Phase-transfer catalysis as a modern technique in organic synthesis

Phase-transfer catalysis (PTC) has been already known for 60 years and has an established position both on a laboratory and industrial scale. It is an energy-saving technique, ensuring high yields and selectivity under mild conditions. PTC is successfully used, among others, in the pharmaceutical, polymer, agrochemical industries, for the production of dyes, fragrances and flavors, to name a few. Currently, the development of phase-transfer catalysis is focused mainly on the search for active catalysts as well as extending the scope of its applications. In particular, catalysts immobilized on an insoluble carrier, which can be easily separated from the reaction mixture and recycled many times, are of great interest. The growing demand for chiral compounds has resulted in the development of phase-transfer catalysts which, while retaining the advantages of conventional PTC, will allow to obtain a product with high enantiomeric excess. This work characterizes the phase-transfer catalysis and presents examples of its applications in organic synthesis

Synthesis of Propylene Carbonate by Urea Alcoholysis—Recent Advances

Organic carbonates are considered the chemicals of the future. In particular, propylene carbonate is widely used as a non-reactive solvent, plasticizer, fuel additive, and reagent, especially in the production of environmentally friendly polymers that are not harmful to human health. This paper reviews recent literature findings regarding the development of propylene carbonate synthetic methods starting from propane-1,2-diol and urea. The ammonia formed during the synthesis is recycled to obtain urea from carbon dioxide

Synthesis of Propylene Carbonate by Urea Alcoholysis—Recent Advances

Organic carbonates are considered the chemicals of the future. In particular, propylene carbonate is widely used as a non-reactive solvent, plasticizer, fuel additive, and reagent, especially in the production of environmentally friendly polymers that are not harmful to human health. This paper reviews recent literature findings regarding the development of propylene carbonate synthetic methods starting from propane-1,2-diol and urea. The ammonia formed during the synthesis is recycled to obtain urea from carbon dioxide

Oxidation of Cyclohexanone with Peracids—A Straight Path to the Synthesis of ε-Caprolactone Oligomers

During Baeyer–Villiger (BV) oxidation of cyclohexanone with peracids, oligo(ε-caprolactone) (OCL) may be formed. In this work, a two-step one-pot method for the synthesis of OCL involving the BV oxidation of cyclohexanone with peracids and then oligomerization of the resulting ε-caprolactone has been developed. The process was carried out in two solvents: toluene and cyclohexane. Based on the studies, it was determined that the increased temperature (45–55 °C) and the longer reaction time (4 h) favor the formation of OCls. Among the tested peracids (perC8-C12), perC10 turned out to be the most effective oxidant. Moreover, the obtained oligomers were characterized by means of NMR, MS MALDI TOF, and TGA analyses, which made it possible to determine the structure of oligomers (length and terminal groups of the chains). Additionally, the oligomers obtained after the distillation of the reaction mixture were analyzed

PTFE-Carbon Nanotubes and Lipase B from Candida antarctica—Long-Lasting Marriage for Ultra-Fast and Fully Selective Synthesis of Levulinate Esters

An effective method for levulinic acid esters synthesis by the enzymatic Fischer esterification of levulinic acid using a lipase B from Candida antarctica (CALB) immobilized on the advanced material consisting of multi-wall carbon nanotubes (MWCNTs) and a hydrophobic polymer—polytetrafluoroethylene (Teflon, PTFE)—as a heterogeneous biocatalyst, was developed. An active phase of the biocatalyst was obtained by immobilization via interfacial activation on the surface of the hybrid material MWCNTs/PTFE (immobilization yield: 6%, activity of CALB: 5000 U∙L∙kg−1, enzyme loading: 22.5 wt.%). The catalytic activity of the obtained biocatalyst and the effects of the selected reaction parameters, including the agitation speed, the amount of PTFE in the CALB/MWCNT-PTFE biocatalyst, the amount of CALB/MWCNT-PTFE, the type of organic solvent, n-butanol excess, were tested in the esterification of levulinic acid by n-butanol. The results showed that the use of a two-fold excess of levulinic acid to n-butanol, 22.5 wt.% of CALB on MWCNT-PTFE (0.10 wt.%) and cyclohexane as a solvent at 20 °C allowed one to obtain n-butyl levulinate with a high yield (99%) and selectivity (>99%) after 45 min. The catalyst retained its activity and stability after three cycles, and then started to lose activity until dropping to a 69% yield of ester in the sixth reaction run. The presented method has opened the new possibilities for environmentally friendly synthesis of levulinate esters

Highly Active Trifloaluminate Ionic Liquids as Recyclable Catalysts for Green Oxidation of 2,3,6-Trimethylphenol to Trimethyl-1,4-Benzoquinone

An effective method for the synthesis of 2,3,6-trimethyl-1,4-benzoquinone via the oxidation of 2,3,6-trimethylphenol as the key step in the in the preparation of vitamin E was presented. An aqueous solution of H2O2 was used as the oxidant and Lewis acidic trifloaluminate ionic liquids [emim][OTf]-Al(OTf)3, χAl(OTf)3 = 0.25 or 0.15 as catalysts. Trifloaluminate ionic liquids were synthesised by the simple reaction between 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (triflate) [emim][OTf] and aluminium triflate used in sub-stoichiometric quantities. The influence of the reaction parameters on the reaction course, such as the amount and concentration of the oxidant, the amount of catalyst, the amount and the type of organic solvent, temperature, and the reaction time was investigated. Finally, 2,3,6-trimethyl-1,4-benzoquinone was obtained in high selectivity (99%) and high 2,3,6-trimethylphenol conversion (84%) at 70 °C after 2 h of oxidation using a 4-fold excess of 60% aqueous H2O2 and acetic acid as the solvent. The catalytic performance of trifloaluminate ionic liquids supported on multiwalled carbon nanotubes (loading of active phase: 9.1 wt.%) was also demonstrated. The heterogeneous ionic liquids not only retained their activity compared to the homogenous counterparts, but also proved to be a highly recyclable catalysts