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991.
Samuel González-Mancebo Javier Lacadena Yolanda García-Alonso Jesús Hernández-Benito Emilio Calle Julio Casado 《Monatshefte für Chemie / Chemical Monthly》2002,133(2):157-166
Summary. Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of
the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction
was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO+/NO2H2
+ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron
donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly
by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.
Received July 13, 2001. Accepted (revised) September 18, 2001 相似文献
992.
(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric
acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures
of the ligand and its complexes have been established by i. r., 1H- and 13C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements. 相似文献
993.
Previous work on the electrochemistry of palladium in aqueous acid solution demonstrated the existence of two multilayer
hydrous oxide reduction peaks, one at ca. 0.24 V and another at ca. 0.55 V vs. RHE, plus the presence of a reversible active
surface state transition at ca. 0.24 V. In the present work with thermally activated palladium it was observed that, in agreement
with the hydrous oxide reduction behaviour of the system, there is a second active state transition at E≥ca. 0.45 V. In most of its reactions in aqueous acid solution, apart from its unusual capacity to absorb hydrogen, palladium
exhibits properties very similar to those of platinum; however, palladium seems to be more prone to dissolution and subsurface
oxygen formation. Also the premonolayer oxidation responses of these two metals are often different as the more active state
of the palladium surface is not as readily generated as that of platinum. The electrocatalytic properties of palladium, as
reported earlier, correlate quite well with the hydrous oxide and premonolayer oxidation behaviour of this electrode system.
Electronic Publication 相似文献
994.
Inmaculada Escorihuela Larry R. Falvello Milagros Tomás 《Journal of Cluster Science》2004,15(4):425-435
The reaction of the tetranuclear cyanide aquo complex [{Pt(CN)4Cu(bipy)(H2O)}2]· 2H2O with aqueous ammonia produces the new tetranuclear ammino-containing product [{Pt(CN)4Cu(bipy)(NH3)}2] (1), with terminal cyanide groups and with NH3 coordinated to the Cu atom. The distorted trigonal bipyramidal coordination about copper in 1 differs from the square-pyramidal coordination present in the starting material. The bipyridine ligand in 1 is nearly perpendicular to the tetranuclear core of the molecule, as opposed to its coplanar disposition in the aquo complex. The two platinum atoms of the tetranuclear core in 1 form Pt···Pt interactions of 3. 2390(8) Å with platinum atoms of neighboring molecules, producing an echelon-shaped supramolecular chain held together by staggered (CN)4Pt···Pt(CN)4 linkages, an aggregate structure which does not have a precedent in chemistry derived from the Pt(CN)4 building block. 相似文献
995.
Katalin Mészáros Szécsényi I. Esztelecki G. Pokol 《Journal of Thermal Analysis and Calorimetry》2007,89(3):829-833
In order to increase the nutrition value of bread, one of the most commonly used foodstuff all over the world, different additives
are used in bread processing. In this paper we describe the thermal changes in bread and that of with 0.5% crude soybean lecithin
additive. Their thermal stability has been investigated by TG, DSC and EGD methods. The thermal changes were also followed
of soy products, lecithin and lysine, ingredients used as bread additives in order to check if they may suffer any thermal
degradation during the baking process. The data obtained can be of use only for qualitative conclusions. According to the
obtained data at the usual bread baking temperature only the additives in crust may partly decompose while in the crumb, at
lower temperatures the additives, due to baking, are not damaged. The thermal methods give a possibility for rapid estimation
of processes induced by heat effects in additives during the baking, and they are suitable to detect the changes during the
bread-making procedure. However, they are neither suitable to provide any quantitative data on these changes nor facts affecting
the nutrition value and of the bread. 相似文献
996.
The photoluminescence properties of xZnO–(100−x)SiO2 (x = 0, 5, 10, 20) containing 1% Eu2O3 prepared by a sol–gel method were systematically investigated. The results indicated that the relative proportion of f–f transitions to charge transfer (CT) absorption decreased with the increase of ZnO concentration. The intensity of 5D0–7FJ transitions of Eu3+ ions was enhanced with the increase of ZnO content due to local structure changes and decreased quantities of Eu3+ ions clusters. The results of fluorescence line narrow (FLN) spectra indicated that Eu3+ ions occupied one site in SiO2 glass and two sites in ZnO–SiO2 glasses. The second-order crystal field parameters were calculated. B20 and B22 for site 1 increased with excitation energy, while ones hardly changed for site 2. 相似文献
997.
