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101.
The electron impact mass spectra of the 4-formyl-1, 3-dihydro-2H-imidazole-2-thione, its six 1-methyl(n-propyl, n-hexyl)-3-methyl(phenyl)-disubstptuted derivatives, and the 1,3-dihydro-1-phenyl-2H-imidazole-2-thiome are discussed. The fragmentation pattern is strongly influenced by the alkyl or phenyl N-substituents, as well as by the length of the alkyl chain. The odd-electron ions containing an N-phenyl substituent, but not a propyl or hexyl group, eject a hydrogen atom from the phenyl ring, while the presence of a long alkyl chain greatly enhances the loss of the sulphyhydryl radical and facilitates the expulsion of several alkenes, and alkyl and alkenyl radicals. 相似文献
102.
α-(N-Carbamoyl)alkylcuprates [R2CuLi·LiX or RCuXLi (X=CN, Cl)] when prepared from THF soluble CuX·2LiCl (X=Cl, CN) undergo a reliable and generally high yield reaction with aroyl, alkanoyl, and alkenoyl chlorides to provide a rapid and efficient synthesis of α-carbamoyl ketones. Cuprates prepared from acyclic, cyclic, and a functionalized carbamate can be utilized. Although yields are a function of cuprate reagent and substrate structure, nearly quantitative yields can be obtained with reagents generated from 2RLi+CuCN·2LiCl. The use of reagents generated from CuCl·2LiCl are more efficient in the α-(N-carbamoyl)alkyl ligand, although yields are slightly lower. Acylation of alkyl(chloro)cuprates generated from one equivalent of CuCl·2LiCl and organolithium or Grignard reagents provides an efficient and high yield procedure for ketone synthesis. 相似文献
103.
V. Balek L. A. Pérez-Maqueda J. Poyato Z. Černý V. Ramírez-Valle I. M. Buntseva J. L. Pérez-Rodríguez 《Journal of Thermal Analysis and Calorimetry》2007,88(1):87-91
The effect of grinding
on thermal behavior of pyrophyllite and talc as commonly used ceramic clay
minerals was investigated by DTA, TG, emanation thermal analysis (ETA), B.E.T.
surface area (s.a.) measurements, X-ray diffraction (XRD) and scanning electron
microscopy (SEM).
A vibratory mill was used in this study, grinding
time was 5 min. It was found that the grinding caused an increase in surface
area and a grain size reduction of the samples. From TG and DTA results it
followed that grinding caused a decrease of the temperature at which the structure
bound OH groups released. The formation of high temperature phases was enhanced
with the ground samples. For the ground talc sample the crystallization of
non-crystalline phase into orthorhombic enstatite was observed in the range
of 800°C. For ground pyrophyllite a certain agglomeration of grains was
observed in the range above 950°C. Moreover, for both clays the ETA characterized
a closing up of subsurface irregularities caused by grinding as a decrease
of the emanation rate in the range 250–400°C. The comparison of
thermal analysis results with the results of other methods made it possible
to better understand the effect of grinding on the ceramic clays. 相似文献
104.
Ram C. Maurya Dinesh C. Gupta Rajesh Shukla Raj K. Shukla Nalmas Anandam Mannar R. Maurya 《Transition Metal Chemistry》1986,11(12):463-464
Summary A new series of cyano-substituted nitrosylchromium(I) complexes having octahedral stereochemistry around the metal ion, and of general formula, [CrNO(CN)2(L)2(H2O)] (L =o-,m- andp-phenetidines oro-,m-, andp-anisidines) have been isolated in the solid state by interaction of potassium pentacy-anonitrosylchromate(I) monohydrate with the appropriately substituted aniline. The complexes, which have been characterised by elemental analysis, conductance, molecular weight determination, magnetic measurements, e.s.r. and i.r. spectral studies, contain chromium(I) in a low-spin d5-configuration. 相似文献
105.
