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Chlorides, alkyl solvolysis

Rate data for substituted allylic chlorides compared wilhbenzylic chlorides and simple alkyl chlorides on solvolysis in 50% aqueous ethanol give us some idea of the magnitude of stabilization (Table 17.8). These rates are mostly SnT but there will be some S]sj2 creeping in with the primary compounds. Note the wide range of rates,... [Pg.418]

There is much additional evidence to support the postulate that the effect of neighboring sulfur is due to anchimeric assistance. Cyclohexyl chloride undergoes solvolysis in ethanol-water to yield a mixture of alcohol and ether. As usual for secondary alkyl substrates, reaction is SnI with nucleophilic assistance from the solvent (see Sec. 14.17). A C5H5S— group on the adjacent carbon can speed... [Pg.908]

Effect of o-Deuteration in f ar -Alkyl Benzhydryl Chlorides on Solvolysis Rate... [Pg.203]

A substantial body of evidence indicates that allylic carbocations are more stable than simple alkyl cations For example the rate of solvolysis of a chlonde that is both tertiary and allylic is much faster than that of a typical tertiary alkyl chloride... [Pg.391]

Additional evidence for the SnI mechanism, in particular, for the intermediacy of carbocations, is that solvolysis rates of alkyl chlorides in ethanol parallel carbocation stabilities as determined by heats of ionization mea.sured in superacid solutions (p. 219). It is important to note that some solvolysis reactions proceed by an Sn2 mechanism." ... [Pg.397]

Kinetics of the solvolysis of acyl chlorides and alkyl chlorides in hydroxylic solvent mixtures have been measured conductimetrically at various temperatures and pressures. The activation parameters A V, AH, and AS were calculated from the rate constants. The authors appear to have been interested mainly in acyl chlorides, but conclude that, whereas p-methylbenzoyl chloride reacts via a dissociative... [Pg.338]

Rate constants and products have been reported for solvolysis of benzhydryl chloride and /7-methoxybenzyl chloride in 2,2,2-trifluoroethanol (TFE)-water and-ethanol, along with additional kinetic data for solvolysis of r-butyl and other alkyl halides in 97% TFE and 97% hexafluoropropan-2-ol. The results are discussed in terms of solvent ionizing power Y and nucleophilicity N, and contributions from other solvation effects are considered. Comparisons with other 3 nI reactions show that the solvolyses of benzhydryl chloride in TFE mixtures are unexpectedly fast an additional solvation effect influences solvolysis leading to delocalized cations. [Pg.340]

Benzhydrylamines are better suited than benzylamines as acid-labile linkers for amines. The MBHA linker ( methylbenzhydrylamine ), which is usually used to prepare peptide amides (see Section 3.3), can also be used as a linker for amines (Entry 1, Table 3.21). Hydrogen fluoride is, however, required as the cleavage reagent. Easier to cleave are alkoxy-substituted benzhydrylamines (Entries 2-5, Table 3.21), which can be prepared from the corresponding benzhydryl chlorides [263] or by reductive alkylation [410] or solvolysis [411] of the Rink amide linker. In the case of benzhydrylamines linked to polystyrene as benzyl ethers, treatment with TFA can lead to the release of the linker into solution (acidolysis of the benzylic C-O bond, see Figure 3.18). [Pg.85]

Figure 5.5 Correlation between stability, measured by solvolysis rate in 80 percent aqueous acetone, and selectivity, determined by relative rate of reaction with azide ion (kN) and water (kw), for carbocations derived from alkyl chlorides. Reprinted with permission from D. J. Raber, J. M. Harris, R. E. Hall, and P. v. R. Schleyer, J. Amer. Chem. Soc., 93, 4821 (1971). Copyright by the American Chemical Society. Figure 5.5 Correlation between stability, measured by solvolysis rate in 80 percent aqueous acetone, and selectivity, determined by relative rate of reaction with azide ion (kN) and water (kw), for carbocations derived from alkyl chlorides. Reprinted with permission from D. J. Raber, J. M. Harris, R. E. Hall, and P. v. R. Schleyer, J. Amer. Chem. Soc., 93, 4821 (1971). Copyright by the American Chemical Society.
A quantitative scale for the structural effect of various silyl groups is established, as shown in entry 57 of Table 1, by the rates of solvolysis of 40 triorganosilyl chlorides in aqueous dioxane under neutral conditions69. The structural effect involves the steric effect and, in some examples, the electronic effect. Because little difference exists in the electronic effect among alkyl groups, their steric effect at silicon follows the order primary < secondary < tertiary substituents. [Pg.483]

