利用碳碳叁键断裂重组反应合成2,4,4-三氯萘-1(4H)-酮衍生物

以炔烃-联烯酮为原料,水作为亲核试剂,通过N-氯代丁二酰亚胺(NCS)介导的[2+2]环加成和碳碳叁键断裂重组反应合成了18个2,4,4-三氯萘-1(4H)-酮衍生物,产率为55%～88%.所得产物的结构经NMR和IR以及HRMS等表征,其中目标产物2e的结构经X单晶分析确认.该反应条件温和、操作简单、无需金属催化剂且产率良好,为合成官能化的1-萘酮衍生物提供了一种新的高效的合成策略.     

菊花烯酮的合成及其Baeyer-Villiger反应

菊花烯酮(Chrysanthenone,2)与其环内酯(1actone,3)以及环内酯3的开环产物4是构成手性药物的重要中间体,本文由马鞭烯酮(Verbenone,1)经光化反应合成得到菊花烯酮(2),菊花烯酮经由Baeyer-Villiger反应得到了主要氧化产物3,对化合物3以1H NMR确定其结构的基础上,又以化学法探讨了构型.3开环得到了4,4再扣环得到了环内酯3,证明化合物4中的羟基(OH)和羧基(COOH)位于六元环的同侧.其反应如下:     

碳正离子重排反应合成Cyclocitrinol核心骨架

Cyclocitrinol是一类具有独特的桥环结构的天然产物,其桥环核心骨架可由高张力的降蒈烯酮开环制备得到.以商品化的19-羟基雄甾为原料,通过高烯丙基碳正离子重排反应,高效地合成了降蒈烯酮关键中间体,完成了Cyclocitrinols天然产物的核心骨架的合成.     

双氢青蒿素-单硝酸异山梨酯拼合物的合成及其体外抗肿瘤活性

青蒿素经硼氢化钠还原制得双氢青蒿素(2); 2在4-二甲氨基吡啶(DMAP)催化下与丁二酸酐反应得到青蒿琥酯(3);以二环己基碳二亚胺为脱水剂,DMAP为催化剂,将3与一氧化氮供体单硝酸异山梨酯反应合成了双氢青蒿素-单硝酸异山梨酯拼合物(1),其结构经NMR和MS表征.采用MTT法初步考察了1对几种肿瘤细胞的增殖抑制活...     

银杏酸的合成新方法

报道了一种合成银杏酸类化合物的新方法。以2-羟基-5-甲基苯甲酸为起始原料,经甲基化和溴代反应后,通过Wittig反应构建不同链长侧链合成了2-甲氧基-6-十三碳-1-烯基苯甲酸甲酯(6a)和2-甲氧基-6-十五碳-1-烯基苯甲酸甲酯(6b);用钯碳氢化还原6中的碳碳双键后脱除甲基合成了两种不同链长银杏酸,总收率分别为46%和40%,其结构经¹H NMR和ESI-MS确证。     

2-乙酰噻吩及其新型席夫碱的合成

以磷钨酸为催化剂,噻吩和乙酸酐反应合成了2-乙酰噻吩(1,收率83.5%);1与不同结构的酰肼反应合成了四种新型席夫碱(2a～2d),收率90%～95%,其结构经UV,~1H NMR,~(13)C NMR,IR及元素分析表征.优化了合成1和2的反应条件.     

二茂铁基三烯酮类姜黄素类似物的合成、晶体结构及电化学性质

以不同取代基的肉桂醛和二茂铁为起始原料,经Vilsmeier-Haack甲酰化反应、Claisen-Schmidt等反应合成5种新型二茂铁基三烯酮类姜黄素类似物,其结构经¹H NMR、¹³C NMR和HRMS(ESI-TOF)表征,并用X-ray单晶衍射确定了5d的晶体结构,其构型为反式构型,电化学研究表明化合物5a具有较高氧化还原活性。     

MMT/FeCl_3催化的α-羰基二硫缩烯酮与二苯甲醇的Friedel-Crafts烷基化反应

研究了MMT/FeCl_3催化α-羰基二硫缩烯酮与二苯甲醇的Friedel-Crafts烷基化反应,合成了22个二硫缩烯酮类化合物(3a~3v),其中3b,3d~3f,3h~3r和3t为新化合物,其结构经1H NMR和13C NMR表征。以3a的合成为例,对反应条件进行优化。结果表明:在最优反应条件[1-(1,3-二噻烷-2-亚甲基)-4-苯基-3-丁烯-2-酮(1a)0.25 mmol,二苯甲醇0.3 mmol,MMT/FeCl_315 mmol%,CH_2Cl_22 m L,回流反应2 h]下,3a产率93%;MMT/FeCl_3循环使用3次,收率基本维持不变。     

含能笼型碳硼烷衍生物的合成及其热性能

以DMSO或DMF为溶剂,1-溴甲基碳硼烷(1)分别与亚硝酸钠和叠氮钠发生亲核取代反应,合成了两种新型的含能笼型碳硼烷——1-硝基甲基碳硼烷(2)和1-叠氮基甲基碳硼烷(3),其结构经1H NMR和FT-IR表征。用DSC分析了1~3的热性能,结果表明:1和2分别在162.2℃和168.7℃分解,分解热分别为130.4 J.g-1和245.6 J.g-1。     

镍(Ⅱ)催化烯酮亚胺的不对称共轭加成反应:高对映选择性构建连续两个全碳季碳中心

正Angew.Chem.Int.Ed.2017,56,13107~13111烯酮亚胺(Silyl ketene imines,SKIs)是一类含有累积多烯结构的化合物,它可以被用来合成含有季碳中心的腈类化合物.目前烯酮亚胺参与的不对称Acylation、Aldol、Mannich、Protonation等反应取得了优秀的结果.然而,由于区域选择性和立体选择性问题,烯酮亚胺参与的不对称共轭加成反应仍存在着挑战.同时,该反应可以一步高效地构建连续两个全碳季碳中心.基于此,四川大学化学学院冯小明课题组使用手性双氮氧配体/镍(II)配合物为催化剂,     

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.     

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.     

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。