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121.
K3 [Fe(CN)6] and KFe[Fe(CN)6] are classical coordination compounds. However, the mechanism of decomposition reactions has not been well expounded. The gas products of thermal decomposition were examined by gas chroma tography (GC) , and the structure of the solid products by Mossbauer spectroscopy(MS) and X-ray diffraction(XRD). The findings are explained in terms of the theory of coordination chemistry and a decomposition mechanism is proposed in this study. On the basis of various experimental results, the first stage of the decomposition of K3[Fe(CN)6] in He was found to be the evolution of(CN)2 resulting in the reduction of Fe(Ⅲ)12K3 [Fe(CN)6]→9K4[Fe(CN)6] + Fe2 [Fe(CN)6] + 6 ( CN )For KFe [Fe(CN) 6 ], the first stage of decomposition man be represented as6KFe[Fe(CN)6]→3K2Fe[Fe(CN)6] + 2Fe2[Fe(CN)6 + 3(CN)2At higher temperatures, the decomposition of both K3[Fe(CN)6) andKFe[Fe(CN)6] to form KCN and Fe2C was accomplished by the release of(CN)2 and N2. 相似文献
122.
V. N. Odinokov G. Yu. Ishmuratov R. Ya. Kharisov E. P. Serebryakov G. A. Tolstikov 《Russian Chemical Bulletin》1993,42(1):100-101
A novel path toS-(+)-hydroprene (1) starting from the technical gradeS-(+)-dihydromyrcene (2, e.e. 50%) is proposed. The latter was selectively transformed intoS-3,7-dimethyloctanal (5) in three steps including hydroalumination. The reactions of5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl2/CuCl or by ozonolysis, affordS,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in 23% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 110–112, January, 1993. 相似文献
123.
3-O-Acetyl-1,2-O-isopropylidene--D-allofuranose (2 b) was prepared from 1,2:5,6-di-O-isopropylidene--D-allofuranose (1 b). Treatment of2 b with triphenylphosphine-diethyl azodicarboxylate afforded regio- and stereospecifically the 5,6-epoxy--D-allo derivative (3). The other diastereomeric compound, 5,6-epoxy-1,2-O-isopropylidene--L-talofuranose (6) was also prepared stereoselectively from2 b
via the intermediates5 a and5 b. The epoxy sugars3 and6 were converted with lithium aluminum hydride to the corresponding 6-deoxy-1,2-O-isopropylidene--D-allofuranose (4 a) and --L-talofuranose (7 a) derivatives. Hydrolysis of4 a and7 a afforded 6-deoxy-D-allose and 6-deoxy-L-talose, respectively. The corresponding 3,5-di-O-acetyl- (4 b and7 b) and the 3,5-O-(tetraisopropyldisiloxane-1,3-diyl) derivatives (4 c and7 c) are also described. Selective removal of the isopropylidene group and subsequent acetylation offers a convenient route to prepare sugar derivatives containing furanose ring, like8 b, as a suitable precursor for nucleoside analogs.Herrn Prof. Dr.K. Komarek mit den besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
124.
A model has been developed to describe the chemistry which occurs in SF6/O2 plasmas and the etching of silicon in these plasmas. Emphasis is placed nn the gas-phase free radical reactions, and the predictions n( the model are compared with experimental results. Forty-seven reactions are included, although a subset of 18 reactions describes the chemistry equally well. Agreement between the calculated and measured concentrations of stable products downstream of the plasma is better than a factor of 2. The need for additional kinetic data and fàr well-characterized diagnostic studies of SF6/O2 plasmas is discussed. 相似文献
125.
N. Ya. Grigorieva 《Russian Chemical Bulletin》2005,54(4):1046-1047
High (Z)-stereoselectivity of olefination of methyl α-phenylthioalkyl and methyl α-phenylthioalkenyl ketones with methyl trimethylsilylacetate
decreases in the case of ketones containing a higher alkyl-substituent in place of the methyl group.
Dedicated to Corresponding Member of the Russian Academy of Sciences E. P. Serebryakov on the occasion of his 70th birthday.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 1020–1021, April, 2005. 相似文献
126.
A chiral stationary phase (CSP) based on (-)-(18-crown-6)-2,3,11,12-tetracarboxylic acid was evaluated for the direct resolution of the enantiomers of dipeptides and tripeptides. The type and concentration of the acid and the methanol content were optimized with regard to retention time and resolution using Ala-Phe as model peptide. A mobile phase consisting of 10 mM sulfuric acid in 70% aqueous methanol was applied to the separation of a set of 16 structurally diverse dipeptides and tripeptides. Generally, the configuration of the amino acid at the N-terminus determined the enantiomer elution order. With a few exceptions the LL- and LD-enantiomers interacted stronger with the CSP compared to the corresponding DD- or DL-enantiomers. The experimental conditions also allowed the simultaneous separation of all four stereoisomers of Ala-Phe. Addition of ammonium sulfate generally reduced retention times and enantiomer resolution. Addition of triethylamine as modifier led to an overall increase of the retention times while the resolution did not show a general trend, increasing in the case of Ala-Ala but decreasing in the case of Ala-Phe. 相似文献
127.
Facile synthesis of 6(E)-geranylgeraniol-19-oic acid 1,a naturally occurring alicyclic diterpene acid, by a Horner-Wadsworth-Emmons olefination of two readily available fragments 2 and 3,is described. 相似文献
128.
Moni Chauhan Claude Chuit Robert J. P. Corriu Catherine Rey Jean-Paul Declercq Antoine Dubourg 《Journal of organometallic chemistry》1996,510(1-2):173-179
The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the
program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects. 相似文献
129.
Roman Luboradzki Janusz Lipkowski Yurii A. Simonov Marina S. Fonari Edward V. Ganin Arkadii A. Yavolovskii 《Journal of inclusion phenomena and macrocyclic chemistry》1995,23(3):181-193
An X-ray—diffraction study is reported for two molecular complexes containing 3,4-diamino-1,2,5-oxadiazole as guest (G) with 18-crown-6 (18-C-6) andcis-anti-cis-dicyclohexano-18-crown-6 (DCH-6B) as host. Both complexes are of the polymeric-chain structure with the guest molecule bridging two crown neighbours. ComplexI: [18-C-6*G*H2O], 111, monoclinic,P21/n,a=8.171(1),b=15.042(2),c=16.209(6) Å, =101.15(2)°, finalR-factor 0.068. ComplexII: [DCH-6B*G], 11, monoclinicC2/c,a=21.212(4),b=9.380(2),c=13.049(3) Å, =108.61(3)°, finalR 0.047. 相似文献
130.
Riccardo d'Agostino Vincenzo Colaprico Francesco Cramarossa 《Plasma Chemistry and Plasma Processing》1981,1(4):365-375
The spectroscopic emission intensities from excited F atoms in SF6-O2 discharges at 1 torr have been correlated to the densities of atoms in their ground electronic state by measuring the excitation efficiencies of the electrons in the energy range 11 to 17 eV with a method which essentially consists in the analysis of the emission of Ar or N2, added as actinometer gases to the discharge mixtures. The general applicability of the method has been tested by a direct titration of F atoms with chlorine. The spectroscopic analysis has allowed the determination of useful information on the trends of both the electron densities and their energies as a function of the oxygen percent in the feed. 相似文献