Chiral Acylsilanes in Organic Synthesis. Part 2. The role of the solvent,the organometallic reagent,and the nature of the substrate for the diastereoselectivity of 1,2-additions to racemic alkoxymethyl-substituted acylsilanes

The role of the solvent, the organometallic reagent, and the nature of the substrate for the diastereoselectivity of 1,2-additions to racemic alkoxymethyl-substituted acylsilanes was investigated with the acylsilanes 1a–d by variation of the reaction parameters. The results obtained in this study support strongly the previously proposed preferred ‘chelate-controlled’ reaction path followed under several reaction conditions: highest stereoselectivities were obtained with the best chelating substrates reacting with the most Lewis-acidic organometallic reagents in the least donating solvents. It is shown that almost complete stereoselectivity can be obtained using optimal reaction conditions.     

有机磷化合物的研究 XXV: 溶剂性质对烯丙在膦酸酯碳阴离子和芳醛反应区域选择性的影响

本文研究烯丙基膦酸二乙酯碳阴离子和苯甲醛, 对甲基苯甲醛的反应, 考察了溶剂对反应区域选择性的影响.     

Kinetics and thermodynamics of the blocking reaction of several aliphatic isocyanates

The oxime-blocking reaction of several aliphatic isocyanates, such as 1,6-Hexane diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4′-diisocyanate (H₁₂MDI), is investigated. The reaction is carried on in various solvents that are divided into two categories: aromatic solvents and oxygen-contained solvents. In situ FT-IR is used to monitor the reaction and show the large difference of solvent and the structure of isocyanate. Kinetic studies indicate that the reaction rate appears faster in aromatic solvents although the polarity of aromatic solvents is lower. Then, thermodynamic parameters of the blocking reaction, such as activation energy (E_a), enthalpy (ΔH*) and entropy (ΔS*), are determined from the Arrhenius and Eyring equations. It is found that activation energy in aromatic solvents is higher, but the reaction rate is much faster, all of which are discussed corresponding to the reaction mechanism.     

Quantitative Evaluation of the Influence of Physicochemical Properties of Solvents on the Kinetics of Formation of Phosphorus-Containing Semicarbazides

The kinetics of the reaction of diphenylphosphinic acid hydrazide with phenyl isocyanate in various solvents at 25°C was studied. The results can be quantitatively correlated with the physicochemical characteristics of solvents using the four-parameter Koppel-Palm equation. This relationship allows quantitative analysis of the solvation effects. The decisive influence on the reaction rate is exerted by the basicity and polarity of solvents. The reaction mechanism is discussed, and the possible scheme of solvation is suggested.     

Enhancing the rate of the Diels-Alder reaction using CO2 + ethanol and CO2 + n-hexane mixed solvents of different phase regions

The reaction rate of the Diels-Alder reaction between N-ethylmaleimide and 9-hydroxymethylanthrance in CO2 + ethanol and CO2 + hexane mixed solvents of different compositions were determined by in situ UV/vis spectroscopy at 318.15 K and different pressures. The density of the mixed solvents at different pressures was also determined and the isothermal compressibility was calculated using the density data. The activation volume of the reaction was calculated based on the dependence of rate constant (kc) on pressure. It was demonstrated that the kc was very sensitive to the pressure in the mixed solvents near the critical region and the kc increased dramatically as pressure approached dew points, critical point, and bubble points of the mixed solvents. However, the kc in the mixed solvents outside the critical region or in pure CO2 was not sensitive to pressure. At suitable conditions, kc could be 40 times larger than that in acetonitrile. The activation volume of the reaction was nearly independent of pressure as the pressure was much higher than the phase separation pressure of the mixed solvents, while it increased considerably as pressure approached the bubble points, critical point, and dew points from high pressure. The clustering of the solvent molecules with the reactants and the activated complex in the reaction systems near the phase boundary in the critical region may be the main reason for the interesting phenomena observed. This work also shows that, using pure CO2 as the solvent, the reaction cannot be carried out in the critical region of the solvent due to the limitations of the reactants, while it can be conducted in the critical region of mixed solvents of suitable compositions, where the solvents are highly compressible and the reaction rate can be tuned effectively by pressure.     

