Substitution reactions definition

The above definition implies that the reactivity of an aromatic compound depends upon the reaction which is used to measure it, for the rate of reaction of an aromatic compound relative to that for benzene varies from reaction to reaction (table 7.1). However, whilst a compoimd s reactivity can be given no unique value, different substitution reactions do generally set aromatic compoimds in the same sequence of relative reactivities. 

Probably the most important development of the past decade was the introduction by Brown and co-workers of a set of substituent constants,ct+, derived from the solvolysis of cumyl chlorides and presumably applicable to reaction series in which a delocalization of a positive charge from the reaction site into the aromatic nucleus is important in the transition state or, in other words, where the importance of resonance structures placing a positive charge on the substituent - -M effect) changes substantially between the initial and transition (or final) states. These ct+-values have found wide application, not only in the particular side-chain reactions for which they were designed, but equally in electrophilic nuclear substitution reactions. Although such a scale was first proposed by Pearson et al. under the label of and by Deno et Brown s systematic work made the scale definitive. 

From the viewpoint of coordination chemistry, a substitution reaction can be defined as a process whereby a ligand in a complex is replaced by another ligand from outside the coordination sphere [1], Substitution reactions by metal complexes have been classified by Saito [2] according to Taube s definition [3] of inertness. Saito classified metal ions into three groups as follows ... 

The experiments presented above definitively established the fact the Lipson s HPD-forming procedure gives dimeric and trimeric porphyrin esters as the high-molecular weight component which is eminently better localized and retained in tumor cells and is responsible for most of the photodynamic activity associated with HPD. Mechanistically, the formation of ester linkage is not only understandable but expected as well. Under the alkaline condition employed in the synthesis of HPD, the nucleophilic substitution reaction illustrated in the following scheme is very similar to the... 

Thiophene is far more reactive than benzene in electrophilic substitution reactions. Reaction with bromine in acetic acid has been calculated to be 1.76 x 109 times faster than with benzene (72IJS(C)(7)6l). This comparison should, of course, be treated with circumspection in view of the fact that the experimental conditions are not really comparable. Benzene in the absence of catalysts is scarcely attacked by bromine in acetic acid. More pertinent is the reactivity sequence for this bromination among five-membered aromatic heterocycles, the relative rates being in the order 1 (thiophene) and 120 (furan) or, for trifluoroacetylation, 1 (thiophene), 140 (furan), 5.3 xlO7 (pyrrole) (B-72MI31300, 72IJS(C)(7)6l). Among the five-membered heteroaromatics, thiophene is definitely the least reactive. 

Photolysis of allyl iodide in thiophene gives a mixture of 2-allyl- (63.8%) and 3-allyl-(36.2%) thiophenes (77JOC1570). This is in contrast to homolytic phenylation, where almost exclusive 2-phenylation takes place (Section 3.14.2.9). It has been suggested that the rate-determining step in the allyl substitution reaction has a small but definite charge-transfer character. 

According to the definition, the partial rate factors express the ratio of the rate constant of a particular substitution reaction at a given site to the rate constant of a single site in an unsubstituted benzene nucleus. To illustrate, this principle would predict that the partial rate factor for position 6 in 4-hydroxy-3-methoxytoluene is equal to the product /wOH X fPOMe X... 

An attempt has been made to analyse whether the electrophilicity index is a reliable descriptor of the kinetic behaviour. Relative experimental rates of Friedel-Crafts benzylation, acetylation, and benzoylation reactions were found to correlate well with the corresponding calculated electrophilicity values. In the case of chlorination of various substituted ethylenes and nitration of toluene and chlorobenzene, the correlation was generally poor but somewhat better in the case of the experimental and the calculated activation energies for selected Markovnikov and anti-Markovnikov addition reactions. Reaction electrophilicity, local electrophilicity, and activation hardness were used together to provide a transparent picture of reaction rates and also the orientation of aromatic electrophilic substitution reactions. Ambiguity in the definition of the electrophilicity was highlighted.15... 

Some of the previously discussed processes, especially cathodic substitution reactions according to eqn (14) with E+ = H+, might also be considered as cleavage reactions. In fact, it is difficult to accommodate electrochemical cleavage reactions within a unique formal scheme (for a review within a rather broad definition, see Horner and Lund, 1973), and we are therefore content merely to show a few examples which conform reasonably well to the commonly accepted notion of cleavage. 

The presence of the methyl group at a double bond therefore involves two new effects in the reaction with carbethoxynitrene—namely the predominance of substitution reactions over addition reactions and the formation of a product in which the double bond is displaced (about 20% of the total mixture). In addition to the products of Structures D, Ei, E2, and E3 expected as the result of Lwowski s work, another product, probably of Structure E4, is formed (Figure 6). This-is now being checked and necessitates the separation of the products either at the urethane stage or more effectively at the amine stage. Once the structure of this product is established definitely, the conditions affecting its formation remain to be studied, and this may yield an explanation of the reaction mechanism involved. 

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