Studies on organic fluorine compounds. LIII. Preparation of functionalized trifluoromethylated compounds using 1-phenylsulfonyl-3,3,3-trifluoropropene

Reaction of 1-phenylsulfonul-3,3,3-trifluoropropene(1) with carbonyl-stabilized enolate anions smoothly proceeded to give the addition products(7) in good yield while with an alkyl-lithium or Grignard reagent the formation of the vinyl anion(8) was one of the reaction pathways. Reaction of 1 with the chiral nucleophiles(11, 16) was carried out to give the functionalized trifluoromethylated compounds(13, 7b) in 4-43% ee     

An application of bis[2-(5-chloro-2-pyridylazo)- 5-diethylaminophenolato]cobalt(III) chloride to the extraction and spectrophotometric determination of sulphonated and sulphated surfactants

Bis[2-(5-chloro-2-pyridylazo)-5-diethylaminophenolato]cobalt(III) is proposed for the extraction and spectrophotometric determination of sulphated and sulphonated surfactants. The complex and the surfactants form ion-pairs which are extracted into benzene from O.1M hydrochloric acid. The absorbance of the benzene phase is measured at 560 nm against a reagent blank. Less than 25 mug of sodium di-(2-ethylhexyl) sulphosuccinate in 50-200 ml of sample solution is determined reproducibly by the proposed method. When applied to river water samples, the proposed method gives results which agree very well with those obtained by the standard Methylene Blue method. However, the proposed method is simpler and more sensitive than the Methylene Blue method.     

Facile formation of water-insoluble cyclodextrin/Nafion composite films on solid surfaces

The water-insoluble poly-beta-cyclodextrin (poly-CD)/Nafion composite film was easily prepared by casting a mixed solution of poly-CD and Nafion onto substrate plates. FT-IR measurements showed that the 50/50 wt% poly-CD/Nafion composite film remained stable on the glass and quartz substrates after immersion in water for more than 3 h, while a pure poly-CD film was almost completely dissolved by immersion within 1 h. The film stability was also evaluated from the amount of p-nitrophenol (p-NP) inclusion in the film, which was determined from the decrease in UV-vis absorbance of the p-NP solution into which the film was immersed. The composition dependence of the inclusion amount showed that the film was stable up to 50 wt% CD, but became less stable with further increase in the CD concentration in the film. From the isotherms for the inclusion of p-NP and 1-naphthoate (1-Naph) into the film, the inclusion (stability) constants were determined to be 3.7x10(3) M(-1) and 1.9x10(2) M(-1), respectively. These results show that the selective inclusion of CD is retained after preparation of the composite film.     

Efficient synthesis of optically active atropisomeric anilides through catalytic asymmetric N-arylation reaction

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)2 catalyst, N-arylation of ortho-tert-butyl-NH-anilides with 4-nitroiodobenzene proceeds with high enantioselectivity (89-95% ee) to give optically active atropisomeric anilides possessing N-C chiral axis. Furthermore, the intramolecular version of the present catalytic asymmetric N-arylation gave atropisomeric lactams with high optical purity (94-96% ee).