Combining Ionic Groups with Methallyl Dichloride Coupling Delivers New Pathways to Ionic/Non-Ionic Hybrid Detergents

Abstract

Strategies for combining ionic and non-ionic functional groups are important for altering detergent properties and exploring new chemical spaces within the detergentome. Previous synthesis protocols for ionic/non-ionic hybrid detergents require asymmetric detergent precursors with independently addressable hydroxyl groups that can be decorated with charged groups. However, preparation of ionic/non-ionic headgroups can be tedious in terms of required synthesis steps and resource consumption. To address this challenge, here we explore if we can fuse ionic and non-ionic groups directly with methallyl dichloride in the first step of detergent synthesis. While this delivers a simplified synthesis strategy for ionic/non-ionic headgroups, we find functional groups for which the modification of asymmetric detergent precursors is still the only viable option to obtain related ionic/non-ionic hybrid detergents. Because previously established debenzylation conditions limit overall yields for asymmetric detergent precursors, here we explore optimization strategies, including silyl protecting groups, ozonolysis-hydrolysis, and hydrogenolysis. In summary, we establish a new synthesis route to ionic/non-ionic hybrid detergents, deliver an optimized debenzylation protocol and obtain building blocks for bridged detergent architectures. Our findings facilitate the modular synthesis of hybrid detergents and expand the chemical space of detergents.