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Nucleophilic assistance

It is claimed that a measures electrophilic assistance by the solvent, b measures nucleophilic assistance, and that at least three, and sometimes four, parameters are required to perform a dissection into these separate effects. These workers also decomposed Y into ir and a contributions, and N into tt and p contributions. Abraham et al. have compared the performance of Eqs. (8-79) and (8-80) and find that they are about equally successful in correlating data. [Pg.444]

One after the other, step through the sequence of structures corresponding to the three nucleophile substitution reactions shown above (reaction 1, reaction 2, reaction 3). Decide whether loss of Br occurs with or without the assistance of RO /ROH. The nucleophile-assisted and unassisted mechanisms are called Sn2 and SnI mechanisms respectively. Label each reaction as Sn2 or SnI as appropriate. [Pg.63]

The mechanism of the reaction has been interpreted in terms of a 4- or 6-centre transition state (LV) or (LVI) in which nucleophilic assistance of C-Si bond cleavage occurs this would not be possible for nitration by nitronium tetrafluoroborate. [Pg.378]

Heterolytic cleavage of the tin-carbon bond is reviewed in references (94-96). Cleavage by electrophiles (e.g, HgXj or halogen) is dominated by electrophilic attack at carbon, and cleavage by nucleophiles principally involves nucleophilic attack at tin. Much of the interest in these processes centers on the intermediate mechanisms that may exist between these extremes, in which electrophilic attack is accompanied by some nucleophilic assistance, and vice versa. Allylic, al-lenic, and propargylic compoimds show a special reactivity by a special (Se2 or SE2y) mechanism. [Pg.10]

It has been shown (ref. 21) that a solvent which is both protic and nucleophilic, assists the formation of the bromination intermediates of moderately reactive olefins as styrenes in two ways, (Scheme 7). Firstly, the solvent initiates bromide ion formation electrophilically and, secondly, favours... [Pg.110]

Most of these results have been obtained in methanol but some of them can be extrapolated to other solvents, if the following solvent effects are considered. Bromine bridging has been shown to be hardly solvent-dependent.2 Therefore, the selectivities related to this feature of bromination intermediates do not significantly depend on the solvent. When the intermediates are carbocations, the stereoselectivity can vary (ref. 23) widely with the solvent (ref. 24), insofar as the conformational equilibrium of these cations is solvent-dependent. Nevertheless, this equilibration can be locked in a nucleophilic solvent when it nucleophilically assists the formation of the intermediate. Therefore, as exemplified in methylstyrene bromination, a carbocation can react 100 % stereoselectivity. [Pg.111]

In these solvents at sufficiently low Br2 concentration (< 10-3 m) the kinetics are first order both in the olefin and in Br2 and the main solvent effect consists of an electrophilic solvation of the departing Br ion. A nucleophilic assistance by hydroxylic solvents has also been recognized recently (ref. 26) (Scheme 10). So far, return during the olefin bromination in methanol had been admitted only for alkylideneadamantanes, and was ascribed to steric inhibition to nucleophilic attack at carbons of the bromonium ion (ref. 26). [Pg.148]

Similar results were obtained in methanol (ref. 30), where for the bis-(trifluoromethyl) derivative the ratio between the return of the trans bromonium ion to the trans olefin and its collapse to products 2 and 6 is 4.5 and is again very strongly reduced by the presence of LiC104 (Table 9). In this solvent, however, return was not observed for unsubstituted stilbene, either. It can be observed that both cis - and trans -stilbene gave methoxybromo adducts in an anti stereospecific way, suggesting a nucleophilic assistance by the solvent. [Pg.149]

This reversal has been demonstrated by both product and kinetic studies. In the absence of solvent nucleophilic assistance and of substituents favouring P-bromo-carbonium ion intermediates, the ionization of CTCs to bromonium (poly)bromide has been shown to occur not only for congested olefins, but more generally for "normal olefins both in aprotic chlorinated hydrocarbons and in protic solvents like acetic acid and methanol. [Pg.150]

Ideally, Y should measure only the ionizing power of the solvent, and should not reflect any backside attack by a solvent molecule in helping the nucleofuge to leave (nucleophilic assistance k, p. 411). Actually, there is evidence that many solvents... [Pg.452]

Besides differences in reactant stability as well as differences in the stability of the intermediate ions, there may also be other reasons, such as differences in solvation and differences in backside nucleophilic assistance, for the large discrepancy in reactivity between alkyl halides and vinyl halides. [Pg.243]

The nucleophile assisted ring-opening reactions of phosphonate bearing phthahmide 13 has been utihzed in the synthesis of mixed primary phosphine-phosphonate and aromatic amide functionahzed primary bisphosphines as out-hned in Scheme 6 [50],... [Pg.128]

Organomercuric compounds require nucleophilic assistance by soft iodide anions (cf. Section 9.6.3.2.2) for participation in cross-coupling reactions.158 The reaction is useful for aryl-aryl cross-coupling in those cases in which the organomercury species are obtained by direct mercuration of aromatic compounds (38).159... [Pg.319]

