Nucleophilic substitution process features

It was also noted that the rates of these reactions were dependent on a number of features, in particular on the protonation of the ligand (Scheme 12). For the complexation of phenylboronic acid with oxalic acid the rate constant was A coohcooh=2000 s for the monobasic form the rate dropped to cooHcoo =330 s with a rate for the dibasic form of kcoo coo 01 s These results were unusual for a nucleophilic substitution process in that the highly nucleophilic dianionic species was almost entirely unreactive, while the most protonated attacking species reacted the most rapidly. 

The ability of a nitro group in the substrate to bring about electron-transfer free radical chain nucleophilic substitution (SrnI) at a saturated carbon atom is well documented.39 Such electron transfer reactions are one of the characteristic features of nitro compounds. Komblum and Russell have established the SrnI reaction independently the details of the early history have been well reviewed by them.39 The reaction of p-nitrobenzyl chloride with a salt of nitroalkane is in sharp contrast to the general behavior of the alkylation of the carbanions derived from nitroalkanes here, carbon alkylation is predominant. The carbon alkylation process proceeds via a chain reaction involving anion radicals and free radicals, as shown in Eq. 5.24 and Scheme... 

Several unique synthetic strategies for bidentate(amino)(oxy)- and (amino)(aryl) carbenes have been described (Scheme 10). For the former, the reaction of the amino(phosphino)carbene with an ort/io-quinone leads to the transient formation of a zwitterionic species featuring both a phosphonio nucleofuge and an aryloxide nucleophile that allow for a subsequent intramolecular substitution process. The... 

If L = halogen, this type of reaction is referred to as dehydrohalogenation. Thus, when assessing the fate of halogenated compounds in natural waters, this process has to be considered in addition to nucleophilic substitution. The question then is what structural features and environmental conditions determine whether only one or both of these two competing types of reactions will be important. 

The main feature of interest is the question whether, in the replacement of X by Y in Reaction 8.55, the substitution is an ordinary nucleophilic substitution, either S 2 (Reaction 8.56), or S l (Scheme 18), or a two-step process with addition of the nucleophile to give an approximately tetrahedral intermediate (26) followed... 

Unlike the nucleophilic substitution reactions which generate stable onium halide after the reaction, nucleophilic additions to electrophilic C=X double bonds (X=C, N, O) provide rather basic onium anion species as an initial product. If the anion is sufficiently stable under the reaction conditions, onium anion will then exchange the counter ion for the other metal carbanion at the interface to regenerate the reactive onium carbanion Q+R. In another scenario, the basic onium anion may abstract the acidic hydrogen atom of the other substrate to provide Q 1 R directly. Such a reaction system ideally requires only a catalytic amount of the base although, in general, a substoichiometric or excess amount of the base is used to lead the reaction to completion. An additional feature of this system is the substantial possibility of a retro-process at the crucial asymmetric induction step, which might be problematic in some cases. 

The reaction of XIII with EtOH in CHjCl EtOH, in 1 1 molar ratio, affords the ethoxy-derivative, [8,8-(q2-dppp)-9-(OEt)-nido-RhSB,H,] (XIV) behavior which is seen in the series of related compounds.12,111 This suggests that the boron vertex at the 9-position in Xm, and the related series of compounds, is prone to nucleophilic substitution reactions. XIV was characterized by NMR spectroscopy, mass spectrometry and X-ray diffraction. In contrast to the parent rhodathiaborane IV, and XIII, compound XIV does not feature fluxional behavior, even at 373 K implying, perhaps, AG values greater than 64 kjmol 1 for a possible dynamic process in XIV. The apparent large difference in the activation energy for the substituted versus the unsubstituted species may be due to either electronic or steric effects. The differences in the structures of XIII and XIV are minimal except for the B(9)-B(10) distances which differ by 0.083 A.4b This tends to suggest a role for this bond in the fluxional process although a purely steric influence of the substituent at the 9-position in XIV cannot be ruled out. 

This equation also describes the overall reaction of either an 5 2 or a nucleophilic aromatic substitution process. In some cases, the only way to distinguish an reaction from these processes is that an is inhibited by radical inhibitors. Another distinguishing feature is that the order of the relative leaving group abilities of halides are opposite that found for nucleophilic aromatic substitution by the addition-elimination mechanism (see Chapter 3). 

An interesting feature of this process is that vicarious nucleophilic substitution of hydrogen usually proceeds faster than conventional nucleophilic substitution of halogen activated by the nitro group. 

The distinctive feature of any ionization mechanism for nucleophilic substitution is the generation of a tricoordinate carbocation in the rate-determining step. It is essential, then, that such a species not be prohibitively high in energy. The production of carbonium ions in the gas phase is a particularly unfavorable process. The heat of formation of (CH3)3C (tert-butyl cation) is +169 kcal/mol, compared with -32 kcal/mol for (CH3)3CH. The reaction... 

A close look at the nature of a nucleophile will emphasize that it shares common features with a Lewis hase (see Chapter 18). Indeed, a nucleophilic species can act as such a base if the reaction conditions are appropriate - it can remove a proton (H ion) from a halc enoalkane and thereby initiate an elimination reaction. In this type of reaction HX is eliminated from the halogenoalkane and an alkene is produced. It is essential to realize that, given the similarity of the reagents involved, the two processes of nucleophilic substitution and elimination are generally in competition with each other. If a primary halogenoalkane is reacted with aqueous alkali (OH (aq)) then the substitution reaction we have discussed earlier is favoured. However, if ethanolic alkali (OH (ethanol)) is used, then the elimination reaction is favoured. 

These Br nsted-type plots often seem to be scatter diagrams until the points are collated into groups related by specific structural features. Thus, p-nitrophenyl acetate gives four separate, but parallel, lines for reactions with pyridines, anilines, imidazoles, and oxygen nucleophiles.Figure 7-4 shows such a plot for the reaction of trans-cmmm c anhydride with primary and secondary aliphatic amines to give substituted cinnamamides.All of the primary amines without substituents on the a carbon (R-CHi-NHi) fall on a line of slope 0.62 cyclopentylamine also lies on this line. If this line is characteristic of normal behavior, most of the deviations become qualitatively explicable. The line drawn through the secondary amines (slope 1.98) connects amines with the structure R-CHi-NH-CHi-R. The different steric requirements in the acylation reaction and in the model process... 

The usual kinetic law for S/v Ar reactions is the second-order kinetic law, as required for a bimolecular process. This is generally the case where anionic or neutral nucleophiles react in usual polar solvents (methanol, DMSO, formamide and so on). When nucleophilic aromatic substitutions between nitrohalogenobenzenes (mainly 2,4-dinitrohalogenobenzenes) and neutral nucleophiles (amines) are carried out in poorly polar solvents (benzene, hexane, carbon tetrachloride etc.) anomalous kinetic behaviour may be observed263. Under pseudo-monomolecular experimental conditions (in the presence of large excess of nucleophile with respect to the substrate) each run follows a first-order kinetic law, but the rate constants (kQbs in s 1 ruol 1 dm3) were not independent of the initial concentration value of the used amine. In apolar solvents the most usual kinetic feature is the increase of the kabs value on increasing the [amine]o values [amine]o indicates the initial concentration value of the amine. 

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