Balderas-Hernández P Rojas-Hernández A Galván M Ramírez-Silva MT 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):569-577
The detailed analysis of the experimental spectrophotometric data obtained from solutions containing the acid-base indicator thymol blue (TB) and mercury(II) (Hg(II)) coupled with data processing by means of the SQUAD program, a chemical model was determined that includes the formation of complexes indicator-metal ion (HgTB and HgOTB), dimer species (H3TB2 and H4TB2) and monomer species (HTB and TB). The values of the overall formation constants (log beta) were calculated for the chemical equilibria involved: TB+Hg<-->HgTB log beta=16.047 +/- 0.043, TB+Hg+H2O<-->HgOHTB+H log beta=7.659 +/- 0.049, 2TB+4H<-->H4TB2 log beta=31.398 +/- 0.083, 2TB+3H<-->H3TB2 log beta=29.953 +/- 0.084 and H+TB<-->HTB-log beta=8.900. To compliment the present research, the values of the absorptivity coefficients are included for all the species involved, within a wide range of wavelengths (250-700 nm). The latter were used subsequently to carry simulations of the absorption spectra at various pH values, thus corroborating that the chemical model proposed is fully capable to describe the experimental information. Voltammetric study performed evidenced the formation of a complex with a 1:1 stoichiometry Hg(II):TB. 相似文献
106.
Mixed valency in the high-temperature phases of transition metal molybdates, A MoO4 ( A =Fe, Co, Ni)
Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods
shows that the phase transition is associated with a valence change of the typeA
2++Mo6+αA
3++Mo5+ in the cases of iron and cobalt molybdates.
Contribution No. 311 from the Solid State and Structural Chemistry Unit. 相似文献
107.
Ramón Serrano Roberto Gaxiola Gabino Ríos Javier Forment Oscar Vicente Roc Ros 《Monatshefte für Chemie / Chemical Monthly》2003,11(3):1445-1464
We have performed functional genomics of salt stress by overexpression of gene libraries in yeast and selection for salt tolerance. Thirty halotolerance genes were isolated from yeast, Arabidopsis, and sugar beet. The results indicate that Na+ transport (uptake, efflux, and compartmentation), sulfate activation, RNA processing, and protein synthesis are crucial for salt tolerance. 相似文献
108.
Submerged culture fermentation studies were carried out in batch mode for optimizing the environmental parameters and carbon
source requirement by Pseudomonas elodea for the production of gellan gum. The maximum production of gellan gum was obtained with 16-h-old culture and 8% inoculum
at 30°C and pH 7.0 after 52 h of incubation (6.0 g/L). Of the various carbon sources tested, 2% sucrose, glucose, and soluble
starch yielded considerably high amounts of gellan. Studies on the concentration of various carbohydrates on gellan gum production
indicated that the optimum concentration of glucose and starch was 3%, whereas for sucrose it was 4%. The addition of glucose
in the medium above 3% had a detrimental effect on gellan yield. The investigation of intermediate two-step addition of glucose
under identical conditions of fermentation showed an enhanced production of gellan (8.12 g/L) as compared with the control
(6.0 g/L). To optimize the recovery of gellan from fermented broth, different solvents were tested for precipitation of gellan
gum. Among the various solvents tested, tetrahydrofuran gave better recovery of gellan (82%) as compared with the conventional
solvent isopropanol (49%). 相似文献
109.
Arturo Battaglia Eleonora Baldelli Gabriele Fontana Andrea Guerrini 《Tetrahedron》2005,61(32):7727-7745
The base induced deprotonation of H-14 of 7-triethylsilyl- (7-TES-) and 7-tert-butoxycarbonyl- (7-BOC-) protected 13-oxo-baccatins gave the corresponding enolates, which were selectively aminated with electrophilic nitrogen donors, such as azodicarboxylates and tosyl azide. In particular, tosyl azide gave the corresponding 7-BOC- and 7-TES-13-oxo-14β-azido-baccatin III. Alternatively, the last compound was prepared via NaN3 induced azidation of the 13-silyl enol ether of 7-TES-13-oxo-baccatin III under oxidative (cerium ammonium nitrate) conditions. The 13-silyl enol ether was obtained in a multistep process by DBU induced silylation of 7-TES-13-oxo-baccatin III. The 7-TES-13-oxo-14β-azido-baccatin III was used as a key intermediate for the synthesis of a new family of antitumour taxanes containing amino based functional groups at the C-14 position, such as: 14β-azido, 14β-amino, 14β-amino 1, 14-carbamate, 14β-amino 1, 14-thiocarbamate, and 14β-amino N-tert-butoxycarbonyl-1,14-carbamate. 相似文献
110.
Carlos Rodríguez-Abreu Massimo Lazzari Dharmesh Varade Masaya Kaneko Kenji Aramaki Manuel Arturo López Quintela 《Colloid and polymer science》2007,285(6):673-680
The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations
in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates
that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer
in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside
the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally,
viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles
with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent;
namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献