Organophosphorus Chemistry

Organophosphorus Chemistry pdf epub mobi txt 电子书 下载 2026

出版者:Science and Behavior Books
作者:D. W. Hutchinson
出品人:
页数:352
译者:
出版时间:1985-08
价格:USD 260.95
装帧:Hardcover
isbn号码:9780851861364
丛书系列:
图书标签:
  • 有机磷化学
  • 磷化学
  • 有机化学
  • 化学
  • 合成化学
  • 催化
  • 配位化学
  • 农药化学
  • 药物化学
  • 有机金属化学
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具体描述

Organophosphorus Chemistry provides a comprehensive annual review of the literature. Coverage includes phosphines and their chalcogenides, phosphonium salts, low coordination number phosphorus compounds, penta- and hexa-coordinated compounds, tervalent phosphorus acids, nucleotides and nucleic acids, ylides and related compounds, and phosphazenes. The series will be of value to research workers in universities, government and industrial research organisations, whose work involves the use of organophosphorus compounds. It provides a concise but comprehensive survey of a vast field of study with a wide variety of applications, enabling the reader to rapidly keep abreast of the latest developments in their specialist areas. Specialist Periodical Reports provide systematic and detailed review coverage of progress in the major areas of chemical research. Written by experts in their specialist fields the series creates a unique service for the active research chemist, supplying regular critical in-depth accounts of progress in particular areas of chemistry. For over 80 years the Royal Society of Chemistry and its predecessor, the Chemical Society, have been publishing reports charting developments in chemistry, which originally took the form of Annual Reports. However, by 1967 the whole spectrum of chemistry could no longer be contained within one volume and the series Specialist Periodical Reports was born. The Annual Reports themselves still existed but were divided into two, and subsequently three, volumes covering Inorganic, Organic and Physical Chemistry. For more general coverage of the highlights in chemistry they remain a 'must'. Since that time the SPR series has altered according to the fluctuating degree of activity in various fields of chemistry. Some titles have remained unchanged, while others have altered their emphasis along with their titles; some have been combined under a new name whereas others have had to be discontinued. The current list of Specialist Periodical Reports can be seen on the inside flap of this volume.

