氢氧化铯促进下硒、端炔及卤代烃反应合成炔硒醚

DMF作溶剂, 4Å分子筛存在下, 将端炔、CsOH、硒粉在室温搅拌2 h, 然后加入溴代烃或二芳基碘盐, 在室温下搅拌20 h, 得炔硒醚, 收率约60%. 反应机理为端炔与氢氧化铯作用形成炔化铯, 然后元素硒进行C—Cs键插入形成炔硒化铯, 炔硒化铯对溴代烃或二芳基碘盐进行亲核取代得到相应的炔硒醚     

FeCl3催化乙酰丙酮的炔丙基化反应

FeCl3,催化炔丙醇与乙酰丙酮在1,2-二氯乙烷中发生亲电加成反应得炔丙基化产物--3-炔丙基-2,4-戊二酮,其结构经1H NMR,13C NMR,IR和MS表征.于90℃反应8 h,产率80.9%-94.2%.     

无过渡金属催化条件下咪唑衍生物与炔基溴的炔基化反应研究

以炔基溴和咪唑衍生物为反应原料,详细探讨了无过渡金属催化条件下的咪唑类芳香炔胺化合物的合成方法.研究结果表明,以N,N-二甲基甲酰胺为溶剂、碳酸钾为碱,于80℃下反应12 h即可获得中等偏上收率的碳-氮偶联产物.通过上述方法合成得到了系列芳香炔胺衍生物,其结构经1H NMR和13C NMR表征.     

1,6-庚二炔类化合物的合成

溴丙炔与含活性亚甲基的丙二酸酯反应,合成了14个4-取代-1,6-庚二炔类化合物,其结构经1H NMR确证;4-二苯基磷酰基-4-乙酯基-1,6-庚二炔未见文献报道,其结构经1H NMR,13C NMR,IR和HR-MS表征.     

三溴化金催化端炔与二芳基二硒醚反应合成炔基硒醚

炔基硒醚是合成一些有机硒化合物的重要起始物。本文研究发现,在三溴化金(Au Br3)催化下,端位炔和二芳基二硒醚在弱碱(如碳酸钾)存在下反应,生成炔基芳基硒醚,产率为69%~98%;在空气参与下,于80℃下进行反应,反应条件简单,且二硒醚的两个硒原子均可以被利用。二甲基亚砜(DMSO)是合适的溶剂,在极性较小的溶剂(如甲苯、四氢呋喃)中,此反应不能进行。芳基炔(如苯乙炔、对甲基苯乙炔、对氯苯乙炔等)、烯基炔(如环己烯乙炔)和烷基炔(如1-壬炔)均能顺利进行此反应。当芳基炔苯环的间位或邻位连有取代基时,反应产率较低(69%~82%),而对位无论是连有吸电子基还是给电子基,该反应均可以得到很高的产率(95%)。     

碳酸铯催化下端炔碘化合成炔基碘

催化量的碳酸铯(0.2 equiv.)、氢氧化钾(2.0 equiv.)及端炔(1.0 equiv.)在无水THF-HMPA中, 室温搅拌3 h, 然后加入碘的THF溶液, 室温搅拌2 h, 生成炔基碘. 产率为70%～93%.     

炔醛参与的直接Mannich反应

首次报道了炔醛参与的Mannich反应。以布朗斯特酸为催化剂,THF为溶剂,芳基炔醛,酮和脂肪胺经Mannich反应合成了一系列新型的含炔基的β-氨基酮,其结构经1H NMR,13C NMR和HR-MS表征。     

氢氧化铯促进下硒、端炔及二芳基碘盐反应合成炔基芳基硒醚

以N,N-二甲基甲酰胺(DMF)作溶剂, 在4 Å分子筛存在及氮气保护下, 将端炔、CsOH、硒粉在室温搅拌2 h, 然后加入二芳基碘盐, 在0 ℃搅拌30 h, 得炔硒醚, 收率约60%.     

1,7-二芳基-1,6-庚二炔化合物的合成

1,6-庚二炔是有机合成的重要中间体,我们以Pd Cl2/Cu I为催化剂,NEt3为碱,在四氢呋喃溶剂中实现了二炔与卤代芳烃Sonogashira偶联反应,合成了10个1,7-二芳基-1,6-庚二炔化合物,该方法也适用于二卤芳烃如1,8-二碘萘与末端炔偶联合成1,8-二苯乙炔基萘.所有合成的目标化合物结构经1H NMR,13C NMR,IR和MS表征.     

炔基取代的新型β-内酰胺化合物的合成

首次报道了以芳香炔醛为起始原料,通过二聚反应、氧化反应、Michael加成及内酰化缩合反应合成了一系列芳炔基取代的新型四元β-内酰胺类化合物,收率57.6%~72.5%,其结构经1H NMR,13C NMR和X-射线单晶衍射表征。     

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。     

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.     

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.     

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.     

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。     

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。