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161.
162.
Stasch A Ferbinteanu M Prust J Zheng W Cimpoesu F Roesky HW Magull J Schmidt HG Noltemeyer M 《Journal of the American Chemical Society》2002,124(19):5441-5448
The reaction of the acetylene RC triple bond CH (R = Ph, CH(2)SiMe(3)) with an excess of AlH(3).NMe(3) in boiling toluene leads to the carbaalane [(AlH)(6)(AlNMe(3))(2)(CCH(2)R)(6)] (R = Ph 1, CH(2)SiMe(3) 2) in good yield. Treatment of 2 with BCl(3) under varying conditions gives the chlorinated products [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(3))(6)] 3 and [(AlCl)(6)(AlNMe(3))(2)(CCH(2)CH(2)SiMe(2)Cl)(6)] 4, respectively. The latter clearly demonstrates that the cluster can be stepwise functionalized within the inner and outer sphere. The X-ray single-crystal structures of 1, 2, and 4 have been determined. All compounds have in common that the central core consists of a cluster having eight aluminum and six carbon atoms. The bonding properties in this cluster are described as a new manifestation of three-dimensional surface aromaticity. Each Al(4)C fragment of the cube is formed by four bonds with three electron pairs, thus leading to a strong delocalization of the electrons. A phenomenological modeling using a three-dimensional Hückel scheme with fitted parameters to reproduce the energies from ab initio calculations revealed that the orbital scheme localized at one Al(4)C fragment possesses an orbital sextet with a large HOMO-LUMO gap. This is in line with the criteria of aromaticity. The idea of aromaticity was sustained also by qualitative valence bond reasons enumerating the different resonance structures by means of graph theoretical methods. 相似文献
163.
K. Wagner 《Angewandte Chemie (International ed. in English)》1970,9(1):50-54
Addition compounds of formic acid with tertiary organic bases in ratios higher than that required for salt formation (3:1 and 2:1 adducts) contain formic acid in a highly activated form. In particular, the 3:1 adducts of formic acid with trimethylamine and triethylamine are liquid reducing agents that are convenient to handle and are suitable for use in many selective reductions. These addition compounds have a surprisingly strong reducing action on sulfur dioxide, which is rapidly converted, even at low concentrations, into crystalline rhombic sulfur. Sulfones and polysulfones can be prepared in good yields by three-component reactions from activated formic acid, sulfur dioxide, and polarized vinyl compounds. 相似文献
164.
An approach based on on-line coupled liquid chromatography-gas chromatography (LC-GC) was developed for the rapid analysis of gamma-oryzanol in rice. Total lipids were extracted from rice and subjected to LC-GC without any prior purification. gamma-Oryzanol was pre-separated by HPLC from rice lipids and transferred on-line to GC analysis in order to separate its major constituents. 24-methylenecycloartanyl ferulate, cycloartenyl ferulate, campesteryl ferulate, beta-sitosteryl ferulate and campestanyl ferulate. The identities of the compounds were confirmed by off-line GC-MS analysis. Total gamma-oryzanol content could be quantified by HPLC-UV detection and the distribution of gamma-oryzanol constituents could be determined by on-line coupled GC analysis. The proposed methodology paves the way for high-throughput investigations providing information on natural variations in gamma-oryzanol content and its composition in different rice varieties. 相似文献
165.
Wang W Buchholz A Ivanova II Weitkamp J Hunger M 《Chemical communications (Cambridge, England)》2003,(20):2600-2601
A general method for the synthesis of quaternary ammonium cations in acidic zeolites by a direct reaction of tertiary amines and alcohols is described. 相似文献
166.
A micro determination for free uronic acids based on Tollens' reaction is proposed. Sources of error in earlier methods are avoided by the use of phosphoric acid, a reagent solution in glacial acetic acid, and extraction of the dye with toluene. Free glucuronic acid can be determined in presence of glucuronosides of the phenol-ether type up to molar ratios of ca. 1 : 5. Reliable results can also be obtained in the presence of other carbohydrates. 相似文献
167.
As supported PtxNi1–x catalysts are used for hydrogenation reactions, it seemed necessary to assess the surface composition of the reduced samples. To approach the usual reduction conditions we applied in situ reduction in a reaction chamber (1 mbar H2 up to 500 °C) placed in ultra high vacuum recipient (UHV: 10–9 to 2.10–10mbar). All ion scattering spectroscopy measurements were performed in UHV. Charging of the samples was avoided by electron bombardment (5 eV). The variation of the surface composition was determined after subsequent sputtering, thermal treatment at 500 °C and during oxygen adsorption. A comparison with previous results of surface compositions of binary alloys (polycrystalline foils [1, 2] and single crystals PtxNi1–x [3]) is given.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
168.
This work presents a study of the thermal
degradation of ultra-high molecular mass polyethylene (UHMWPE) stabilized
with natural (α-tocopherol and carvacrol) and synthetic antioxidants.
Thermogravimetric analysis in dynamic mode was used to determine the apparent
activation energies of different samples. The stabilization of UHMWPE with
low concentrations (around 0.3%) of α-tocopherol is enough to obtain
an efficient thermal performance of the polymer. Carvacrol is also a good
stabilizer for UHMWPE, but at higher concentration than in the case of α-tocopherol.
The comparison of apparent activation energy between samples with natural
and synthetic antioxidants in similar concentration shows that α-tocopherol
is a better stabilizer in terms of their thermal performance. 相似文献
169.
Wagner?M.?Teles Flávia?C.?Machado Carlos?A.?Montanari Carlos?A.?L.?FilgueirasEmail author Terence?C.?Jenkins 《Transition Metal Chemistry》2005,30(6):733-737
The mesoionic compound, 1,4,5-triazole-2-thiolate, is a versatile ligand, capable of binding metal centres in different ways. The present study shows how it reacts with the bridging platinum(II) complex μ-dichlorobis[(chlorotriethylphosphineplatinum(II)], [Pt2(PEt3)2Cl4], originating a bimetallic complex. Both the sulphur atom and nitrogen 3 behave as basic sites, coordinating different platinum centres. An interesting isomerization process, shown by 31P{1H} n.m.r. spectroscopy, occurs at the S-bonded platinum moiety, resulting in a fluxional behaviour of the complex. It is also shown to target CT-DNA with moderate binding affinity.To the memory of Dr. Wagner M. Teles (1971–2004). 相似文献
170.
It is possible directly to separate and analyse, quantitatively and qualitatively, the valepotriates from Valeriana crude extracts or from commercial Valeriana preparations by high-performance liquid chromatography. The separations are achieved on 4 or 8 mm I.D. columns packed with silica gel (particle size 10 micron) with n-hexane-ethyl acetate mixtures as eluent. A refractive index detection system is necessary for determining all of the valepotriates. If the concentration differences between didrovaltratum and valtratum are very great, an ultraviolet (UV) detector must be used and the determination must be conducted in two steps. For valtratum drugs UV detection alone will suffice. As internal standards p-dimethylaminobenzaldehyde should be used for extracts and preparations from valtratum races, and benzaldehyde in the presence of didrovaltratum races. This determination is superior to the combined thin-layer chromatographic-hydroxamic acid method used hitherto with respect to time consumption, precision, and sensitivity. 相似文献