Stereoelectronic control of exo/endo rate ratios in the solvolysis of 2-norbornyl p-toluenesulfonates

The variable exo/endo rate ratios observed in the solvolysis of 6-exo-substituted exo- and endo-2-norbornyl p-toluenesulfonates are due to differential transmission of polar effects in the transition state for ionization.     

Etude par RPE de l'Ion NO2−2 dans une apatite nitrée

A calcium phosphate apatite which contains some different nitrogen oxides is studied by the ESR technique. NO^2?₂ ions are evidenced and characterized. They stay in the apatite channels with their OO direction along the channel axis. ESR experiments at different temperatures show that these ions rotate around this axis when the temperature becomes higher than that of liquid nitrogen.     

STUDIES ON THYMINE AND URACIL TRIPLET EXCITED STATE IN ACETONITRILE AND WATER

Abstract— Thymine and uracil triplet-triplet absorption spectra and triplet excited state lifetimes have been observed in acetonitrile and water by nanosecond laser flash spectroscopy. A study of triplet energy transfer from these pyrimidines to retino! has also allowed an estimation of the triplet extinction coefficient ε_TT of thymine and uracil. These ε_TT were then used to determine the triplet quantum yields Ø_T of both pyrimidines in acetonitrile and water.     

Rearrangements in cobaltic fluoride fluorinations of cycloalkanes with seven or more ring carbons

Cyclo-heptane, -octane, -decane, -dodecane and -octadecane have been fluorinated in the vapour phase with cobaltic fluoride. The perfluorocarbons obtained revealed varying degrees of skeletal rearrangements. Thus, cycloheptane gave perfluoro-cycloheptane and -methylcyclohexane; cyclooctane gave at least eight fluorocarbons including-bicyclo(3,3,0)octane and -cyclooctane; cyclodecane gave a complex mixture from which were isolated perfluoro cis- and trans-bicyclo(4,4,0)decanes but no perfluorocyclodecane; cyclododecane and cyclooctadecane gave complex fluorocarbon mixtures in which none of the fluorocarbons with the original cycloalkene skeleton could be detected.Tetradecafluorobicyclo(3,3,0)octane gave dodecafluorobicyclo (3,3,0)oct-1(5)-ene and decafluorobicyclo(3,3,0)octa-di-1(5), 2-ene when pyrolysed over iron gauze.The fluorination of cyclooctane also afforded 1$\text{H}$-pentadecafluorocyclooctane which was dehydrofluorinated to tetradecafluorocyclooctene. This was converted to a range of derivatives including dodecafluorosuberic acid, 1,2-dichlorotetradecafluorocyclooctane, 1-methoxy tridecafluorocyclooctene and tetradecafluorocyclooctanone.     

Buchbesprechungen

Ohne Zusammenfassung     

Contribution a l'électrochimie des thiols et disulfures : Partie I. Cystéine et cystine

A study of the electrochemical characteristics of cysteine and cystine was carried out by d.c., a.c. and differential pulse polarography. Up to three waves were observed depending on the concentration and pH. The waves of the two amino acids could be separated in a borate buffer of pH 9.2. Differential pulse polarography made it possible to determine as little 0.12 mg of cysteine and 0.24 mg of cystine per litre.     

The application of column redox-extraction chromatography to the separation of some actinide elements

The application of a new technique to the separation of some actinide elements by means of a single reducing and extracting column is described. Tri-n-octylphosphine oxide (TOPO) was used as the extractant. The following reducing agents were supported on microporous polyethylene together with TOPO: tetrachlorohydroquinone, 2,3-dichloro-1,4-naphthahydroquinone, 2,5-di-tert-butylhydroquinone and 2,5-di-tert-pentylhydroquinone. The last compound was chosen for the separation experiments; it allowed quantitative reduction of plutonium to Pu(III) and of neptunium to Np(IV). The separations Pu(III)-Np(IV), Pu(III)-U(VI) and Am(III)-Np(IV) in 6 M hydrochloric acid were obtained.