Facile synthesis of aromatic unsymmetrical fluorine-containing acyloins through the reductive trifluoroacetylation of benzaldehyde and transposition of the carbonyl group

The reductive coupling reaction between benzaldehyde and ethyl trifluoroacetate in the presence of magnesium and chlorotrimethylsilane in N-methyl-2-pyrrolidinone gave the acetal of the corresponding coupling compound in good yields. The yield of the coupling product largely depended on the benzaldehyde concentration in the solution and it was essential to avoid the formation of pinacol type compounds in order to obtain the coupling product in high yields. The subsequent desilylation of the acetal using tetrabutylammonium fluoride easily yielded an acyloin compound as the sole product after the transposition of the carbonyl group through keto–enol tautomerism.     

Detection of Anabolic Steroids By Gc/Sim/Ms With Trifluoroacetylation in Equine Plasma and Urine

ABSTRACT

A method to detect three anabolic steroids (boldenone, nandrolone and mesterolone) is presented. The anabolic steroids are isolated from equine plasma and urine by extraction with diethyl ether and C₁₈ Sep-Pak cartridge adsorption, respectively. The extracts obtained were derivatized with trifluoroacetyl anhydride and analyzed by GC/SIM/MS. The selected ion monitoring (SIM) mode was applied to increase the sensitivity and, when possible, the higher m/z ions were selected to improve identification. Stability of derivatives was good and compounds having hydroxy and conjugated ketone groups produced trifluoroacetyl ester derivatives that were also stable. Repeatability of the chromatographic analysis was evaluated on the basis of area repeatability, and the coefficient of variation obtained was lower than 4.4. The detection limit was 1 and 5 ng/ml for all the anabolic steroids studied in equine plasma and urine, respectively.     

Access to Trifluoromethylketones from Alkyl Bromides and Trifluoroacetic Anhydride by Photocatalysis

Aliphatic trifluoromethyl ketones are a type of unique fluorine-containing subunit which play a significant role in altering the physical and biological properties of molecules. Catalytic methods to provide direct access to aliphatic trifluoromethyl ketones are highly desirable yet remain underdeveloped, partially owing to the high reactivity and instability of trifluoroacetyl radical. Herein, we report a photocatalytic synthesis of trifluoromethyl ketones from alkyl bromides with trifluoroacetic anhydride. The reaction features dual visible-light and halogen-atom-transfer catalysis, followed by an enabling radical-radical cross-coupling of an alkyl radical with a stabilized trifluoromethyl radical. The reaction provides straightforward access to aliphatic trifluoromethyl ketones from readily available and cost-effective alkyl halides and trifluoroacetic anhydride (TFAA).