Redefining q: quaternary ammonium cross sectional area (XSA) as a general descriptor for transport-limiting PTC rate approximations.

Abstract

The relationships of several key molecular descriptors with the rate of the O'Donnell alkylation under phase transfer catalysis (PTC) have been investigated. The most common parameter used to predict PTC rates, the ammonium ion accessibility, q , is defined in such a way that limits its use to straight-chain tetraalkylammonium catalysts. To find a general descriptor of rate, eight linear, symmetrical tetraalkylammonium cations were examined to determine if a model containing broadly applicable descriptors could be found. The catalytic activity of these salts was determined under PTC conditions (operating under an interfacial, transport-rate limiting mechanism) and was compared with these molecular descriptors. Models could be generated from the ammonium ion accessibility parameter q and the amphiphilic cross sectional area descriptor (XSA), and each gave a correlative model predicting the rate of alkylation. However, a similar model cannot be generated from a descriptor that is a direct measure of ammonium ion accessibility, the solvent accessible ammonium surface area (NC4_SA). These models lead to the conclusion that q must approximate catalyst properties other than ammonium ion accessibility. Additionally, the relationship between XSA and rate demonstrates that XSA approximates the complex behavior of ammonium ions at the interfacial region of a biphasic system, allowing for its use as a general descriptor for transport-limiting PTC rate approximations.