Solvent-dependent changes in the ene reaction of RTAD with alkenes: the cyclopropyl group as a mechanistic probe

[reaction: see text] The vinylcyclopropyl moiety was used as an efficient probe to test mechanistic possibilities of the triazolinedione-alkene ene reaction. In non-hydroxylic solvents, this reaction afforded only the ene adducts via a closed three-membered aziridinium imide (AI) intermediate, whereas in hydroxylic solvents a dipolar intermediate is favored and trapped by the cyclopropyl moiety to form the corresponding cyclopropyl-rearranged solvent-trapped adducts.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXI. Solvent Effect on the Rate of 1-Methyl-1-chlorocyclopentane Heterolysis. Correlation Analysis of Solvation Effects

Heterolysis of 1-methyl-1-chlorocyclopentane in protic and aprotic solvents occurs by the E1 mechanism. The reaction rate in aprotic solvents or in a set of protic and aprotic solvents is satisfactorily described by the parameters of the polarity and electrophilicity or ionizing power of the solvents. In protic solvents, the reaction rate grows with increasing polarity or ionizing power of the solvent and decreases with increasing nucleophilicity.     

The influence of a medium on the rate of the reaction between N,N′-dioctylurea and <Emphasis Type="Italic">n</Emphasis>-octanol

The kinetics and mechanism of alcoholysis of symmetrical dioctylurea in inert solvents were studied. The reaction was found to follow two parallel pathways, one involving the destruction of initial urea and the other, bimolecular interaction. For the reaction series under consideration, the influence of the nature of solvents on the rate of the reaction was studied.     

磷酸铈对磷化镍催化苯酚转移加氢的促进作用

通过氢气原位程序升温还原法制备了一系列不同Ce/Ni摩尔比的CePO₄-Ni₃P及Ni₃P催化剂, 考察了其在苯酚催化转移加氢反应的催化性能. 研究了Ce/Ni摩尔比、 供氢溶剂、 反应温度和反应时间对催化剂性能的影响, 并初步考察了苯酚转移加氢的反应动力学. 研究结果表明, CePO₄的加入能显著提升体相Ni₃P催化苯酚转移加氢的转化率, 且Ce/Ni摩尔比为0.2时促进作用最显著; 在所考察的供氢溶剂中异丙醇展现出最好的性能; 使用CePO₄(0.2)-Ni₃P作为反应催化剂, 异丙醇作为供氢溶剂, 220 ℃下反应6 h, 苯酚转化率和环己醇选择性分别可达93.1%和92.0%.     

Experimental and theoretical studies on the isomerization of allyl thiocyanate to allyl isothiocyanate

The mechanism of isomerization of allyl thiocyanate to allyl isothiocyanate has been investigated both experimentally and theoretically. The kinetic study indicates that the reaction is unimolecular and is not ionic. The entropy of activation suggests strongly that the mechanism involves a cyclic transition state. The rate of reaction was retarded to a small extent in polar solvents relative to that in nonpolar solvents. Ab initio MO calculations indicate, in agreement with the experimental results, that the reaction proceeds through a cyclic transition state, one in which the SCN moiety is almost linear. Thus, this is a [3,3] sigmatropic rearrangement. The charge separation in the transition state was substantial. The retardation of the reaction in polar solvents was attributed to the difference in solvation in the original state and in the transition state. © 1997 John Wiley & Sons, Inc.     

Allylindation of cyclopropenes in organic and aqueous media: switching the regio- and stereoselectivity based on the chelation with a hydroxyl group and the crystal structure of the cyclopropylindium product

Hydroxy-bearing cyclopropenes react with allylindium reagents to undergo clean allylindation both in organic and aqueous media, in which the chelation of the hydroxyl group to indium plays the central role. The regio- and stereoselectivity have been regulated both by the location of the hydroxyl group in the molecules and the reaction solvents. In particular, the allylindation in water shows marked differences from that in organic solvents; the regio- and stereoselectivity have totally been reversed compared with those in organic solvents. Unusually stable cyclopropyl-indium compounds have been isolated from the reaction of 1-(omega-hydroxyalkyl)cyclopropenes and the structure has fully been established by X-ray crystallography.     

Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF_6

Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles. 1 Aryl allyl et…     

疏水作用对光化学和光物理过程的影响 Ⅹ. 非平面分子2,2’-联萘在促簇性溶剂中的簇集和激基缔合物的形成

激基缔合物是由一个激发态分子和一个基态分子形成的复合物,组成激基缔合物的两个分子平面必须彼此平行呈夹心面包式构型^[1]。在某些情况下,两个芳香环在基态时就呈激基缔合物的构型并有很强的相互作用,形成基态复合物一二聚体^[2,3]。人们对平面结构的芳香化合物分子形成的激基缔合物已经进行了大量研究,并且注意到非平面的芳香化合物分子很难形成激基缔合物^[4]。     

Application of pulse radiolysis to the study of the chemistry of radical anions

The application of pulse radiolysis to the measurement of rates of reaction of aromatic and olefinic radical anions in organic solvents is discussed, emphasis being placed on the problem of reaction of the radical anion with the radiolytically-generated-counter ion. Some previous experiments of the authors that utilised tetrahydridoaluminate salts to scavenge the counter ion are reviewed. Some new data on the rates of electron transfer from aromatic-radical anions to some substituted styrenes are presented and experiments aimed at using organic amides as solvents for these studies are described.     

Organic solvent-free, enantio- and diastereoselective, direct Mannich reaction in the presence of water

An organocatalyst-mediated, asymmetric Mannich reaction in the presence of water without using organic solvents has been developed. A highly reactive siloxytetrazole hybrid catalyst has been developed for the reaction of dimethoxyacetaldehyde, while the sodium salt of siloxyproline is an effective catalyst of alpha-imino glyoxylate. Excellent enantioselectivity can be realized, and the usage of organic solvents can be reduced compared to the conventional reactions in organic solvents.     

Reaction of hexadecafluorobicyclo[4.4.0]dec-1(6)-ene with diethylamine

The spectral characteristics of products formed in the reaction of an incompletely fluorinated impurity in perfluorodecalin, hexadecafluorobicyclo[4.4.0]dec-1(6)-ene, with amines in various solvents were studied. The reaction rates in various solvents were compared, and the distribution of the reaction products between perfluorodecalin and solvents was examined.     

On the Decarboxylation of Metal Trichloroacetates

The decarboxylation of trichloroacetate ion in basic solvents produces the intermediate trichlorocarbanion which may split into chloride and dichlorocarbene or combine with a proton to chloroform. Conditions under which protonation predominates were examined for possible use of the reaction for synthesizing metal compounds in non-aqueous solvents.     

Stereochemistry of the hydrogenation of o-xylene over a silica-supported polysilazane–platinum complex

Silica-supported polysilazane (SiO₂-Si-N), and its platinum complex (SiO₂-Si-N-Pt) were prepared. It was found that SiO₂-Si-N–Pt can catalyze hydrogenation of o-xylene under mild conditions (40–50°C, 1 atm). The products of the reaction were cis-and trans-1,2-dimethylcyclohexane. The formation of trans-1,2-dimethylcyclohexane may be adequately explained according to the ‘roll-over’ model. The stereoselectivity was influenced by temperature and catalyst concentration, the proportion of the cis isomer decreasing with an increase in each of the two factors. The effects of other reaction parameters, such as the N/Pt mole ratio in the complex, solvents and reaction time, etc. on the hydrogenation of o-xylene were also studied. The SiO₂-Si-N–Pt catalyst is very stable in reaction and turnover numbers amount to 200 in 80 hr.     

PVP-Pd催化剂六氯苯加氢脱氯中两种氢源的贡献

近年来,随着环境问题的日益突出,含卤有机化合物作为一类主要的环境污染物,其加氢脱卤反应的研究越来越多地受到人们的关注.     

硫碘循环制氢中Bunsen反应新方法的研究进展

热化学硫碘(S-I)循环分解水是目前有较高效率且可以在相对较低温度条件下进行的制氢方法之一。 其中的Bunsen反应作为循环的核心步骤尤为重要。 为了更方便有效地分离Bunsen反应的生成物硫酸与氢碘酸,许多学者研究了Bunsen反应的新方法。 本文对非水溶剂中的Bunsen反应和电化学Bunsen反应两种新方法进行了综述。 讨论了非水溶剂中实现反应生成物分离的方法,对比了各种非水溶剂的性质及其优缺点。 目前,所发现的溶剂在分离生成物方面已达到要求,可用于Bunsen反应,但溶剂的回收再利用比较困难。 概述了电化学Bunsen反应的研究现状,对目前在电化学Bunsen反应中有突破进展的两个团队的工作进行了对比。 现今对该方法的探讨主要集中在反应基础特性方面,未来可以加强电化学Bunsen反应机理、反应电池结构设计与优化、以及新型S-I循环系统构造的研究。