Phase Transfer Catalysts and Role of Reaction Environment in Nucleophilc Radiofluorinations in Automated Synthesizers

Incorporation of [18F]fluorine into PET radiotracer structure has traditionally been accomplished via nucleophilic pathways. The [18F]fluoride is generated in an aqueous solution via proton irradiation of oxygen-18 enriched water and must to be introduced into water-free organic solutions in order to generate reactive species. Thus nucleophilic 18F-fluorination traditionally included steps for [18F]fluoride concentration on the anion exchange resin, followed by removal of residual water via azeotropic distillation with MeCN, a time-consuming process associated with radioactivity losses and difficult automation. To circumvent this, several adsorption/elution protocols were developed based on the minimization of water content in traditional kryptofix-based [18F]fluoride eluents. The use of pre-dried KOH/kryptofix solutions, tertiary alcohols, and strong organic bases was found to be effective. Advances in transition metal-mediated SNAr approaches for radiolabeling of non-activated aromatic substrates have prompted development of alternative techniques for reactive [18F]fluoride species generation, such as organic solutions of non-basic alkyl ammonium and pyridinium sulfonates, etc. For radiofluorinations of iodonium salts precursors, a “minimalist” approach was introduced, avoiding the majority of pitfalls common to more complex methods. These innovations allowed the development of new time-efficient and convenient work-up procedures that are easily implementable in modern automated synthesizers. They will be the subject of this review.

INFLUENCE OF WATER EXTRACTION METHODS FROM ENVIRONMENTAL SAMPLES ON MEASURED TRITIUM LEVEL

In order to validate the laboratory routine procedure of tritium activity concentration determination in tissue free water of environmental samples, parallel measurements were performed in water extracted from wild vegetation by two methods: azeotropic distillation and lyophilization (recommended by a French standard method). The sample humidity was established using the drying procedure to constant mass of the sample, and isotopic effect that may occur during lyophilization procedure was investigated by deuterium ratio determination in sample and extracted water. Traces of toluene in extracted water by azeotropic distillation made deuterium ration determination useless.

Method for Efficient Regeneration of Solvent Mixture: Extractive Heterogeneous-Azeotropic Distillation

The fine chemical and pharmaceutical industries use large amounts of various organic solvents in their manufacturing processes. By reusing them, production costs can be significantly reduced. If we can regenerate waste solvent mixtures, we have the opportunity to reuse them in the production process or in other production processes. Our study illustrates an efficient regeneration process using the example of a four-component solvent mixture. Calculations were performed in a professional process simulator to demonstrate that the highly non-ideal Water-Ethyl Alcohol-Methyl Ethyl Ketone-Ethyl Acetate solvent mixture can be efficiently decomposed into azeotropic pairs and thus regenerated by the extractive heterogeneous-azeotropic distillation technique.

SYNTHESIS AND PROPERTIES OF OLIGODIURETANEDIOLS BASED ON A MIXTURE OF (2,4–2,6) TOLUILENDIISOCYANATE

The paper describes the synthesis, the reaction of a mixture of isomers (2,4–2,6) of toluilendiisocyanate with a double molar excess of aliphatic individual or oligomeric diols, a number of previously unknown oligodiuretanediols and their physicochemical constants. It is shown that with an increase in the synthesis temperature from 50 to 70 °C, the reaction time to complete depletion in the mixture of free NCO-groups decreases from 8–9 hours to 3–4 hours. The reaction temperature of 70–2 °С should be considered optimal, because at higher temperatures side reactions of free NCO-groups with already formed urethane ones are possible. Because the presence of even a small amount of moisture in the diols can provoke side effects during the urethane formation reaction, all of the above diols were dried from the adsorbed moisture by azeotropic distillation with toluene before use in the reaction. Since the final products are even at the synthesis temperature (68–70 °C) viscous liquids, and there are difficulties with the homogenization of the reaction mass during synthesis, and when unloading the finished product from the reaction plant, in all cases, the synthesis was performed in solution cyclohexanone by 50 % by weight of the final product. Control of the reaction was performed by changing the % wt. free NCO-groups in time. The reaction was considered complete if the measured % wt. free NCO-groups in the reaction mixture for at least one hour twice showed zero. The isolated oligodiuretanediols range from solid at room temperature to very viscous products, which significantly depends on the molecular weight of the diol used in the reaction (ie the concentration of urethane groups formed). They are homogeneous, transparent compounds that are readily soluble in esters, ethers, aromatic and halide-containing, aprotic solvents, ketones, poorly or completely insoluble in aliphatic saturated hydrocarbons. The structure of the synthesized oligomeric products is confirmed by functional analysis, IR–spectra. In the IR-spectra of each of the synthesized oligodiuretanediols there are no absorption bands in the region of 2270 cm-1, which confirms the complete completion of the reaction of urethane formation according to the scheme. At the same time, the absorption bands in the region of 3450 cm-1, 1720 cm-1, 1540 cm-1 are fixed, which are characteristic of the presence of urethane groups in the structure of the target products. As the chain length of the diol component –R– increases in the target product (which synchronously leads to an increase in molecular weight), the intensity of these absorption bands decreases, which is associated with a decrease in the concentration of formed urethane groups in the structure of oligodiuretanediols. The refractive index also decreases synchronously. Synthesized series of oligodiuretanediols can be used for synthesis on its basis of other classes of oligomers with the simultaneous presence in the structure of urethane groups. The ability of such compounds to be soluble in solvents of different nature has been studied, which provides information for the directions of their further use (varnishes, enamels, primers).

Separation of the Mixture 2-Propanol + Water by Heterogeneous Azeotropic Distillation with Isooctane as an Entrainer

Advanced processes, which are alternatives to ordinary distillation, are essential to dehydrate azeotropic alcoholic mixtures for biofuel production. In that regard, this work focuses on the analysis of heterogeneous azeotropic distillation for the separation of a 2-propanol + water mixture in order to recover the alcohol with a sufficiently low water content. By comparing the performances of various entrainers on the basis of ternary maps, isooctane was selected for further process analysis. An advantage it poses is related to the fact that traces of it within the recovered dehydrated alcohol are highly welcome with a view to its subsequent use as a fuel. Aspen Plus® V11 software was employed for the simulation of the process, thus filling the gap existing in the literature due to the lack of studies on the process analysis of the heterogeneous azeotropic distillation of the 2-propanol + water system using isooctane as an entrainer.

Process Intensification in Bio-Ethanol Production–Recent Developments in Membrane Separation

Ethanol is considered as a renewable transport fuels and demand is expected to grow. In this work, trends related to bio-ethanol production are described using Thailand as an example. Developments on high-temperature fermentation and membrane technologies are also explained. This study focuses on the application of membranes in ethanol recovery after fermentation. A preliminary simulation was performed to compare different process configurations to concentrate 10 wt% ethanol to 99.5 wt% using membranes. In addition to the significant energy reduction achieved by replacing azeotropic distillation with membrane dehydration, employing ethanol-selective membranes can further reduce energy demand. Silicalite membrane is a type of membrane showing one of the highest ethanol-selective permeation performances reported today. A silicalite membrane was applied to separate a bio-ethanol solution produced via high-temperature fermentation followed by a single distillation. The influence of contaminants in the bio-ethanol on the membrane properties and required further developments are also discussed.