while haloalkyl radicals40 and oxygcn-ccntcrcd radicals " have electrophilic character (Tabic 1.4). It is anticipated that electron-withdrawing substituents (e.g. Cl, F, C02R, CN) will enhance overall reactivity towards nucleophilic radicals and reduce reactivity towards electrophilic radicals. Electron-donating substituents (alkyl) will have the opposite effect. 

The effects of cyclic 6n electron conjugation have been found in the optimized geometries of pentazole 17 [102] and hexazine 18 [97], The N=N bond is longer than the isolated double bond in NH=NH. The N-N single bond in the tetrazadiene moiety is shorter than the single bond in NH NH. The bond lengths in 18 are nearly intermediate between those in NH NH and NH=NH. The aromatic character of pentazoles was supported by the effect of electron donating substituents on the thermodynamic and kinetic stabilization [103],... 

Wedekind and Stauwe" studied the oxidation of 3-substituted formazans and concluded that ease of oxidation depended on the steric effects of the 3-substituent. More recently, Hegoraty et al. 100 studied the reaction of formazans with bromine. It proceeds via an odd-electron species such as 52 favoring an electronic substituent effect (Scheme 5). The rate of reaction increases with electron-donating substituents. Similar conclusions have been reached using thalium(III) as the oxidant.101,102... 

Phenyl indandiones With an acidic hydrogen often interfere with clot formation. When electron withdrawing groups are present in the p-position, acidity is increased and activity goes up. The opposite effect is seen with electron-donating substituents. Synthesized in the usual way, the anticoagulant bromindione (15) results from sodium acetate-catalyzed condensation of phthalic anhydride and p-a-bromophenyl-acetic acid. ... 

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