1. The study of N-heterocyclic carbenes (NHCs) in ionic liquids
- Author
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Bin Nik Daud, Nik Muhammad Azhar and Welton, Tom
- Abstract
The formation of N-heterocyclic carbenes (NHCs) from imidazolium based ionic liquids (ILs) has attracted great interest, especially for synthetic chemistry. Carbenes can be used as catalysts for C-C bond formation reactions, such as the benzoin condensation or Stetter reaction. In this project, ILs were used as the source of carbene in the benzoin condensation in neat conditions, which was successfully performed. The imidazolium acetate ILs proved to be useful catalysts as well as solvents for the benzoin condensation, with their activity likely arising from the in-situ formation of NHCs. For example, it was found that the reaction of benzaldehyde with 1-butyl-3-methylimidazolium acetate, [C4C1im][OAc] and 1-ethyl-3-methylimidazolium acetate [C2C1im][OAc] as catalysts produced benzoin with good to excellent yield. These results show that the acetate anion in the [C2C1im][OAc] can act as base in the reaction. This result triggered us to investigate the reaction kinetics for the benzoin reaction using ILs. The results show that the reaction is a complex reaction which depends on a lot of parameters. The results also showed that the rate determining step is the second step, where the Breslow intermediate reacts with a second aldehyde. The first step is very fast. This result also brings another interesting question on the existence of NHCs in the reaction; did the NHC form during the reaction or did NHC is already exist in the ionic liquid. To investigate this, we have performed the kinetics of Breslow intermediate formation and isotope effect experiments were performed using deuterated C2 position of [C2C1im][OAc] with anisaldehyde and compared the rate of the reaction with normal [C2C1im][OAc]. The result showed no significant difference in the reaction rate. This suggests that the carbene already existed in ionic liquid rather than being form during the reaction. The ability of ILs to react with the carbonyl group in cellulose is well established. A proposed method was performed to protect the aldehyde group from reacting with the ILs by using the diol compound as the protecting group. Two different methods were employed and the result showed that the protection group can prevent the ILs from reacting with the carbonyl group. As this result only used benzaldehyde as model compound, the applicability of the method in the actual cellulose compound remain question and further study is needed.
- Published
- 2019
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