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51.
溶剂对钯催化的叔丁基乙炔低聚反应化学选择性的调控作用 总被引:1,自引:0,他引:1
报道了溶剂对钯催化的叔丁基乙炔低聚反应化学选择性的调控作用. 反应可在苯-正丁醇双组分溶剂体系中顺利进行, 当双组分溶剂体系中苯占优势比例时, 反应发生递次的三分子炔烃顺式插入, 经由顺式s-烯钯中间体生成环三聚产物1,3,5-三叔丁基苯; 而当双组分溶剂中正丁醇组分上升至一定比例, 反应选择性生成(3Z,5Z)-2,2,7,7-四甲基-
3,6-二氯-3,5-辛二烯或(3Z,5Z)-2,2,7,7-四甲基-3,6-二溴-3,5-辛二烯, 这是由于正丁醇可显著加快C—Pd σ键的断裂, 并与叔丁基乙炔、σ-烯钯中间体形成弱氢键作用力, 同时也与Pd(II)和Cu(II)等离子存在配位效应. 在强极性质子溶剂H2O中, 反应生成偶联双炔: 2,2,7,7-四甲基-3,5-辛二炔. 文中就反应溶剂体系、钯铜催化剂及反应可能机理等分别进行了探讨. 相似文献
52.
53.
Takeshi Hanamoto Yuhko Iwamoto Kenji Yamada Ryoko Anno 《Journal of fluorine chemistry》2007,128(10):1126-1130
The 1,3-dipolar cycloaddition reaction of fluoro(trimethylsilyl)acetylene prepared in situ with an excess of diazomethane smoothly proceeded to give the corresponding 4-fluoro-5-trimethylsilyl-1H-pyrazole in 84% yield. The copper iodide-catalyzed N-arylation of the fluorinated pyrazole with a variety of aryl iodides afforded N-aryl-4-fluoropyrazoles as desilylation products in good to excellent yields. 相似文献
54.
Plasma Thermal Conversion of Methane to Acetylene 总被引:2,自引:0,他引:2
Fincke J. R. Anderson R. P. Hyde T. Detering B. A. Wright R. Bewley R. L. Haggard D. C. Swank W. D. 《Plasma Chemistry and Plasma Processing》2002,22(1):107-138
This paper describes a re-examination of a known process for the direct plasma thermal conversion of methane to acetylene. Conversion efficiencies (% methane converted) approached 100% and acetylene yields in the 90–95% range with 2–4% solid carbon production were demonstrated. Specificity for acetylene was higher than in prior work. Improvements in conversion efficiency, yield, and specificity were due primarily to improved injector design and reactant mixing, and minimization of temperature gradients and cold boundary layers. At the 60-kilowatt scale cooling by wall heat transfer appears to be sufficient to quench the product stream and prevent further reaction of acetylene resulting in the formation of heavier hydrocarbon products or solid carbon. Significantly increasing the quenching rate by aerodynamic expansion of the products through a converging–diverging nozzle led to a reduction in the yield of ethylene but had little effect on the yield of other hydrocarbon products. While greater product selectivity for acetylene has been demonstrated, the specific energy consumption per unit mass of acetylene produced was not improved upon. A kinetic model that includes the reaction mechanisms resulting in the formation of acetylene and heavier hydrocarbons, through benzene, is described. 相似文献
55.
L. I. Belen’kii A. V. Kolotaev V. Z. Shirinyan M. M. Krayushkin Yu. P. Strokach T. M. Valova Z. O. Golotyuk V. A. Barachevskii 《Chemistry of Heterocyclic Compounds》2005,41(1):86-92
The polar [4+2] cycloaddition reaction of 1,2-bis(2,5-dimethyl-3-thienyl)acetylene with thiobenzamide and certain aldehydes of the thiophene and furan series catalyzed by boron trifluoride etherate gives the corresponding 4-hetaryl-5,6-di(2,5-dimethyl-3-thienyl)-2-phenyl-4H-1,3-thiazines. The photochromic properties of the products have been studied.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 100–106, January, 2005. 相似文献
56.
E. T. Denisov 《Russian Chemical Bulletin》2005,54(4):914-923
Interatomic distances in the reaction centers of the addition reactions of (i) H· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ·CH3 radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined
using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the
type X· + Y=Z → X— Y—Z· the r
#
X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined
for seventeen classes of radical addition reactions. The bond elongation, Δr
#
X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the
reaction center, and the force constant of the attacked multiple bond increase.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005. 相似文献
57.
