Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy.

Abstract

A new family of bio-based herbicidal ionic liquids (HILs) has been synthesized starting from the renewable resource glycine betaine (a derivative of natural amino acids). After esterification, the obtained alkyl betainate bromides containing straight alkyl chains varying from ethyl to octadecyl were combined with a herbicidal anion from the sulfonylurea group (iodosulfuron-methyl). The melting points of the iodosulfuron-methyl-based salts were in a range from 51 to 99 °C, which allows their classification as ionic liquids (ILs). In addition, the new HILs exhibited good affinity for polar and semipolar organic solvents, such as DMSO, methanol, acetonitrile, acetone, and chloroform, while the presence of bulky organic cations reduced their solubility in water. The synthesized products turned out to be stable during storage at 25 °C for over 6 months; however, at 75 °C they underwent fast, progressive degradation and released volatile byproducts. The values of the logarithm of the octanol–water partition coefficient of ILs with alkyls longer than hexyl occurred in the “safe zone” (between 0 and 3); hence, the risk of their migration into groundwater after application or the possibility of their bioaccumulation in the environment is lower in comparison with the currently available commercial form (iodosulfuron-methyl sodium salt). Greenhouse studies confirmed a very high herbicidal efficacy for the obtained salts toward tested plants of oilseed rape, indicating that they may become an attractive replacement for the currently available sulfonylurea-based formulations.