The use of ionic liquids (ILs) as a novel class of environmentally friendly solvents is now of topical interest among the chemical community, worried about the environmental impact of chemicals. Many reactions of organic chemistry have thus been re-examined since the 1990s. Nevertheless, even if a given preparation of ILs does not represent any particular difficulty, the reaction times appear to be long and the use of large amounts of classical solvents for the synthesis and the purification steps is crucial. This article presents preliminary work performed for the ultrasound assisted preparation of several 1-butyl-3-methylimidazolium salts (BF4, PF6, CF3SO3 and BPh4). In all cases a clear yield increase results and a dramatic reduction of the reaction time accompanied by an improved quality of the products occurs. After a short and simple work-up, the ILs are ready to use without a further purification step. Moreover, an original and simple analytical way to follow the reaction in real time is also presented.
Non-conventional techniques, such as microwave (MW) and power ultrasound(US) as well as combined MW/US irradiation, have been used to promote one-potsynthesis of second-generation ionic liquids (ILs), cutting down reaction times andimproving yields. However, the use of chloroalkanes in the alkylation of N-heterocyclesrequires more drastic conditions if results are to match those obtained with more reactivealkyl halides. The present paper describes a series of MW- or MW/US-promoted ILpreparations starting from chloroalkanes and classic heterocycles (1-methylimidazole,pyridine and 1-methylpyrrolidine). When reactions were carried out under conventionalheating in an oil bath they required longer reaction times and gave poorer yields. 1H-NMRanalysis and ion-exchange chromatography showed that the present solventless procedureafforded ILs of satisfactory purity. The observed high yields (usually 70-98% isolated),and short reaction times showed that a straightforward access to ILs can be also achievedwith the use of alkyl chlorides, resulting in a considerable reduction of costs.
27 August 2007 in Monatshefte für Chemie - Chemical Monthly
Biodiesel production via esterification/transesterification reactions can be catalyzed by homogenous or heterogeneous catalysts. Development of heterogeneous catalysts for biodiesel production is highly advantageous due to the ease of product purification and of catalyst recyclability. In this current work, a novel acidic [DABCODBS][CF3SO3]2 dicationic ionic liquid (DIL) was used as heterogeneous catalyst to produce biodiesel using oleic acid as model oil. The esterification was conducted under ultrasonic irradiation (20 kHz) using a 14 mm ultrasonic horn transducer operated at various duty cycles. It was observed that the duty cycle, amplitude, methanol to oil molar ratio, catalyst amount and reaction temperature were the major factors that greatly impact the necessary reaction time to lead to a high yield of biodiesel. The reaction conditions were optimized with the aid of Response Surface Methodology (RSM) designed according to the Quadratic model of the Box Behnken method. The optimum conditions were found to be at catalyst amount of 0.64 mol%, methanol to oil ratio of 14.3:1, temperature of 59 °C, reaction time of 83 min and amplitude of 60% in continuous mode. The results showed that the oleic acid was successfully converted into esters with conversion value of 93.20% together with significant reduction of reaction time from 7 h (using mechanical stirring) to 83 min (using ultrasonication). The results also showed that the acidic DIL catalyst we designed purposely was efficient to catalyze the ultrasonic-assisted esterification yielding high conversion of oleic acid to methyl oleate on short times. The DIL was also recycled and reused for at least five times without significant reduction in performance. Overall, the procedureoffersadvantages including short reaction time, good yield, operational simplicity and environmentally benign characteristics.
6 May 2013 in ACS Sustainable Chemistry & Engineering