Enzymatic kinetic resolution of (±)-hydroxytetrahydropyrans has been achieved for the first time by means of lipase-mediated transesterification to afford optically active (2S,4R)-tetrahydropyranyl acetates and (2R,4S)-tetrahydropyranols in excellent yields with high enantioselectivity. Absolute configurations of the tetrahydropyranyl acetates were assigned as (S) by chemical correlation. 相似文献
On the Crystal Chemistry of a New Barium Rare-Earth Oxozincate: Ba2Er2Zn8O13 High temperature reactions led to single crystals of Ba2Er2Zn8O13. It crystallizes with orthorhombic symmetry, space group C122v? Cmc21, a = 6.276, b = 10.871, c = 10.195 Å, Z = 2. The hitherto unknown crystal structure shows Zn2+ with tetrahedral, Er3+ octahedral and Ba2+ cuboctahedral coordination by O2?. It will be shown that parts of the [Zn8O13] network are fragments of the ZnO structure showing O2? within a tetrahedral zinc coordination. A deficit of two O2? ions per unit cell is focused on two point positions. 相似文献
Collision-induced rotational transitions in the electronically excited NaLi molecule have been studied using laser excited fluorescence. Due to the greater number of allowed transitions as compared with Na2 and Li2, more cases were found of transitions +ΔJ and ?ΔJ having greatly different cross sections (“+/ - asymmetry”). This observation is in agreement with recent predictions on the basis of Born's approximation. All observed transitions are classified according to the symmetry of the contributing potential terms. Data are presented which indicate the necessity for refinements of the theory. 相似文献
It is shown by i.r. spectroscopy that the anionic polymerization of methacrylonitrile using organomagnesium compounds as initiators leads to two types of “living” ends i.e. and The active centres form complexes with the monomer, as well as with the nitrile groups of the monomer units in the polymer chain, in a hydrocarbon medium. The complexes are characterized by bands in the 2250–2280 cm?1 region. Addition of donors destroys the complexes and in some cases (hexamethylphosphorous triamide) converts the complex of organomagnesium compound with monomer into a “living” end. In ethers as solvent, the dominant side-reaction is addition of the initiator to the nitrile group of the monomer. 相似文献
Zusammenfassung Monomere Phosphinimine der allgemeinen Formel C6H5N= =PCln(NEt2)3-n (n=0,1,2) lassen sich (I) aus dimerem Phenylimino-phosphorsäure-trichlorid und Diäthylamin in Gegenwart eines Chlorwasserstoffakzeptors und (II) durch Reaktion der Phosphine PCln(NEt2)3-n mit Phenylazid darstellen. Die Phosphorane Et2NPCl4, (Et2N)2PCl3 und (Et2N)3PBr2 reagieren mit Anilin nicht zu Phenylimino-Verbindungen. Durch alkalische Hydrolyse von C6H5N=PCl(NEt2)2 entsteht das Phosphorsäure-bis[diäthylamino]-anilid. Die IR- und1H- und31P-NMR-Spektren der Verbindungen werden mitgeteilt.
Monomeric phosphinimines of the general formula C6H5N= =PCln(NEt2)3-n (n=0,1,2) are formed (I) from dimeric phenyliminophosphoricacid-trichloride and diethylamine in the presence of a HCl-acceptor and (II) by reacting the phosphines PCln(NEt2)3-n with phenylazide. The phosphoranes Et2NPCl4, (Et2N)2PCl3 and (Et2N)3PBr2 do not give the corresponding phenylimines with aniline. Alkaline hydrolysis of C6H5N= =PCl(NEt2)2 gives bis[diethylamino]-anilido-phosphinoxid. IR-,1H- and31P-NMR-spectra are given.
Routine pH measurements are carried out with pH meter-glass electrode assemblies. In most cases the glass and reference electrodes are thereby fashioned into a single probe, the so-called 'combination electrode' or simply 'the pH electrode'. The use of these electrodes is subject to various effects, described below, producing uncertainties of unknown magnitude. Therefore, the measurement of pH of a sample requires a suitable calibration by certified standard buffer solutions (CRMs) traceable to primary pH standards. The procedures in use are based on calibrations at one point, at two points bracketing the sample pH and at a series of points, the so-called multi-point calibration. The multi-point calibration (MPC) is recommended if minimum uncertainty and maximum consistency are required over a wide range of unknown pH values. Details of uncertainty computations for the two-point and MPC procedure are given. Furthermore, the multi-point calibration is a useful tool to characterise the performance of pH electrodes. This is demonstrated with different commercial pH electrodes. ELECTRONIC SUPPLEMENTARY MATERIAL is available if you access this article at http://dx.doi.org/10.1007/s00216-002-1506-5. On that page (frame on the left side), a link takes you directly to the supplementary material. 相似文献
We derive for the first time a mechanism of reactive plasma etching in the system Si/F by the quantum-chemical approach. SiF2-like species at the surface play an important role. SiF3 surface complexes also occur. The final etching product SiF4 is formed with high probability in the gas phase. 相似文献
The evidence for the stabilizing nature of the H–H bonding in planar biphenyl is succinctly reviewed. The stabilizing nature
of the H–H bonding is revealed through a comparison of the atomic energy of every atom in planar biphenyl with the same atom
in the twisted equilibrium structure. It is shown that the barrier to rotation via the planar transition state is the net
resultant of a stabilisation of the four ortho-hydrogen atoms (by 8 kcal/mol each), a stabilisation of the two para-carbon atoms (by 3 kcal/mol each) and by the dominant destabilisation of the two carbon atoms joining the two rings—the two
junction carbon atoms—(by 22 kcal/mol each). The energetic stabilisation of the four ortho-hydrogen atoms is further shown to be in large proportion due to the formation of the hydrogen–hydrogen interatomic surface.
Furthermore, neither the “bond order” between the two junction carbon atoms nor the total electron delocalisation between
the two rings exhibit a significant change in going from the planar to the twisted equilibrium geometry. These findings are
in contrast with the classical view of a balance between “steric non-bonded repulsion” and better electron delocalisation
as a function of the twist dihedral angle. Similar conclusions have been recently reached by Pacios and Gómez through a study
of the electrostatic potential at the position of the hydrogen nuclei.
We dedicate this article to Professor TM Krygowski on the occasion of his 70th birthday wishing him a long and productive
life. 相似文献