Oxidative transformations of cembrane diterpenoids III. Epoxycembrenes
Summary1. It has been established that the epoxidation of cembrene with perbenzoic and peracetic acids takes place stereospecifically at each of the trisubstituted double bonds with the formation of 4S,5R-, 7S,8S-, and 11S,12S-monoepoxycembrenes, the structures and absolute configurations of which have been established by spectral methods.2. Epoxidation of cembrene at the C11–C12 double bonds under the conditions used takes place preferentially as compared with epoxidation at the C7–C8 double bond.
New methods for the preparation of 1-phenyl-trans-cyclohexane-1,2-diol
Abstract In contrast with previous reports, it was found that the reaction of 1-phenylcyclohexene with peroxyformic acid is not entirely stereospecific, but gives some trans -1-phenylcyclohexane-1, 2-diol (IV) beside the cis -isomer (III). The reaction of 1-phenylcyclohexene oxide (II) with formic acid yielded a similar mixture of III and IV, while addition of trichloroacetic acid in benzene was entirely cis -stereospecific. Reaction of the epoxide II with potassium hydroxide took place only under very drastic conditions to give a small yield of III, while sodium 2-dimethylaminoethoxide added exclusively in a trans way, leading to the amino ether X, which was easily transformed into the trans -glycol IV. The latter compound was also the main product of the borohydride reduction of 2-hydroxy-2-phenylcyclohexanone (IX). Possible explanations of the observed stereochemical results are discussed.
Photoinduced spin-state transition of Co3+ in the layered perovskite manganite thin film
The photoinduced effect, at different temperatures, on layered perovskite manganite La1.2Sr1.8Mn1.8Co0.2O7 thin film deposited on a SrTiO3(100) substrate has been studied using a He–Ne laser (632.8 nm) with the power of output 25 mW at low temperatures. The electrical transport and magnetic properties of the film are investigated systematically in the temperature region from 20 to 300 K. The resistance shows a significant decrease at low temperatures (T<90 K) under laser irradiation, which can be interpreted in terms of the spin-state transition of Co3+ ions. The magnetic field combined with the laser is also used to detect the photoinduced effect of the spin-glass state. The time dependence of the metastable system under several applied fields was also discussed. The system has the ability to keep a persistent memory of the magnetic history imprinted in its zero-field resistance.