Asymmetric copper chemistry …︁ done heterogeneously? It's doable: Copper‐in‐charcoal (Cu/C) is introduced as an easily prepared catalyst that is readily converted in situ into a nonracemically ligated form of copper hydride that effects asymmetric hydrosilylations. DTBM=3,5‐di‐tert‐butyl‐4‐methoxydiphenylphosphinyl.
The use of chiral reagents for the derivatization of optically-active amines and alcohols for the purpose of determining their enantiomeric purity or absolute configuration is a tool used by many chemists. Among the techniques used, Mosher's amide and Mosher's ester analyses are among the most reliable and one of the most often used. Despite this, these techniques are rarely introduced in the undergraduate organic laboratory. In this experiment teams of students are given optically-pure amines of known structure but unknown stereochemistry. One half of the team derivatizes a sample of the amine with optically-pure (R)-Mosher's acid chloride and the other half of the team derivatizes a sample of the amine with optically-pure (S)-Mosher's acid chloride. The resulting amide diastereomers can be analyzed by 1H NMR spectroscopy and, using Mosher's model, distinguished from one another. Through careful analysis the students can determine the absolute configuration of their starting amine. Sample reactions are presented as well as spectral data for 18 Mosher amides that have been used in this experiment.
Asymmetrische Kupferchemie …︁ heterogen durchgeführt? Ja, es geht: Der leicht herstellbare Katalysator Kupfer‐in‐Aktivkohle (Cu/C) wird problemlos in situ in eine nichtracemisch ligierte Kupferhydrid‐Form überführt, die asymmetrische Hydrosilylierungen bewirkt.
The goal of this work is to evaluate how emulsions in total nutrition admixtures are affected by the containers within which they are stored. Specifically, the study examines how the emulsion globule size distribution in different containers is related to adsorption or absorption of the lipids onto or into the container. The admixtures were prepared from a commercial lipid emulsion, 20% ClinOleic®, and the containers were either glass (borosilicate) or plastic (ethylene vinyl acetate, EVA). The large globule size distribution was monitored continuously for both containers over the course of 24 h, and the quantity of triglycerides taken up by both containers was measured by liquid chromatography. The lipid uptake by the EVA containers was also monitored by gravimetric methods. Briefly, the percent of fat globules greater than 5 micrometers (PFAT5) in EVA containers showed a 75% reduction compared to a marginal decrease of PFAT5 when in the glass container. Extraction of the lipids from the containers showed that the quantity of triglycerides associated with the EVA surfaces steadily increased with admixture exposure time, while the glass showed a significantly lower triglyceride content. Gravimetric measurements confirmed that the EVA containers gained measurable mass during exposure to the emulsion admixture.
Formation of C-C, C-N, and C-H bonds using three heterogeneous catalysts in the form of nickel-in-charcoal (Ni/C), nickel-on-graphite (Ni/Cg), and copper-in-charcoal (Cu/C) are described.
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