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1.
Georgiy B. Shul’pin Camilla C. Golfeto Lidia S. Shul’pina 《Tetrahedron letters》2005,46(27):4563-4567
The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60 °C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide. 相似文献
2.
3.
S. Stupnikova E. Petushkova D. Muceniece V. Lūsis 《Chemistry of Heterocyclic Compounds》2007,43(1):41-49
The recyclization of 1,4-dihydropyridines in aqueous-alcoholic hydrochloric acid medium proceeds with cleavage of a C-N bond
and pyridine ring opening. Cyclohexenone derivatives are formed as a result of the subsequent intramolecular crotonic condensation
of the acyclic intermediate. The leaving carbonyl substituents depart simultaneously with recyclization, depending on the
acidity of the reaction medium.
Dedicated to Prof. Dr. E. Lukevics on the occasion of his 70th birthday.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 49–58, January, 2007. 相似文献
4.
A simple new protocol for the high yielding Suzuki-Miyaura cross-couplings of aryl chlorides with aryl boronic acids using a palladium/imidazolium salt catalytic system is presented. The first examples of a palladium/imidazolium salt protocol for sp3-sp3 Suzuki-Miyaura couplings of alkyl halides are also disclosed. 相似文献
5.
Luigi Ambrosone Lucia Costantino Gerardino D'errico Vincenzo Vitagliano 《Journal of colloid and interface science》1997,190(2):286
The densities and viscosities of binary aqueous mixtures of poly(ethylenoxide)hexanols [C6H13(OCH2CH2)mOH, C6Em] (m= 3, 4, and 5) have been studied in the micellar composition range. For the same surfactants the self-diffusion coefficients in mixtures with heavy water have been determined by the spin-echo pulsed field gradient method. The volumetric data are interpreted by means of the phase separation model, and values of the CMC, volume change, and standard free energy change of micellization are obtained. From the viscosity data the hydration numbers of the surfactant hydrophilic head in the micellar state are computed; they are in agreement with those obtained from HDO self-diffusion data. The surfactant self-diffusion data are used to calculate the apparent micelle radius and the aggregation number. The micellization parameters obtained for the different surfactants are compared and discussed. 相似文献
6.
Mohamed R. Mahran Wafaa M. Abdou Maha D. Khidre 《Monatshefte für Chemie / Chemical Monthly》1990,121(1):51-58
Summary The reaction of furil (1) with trialkyl phosphites2 yielded caged phosphorane derivatives of types3a-c. Dry hydrogen chloride gas converted3a-c into the respectivea-hydroxyvinyl-phosphates8a-c which are equally produced by reacting furil with the appropriate dialkyl phosphite7. The reaction of furil with ylide-phosphoranes10 proceeded according to the Wittig reaction mechanism to give the respective ethylenes11a-c. The new compounds have been characterized by their spectroscopic data (IR, PMR,31P-NMR, MS) and elementary analyses.Dedicated to Prof. M. Sidky on the occasion of his 60th birthday 相似文献
7.
Summary A theoretical treatment is presented which considers differences between the composition of the mobile phase and solvents
that are incorporated into the bonded phase via preferential sorption. Equations are derived and used to analyze retention
data for various homologs chromatographed under reversed-phase conditions using alkyl bonded phases and combinations of water-methanol,
water-acetonitrile and watertetrahydrofuran as mobile phases. In the case of water-methanol the surface phase and bulk mobile
phase compositions are similar. However, significant differences in composition between the two phases are observed when binary
combinations of water-acetonitrile and water-tetrahydrofuran are used as the cluents. 相似文献
8.
以邻苯二胺为原料合成表征了一类喹喔啉衍生物;1-烷基-3-甲基-2(1H)-喹喔啉-2-酮(1-alkyl-3-methly-2(1H)-quinoxalin-2-one,简称AMQ,其中alky=H、CH3、Et、n-C3H5、n-C5H11、n-C16H33)。用电子轰击电离质谱(EI-MS)和核磁共振谱图(^1H-NMR)鉴定了AMQ,研究了不同取代基对这类化合物EI-MS谱图的影响,分析得到一些裂解规律。结果表明:所有样品谱图中均有芳香化合物的特征CnHn^ 系列峰m/z78,65,52,39和(或)m/z77、76、64、63、51、50、38、37。对于末取代的样品及低级烷烃取代的样品,谱图中的基峰为分子离子峰,对于取代基中碳数大于等于3的样品。谱图中的基峰不是分子离子峰,分子离子峰强度随着碳数的增加而降低。这些样品一般容易发生骨架重排,丢失一分子CO,生成1-烷基-2-甲基苯并哒唑正离子。此外,还讨论了谱图中其它的一些碎片离子峰。这对于研究和指导喹喔啉衍生物 的合成,探讨它们在药效及结构特征与生理活性的关系等方面具有重要的应用价值和理论意义。 相似文献
9.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
10.
The reaction of the tetramethylcyclopentadiene-silyl substituted derivative C5Me4(SiMe3)(SiMe2Cl) with MCl4 afforded the trichloro mono-tetramethylcyclopentadienyl complexes M(η5-C5Me4SiMe2Cl)Cl3 [M=Ti (1), Zr (2)] with selective elimination of SiMe3Cl. Compound 1 reacts with deoxygenated water in methylene chloride, with the evolution of HCl, to give the dinuclear titanium compound {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl2}2 (3), which was converted into the μ-oxo complex {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl}2(μ-O) (4) by a further hydrolysis reaction which occurred when a solution of 3 in toluene was refluxed for a long period of time in the air. Depending on the size of the alkyl ligand, reactions of the mononuclear compound 1 with an appropriate alkylating reagent rendered the peralkylated Ti(η5-C5Me4SiMe2R)R3 [R=Me (5), CH2Ph (6)] or partially alkylated {Ti[(η5-C5Me4SiMe2(CH2SiMe3)]Cl(CH2SiMe3)2} (7) compounds by a salt metathesis route. Attempts to synthesise a partially methylated or benzylated complex were unsuccessful. Treatment of the dinuclear compound 3 with four equivalents of MgClMe yielded the tetramethyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Me2}2 (8), while the same reaction carried out with MgCl(CH2Ph) or Mg(CH2Ph)2·2THF gave the chloro-benzyl derivative {Ti[μ-(η5-C5Me4SiMe2O-κO)]Cl(CH2Ph)}2 (9) as an equimolar mixture of diastereomers, regardless of the molar ratio of the alkylating reagent used. All of the new compounds were characterised by elemental analysis and NMR spectroscopy. 相似文献