α-羰基二硫缩烯酮的研究进展

综述了α-羰基二硫缩烯酮的结构特征、合成方法及作为1,3-亲电体的普通环合反应、环合芳构化和取代-环合芳构化反应、合成杂环化合物、缩合反应、极性翻转合成策略、还原反应等在有机合成中的应用.     

无溶剂法合成5-(3-羟基-1,3-二苯基烯丙基)麦氏酸的研究

以麦氏酸(2,2-二甲基-1,3-二氧六环-4,6-二酮)和α,β-不饱和酮为原料,合成了5-(3-羟基-1,3-二苯基烯丙基)麦氏酸.重点考察了物料配比、反应温度和反应时间对产物收率的影响、并通过红外光谱(FT-IR)和核磁共振波谱(1 HNMR,13C NMR)等对产物结构进行了表征.研究结果表明,采用该方法合成5-(3-羟基-1,3-二苯基烯丙基)麦氏酸的最佳反应条件为:n(α,β-不饱和酮)∶n(麦氏酸)=1.2,85℃下反应5h,收率达86.7%.     

一类新型缩二胺类化合物的合成研究

利用苯甲酸甲酯和二甲亚砜在氢化钠的存在下发生缩合反应,经Pummerer重排生成α-羰基-硫代半缩醛.α-羰基-硫代半缩醛具有两个亲电中心,与两个氨基的化合物1,4-丁二胺、1,3-丙二胺反应,合成了一类新型的缩二胺类化合物.以红外、核磁和元素分析进行了结构表征.     

系列樟脑型β-二酮化合物的合成

樟脑由于具有较大的空间位阻,其α位的亚甲基较直链α位碳难活化.从D(+)-樟脑出发,采用高沸点的乙二醇二乙醚做溶剂,氢化钠作碱催化剂,合成了3-苯甲酰基樟脑,3-乙酰基樟脑和3-三氟乙酰基樟脑等系列樟脑型β-二羰基化合物,产率为30%～58.3%.目标产物用1H NMR,质谱(MS)来表征.并讨论了溶剂,碱催化剂以及提纯方法对反应的影响.     

2-烯-1,4-二酮及其衍生物的合成及晶体结构

通过对三取代-2-烯-1,4-二酮及其衍生物进行了探索合成。在环戊二烯基三苯基膦氯化镍[C_5H_6(PPh_3)NiCl]作用下,由N-甲基-N-苯(/4-甲基苯基)甲酰基亚甲基苯胺与1,3–二苯基-1,3-丙二酮在二氯乙烷(DCE)介质中发生Knoevenagel交叉偶联反应,得到α位具有三个羰基的乙烯化合物,即三取代2-烯-1,4-二酮。同时,对上述产物与胺类亲核试剂进行了自动串联催化反应的探索合成,并摸索条件进行优化。通过核磁共振氢谱、核磁共振碳谱及X-单晶衍射等手段对合成产物的结构进行了表征,证明了合成方法的可靠性。     

不同结构的α-羰基二硫缩烯酮化合物的合成及表征

以3种β-二羰基化合物为底物,用碳酸钾为拔氢试剂, N,N-二甲基甲酰胺为溶剂,分别与二硫化碳发生亲核加成,然后与不同结构卤代烃进行亲核取代合成α-羰基二硫缩烯酮.实验结果表明,该反应具有原料简单、反应条件温和、生成产物产率高等特点.用核磁、红外等测试手段对化合物进行了表征.     

铁催化1,6-共轭烯丙基化反应

二芳基甲烷衍生物是一种生产香料、染料以及医药的重要中间体.合成类似复杂化合物分子最重要的方法是利用碳亲核试剂与缺电子烯烃的共轭加成从而构建新的碳-碳键形成,其中活性烯丙基化合物与对亚甲基苯醌(p-QMs)之间的1,6-共轭烯丙基化反应是合成二芳基甲烷衍生物的高效方法之一.在本文中,我们利用廉价铁Lewis酸催化烯丙基三甲基硅烷和p-QMs的1,6-共轭烯丙基化反应,以优异的收率高效合成一系列烯丙基二芳基甲烷衍生物.该反应以廉价的FeCl_3·6H_2O为催化剂,在室温下甲苯溶液中2 h即可完全反应,操作简单,底物范围广泛,产率最高可达99%以上.     

用"一锅法"合成取代吲哚衍生物

利用取代苯肼盐酸盐与丙酮酸、1,3-二苯基-1,3-丙二酮反应合成了3种取代吲哚衍生物.采用"一锅法"对酯化反应进行了改进,以盐酸酸化的乙醇作溶剂,苯磺酸催化,一步得到取代的吲哚酸酯.本文对吲哚环化的反应机理、合成条件进行了探讨,发现反应温度不同所得产物也不同.合成产物用IR, 1H NMR和MS进行了分析表征.     

N,N-二取代-α-羰基硫代甲酰取代胺的合成研究

以取代苯乙酮为原料,首次得到了反应中间体二-（1,1-二氯-1-芳酰基）三硫醚,对其进行了红外、核磁、质谱和X-衍射分析.并且用该化合物与仲胺反应得到了六个α-羰基硫代甲酰取代胺.     