Organophosphorus Chemistry: An In-Depth Exploration of Vital Chemical Compounds Organophosphorus chemistry is a fundamental and rapidly expanding field that delves into the fascinating world of molecules containing the phosphorus-carbon bond. These compounds, often referred to as organophosphorus compounds, are ubiquitous in nature and play a pivotal role in a vast array of biological processes and industrial applications. This book offers a comprehensive and detailed exploration of organophosphorus chemistry, providing readers with a deep understanding of its theoretical underpinnings, synthetic methodologies, and diverse applications. A Foundation in Phosphorus Chemistry: The journey into organophosphorus chemistry begins with a solid grounding in the unique properties of phosphorus itself. As a Group 15 element, phosphorus exhibits remarkable versatility in its bonding and oxidation states, leading to a rich and diverse chemistry. We will explore the electronic structure of phosphorus, its various allotropes, and the fundamental principles that govern its reactivity. This section lays the groundwork for understanding the specific characteristics of organophosphorus compounds, including the nature of the phosphorus-carbon bond, its polarity, and its propensity for various reactions. The Pillars of Organophosphorus Synthesis: A significant portion of this book is dedicated to the art and science of synthesizing organophosphorus compounds. We will dissect the most important and widely used synthetic routes, providing detailed mechanistic explanations and practical considerations for each. Key synthetic strategies covered include: The Arbuzov Reaction: This cornerstone reaction, crucial for the synthesis of phosphonates, will be examined in detail. We will explore its scope, limitations, and variations, along with the underlying mechanism involving phosphite alkylation and halide elimination. The Michaelis-Becker Reaction: Another essential method for phosphonate synthesis, this reaction involving the reaction of dialkyl phosphites with alkyl halides in the presence of a base will be thoroughly discussed. We will highlight its advantages and disadvantages compared to the Arbuzov reaction. Grignard and Organolithium Reagents in Phosphorus Chemistry: The power of organometallic reagents in forming carbon-phosphorus bonds will be a central theme. We will investigate the reactions of Grignard and organolithium compounds with phosphorus halides and oxyhalides, demonstrating their utility in constructing a wide range of organophosphorus structures. Wittig Reaction and its Variants: The Wittig reaction, a revolutionary method for alkene synthesis, often involves phosphorus ylides. This chapter will delve into the formation of these ylides, their reactivity, and the factors influencing the stereochemistry of the resulting alkenes. Variations such as the Horner-Wadsworth-Emmons reaction will also be explored. Phosphorus(III) and Phosphorus(V) Chemistry: A systematic approach will be taken to differentiate and synthesize compounds of phosphorus in its lower oxidation states (P(III)) and higher oxidation states (P(V)). This will involve discussing reactions like the phosphorylation of alcohols and amines, as well as the oxidation and reduction of phosphorus species. Cyclic Organophosphorus Compounds: The synthesis of organophosphorus compounds containing phosphorus within a ring structure will be a significant area of focus. We will examine methods for constructing phospholanes, phospholenes, and larger phosphorus-containing heterocycles, highlighting their unique reactivity and applications. The Diverse Landscape of Organophosphorus Compounds: Once the fundamental synthetic pathways are understood, we will explore the diverse classes of organophosphorus compounds and their characteristic properties. This exploration will encompass: Phosphines (R3P): These trivalent phosphorus compounds are key ligands in catalysis and are important intermediates in many reactions. We will discuss their synthesis, nucleophilicity, basicity, and their role in coordination chemistry. Phosphonates (RP(O)(OR')2): Crucial in biological systems and in flame retardants, phosphonates will be examined for their synthetic accessibility and their diverse applications. Phosphates (ROP(O)(OR')2): While the simple phosphate ester linkage is vital in biology (DNA, ATP), this book focuses on organophosphorus compounds with P-C bonds. However, the related phosphonates and phosphinates will be studied for their synthetic and industrial significance. Phosphinates (R2P(O)OR'): Similar to phosphonates, phosphinates possess important properties that make them valuable in various applications. Phosphine Oxides (R3P=O): These pentavalent phosphorus compounds are stable and often used as ligands or extractants. We will investigate their synthesis, coordination behavior, and applications. Phosphonium Salts ([R4P]+ X-): These positively charged phosphorus species are key intermediates in reactions like the Wittig reaction and find applications in phase-transfer catalysis. Applications That Shape Our World: The impact of organophosphorus chemistry extends far beyond the laboratory bench, influencing numerous aspects of modern life. This book will illuminate these vital applications: Catalysis: Organophosphorus compounds, particularly phosphine ligands, are indispensable in homogeneous catalysis. We will explore their role in cross-coupling reactions (e.g., Suzuki, Heck, Sonogashira), hydrogenation, hydroformylation, and many other industrially important transformations. The tunability of phosphine ligands allows for fine-control over catalyst activity, selectivity, and stability. Agrochemicals: Many organophosphorus compounds serve as highly effective pesticides, herbicides, and insecticides. We will delve into the mechanisms of action of these compounds, their synthesis, and the considerations regarding their environmental impact and selective toxicity. Flame Retardants: The ability of certain organophosphorus compounds to inhibit combustion makes them crucial additives in polymers, textiles, and electronic materials. We will discuss how these compounds function to suppress flames and the types of organophosphorus structures that exhibit this property. Medicinal Chemistry and Pharmaceuticals: Organophosphorus compounds are found in a range of pharmaceuticals, including antiviral agents, antibiotics, and drugs for cardiovascular diseases. Their ability to mimic natural biomolecules or interact with specific biological targets makes them valuable in drug design. Materials Science: Organophosphorus compounds are incorporated into novel materials for various purposes, including lubricants, surfactants, and specialized polymers. Their unique properties can enhance the performance and functionality of these materials. Coordination Chemistry and Supramolecular Chemistry: The ability of phosphorus atoms to coordinate with metal ions makes organophosphorus compounds essential building blocks in coordination complexes and in the construction of intricate supramolecular architectures. Looking Ahead: Future Directions and Challenges: The field of organophosphorus chemistry is continuously evolving. This book will conclude by highlighting emerging trends and future challenges. We will discuss advancements in the synthesis of complex organophosphorus structures, the development of more sustainable and environmentally friendly synthetic methodologies, and the exploration of novel applications in areas such as bioimaging, sensors, and organocatalysis. Understanding the challenges related to toxicity and environmental persistence of some organophosphorus compounds will also be a crucial part of this forward-looking perspective. This book aims to be an invaluable resource for advanced undergraduate and graduate students, researchers, and anyone interested in the captivating and impactful realm of organophosphorus chemistry. Through its detailed explanations and comprehensive coverage, it will equip readers with the knowledge and understanding necessary to contribute to this dynamic and essential field.