Four new triphenylgermylruthenium carbonyl compounds HRu(CO)4GePh3, 14; Ru(CO)4(GePh3)2, 15; Ru2(CO)8(GePh3)2, 16; and Ru3(CO)9(GePh3)3(μ-H)3, 17 were obtained from the reaction of Ru(CO)5 with Ph3GeH in hexane solvent at reflux, 68 °C. The major product 14 was formed by loss of CO from the Ru(CO)5 and an oxidative addition of the GeH bond of the Ph3GeH to the metal atom. This six coordinate complex contains one terminal hydrido ligand. Compound 15 is formed from 14 and contains two trans-positioned GePh3 ligands in the six coordinate complex. Compound 16 contains two Ru(CO)4(GePh3) fragments joined by an Ru–Ru single bond. Compound 17 contains a triangular cluster of three ruthenium atoms with three bridging hydrido ligands and one terminal GePh3 ligand on each metal atom. When heated to 125 °C, 14 was converted to the new triruthenium compound Ru3(CO)10(μ-GePh2)2, 18. Compound 18 consists of a triangular tri-ruthenium cluster with two GePh2 ligands bridging two different edges of the cluster and one bridging CO ligand. Ru3(CO)12 was found to react with Ph3GeH at 97 °C to yield three products: 15, and two new compounds Ru3(CO)9(μ-GePh2)3, 19 and Ru2(CO)6(μ-GePh2)2(GePh3)2, 20 were obtained. Compound 19 is similar to 18 having a triangular tri-ruthenium cluster but has three bridging GePh2 ligands, one on each Ru–Ru bond. Compound 20 contains only two ruthenium atoms joined by a single Ru–Ru bond that has two bridging GePh2 ligands and a terminal GePh3 ligand on each metal atom. All compounds were characterized by a combination of IR, 1H NMR, single-crystal X-ray diffraction analyses.
This report is dedicated to Professor Dieter Fenske on the occasion of his 65th birthday for his many pioneering contributions
to the chemistry of metal chalcogenide cluster complexes. 相似文献
998.
999.
Stable oxygen isotopic compositions of a coral colony ofPorites lutea obtained on a core allowed the reconstruction of a 56-a (1943–1998) proxy record of the sea surface temperatures. This coral δ18O data are from the east of Hainan Island water (22°20’N, 110°39’E), South China Sea. The relationship between δ18O in the skeletal aragonite carbonate and the sea surface temperature (SST) is SST = -5.36 δ18OPDB-3.51 (r = 0.73,n = 470), dδ18O/d(SST) = -0.187?/ °C; and the thermometer was set at monthly resolution. The 56-a (1943–1998) proxy record of the sea surface temperatures reflected the same change trend in the northern part of South China Sea as the air temperature change trend in China. 相似文献
1000.
Peter Gajdoš Soňa Pavlíková Filip Bureš Alžbeta Krutošíková 《Central European Journal of Chemistry》2005,3(2):311-325
The synthesis and reactions of methyl 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole-5-carboxylate (1a) are described. Upon reaction with methyl iodide, benzyl chloride, or acetic anhydride, this compound gave N-substituted products 1b-d. By hydrolysis of compounds 1a-c, the corresponding acids 2a-c were formed, or by reaction with hydrazine-hydrate, the corresponding carbohydrazides 3a-c were formed. By heating 2-[3-(trifluoromethyl)phenly]-4H-furo[3,2-b]pyrrole-5-carboxylic acid (2a) in acetic anhydride, 4-acetyl-2-[3-(trifluoromethyl)phenyl]furo[3,2-b]pyrrole (4) was formed. By hydrolysis of 4, 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole (5a) was formed, and reactions with methyl iodide or benzyl chloride gave N-substituted products 5b-c. The reaction of 4 with dimethyl butynedioate gave substituted benzo[b]furan 6. Compound 3a reacted with triethyl orthoesters giving 7a-c, which afforded with phosphorus (V) sulphide the corresponding thiones 8a-c. The thiones 8a-c reacted with hydrazine hydrate to form hydrazine derivatives 9a-c. The reaction of triethyl orthoformiate with compounds 9a-c led to furo[2′,3′: 4,5]pyrrolo[1,2-d][1,2,4]triazolo[3,4-f][1,2,4]triazines 10a-c. Hydrazones 11a-c were formed from 3a-c and 5-[3-(trifluoromethyl)phenyl]furan-2-carboxaldehyde. The effect of microwave irradiation on some condensation reactions
was compared with “classical” conditions. The results showed that microwave irradiation shortens the reaction time while affording
comparable yields. 相似文献