Abstract A side selective single‐fluorination of pyridines is presented using commercially available AgF2 as fluorination agent and avoiding tedious multiple step procedures.
Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.
The present study investigated the role of cognitive processes in the maintenance of clinically significant sleep disturbance across two cultures. A questionnaire was administered to 60 Japanese and 60 English university students to assess the presence of sleep disturbance, predominance of pre-sleep cognitive activity, use of thought management strategies to control pre-sleep cognitive activity, and the content of pre-sleep cognitive activity. The results indicated that across both cultures poor sleepers attributed their sleep disturbance to the presence of uncontrollable pre-sleep cognitive activity. Minor differences between the Japanese and English samples included the strategies employed to control pre-sleep cognitive activity. The English participants were more likely to engage in reappraisal whereas the Japanese sample were more likely to engage in punishment and worry. These results are suggestive of the cross-cultural applicability of cognitive models of insomnia.