发烟硫酸条件下环己酮肟贝克曼重排工艺进展

综述了环己酮肟在发烟硫酸条件下液相重排生成己内酰胺的相关新工艺、新设备及新技术,并对其进行了概括和分析.     

Formation of Furan Fatty Alkyl Esters from their Bis‐Epoxide Fatty Esters

Reactions of epoxidized alkyl soyate with four different alcohols: ethanol, isopropyl alcohol, 2‐ethylhexanol, benzyl alcohol, in the presence of Brønsted acid catalyst, were investigated. Products, not reported in prior studies of similar reactions, were found. These were furan fatty acid alkyl esters (FFE, mixture of alkyl 8‐(5‐hexyl‐2‐furyl) octanoate and alkyl 9‐(5‐pentyl‐2‐furyl)nonanoate) which were unambiguously identified by means of GC–MS and two‐dimensional NMR. Evidence suggests that the FFE are formed by an acid‐catalyzed rearrangement of the epoxidized linoleates. The FFE were formed in presence of all four alcohols tested and in the presence of either sulfuric acid or Amberlyst 15 catalyst. Yields of up to 13 %, as quantified by GC and NMR spectroscopies, were observed.     

Gold(I)‐Catalyzed Tandem Reaction of γ‐Amino‐Substituted Propargylic Esters to Pyrrolines and its Application in the Formal Synthesis of (±)‐Aphanorphine

An effective synthesis of structurally diverse pyrroline derivatives has been accomplished by a gold(I)‐catalyzed tandem 1,3‐acyloxy rearrangement/intramolecular azacylization reaction of γ‐amino‐substituted propargylic esters in good to excellent chemical yields (52–98%). The reaction proceeds under extremely mild conditions and has also demonstrated its potential in a concise formal synthesis of (±)‐aphanorphine with a catalyst loading as low as 0.5 mol% to provide the key intermediate 5‐(4‐methoxybenzyl)‐1‐tosyl‐2,5‐dihydro‐1H‐pyrrol‐3‐yl pivalate on a gram scale.

     

Restructuring Software: A Case Study

We use knot count and path count metrics to identify which routines in the Level 1 basic linear algebra subroutines (BLAS) might benefit from code restructuring. We then consider how logical restructuring and the improvements in the facilities available from successive versions of Fortran have allowed us to improve the complexity of the code as measured by knot count, path count and cyclomatic complexity, and the user interface of one of the identified routines which computes the Euclidean norm of a vector. With these reductions in complexity we hope that we have contributed to improvements in the maintainability and clarity of the code. Software complexity metrics and the control graph are used to quantify and provide a visual guide to the quality of the software, and the performance of two Fortran code restructuring tools is reported. Finally, we give some indication of the cost of the extra numerical robustness offered by the BLAS routine over the use of new Fortran 90 intrinsic functions.     

3-乙酰基-4-羟基苯甲酸的合成及正交工艺优化

以4-乙酰氧基苯甲酸甲酯为原料,经无溶剂的Fries重排法合成了3-乙酰基-4-羟基苯甲酸,并对其结构进行了表征.采用L9(34)正交实验,考察了物料投料比、反应温度和反应时间等参数对目标产物收率的影响,并对重排反应机理进行了探讨.结果表明,3-乙酰基-4-羟基苯甲酸的最佳合成工艺为:n(4-乙酰氧基苯甲酸甲酯):n(...     

A relationship between software coverage metrics and reliability

Software engineers have tacitly assumed that there exists a link between coverage and reliability. An argument is presented which leads to an inverse logarithmic relationship which depends upon the structure of the software and on a parameter called the strength of the coverage metric. The relationship is developed by considering reliability as a function of an idealized coverage metric and then interpreting the result for a range of actual coverage metrics.     

“一锅三步法”合成苯基-2-吡啶基甲醇

以2-苄基吡啶氮氧化物和三氟乙酸酐为原料,通过“一锅三步法”（串联“酰化、[3,3]σ重排和水解”反应）合成了关键药理活性中间体苯基-2-吡啶基甲醇,并对反应条件进行了优化。结果表明：当n（2-苄基吡啶氮氧化物）：n（三氟乙酸酐）=1 : 1.2、N, N-二异丙基乙胺（DIPEA）为碱、甲苯为反应溶剂,室温反应6小时,经硅胶柱层析分离即可得到苯基-2-吡啶基甲醇,收率为81.0%。产物经1H NMR,13C NMR 和HRMS进行结构表征。本文以原子经济学的理念首次实现了由2-苄基吡啶氮氧化物到苯基-2-吡啶基甲醇的直接转化。     

数字表面模型(DSM)参数指示林窗特征的有效性研究

林窗的空间格局不仅对林下物种多样性有重要作用,而且也是量化不同林型结构特征的重要指标.近年来,灵活便捷的小型无人机航拍技术的快速发展为获取高分辨率的森林冠层三维结构信息提供了可低成本获取的途径.利用航拍影像提取林窗斑块来计算景观指数是描述林窗格局有效的传统方法,但提取细小林窗往往难度大,尤其是在需要处理大量航拍数据时会...     

Catalytic Performance of B2O3/TiO2–ZrO2 for Vapor-Phase Beckmann Rearrangement of Cyclohexanone Oxime: The Effect of Boria Loading

A series of boria catalysts supported on titania–zirconia mixed oxide (B₂O₃/TiO₂–ZrO₂) with different boria loadings (8–20 wt%) were prepared and characterized by X-ray diffraction, adsorption of nitrogen, ¹¹B magic angle spinning (MAS) NMR measurements and temperature-programmed desorption (TPD) of ammonia. The catalytic performance of B₂O₃/TiO₂–ZrO₂ for vapor-phase Beckmann rearrangement of cyclohexanone oxime to -caprolactam was studied at 300°C. It was found that the lactam selectivity increased with increasing of boria loading, whereas a maximum oxime conversion was obtained at the boria loading of 12 wt%. The acid sites of medium strength on the surface of the catalyst play an important role in the selective formation of lactam.     

普光高酸性气田投产测试关键技术综述

在普光高酸性气田产能建设的过程中,气井的投产测试是一个非常关键的阶段。这个阶段的关键技术主要有高含硫气井入井液技术、完井管柱配套技术、长井段射孔工艺技术、长井段大规模酸压技术、合金油管作业技术、作业随钻录井技术、长时间试气测试技术。普光气田的投产实践证明只有这些关键技术的成功应用,才能确保高酸性气田投产测试的顺利实施,才能为高酸性气田的产能建设打下了坚实的技术基础。