Online-Analysis on Acoustically Levitated Droplets

Summary: Aqueous solutions of acrylic acid were levitated in a 40 kHz acoustic levitator. The monomer amount in the levitated droplets was monitored by Raman spectroscopy relating to an internal standard. Thus evaporation of the monomer as well as polymerization reactions initiated by a redox system were investigated by Raman spectroscopy and resultant data were compared to HPLC data. Decreases in monomer amount due to evaporation can be clearly distinguished from polymerization reactions. Additionally, temperature measurement within the droplet throughout a polymerization reaction shows the typical temperature course originating from the heat of polymerization.     

Temperature and pH Dependency of Copolymerization Parameters of Acrylic Acid and 2-Hydroxypropyl Acrylate

Summary: Since copolymerization parameters of acrylic acid (AA) and 2-hydroxypropyl acrylate (HPA) in aqueous solutions are scarcely investigated a new method and different experimental setups were developed to run copolymerization experiments at different temperatures and pH values. The experiments were done with UV- or azo- initiation and analyzed by residual monomer analytics with HPLC and GPC methods. Based on the data obtained the conversion and copolymerization parameters were calculated with different mathematical models.     

Process Intensification of Emulsion Polymerization in the Continuous Taylor Reactor

Summary: Process intensification is investigated by the emulsion polymerization of styrene in the continuous Taylor reactor. The result is an increase in space time yield up to a factor 200 in comparison to a semi-batch polymerization process. This is obtained by a fast emulsion polymerization with a mean residence time, which is reduced to 60 seconds. The article presented the results of the process and the economical aspects of the Taylor reactor plant.     

The [4+2]-Cycloaddition of α-Nitrosoalkenes with Thiochalcones as a Prototype of Periselective Hetero-Diels–Alder Reactions—Experimental and Computational Studies

The [4+2]-cycloadditions of α-nitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styryl-substituted 4H-1,5,2-oxathiazines in moderate to good yields. Of the eight conceivable hetero-Diels–Alder adducts only this isomer was observed, thus a prototype of a highly periselective and regioselective cycloaddition has been identified. Analysis of crude product mixtures revealed that the α-nitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bis-heterocyclic [4+2]-cycloadducts. The experiments are supported by high-level DFT calculations that were also extended to related hetero-Diels–Alder reactions of other nitroso compounds and thioketones. These calculations reveal that the title cycloadditions are kinetically controlled processes confirming the role of thioketones as superdienophiles. The computational study was also applied to the experimentally studied thiochalcone dimerization, and showed that the 1,2-dithiin and 2H-thiopyran isomers are in equilibrium with the monomer. Again, the DFT calculations indicate kinetic control of this process.     

Microscale determination of the absolute configuration of alpha-aryl-substituted alcohols by the CD exciton chirality method

The absolute configurations of a broad spectrum of aryl alcohols 1 have been determined for the first time by the CD exciton chirality method. The configurational assignment is additionally verified by computer modeling and lipase-catalyzed acetylation of the racemic alcohols. The CD-spectroscopic data have revealed that the S enantiomers of the benzoate derivatives 2 display a positive first Cotton effect and the R enantiomers a negative one at around 228 nm. Thus, the sense of the first Cotton effect of the benzoate derivative 2 allows a reliable assignment of the absolute configuration of the corresponding alcohol 1.     

New Applications of the CD Exciton Chirality Method. Stereochemical Assignment of Organic Compounds Containing Carboxylic Acid Groups

CD exciton chirality methods are described for the stereochemical assignment of organic compounds containing carboxylic acid groups. Using the chromophoric combination 2-naphthoate or 2-anthroate and 9-anthrylmethyl group the absolute stereochemistry of - and -hydroxy carboxylic acids can be deduced from a single CD measurement. Furthermore, as demonstrated with cyclic and acylic dicarboxylic acids, the direct esterification of sterically hindered carboxyl groups with 2-naphthol also allows the stereochemical assignment via CD spectroscopy.