Yi Peng Junhui Xu Jia Zhao Bailin Hu Shengshui Hu 《Russian Journal of Electrochemistry》2008,44(2):206-212
The electrochemical response of phenol at acetylene black (AB)-dihexadecyl hydrogen phosphate (DHP) composite modified glassy
carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) was investigated. In this system, a sensitive oxidation
peak at 0.62 V (SCE) was obtained. The electrode process and the influence of CTAB on the oxidation of phenol were explored
by chronocoulometry and linear sweep voltammetry (LSV). Experimental conditions for the determination of phenol were optimized.
In the range of 5.0 × 10−7 to 1.2 × 10−5 M, the phenol concentration was linear with the oxidation peak current and the detection limit was found to be 1.0 × 10−7 M for 3 min accumulation. The method was applied for the determination of phenol in lake water and the results were satisfactory.
Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 222–229.
The text was submitted by the authors in English. 相似文献
58.
Harald Brand Peter Mayer Dr. Axel Schulz Prof. Dr. Thomas Soller Alexander Villinger 《化学:亚洲杂志》2008,3(6):1050-1058
In a new synthetic approach phenylcyanamide (Hpca) was synthesized by methylation of phenylthiourea followed by a basic work‐up. All products along the synthetic route have been fully characterized by means of NMR, IR, and X‐ray studies. The first structural report of neutral mixed crystals of phenylcyanamide containing monomeric and trimeric Hpca is presented. Examination of these intriguing mixed crystals revealed the formation of distinct layers of monomeric and trimeric Hpca. These layers are interconnected by weak hydrogen bonds. The trimer represents triphenylisomelamine, which readily isomerizes to the triphenylmelamine in the melt, in accord with computations at the B3LYP level, indicating an exothermic process (ΔH=?49.4 kcal mol?1). Pure trimeric Hpca (triphenylisomelamine) was obtained either by recrystallization of the mixed crystals from boiling water or by trimerization of monomeric Hpca in isopropanol for 12 h under reflux conditions. For comparison tritylcyanamide (Htca) and potassium phenylcyanamide as an [18]crown‐6 complex [K([18]crown‐6)pca] have been synthesized, and the solid‐state structures were determined using X‐ray diffraction techniques. The thermal behavior was studied by thermo‐analytical experiments. In agreement with the experimental results, computations predict an exothermic cyclotrimerization process for Hpca (ΔH=?41.3 kcal mol?1). 相似文献
59.
Formation of Acetylene in the Reaction of Methane with Iron Carbide Cluster Anions FeC3− under High‐Temperature Conditions 下载免费PDF全文
Dr. Hai‐Fang Li Li‐Xue Jiang Dr. Yan‐Xia Zhao Dr. Qing‐Yu Liu Ting Zhang Prof. Dr. Sheng‐Gui He 《Angewandte Chemie (International ed. in English)》2018,57(10):2662-2666
The underlying mechanism for non‐oxidative methane aromatization remains controversial owing to the lack of experimental evidence for the formation of the first C?C bond. For the first time, the elementary reaction of methane with atomic clusters (FeC3?) under high‐temperature conditions to produce C?C coupling products has been characterized by mass spectrometry. With the elevation of temperature from 300 K to 610 K, the production of acetylene, the important intermediate proposed in a monofunctional mechanism of methane aromatization, was significantly enhanced, which can be well‐rationalized by quantum chemistry calculations. This study narrows the gap between gas‐phase and condensed‐phase studies on methane conversion and suggests that the monofunctional mechanism probably operates in non‐oxidative methane aromatization. 相似文献
60.
S. A. Mitchenko T. V. Krasnyakova I. V. Zhikharev 《Theoretical and Experimental Chemistry》2008,44(5):316-319
We report the catalysis of the hydrochlorination of acetylene on the surface of dry K2PdCl4 subjected to prior mechanical activation in an atmosphere of acetylene or propylene. The stereochemistry of the reaction
corresponds to trans addition of the halogen and hydrogen atoms to the C-C triple bond. The hydrogen halide is the source
of the halogen atom in the reaction product. The mechanical activation of K2PdCl4, in contrast to the case of K2PtCl4, is also capable of activating the C-C double bond: propylene is hydrochlorinated under similar conditions to isopropyl chloride.
Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 44, No. 5, pp. 306–309, September–October, 2008. 相似文献