Swain-Scott Relationships for Nucleophile Addition to Ring-Substituted Phenonium Ions.

The products of the reactions of 2-(4-methoxyphenyl)ethyl tosylate (MeO-1-Ts) and 2-(4-methyphenyl)ethyl tosylate (Me-1-Ts) with nucleophilic anions were determined for reactions in 50/50 (v/v) trifluoroethanol/water at 25°C. In many cases the nucleophile selectivity kNu/ks (M-1) for reactions of nucleophile and solvent, calculated from the ratio of product yields, depends upon [Nu-]. This demonstrates the existence of competing reaction pathways, which show different selectivities for reactions with nucleophiles. A carbon-13 NMR analysis of the products of the reactions of substrate enriched with carbon-13 at the α-carbon, X-1-[α-13C]Ts, (X = -OCH3, -Me) with nucleophilic anions in 50/50 (v/v) trifluoroethanol/water at 25°C shows the formation of X-1-[β-13C]OH, X-1-[β-13C]OCH2CF3 and X-1-[β-13C]Nu (Nu = Br, Cl, CH3CO2, Cl2CHCO2) from the trapping of symmetrical 4-substituted phenonium ion reaction intermediates X-2+ . The observation of excess label in the α-position, [α-13C]/[β-13C] > 1.0, for both the water and nucleophile adducts, shows that water and anionic nucleophiles also react by direct substitution at X-1-[α-13C]Ts. The ratios of product yields, [α-13C]/[β-13C], and observed nucleophile selectivity (kNu/ks)obs were used to dissect the contribution of direct nucleophile addition at Me-1-Ts and trapping of X-2+ to the product yields. The product yields from partitioning of the intermediate gave the nucleophile selectivity kNu/ks (M-1) for X-2+ . Swain-Scott plots of log (kNu/ks) are correlated by slopes of s = 0.78 and s = 0.73 for reactions of MeO-2+ and Me-2+ , respectively. This shows that the sensitivity of bimolecular substitution at X-2+ to changes in nucleophile reactivity is smaller than for nucleophilic substitution at the methyl iodide. Evidence is presented that nucleophile addition to X-2+ proceeds through an "exploded" transition state.