The stereochemistry of N -acyl/ N -sulfonyl 5 H -dibenzo[ b , d ]azepin-7(6 H )-ones ( I , II ) was examined in detail by freezing the conformation with a methyl group at the C-4 of dibenzoazepine. Because the two axes (axis 1, axis 2) move together concertedly, I and II exist only as a pair of enantiomers [(a 1 R , a 2 R ) and (a 1 S , a 2 S )], which was confirmed by X-ray analysis of IIBc . It was elucidated that the amide derivatives I exist in equilibrium with the E / Z -amide (100:2–100:34), which means that the exocyclic bond (axis 3) is not in concert with the endocyclic axes (axis 1, axis 2). For the preparation of 5 H -dibenzo[ b , d ]azepin-7(6 H )-one, the intramolecular Friedel–Crafts acylation of N -(1,1′)-biphenyl-2-yl-glycine derivatives was revisited. It was revealed that the electron-withdrawing property of the amino-protective group was a key to the success of seven-membered cyclization.

The conformational properties of 2′-fluoro-substituted acetophenone derivatives were elucidated based on H α –F and C α –F through-space spin–spin couplings (TS-couplings), which occur between two atoms constrained at a distance smaller than the sum of their van der Waals radii. This study revealed that 2′-fluoro-substituted acetophenone derivatives in solutions form exclusively s - trans conformers by analyzing their NMR spectra focused on the TS-couplings. The magnitudes of the coupling constants 5 J (H α , F) and 4 J (C α , F) correlate linearly with the value of the dielectric constant of the solvents. Furthermore, s - trans conformations of the two derivatives were confirmed by X-ray crystallographic analysis. These conformational preferences were consistent with the DFT calculations. The s - cis conformer, in which fluorine and oxygen atoms lie in a syn -periplanar mode, may be subject to strong repulsion between the two polar atoms and become unstable. The s - trans preference of the 2′-fluoro-substituted acetophenone derivatives may be utilized in drug design.

Atomic scale characterization of fine precipitates in an under-aged Cu added Al-Mg-Si alloy was carried out by combination of atomically-resolved annular dark-field scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Two types of precipitates were observed in the alloy. In the case of ordered β” precipitates, β” was proposed as Mg5-xAl2+xSi4 (x ≈ 1) with solute Cu atoms replacing Al site of β” precipitate. In the case of disordered precipitates, the precipitates were found to consist of β” sub-unit cells, three-fold symmetric structure without Cu atoms, Cu containing structures termed as “Cu sub-unit cluster”, and Q’ sub-unit cells. Among these structures, the morphologies of three-fold symmetric structure without Cu atoms, Cu sub-unit cluster, and Q’ sub-unit cell were almost the same, so that these structures should be the clusters of Q’ phase. Since the areal density, length and diameter of precipitates were almost equal between Cu free Al-Mg-Si alloy and Cu added Al-Mg-Si alloy, the increase of hardness by Cu addition should be due to the precipitation of Cu related precipitates, such as Cu sub-unit clusters and Q’ sub-unit cells.