超强酸催化2-芳基-1,3-二氧环己烷与芳烃的Friedel-Crafts反应(Ⅰ)

研究了２－芳基－１， ３－二氧环己烷与苯的超强酸催化Ｆｒｉｅｄｅｌ－Ｃｒａｆｔｓ反应，

溴化[2—(5—己基—1,3—二氧环己烷——2—基)乙基]三乙基铵的合成<英>

以1—溴己烷,丙二酸二乙酯和丙烯醛为原料,经五步反应首次合成了溴化[2—(5—己基—1,3—二氧环己烧—2—基)乙基]三乙基铵(h).

2,5-二氧-1,4-环己烷二甲酸二甲酯合成工艺研究

采用过量的丁二酸二甲酯作为反应溶剂 ,以甲醇钠与丁二酸二甲酯合成 2 ,5 二氧 1,4 环己烷二甲酸二甲酯的合成工艺 ,研究了原料配比、反应温度及反应时间对产品收率的影响。在n(丁二酸二甲酯 )∶n(甲醇钠 ) =4 3∶1 0、反应温度 10 0℃及回流反应时间 2 5～ 30min的最佳合成工艺条件下 ,得到质量分数为 97 5 %的 2 ,5 二氧 1,4 环己烷二甲酸二甲酯 ,以甲醇钠计其收率为 88 1%。

3,5-二羟基苯甲酸转移加氢制备-3,5-二氧代环己烷羧酸

以3,5 二羟基苯甲酸为原料,采用Pd/C〔w(Pd)=5%〕催化剂,通过转移加氢法合成了3,5 二氧代环己烷羧酸。考察了适宜的催化剂制备及反应条件:浸渍制备的PdCl2/C经氢气还原,以甲酸钠为氢供体,水作溶剂,在90℃下反应2h,经HPLC分析得3,5 二氧代环己烷羧酸的收率为95%。得到的3,5 二氧代环己烷羧酸粗产物经柱层析分离得到纯品,并以1HNMR和元素分析法进行确证。催化剂经过XRD表征,确认了活性组分是原子态的Pd。并对催化剂失活原因做了初步分析。

3,5-二氧代环己烷羧酸乙酯的合成方法改进

以3,5-二羟基苯甲酸为原料,经Pd／C[w(Pd)=5%]催化转移加氢合成3．5-二氧代环己烷羧酸, 然后酯化生成3-乙氧基-5-乙氧羰基-2-环己烯酮,最后水解得到3,5-二氧代环己烷羧酸乙酯。各产物通过1HNMR 和GC-MS得以确认。

超强酸催化2—芳基—l,3—二氧环已烷与芳烃的FriedeL-Crafts反应

研究了 2—芳基—l,3—二氧环己烷与苯的超强酸催化Friedel-Crafts反应 。

调环酸钙的合成工艺

以顺丁烯二酸二乙酯、乙醇钠、丙酰氯和三乙胺为原料,经4步反应,合成3,5-二氧代-4-丙酰基环己烷羧酸钙(调环酸钙),产品经核磁、质谱检验,产物收率为56.6%,纯度大于95%。该合成工艺具有原料廉价易得、反应条件温和、对环境污染小、中间体纯度和收率高的特点,具有工业应用价值。

Synthesis and Crystal Structure of t he Complex of Antimony Trichloride and Dioxane

New solid complex of the antimony trichloride and dioxane was obtained th rough a reaction of the dioxane and the absolute methanol solution of the antimony trichloride.The formula of the complex is[SbCl_(3)·{(CH_(2))_(4)O_(2)}_(1.5)].The crystal structure of the comple x belongs to cubic system,space group I-43d,a=17.1417(5)?,Z=16.The trivalent antimony ion not only bonds directly to three chlorine anions,but also is co ordinated by three oxygen atoms of th e dioxane molecules.Two oxygen atoms in a dioxane molecule wi ll coordinate to different antimony ions,respectively.

Study on Synthesis, Characterization and Catalytic Activity of Polystyrene-supported Mo (VI) Complex in Epoxidation of Cyclohexene

Molybdenum (VI) complex, namely molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] used as epoxidation catalyst species, was synthesized and characterized by elemental analysis and infrared spectrum. Polystyrene-supported molybdenum dioxobis(2,4-pentanedione) [MoO2(acac)2] for synthesis of epoxycyclohexane was prepared by phase transfer catalysis method. Effects of various factors in synthesis of epoxycyclohexane by reaction of cyclohexene and t-BuOOH in the atmosphere of nitrogen catalyzed by polystyrene-supported MoO2(acac)2 were also investigated. Under the following conditions, n(cyclohexene):n(t-BuOOH)=3.5:l (based on 0.1 mol of t-BuOOH), volume of solvent -10ml, reaction temperature -80℃, reaction time -60min, and mass of molybdenum in the catalyst -2.30×0^(-3)g, the yield of epoxycyclohexane on the basis of t-BuOOH is over 99.5%, and the purity of epoxycyclohexane is about 99.9% by gas chromatogram(GC) analysis.

