椰壳炭磺酸催化环氧苯乙烷的醇解反应

利用椰壳制备的固体炭磺酸催化环氧苯乙烷的醇开环反应.考察了椰壳炭磺酸催化剂用量,溶剂对产率的影响.比较了椰壳炭磺酸与磺酸树脂、对甲苯磺酸和硫酸氢钠等传统磺酸型催化剂在该反应中的催化性能.结果表明,椰壳炭磺酸是一种绿色高效的固体酸催化剂.     

活性炭负载磷钨酸催化合成环己酮缩乙二醇

研究了活性炭负载磷钨酸催化合成环己酮缩乙二醇的反应 ,考察了催化剂负载量、反应时间、酮醇物质的量比、反应温度等因素对缩酮反应的影响 .结果表明 ,活性炭负载磷钨酸是合成缩酮的良好催化剂 ,在优化条件下 ,缩酮产率达 94.8% ,催化剂可重复使用     

新固体超强酸的制备和缩酮的合成

报道了新型固体超强酸Fe2O3／S2O8^2-催化剂的制备及其催化合成缩酮的研究工作,探讨了Fe2O3／S2O8^2-的制备方法和合成缩酮的反应条件。结果表明：酮(醛)117mmol,苯为带水剂,催化剂Fe2O3／S2O8^2-用量为原料总质量的8．4％,酮醇摩尔比为1．0：3．0,回流反应时间为4h,缩酮平均产率高达95．5％。     

钛基固体超强酸对环己酮乙二醇缩酮催化反应的特性

合成S042-/TiO2、SO42-/TiO2-Ce(Ⅳ)、SO42-/TiO2-ZrO2三种不同的固体超强酸,以环己酮乙二醇缩酮为探针反应,发现550℃下焙烧的SO4 2-/TiO2-Ce(Ⅳ)催化活性最好.并以SO42-/TiO2-Ce(Ⅳ)为催化剂,考察反应温度、催化剂用量、反应时间、反应物配比和带水剂对缩酮化反应转化率和选择性的影响.结果表明,反应温度为110～125℃、催化剂用量占反应物料总质量的0.5%、环己酮和乙二醇物质的量比为1:1.5、反应时间为1 h、环己烷为带水剂时,环己酮的转化率达95.2%,环己酮乙二醇缩酮的选择性98.7%,催化剂的重复使用效果好.     

二丁基锡(IV)磺酸酯催化合成缩醛(酮)

用二丁基氧化锡与苯磺酸、甲磺酸反应制备了两种新的有机锡化合物——二丁基锡(IV)磺酸酯. 以二丁基锡(IV)磺酸酯作催化剂, 合成了一系列缩醛(酮), 并通过正交实验, 优化了有机锡催化缩醛(酮)合成反应的反应条件. 实验表明该催化反应产率高, 反应时间短, 催化剂用量少且能回收再利用.     

Keggin型多元杂多酸催化合成苯乙酮环乙二缩酮

合成了一系列具有Keggin结构的P-V-Mo-W四元杂多酸H3+xPVxMoyW12-x-yO40.nH2O(其中,x=1,2和3),采用傅里叶变换红外光谱和X射线衍射等方法表征了杂多酸的结构;以磷钒钼钨杂多酸为催化剂合成苯乙酮环乙二缩酮.考察了催化剂的种类、醇酮摩尔比、带水剂的种类和反应条件(催化剂用量、带水剂用量、反应温度、反应时间)对苯乙酮乙二醇缩酮反应的影响.在优化条件下,即苯乙酮0.1 mol、乙二醇0.14 mol、催化剂H6PV3MoW8O400.4 mmol、在110℃反应6 h、带水剂环己烷15 mL,苯乙酮的转化率达到84.1%、苯乙酮环乙二缩酮的选择性达到99.4%.     

生物质炭基固体磺酸的制备及其酸催化性能研究

以马尾松木屑为原料,通过炭化、磺化法制备生物质炭基固体磺酸催化剂。通过中和滴定法测定催化剂表面比磺酸量,并应用于油酸与甲醇的酯化反应。以油酸的转化率作为考察指标评价其酸催化活性,考察了制备条件对固体酸催化剂催化活性的影响。采用傅里叶变换红外光谱仪(FTIR)、X射线衍射(XRD)等手段对催化剂进行了表征。通过正交试验确定固体酸催化剂的最佳条件为反应时间2 h;浓硫酸用量100 ml;催化剂用量13%;磺化温度165℃;油酸转化率可达91.36%。     

二丁基锡（Ⅳ）磺酸酯催化合成缩醛（酮）

用二丁基氧化锡与苯磺酸、甲磺酸反应制备了两种新的有机锡化合物——二丁基锡（Ⅳ）磺酸酯．以二丁基锡（Ⅳ）磺酸酯作催化剂,合成了一系列缩醛（酮）,并通过正交实验,优化了有机锡催化缩醛（酮）合成反应的反应条件．实验表明该催化反应产率高,反应时间短,催化剂用量少且能回收再利用．     

负载型CaSO4/离子交换树脂催化合成单十二烷基磷酸酯

采用浸渍法制备了负载型金属盐离子交换树脂催化剂,考察了以磷酸与月桂醇为原料催化合成单十二烷基磷酸酯的催化性能.负载不同金属盐离子对单十二烷基磷酸酯的收率的影响表明,CaSO4负载离子交换树脂催化合成单十二烷基磷酸酯效果最好.研究发现,在CaSO4负载量1.2%,催化剂用量为总反应物质量的3%,反应温度90℃,反应12h工艺条件下,月桂醇的转化率为79.4%,单酯选择性为99.9%;加入环己烷作为带水剂,相同条件下,月桂醇转化率为92.3%,单酯选择性为99.9%,并且催化剂重复使用7次之后,催化性能仍保持不变.     

固体超强酸催化下的醛酮自身缩合及其溶剂效应的研究

研究了在三种固体超强酸催化下醛(酮)自身的羟醛缩合反应,系统考察了反应时间,催化剂用量等因素对反应的影响,优化了反应条件.同时,对该反应的溶剂效应进行了研究.结果表明,当催化剂用量为2 g/1 mol醛(酮),反应5 h,转化率可达40%,溶剂对该反应有明显的抑制作用.超强酸对各种醛都具有较好的催化活性,其催化醛类化合物自身缩合的转化率都在48%以上,选择性在95%以上,证明固体超强酸对该缩合反应有较好的催化活性和选择性.     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。