1-乙基-4-氧-7-甲基-1,8-萘啶-3-羧酸的合成

乙基氧甲基萘啶羧酸;缩合反应;成环反应;乙基化反应;水解反应;光谱特征     

4-取代-3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮的合成及生物活性

为寻找活性强、作用时间长的新型非肽类血管紧张素II AT₁受体拮抗剂, 从易得原料3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮出发, 经过N-烃化反应、1,3-偶极反应、氢解、水解和酰化等反应, 合成得到一系列4-取代-3-烷基-4,5-二氢-1-(3-氯-4-氟苯基)-1,2,4-三唑-5-酮类衍生物, 总收率为58%～87%, 其结构经IR, ¹H NMR, MS和元素分析确证. 初步药理试验结果表明: 所有目标化合物均有一定的AT₁受体拮抗活性, 其中化合物12d抑制AII诱导的兔主动脉环收缩的IC₅₀值为4.0×10^－9 mol/L, 与阳性药坎地沙坦(candesartan)相当, 具有进一步的研究意义.     

3-甲基-1-戊烯-4-炔-3-醇的合成

以甲基乙烯酮为原料,用乙炔基格氏试剂对其加成,然后水解得到目标物3-甲基-1-戊烯-4-炔-3-醇。研究了温度对反应的影响,发现在25℃的反应温度下,目标化合物的气相色谱产率为50%,减压蒸馏纯化后收率为30%。目标产物用1HNMR、IR进行了表征。     

2-乙氧羰基-3-溴-4-甲基-5-甲酰基-吡咯的合成

2-乙氧羰基-3-溴-4-甲基-5-甲酰基-吡咯的合成;乙氧羰基二甲基吡咯;乙氧羰基溴二甲基吡咯;乙氧羰基溴甲基甲酰基吡咯     

1-苯基-5-芳基-1,2-二氢-1,2,4-三唑-3-硫酮的合成

将取代苯甲酰氯1a～1f与硫氰酸钾反应, 得到的中间体不需纯化直接与苯肼反应, 成功地合成了1-苯基-5-芳 基-1,2-二氢-1,2,4-三唑-3-硫酮(2a～2f). 化合物2的结构通过红外光谱、核磁共振光谱和高分辨质谱进行了表征.     

1-芳基-2-苯基-3-甲基-3-异丙基-2-氧代-1,4,2-二氮磷杂环戊-5-酮的合成及除草活性

利用取代苯基脲与苯基二氯化膦和3-甲基-2-丁酮进行的类Mannich反应合成了15种新的1,4,2-二氮磷杂环戊-5-酮类化合物(2a_2o), 其结构经     

6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸的合成

以脱氢松香酸为原料,经酯化、溴代、氧化、异构化、水解等反应,合成了一种新型的四氢蒽羧酸类衍生物———6-溴-7-异丙基-1,10-二甲基-1,2,3,4-四氢蒽-1-羧酸,其结构经1H NMR,13C NMR,MS和元素分析表征。     

3,7-二甲基-7-羟基-2-辛烯-1,6-内酯和(E)-6,7-二羟基-3,7-二甲基-2-辛烯酸的全合成

以甲基庚烯酮为原料经Wittig反应、水解、环氧化和分子内环化或开环等4步反应分别以6.4%和23.7%的总收率完成了天然产物3,7-二甲基-7-羟基-2-辛烯-1,6-内酯和(E)-6,7-二羟基-3,7-二甲基-2-辛烯酸的全合成,它们的结构经1H NMR,13C NMR和ESI-MS的确证.     

超声辐射下合成1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲

1-苯基-3-甲基-5-氯吡唑-4-甲酸与氨基硫脲在三氯氧磷中反应得到2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1), 然后分别采用超声辐射法和常规加热法与(未)取代苯甲酰基异硫氰酸酯(2)反应合成了一系列未见报到的1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲(3a～3j). 化合物的结构经元素分析, IR, ¹H NMR确证.     

3,3-二甲基-9-(5,5-二甲基-3-羟基-2-环己烯-1-酮-2-基)-1-氧代-2,3,4,9-四氢化氧杂蒽的合成和晶体结构

标题化合物C23H26O4是由水杨醛与5，5-二甲基-1，3-环己二酮在N，N-二甲基甲酰胺中反应而得．结构通过单晶X-射线行射法确定，其晶体属于单料晶系，空间群P21/c，a=7．056（7），b=20.263（3），c=13．665（2）A，β＝93．32（1）°，V=1950．7（4）A3，Mr=366．46，Dc=1.248g／cm3，Z=4，μ（MoKa）=0．84cm－1，F（000）=784。晶体结构用直接法解出，经全矩阵最小二乘法对原子参数进行修正，最后的偏离因子R=0．068，Rw=0．075。晶体结构分析结果表明，分子中存在一个共轭的烯醇式结构。     

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。