Previous investigations (Brady, 1949 Grayson, 1952 Bonner, 1952) in the Purdue laboratories were concerned with the influence of alkyl groups on the rate of ionization of phenyldimethylcarbinyl chloride. These studies indicated that first-order rate constants could be determined with high accuracy for the solvolysis reaction. Moreover, the entropies of activation were invariant in this series of halides. These considerations led to further study of other substituted phenyldimethylcarbinyl chlorides in an attempt to gain a further understanding of the influence of substituent groups on relative reactivity and as a possible model reaction for the assessment of parameters for electron-deficient reactions. [Pg.84]

Alkyl, halo, and the other substituents exhibiting a modest influence on the rate of solvolysis of the tertiary chloride were examined under the standard conditions selected as 90% aqueous acetone at 25° (Brown et al., 1957a Brown et al., 1957b). The extension of the study to highly activating and deactivating substituents required the use of special procedures for the estimation of rate data under the standard conditions. It was convenient in most instances to determine the activation parameters at suitable temperatures and calculate the rate at 25°. For more extreme variations in reactivity, as with p-methoxy- and p-nitro-phenyldimethylcarbinyl chloride, both the temperature and composition of the solvent were modified (Okamoto and Brown, 1957b). These... [Pg.85]

To assess the accuracy and precision of these other factors influencing relative reactivity. Recently, solvent effects were shown to produce important variations in the relative reactivity of very similar molecules. Thus the relative influence of m-methyl and m-t-butyl substituents on the rate of solvolysis of benzhydryl chloride depends on the solvent (Shiner and and Verbanic, 1957). Less remarkable but equally important variations in reactivity were detected among the p-alkylated benzhydryl chlorides (Shiner and Verbanic, 1957 Berliner and Chen, 1958). A full analysis of solvent influences (Clement et al., 1960) requires much detailed... [Pg.89]

Aroyl esters of anthracene-9-methanol are photolysed in methanol to give products consistent with the anthracene-9-methyl cation as an intermediate.41 Rate constants for the solvolyses of secondary alkyl tosylates in fluorinated solvents were analysed in terms of the possible involvement of very short-lived carbocation-tosylate ion pair intermediates.42 The effect of added electrolytes on the rate of solvolysis of cumyl chloride and its -methyl derivative was studied in 90% aqueous acetone and 80% aqueous DMSO, with the results revealing a combination of a special salt effect and a mass law effect.43 Kinetic parameters obtained for the solvolysis of (8) (R1 = R2 = Me and R1 = Ar, R2 = H) show that there is substantial n, n participation in the transition state [e.g. (9). 44... [Pg.183]

A quite different heterolytic mechanism has been put forward for the reaction of diphenylmethylene with alcohols to form diphenylmethyl alkyl ethers (Kirmse, 1963). The ability of alcohols to suppress the reaction of the photolytically generated carbene with oxygen increased with increasing acidity of the alcohol. When sodium azide was present, the ylids of diphenylmethyl azide and alkyl ether were close to those obtained by solvolysis of diphenylmethyl chloride under the same conditions. Equation (22) is a plausible formulation of the reaction. [Pg.193]


See other pages where Chlorides, alkyl solvolysis is mentioned: [Pg.149]    [Pg.733]    [Pg.298]    [Pg.114]    [Pg.366]    [Pg.111]    [Pg.146]    [Pg.525]    [Pg.61]    [Pg.299]    [Pg.63]    [Pg.252]    [Pg.110]    [Pg.230]    [Pg.733]    [Pg.226]    [Pg.356]    [Pg.317]    [Pg.36]    [Pg.72]    [Pg.317]    [Pg.146]    [Pg.35]    [Pg.127]   
See also in sourсe #XX -- [ Pg.1062 ]




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