Fischer esterification can be a time-consuming process, requiring days for a reaction to reach equilibrium. In this article, researchers developed a way to hasten this process by using a specially designed microwave to heat the reaction quickly and evenly and at an increased pressure. In order to test the efficiency of the device, they synthesized 2-ethylhexyl benzoate from benzoic acid and 2-ethylhexanol as shown below.
Sulfuric acid as well as para-toluene sulfonic acid (PTSA) were used to catalyze the reaction. In order to shift the reaction towards the products, a large excess of 2-ethylhexanol was used and the water produced was constantly removed. One of the disadvantages of Fischer esterification is that dehydration can also occur, resulting in unwanted ether and alkene products. Because of this, the temperature and catalyst concentration must be carefully monitored. The researchers were able to show that microwave heating causes no ill effects on the reaction and reduces the time required to a matter of minutes while still producing a high level of the desired product.
Polymers have important uses in both research and industry. Alkoxyamines are used in ATRP (atom transfer radical polymerization)-based polymerizations and can serve as efficient regulators in the preparation of polymers. In the past, the alkoxyamines were produced by the creation of radicals that are carbon-centered and were then trapped by nitroxide. This method, however, gave low yields and undesired byproducts. The reaction shown here takes place at low temperatures and in the presence of a nitroxide, utilizing an ATRP-based initiator that is treated with copper bromide. The ATRP is involved in the living radical polymerization system. Me6-tren ligand forms a catalyst complex for the reaction of the initiator with nitroxide. Equilibrium between the transfer to and from radicals and dormant species in the reaction is controlled by the Me6-tren ligand forming a complex with the Cu(II), which the free radicals can then interact with. The catalyst name Me6-tren stands for the chemical tris(2-(dimethylamino)ethyl)-amine. This is a more effective procedure for preparation that results in high yields. Discoveries such as this are important in areas such as nanotechnology.