Recent advances on controllable and selective catalytic oxidation of cyclohexene

Because of multiple potential reaction sites and variable oxidation depths,oxidation of cyclohexene can lead to a mixture of products with different oxidation states and functional groups,such as 7-oxabicyclo[4.1.0]heptane,trans/cis-cyclohexane-1,2-diol,cyclohex-2-en-1-ol,cyclohex-2-en-1-one,and even adipic acid.These products are broadly and abundantly used intermediates in the chemical industry;therefore,controllable oxidation reactions for cyclohexene that can selectively afford the targeted products are synthetically valuable for applications in both the academy and industry,thus becoming the aim of synthetic and catalytic chemists in the field.Many reports on selective oxidation of cyclohexene have recently appeared in the literature because of its significance.This short review summarizes the recent advances on this subject,and the contents are mainly classified based on the chosen oxidants.We hope that this review can provide a useful guide for controllable and selective catalytic oxidation of cyclohexene for interested readers from both the academy and industry.

Degradation of 1,4-Dioxane Using Ozone Oxidation with UV Irradiation （Ozone/UV） Treatment

A method for oxidative degradation of 1,4-dioxane （1,4-D） in waste water using a combination of ozone oxidation with UV irradiation （ozone/UV） treatment was investigated. The results showed that 1,4-D was degraded by ozone/UV treatment up to 90 min. The optimum concentration for the injected ozone gas was about 40 g·m^3 under a constant level of UV irradiation. Furthermore, solid phase extraction and GC-MS analysis showed no specific or reproducible peaks due to by-products of 1,4-D. It was therefore concluded that 1,4-D was completely degraded by ozone/UV treatment. In contrast, the amount of 1,4-D remaining decreased slowly in the presence of HCOf or CI. It was suggested that the degradation of 1,4-D, which results from .OH oxidation, was retarded by the presence of HCO3 or CI, which act as radical scavengers.

Measurement and Correlation of Vapor-Liquid Equilibrium of the 1,2-Epoxycyclohexane-Cyclohexanone Binary System at 101.3kPa

Many by-products are generated in the process of oxidizing cyclohexene to produce 1,2-epoxycyclohexane by hydrogen peroxide, including cyclohexanol, cyclohexanone, etc. To obtain high-purity 1,2-epoxycyclohexane, the by-products must be removed through rectification. Refining 1,2-epoxycyclohexane through rectification requires vapor-liquid equilibrium(VLE) data of the related system. Therefore, the VLE data of 1,2-epoxycyclohexane- cyc-lohexanone system were measured at 101.3 kPa using an improved EC-2 VLE still. The thermodynamic consistency of the data was then tested by Herington's method and the rigorous point-to-point method. The results obtained were exemplary. The VLE data were correlated by the Wilson and non-random two-liquid(NRTL) equations, using the error sum squares of the vapor composition as the objective function to obtain the model parameters. The difference between the calculated values and the experimental data is minor, indicating that the VLE data are suitable for engineering design.

Measurement and Correlation of Vapor-Liquid Equilibrium for a Cyclohexene-Cyclohexanol Binary System at 101.3 kPa

Many by-products are generated in the process of oxidizing cyclohexene to produce 1,2-epoxycyclohexane by hydrogen peroxide,including cyclohexanol,cyclohexanone,etc.To obtain high-purity 1,2-epoxycyclohexane, the by-products and unreacted cyclohexene must be removed through rectification,in which the vapor-liquid equilibrium(VLE)data of the system are needed.In this study,the VLE data of cyclohexene-cyclohexanol system were studied at 101.3 kPa using an improved EC-2 VLE still.The thermodynamic consistency of the data was examined by Herington's method.The results obtained were exemplary.The VLE data were correlated by the Wilson equation. The difference between the calculated values and the experimental data is minor,indicating that the VLE data are suitable for engineering design.

Measurement and Correlation of Vapor-Liquid Equilibrium for Binary System 1,2-Epoxycyclohexane ＋ 1,2-Dlchloroethane

Vapor-liquid equilibrium data (T, x, y) of binary system 1,2-epoxycyclohexane + 1,2-dichloroethane were determined experimentally by using a modified ROSE-Williams equilibrium vaporization system at 101.33 kPa. The results show that this binary system does not have azeotropic point. The vapor-liquid equilibrium data are in thermodynamic consistency. The binary interaction parameters in the Wilson equation are presented with the correlation of vapor-liquid equilibrium data. The measurements of liquid phase composition and bubble point temperature are well represented by the Wilson equation. Values of vapor molecular fractions and activity coefficients from the Wilson equation are presented. This work provides important engineering data for the separation of 1,2-dichloroethane and 1,2-epoxycyclohexane .

Hot water as a mild Brφnsted acid catalyst in ring opening reactions of epoxides

Ring opening of extremely hydrophobic epoxides with water, amines, sodium azide and thiophenol was realized in the mixture solvent of water and 1, 4-dioxane under reflux condition. Hot water was believed to act as a mild Bronsted acid catalyst in the epoxide-opening reactions.