N-octyl methanesulfonate

It is interesting to compare the nucleophilicity sequence found by Liotta and Grisdale (1975) for crown ethers, with the sequence recently reported by Landini et al. (1978) for onium compounds. For hexadecyltributylphos-phonium as the cation, the reactivity sequence (for n-octyl methanesulfonate) in chlorobenzene was CN- > > Cl- > Br- > I- > SCN- (Table 28), which... 

Table 5.3 The effect of catalyst structure and its organophilicity on the rate of reaction between n-octyl methanesulfonate and potassium bromide...

A study of the anion displacement reactions of n-octyl methanesulfonate reveals striking differences in the reactivity of various anions under phase transfer and homogeneous conditions [43], In the phase transfer catalysed reactions the reactivities of the anions were found to decrease in the order ... 

Table II. Catalytic Activity of Sandwich Ligands 1 and 2 in Nucleophilic Substitutions on n-Octyl Methanesulfonate with Alkali Halides (MY) under Solid-Liquid Conditions in Toluene at 50°C...

Nucleophilic displacements under two-phase conditions in the presence of catalytic amounts of crown ether, 4, which is completely dissolved in the organic phase, follow the classical PTC mechanism and the observed pseudo first-order rate constants are linearly correlated with the amount of complexed crown ether in the organic phase. A narrow reactivity range was found for different anionic nucleophiles in the displacement of n-octyl methanesulfonate (Scheme 10). 

In the nucleophilic displacement of n-octyl methanesulfonate (Eq. (17)) taken as standard substrate, by a series of anions, a rather restricted reactivity range in the following order was found > CN > Br = 1" > Cl > SCN . This is... 

Table 5. Second-order rate constants for the reaction of n-octyl methanesulfonate with various nucleophiles (Y ) under PTC conditions, and in anhydrous and wet homogeneous organic solutions...

Table 6. Solvent effect on the rate of the reaction of n-octyl methanesulfonate with bromide ion" under PTC and anhydrous homogeneous conditions...

Table 9. Reaction of n-octyl methanesulfonate with various nucleophiles (Y") under PTC conditions in the presence of perhydrodibenzo[18]crown-6(PHDB) or hexadecyl-tributylphosphonium salts...

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