《高分子化学》聚合机理教学中有机化学知识的衔接利用

高分子化学是在有机化学基础上发展而成一门学科,高分子的合成反应与有机小分子的合成反应密切相关,特别是高分子合成反应机理的学习中大量应用到有机化学的基础知识.因此,在高分子化学教学中有效利用有机化学知识是帮助学生更好理解和掌握高分子化学反应机理相关知识的关键.本文根据笔者教学实践,从烯类单体聚合活性及机理、自由基聚合阻聚机理、配位聚合机理等方面以实例形式探讨了如何利用有机化学知识帮助解释高分子化学中反应活性及反应机理.     

单取代苯环定位效应定量分析和图形可视化解释

目前对于苯环上亲电取代反应定位规律的解释基本上都停留在基于实验的定性层面。本文以5个典型的单取代苯分子(苯胺、甲苯、氯苯、硝基苯和苯甲醛)为代表,采用多种量子化学方法(静电势、原子电荷、前线分子轨道理论、福井函数及双描述符等),对它们的亲电取代反应位点进行了研究。通过定量的数据和直观的图形,揭示苯分子亲电取代反应定位规律的本质,弥补了教材与教学中存在的不足,研究结果可以为大学《有机化学》教材的编写和课程教学提供有用的参考。     

对比法在有机反应机理教学中的运用

对比是在分析和综合的基础上将各种事物加以比较 ,并确定它们之间异同的一种思维方法 ,是认识客观事物的科学方法之一。在教学中如果善于运用 ,就能更好地提高教学质量。　　在有机化学教学过程中 ,可以进行对比的概念和反应很多 ,如基本概念的对比 ,反应类型的对比 ,反应条件的对比 ,中间体的对比 ,反应活性的对比等。本文仅就对比法在有机反应机理教学中的运用作一探讨。　　在基础有机化学教学中 ,所涉及到的有机反应机理从反应类型上来分主要有自由基反应(包括自由基取代和自由基加成 ) ,离子型反应 (包括亲电取代、亲电加成、亲核取代…     

1H—NMR谱的化学位移与芳烃亲电取代反应定位效应

在芳烃亲电取代反应中,取代基的定位效应是有机化学工作者普遍关心的问题。从本世纪初就开始研究苯环上取代基对芳烃亲电取代反应定位效应的影响,根据反应中取代产物的     

~(13)C-NMR谱的化学位移与芳烃亲电取代定位效应

在芳烃亲电取代反应中,取代基的定位效应问题是有机化学工作者所普遍关心的。从本世纪初期就开始研究苯环上取代基对芳烃亲电取代反应的影响因素。根据亲电取代反应中取代产物的比例关系,归纳出苯环上不同取代基定位能力的相对强弱序列。此序列定性地解释了许多简单的芳烃亲电取代反应的事     

谈吡咯α位、吡啶β位的亲电取代反应

有机化学杂环化合物这章,有一个较难向学生解释清楚的问题.就是为什么吡咯的亲电取代反应首先发生在A位的碳原子上,而吡啶的亲电取代反应则首先发生在B位的碳原子上.     

有机化学科研渗透教学法的尝试

有机化学涉及的有机反应类型繁多,反应机理复杂,理论性强,难以理解和掌握。而大学有机化学的教学模式基本以教师为中心,以课堂讲授为主,这在某种程度上束缚了学生的创造思维和积极性。融入科研的有机化学教学法的尝试,可以破解有机化学授课的困惑,调动了学生对有机化学的兴趣及精准掌握。科研渗透的教学可以拓宽学生知识视野,激发学习兴趣,实现理论联系科研、实际生产,能够加强学生对有机化学知识的掌握。     

浅析有机化学反应机理的教与学

有机化学的基本理论和反应机理是有机化学的核心内容。反应机理的教与学是有机化学教学过程中的难点,一直困扰着教师和学生。笔者采用了"教师引导–学生练习–学生综合讲解"三段式的反应机理教学方式。首先是教师引导:教师结合国内外教材和文献,先讲授基本理论,再详细讲解反应机理;接着是学生练习:教师根据教学进度布置习题让学生练习,然后结合前后相关的反应机理,组装成比较复杂的多步反应,要求学生根据机理推导反应产物;最后是学生综合讲解:给每个学生分配一个反应,要求围绕该反应,通过查阅文献和资料,整理好素材,在课堂上讲解展示反馈,教师据此进行补充和修改。经过实践证明,该方式便于学生理解有机化学反应机理,从而达到事半功倍的教学效果。     

几种经典有机反应的分子轨道描述

用分子轨道来描述有机反应的过程对于正确理解有机反应的机理非常重要,分子轨道可以清楚地描述出反应的选择性和立体化学等信息。本文讨论了脂肪和芳香亲核取代、芳香亲电取代、加成和消除等几种经典有机化学反应过程的分子轨道描述。     

碳硼烷硼顶点选择性亲核取代反应

碳硼烷是一类由两个碳氢及十个硼氢顶点组成的笼状分子,在医学、材料、配位化学和金属有机化学等领域都有重要的应用,因此发展高效、简便的方法高选择性获取碳硼烷官能化衍生物具有重要的理论和现实意义.近年来,通过亲电取代、过渡金属催化、亲核取代等策略,实现了碳硼烷硼–氢键高效、高选择性官能化.本文根据硼–氢键的不同反应位点,评述了利用亲核取代反应策略进行碳硼烷选择性官能团化的研究进展,详细讨论了反应底物普适性、选择性控制及反应机理,并对该领域后续研究所面临的挑战和发展前景进行了展望.     

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.     

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。     

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.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。