金(Ⅰ)配合物室温催化三组分反应构建多取代吡咯衍生物

在室温条件下,以金(Ⅰ)配合物为催化剂,在乙醇溶剂中通过"一锅法"有效地催化取代β-硝基苯乙烯、芳香伯胺和1,3-二羰基化合物以63%～82%收率合成多取代吡咯衍生物。产物的结构经~1H NMR、~(13)C NMR和HRMS确证,其中化合物1-(1-(4-溴苯基)-2-甲基-4-苯基-1H-吡咯-3-基)乙酮的结构经X射线单晶衍射进一步确认。该方法具有合成原料易得、反应条件温和、高选择性等优点,是一种合成多取代吡咯衍生物的新途径。     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

A computer generator for randomly layered structures

AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…     

海南岛地体及其毗邻陆缘晚中生代—新生代古地磁研究和构造演化

本文叙述了对海南岛及其毗邻大陆边缘白垩纪到第四纪地层岩石进行古地磁研究的全部工作过程。通过分析岩石中剩余磁矢量的磁偏角及磁倾角的变化,提出海南岛白垩纪以来经历的构造演化模式如下:早期伴随顺时针旋转而向南迁移,后期伴随逆时针转动并向北运移。联系该地区及邻区的地质、地球物理资料,对海南岛上述的构造地体运动提出以下认识:北部湾内早期有一拉张作用,主要是该作用使湾内地壳显著伸长减薄,形成北部湾盆地。从而导致了海南岛的早期构造运动,而海南岛后期的构造运动则主要是受南海海底扩张的影响。海南地体运动规律的阐明对于了解北部湾油气盆地的形成演化有重要的理论和实际意义。     

Exciton Seebeck in Molecular Systems

Various applications relevant to the exciton dynamics,such as the organic solar cell,the large-area organic light-emitting diodes and the thermoelectricity,are operating under temperature gradient.The potential abnormal behavior of the exicton dynamics driven by the temperature difference may affect the efficiency and performance of the corresponding devices.In the above situations,the exciton dynamics under temperature difference is mixed with     

Achieving Unusual States of Matter Under High Pressure

The elongation method,originally proposed by Imamura was further developed for many years in our group.As a method towards O(N)with high efficiency and high accuracy for any dimensional systems.This treatment designed for one-dimensional(ID)polymers is now available for three-dimensional(3D)systems,but geometry optimization is now possible only for 1D-systems.As an approach toward post-Hartree-Fock,it was also extended to     

《Chinese Science Bulletin》SUBJECT INDEX TO VOLUME 59(2014)

正~~     

An on-line scaling method for improving scalability of a database cluster

The explosive growth of the Internet and database applications has driven database to be more scalable and available, and able to support on-line scaling without interrupting service. To support more client's queries without downtime and degrading the response time, more nodes have to be scaled up while the database is running. This paper presents the overview of scalable and available database that satisfies the above characteristics. And we propose a novel on-line scaling method. Our method improves the existing on-line scaling method for fast response time and higher throughputs. Our proposed method reduces unnecessary network use, i.e. , we decrease the number of data copy by reusing the backup data. Also, our on-line scaling operation can be processed parallel by selecting adequate nodes as new node. Our performance study shows that our method results in significant reduction in data copy time.     

An improved R-tree based on childnode''s probability

R-Tree is a good structure for spatial searching. But in this indexing structure,either the sequence of nodes in the same level or sequence of traveling these nodes when queries are made is random. Since the possibility that the object appears in different MBR which have the same parents node is different, if we make the subnode who has the most possibility be traveled first, the time cost will be decreased in most of the cases. In some case, the possibility of a point belong to a rectangle will shows direct proportion with the size of the rectangle. But this conclusion is based on an assumption that the objects are symmetrically distributing in the area and this assumption is not always coming into existence. Now we found a more direct parameter to scale the possibility and made a little change on the structure of R-tree, to increase the possibility of founding the satisfying answer in the front sub trees. We names this structure probability based arranged R-tree (PBAR-tree).     

Integrating GIS Web services based on mediating architecture

The geographic information service is enabled by the advancements in general Web service technology and the focused efforts of the OGC in defining XML-based Web GIS service. Based on these models, this paper addresses the issue of services chaining,the process of combining or pipelining results from several interoperable GIS Web Services to create a customized solution. This paper presents a mediated chaining architecture in which a specific service takes responsibility for performing the process that describes a service chain. We designed the Spatial Information Process Language (SIPL) for dynamic modeling and describing the service chain, also a prototype of the Spatial Information Process Execution Engine (SIPEE) is implemented for executing processes written in SIPL. Discussion of measures to improve the functionality and performance of such system will be included.     

Tracking data management using topology of moving object database system for moving object constrained trajectory in LBS application

Advances in wireless technologies and positioning technologies and spread of wireless devices, an interest in LBS (Location Based Service) is arising. To provide location based service, tracking data should have been stored in moving object database management system (called MODBMS) with proper policies and managed efficiently. So the methods which acquire the location information at regular time intervals then, store and manage have been studied. In this paper, we suggest tracking data management techniques using topology that is corresponding to the moving path of moving object. In our techniques, we update the MODBMS when moving object arrived at a street intersection or a curved road which is represented as the node in topology and predict the location at past and future with attribute of topology and linear function. In this technique, location data that are corresponding to the node in topology are stored, thus reduce the number of update and amount of data. Also in case predicting the location,because topology are used as well as existing location information, accuracy for prediction is increased than applying linear function or spline function.