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这本厚厚的《Organophosphorus Chemistry》简直是本领域的百科全书,我花了好几个月才勉强啃完第一遍。它深入浅出地剖析了磷有机化合物的合成、反应机理以及它们在现代化学,尤其是在催化和材料科学中的广泛应用。书中的图表和实例非常详尽,光是关于Wittig反应及其变体的章节,就足以让人对磷化学的精妙之处拍案叫绝。作者似乎对每一个反应的细微差别都有着近乎偏执的关注,比如手性磷配体的设计与合成,里面详细阐述了如何通过控制立体电子效应来优化催化剂的性能,这对我正在进行的一个不对称合成项目提供了极大的启发。不过,坦白说,对于初学者来说,这本书的门槛确实有点高,很多高级的量子化学计算结果和复杂的谱学分析直接穿插在理论阐述中,没有足够的基础知识储备,很容易在阅读过程中迷失方向。我尤其欣赏它在工业应用方面的章节,它不仅仅停留在实验室的精巧实验上,还探讨了大规模生产中遇到的挑战和解决方案,比如某些高活性中间体的稳定化处理,这让这本书的实用价值倍增。

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我得说,这本书的排版和插图设计是我近年来读过的专业化学书籍中最具“古典美感”的一本。它没有采用那种充斥着高饱和度色彩的现代设计,而是选择了低调而沉稳的墨绿色和米黄色作为主色调,使得长时间阅读时眼睛的疲劳感大大降低。内容上,它对于磷-碳键、磷-氮键等关键官能团的电子特性分析做得尤为出色。作者似乎是想重建整个磷有机化学的理论基石,从路易斯酸碱性到过渡态的能量剖面,每一个论点都有坚实的理论依据支撑。我特别喜欢其中一个章节,专门对比了五价和三价磷试剂的反应选择性差异,通过大量的比较实验数据,清晰地展示了“软硬”酸碱理论在磷化学中的实际应用边界。虽然整体学术性很强,但章节之间的过渡衔接却出乎意料地自然,像是在与一位经验丰富的大师进行一对一的学术交流,而不是在被动地接收信息。唯一的小遗憾是,一些最新的、发表在近两年顶级期刊上的高尖端应用案例更新得稍微慢了一点,但考虑到本书的深度和广度,这也可以理解。

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说实话,我买这本书是冲着它在生物化学交叉领域的潜力去的。我原本以为它会花大量的篇幅讨论磷酸酯在DNA/RNA结构中的作用或者作为信号传导分子(如ATP)的化学性质,结果发现,这本书的重心明显更偏向于合成化学和材料科学。它对磷酸酯的讨论更多集中在如何利用它们作为离去基团或活化试剂,而不是它们在生命体内的功能。然而,即使如此,它关于磷化学在阻燃剂和液晶材料开发中的应用部分,依然是教科书级别的深度。作者对不同取代基对热稳定性的影响进行了系统性的回归分析,这为材料工程师提供了宝贵的指导手册。这本书的语言风格非常严谨,几乎不带任何情感色彩,但正是这种客观和精确,使得它成为了一个可靠的参考工具。我发现自己经常需要查阅其中的特定反应条件,它提供的收率范围和副产物信息精确到小数点后一位,体现了极高的实验严谨性。

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这本书的结构组织方式非常独特,它没有完全按照传统的官能团分类,而是采取了一种“功能导向型”的编排思路。例如,有一整章是专门讨论如何利用磷物种的还原性来构建C-C键,而不是将所有还原反应集中在一个通用的章节里。这种组织方式的优势在于,它能让研究人员迅速找到解决特定合成挑战的化学工具箱。我个人尤其推崇它对“自由基”磷化学的论述,这是一个在很多基础教材中容易被轻描淡写的领域,但本书详尽地介绍了光化学引发的磷烷基化反应,并配上了详细的机理草图,解释了单电子转移的微妙过程。对于那些希望拓展自己研究边界的化学家来说,这本书提供了许多“非主流”但潜力巨大的合成路线。不过,我必须指出,书中的一些术语缩写(尤其是在早期文献引用部分)没有进行充分的解释,这对于需要快速入门的读者来说,可能会造成一些初期阅读障碍,需要不断地在附录和正文之间来回跳转。

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我感觉这本书更像是为资深博士后或领域内的资深研究人员准备的“进阶手册”,而不是本科生或研究新手的入门读物。它的深度简直令人望而生畏,尤其是关于过渡金属催化的磷氢化反应和C-H键活化的章节,引入了大量复杂的配位化学和轨道对称性的概念。书中对特定催化剂中毒机理的分析极其到位,它不仅描述了“什么反应”,更深入解释了“为什么会失败”以及“如何避免失败”。我对比了手头几本同主题的经典教材,这本书在对“活性中间体寿命和稳定性”的量化描述上,远超其他同类书籍。它像是一个经过数十年沉淀的化学家对所有失败和成功的经验总结,没有任何浮夸的言辞,全是硬核的知识。读完后,我感觉自己对磷原子在化学反应中的“多面性”有了全新的认识,它不再只是一个简单的取代基,而是一个可以被精确调控的反应中心。这本书是那种你会反复翻阅、每次都有新收获的经典之作。

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