Intramolecular nucleophilic assistance is another distinct possibility for providing activation, and can be realized by coordination of the metal center by a heteroatom (O, N, etc.) within the ligand which transiently forms a chelate-like attachment to the metal. Such a mode of activation was supposed to account for the ease of reaction of vinyl triflates with (zp-isomers of alkenyl-stannanes bearing OH groups in the proximity of the reaction center (71).2 5... [Pg.329]

Table 20 Solvent effects in alkene bromination dependence of the electrophilic (KSIEs) and nucleophilic assistances (R) on the alkene. Table 20 Solvent effects in alkene bromination dependence of the electrophilic (KSIEs) and nucleophilic assistances (R) on the alkene.
Kinetic solvent isotope effect as a measure of electrophilic assistance to bromide ion departure limiting values rate data in ethanol, methanol and their aqueous mixtures using Bentley s TBr scale its decrease corresponds to the involvement of nucleophilic assistance. R = (/caqhtOII//cAcoH)r as a measure of nucleophilic solvent assistance. Model for a limiting bromination mechanism. Ruasse et al. (1991). /Ruasse and Zhang (1984). 9Argile and Ruasse (to be published). Modro et al. (1979). [Pg.268]

Fig. 14 Typical log k/YBr plots for assisted and unassisted alkene brominations. Allylbenzene and 1-pentene, less crowded than cis-methyl-t-butylethylene and methylideneadamantane, exhibit the smallest m-values. The points corresponding to acetic acid (O) and trifluoroethanol (A), two weakly nucleophilic solvents, are below the regression line for water, methanol, ethanol and their aqueous mixtures ( ) of similar nucleophilicity. In contrast, they are on the line for the branched alkenes where steric crowding inhibits nucleophilic assistance by alcoholic solvents (Ruasse et al, 1991, Ruasse and Motallebi, 1991). Fig. 14 Typical log k/YBr plots for assisted and unassisted alkene brominations. Allylbenzene and 1-pentene, less crowded than cis-methyl-t-butylethylene and methylideneadamantane, exhibit the smallest m-values. The points corresponding to acetic acid (O) and trifluoroethanol (A), two weakly nucleophilic solvents, are below the regression line for water, methanol, ethanol and their aqueous mixtures ( ) of similar nucleophilicity. In contrast, they are on the line for the branched alkenes where steric crowding inhibits nucleophilic assistance by alcoholic solvents (Ruasse et al, 1991, Ruasse and Motallebi, 1991).
The redistribution reaction of MeSnCl3 to give Me2SnCl2 and S11CI4 in solution at 50 °C follows second-order kinetics, and is faster in coordinating solvents and in the presence of alcohols or amines, suggesting a nucleophile-assisted electrophilic mechanism.330... [Pg.845]

In contrast, in protic solvents and at low bromine concentration, the addition process is characterized by a second order rate law (first order in bromine), Scheme 2, path b. In this case, due to the ability of the solvent to provide a specific electrophilic solvation to the leaving bromide ion, the reaction occurs via an SN1 -like unimolecular ionization of the 1 1 it complex to form a bromonium or P-bromocarbenium bromide ion pair. It is worth noting that protic solvents can also give nucleophilic assistance, depending on their specific solvent properties. [Pg.391]

Again, bromination of 11 in methanol shows (21) an inconsistent behavior with reactions found in all the other solvents, and in particular in TFE. Despite the fact that its polarity should favor ion pair dissociation, the reaction gives at all reagent concentrations examined, practically only the bromomethoxy derivative. This behavior may be attributed to the ability of MeOH to provide nucleophilic assistance a reaction pathway occurring through ion sandwich could account for the absence of the elimination product. [Pg.403]

Acid-induced wagner-meerwein rearrangements in chiral alcohols. In view of the considerable interest on ion-molecule complexes involved in gas-phase analogues of solvolytic reactions," ° " a sustained research effort has been directed to the study of Wagner-Meerwein rearrangements in cationized )8-arylaIkyl systems, under conditions excluding nucleophilic assistance by the solvent which in these systems normally interferes with anchimeric assistance of groups adjacent to the... [Pg.245]

Solvolyses of the A(A -diphenylcarbamoylpyridinium ion (126) were found to be subject to specific and/or general base catalysis, which could be eliminated by addition of perchloric acid or increased, especially in fluoroalcohol-containing solvents, by addition of pyridine. The uncatalysed solvolyses in aqueous methanol and aqueous ethanol involve a weakly nucleophilically assisted (/ = 0.22) heterolysis and the solvolyses in the pure alcohols are anomalously slow. ... [Pg.56]


See other pages where Nucleophilic assistance is mentioned: [Pg.269]    [Pg.283]    [Pg.343]    [Pg.414]    [Pg.110]    [Pg.452]    [Pg.23]    [Pg.327]    [Pg.339]    [Pg.243]    [Pg.271]    [Pg.275]    [Pg.276]    [Pg.157]    [Pg.169]    [Pg.393]    [Pg.573]    [Pg.577]    [Pg.314]    [Pg.315]    [Pg.427]    [Pg.55]    [Pg.56]   
See also in sourсe #XX -- [ Pg.577 ]

See also in sourсe #XX -- [ Pg.108 ]

See also in sourсe #XX -- [ Pg.577 ]

See also in sourсe #XX -- [ Pg.577 ]

See also in sourсe #XX -- [ Pg.456 , Pg.645 ]




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