國科會化學中心-綠色/永續化學網路資源共享網
http://gc.chem.sinica.edu.tw/
Microwave
 
引言   友善列印

微波技術的應用已有很長的歷史,微波是一種以電磁波型式存在的能量,其能量值介於紅外線與無線電波之間,早期是以通訊領域的應用為主,而隨著為波技術的發展,在分析樣品的製備及食品加工方面亦逐見有廣泛的應用。1986年,加拿大的Gedye等人,首次成功地在Dies-Alder反應系統中,引進微波加熱技術,而將微波技術帶進有機合成化學的領域。

微波加熱法與傳統加熱法的最大差異,乃在於能量傳遞的方式,傳統加熱法的熱能是經由接觸傳導,由容器傳遞至溶液中,而溶液則再經由對流傳導,將熱散佈,使得溶液溫度升高;而微波加熱法則是直接以輻射方式傳遞微波能量,不僅可快速加熱,同時也可減少因傳導所導致的能量損失,因此相較於傳統加熱法,微波加熱法可以明顯大幅地縮短反應時間。而微波之所以可以快速加熱的原因是因為極性分子在微波場中,其分子偶極距會隨著微波磁場的高速振動而快速旋轉,旋轉時因分子摩擦所產生的熱能被分子吸收,而使得分子溫度升高,即分子偶極的振動與微波場相作用,使物質與微波的偶合能力除了受制於微波的輸出功率外,也取決於物質本身的性質。當物質分子能吸收電磁能,以每秒數十億次的高速振動而產生熱能,所以,微波對物質的加熱方式是從物質分子本生開始的,在熱力學上來說稱為內加熱法。

而一般來說,物質吸收微波的途徑主要可分為兩種,一種是偶極轉動(dipole rotation):當一極性分子在無微波場作用時,其分子的排列會趨於最大亂度,但當相同極性分子處於微波磁場中時,則分子的偶極矩會立刻依照磁場極性的方向而呈規則性的排列,所以極性分子的偶極矩會隨著微波磁場,以每秒數十億次的高速振動而快速轉動,使分子產生摩擦而釋放出大量的熱能,導致溶液達到快速加熱分子的目的。另一種物質吸收微波的途徑是藉由離子導電(ionic conductance):溶液中含有離子性物質,因微波場作用使得離子性物質隨著磁場振盪而遷移,進而產生電流傳導。

目前利用微波技術應用於有機合成方面的文獻報導,多針對微波快速加熱方式,可縮短反應時間,達到節省能源的目的,但是也有不少文獻報導微波除了可以加快反應速率之外,通常也可將產率提高、減少副產物、並降低傳統加熱法對環境所產生的污染因子,因此化學家認為微波技術是結合了高速率、高產率、高選擇性及綠色能源的新領域。
 
實例
Microwave-promoted Efficient Synthesis of C6-cyclo Secondary Amine Substituted Purine Analogues in Neat Water — The synthesis of C6-cyclo secondary amine-substituted purine analogues in neat water was achieved with the aid of microwave irradiation. New(2008.10.2)
Microwave-assisted Synthesis of Oligothiophene Semiconductors in Aqueous Media Using Silica And Chitosan Supported Pd Catalysts — 運用 microwave-assisted 在水溶液下合成 oligothiophene semiconductors. New(2008.10.2)
Recent Developments in Microwave-assisted Polymerization With A Focus on Ring-opening Polymerization — 運用 microwave-assisted 進行 polymerization. New(2008.10.2)
Microwave-Assisted Synthesis of Amides from Various Amines and Benzoyl Chloride under Solvent-Free Conditions: A Rapid and Efficient Method for Selective Protection of Diverse Amines — 運用 microwave-assisted 和 Solvent-Free 來合成 Diverse Amines. New(2008.10.2)
A Microwave-Assisted and Heteropolyacids- Catalysed Cyclocondensation Reaction for the Synthesis of 4(3H)-Quinazolinones — 運用 microwave-assisted 合成 4(3H)-Quinazolinones.
Microwave Induced Synthesis and Anti bacterial Activity of Some 6-(2-Hyroxy phenyl)-4-(substituted phenyl) -3-oxo-2, 3, 4, 5- tetrahydro-1H-indazoles — 運用 microwave-assisted合 成 6-(2-Hyroxy phenyl)-4-(substituted phenyl) -3-oxo-2, 3, 4, 5- tetrahydro-1H-indazoles. New(2008.10.2)
Microwave-Assisted One-Pot Synthesis of Symmetrical 4H-Pyran-4-ones — 運用 microwave-assisted 和 Solvent-Free 來合成 4H-Pyran-4-ones. New(2008.10.2)

微波合成金屬紫質化合物 — 清華大學化工系。 update(2008.9.9)

   
書籍
Practical Microwave Synthesis for Organic Chemists — With the novice user in mind, this beginner's guide explains the basics behind microwave technology, evaluates available instruments and reaction modes, and provides practical hints for every eventuality. Includes detailed protocols for 27 often-used reactions. New(2008.10.2)
Microwaves in Organic and Medicinal Chemistry — A handy guide for organic and medicinal chemists focusing on common reaction types in medicinal chemistry, including solid-phase and combinatorial methods. Microwave theory, latest developments in instrumentation and a variety of examples from the recent literature are included.
Microwave Technology—Chemical Synthesis Applications — Microwave-accelerated chemical syntheses in various solvents as well as under solvent-free conditions have witnessed an explosive growth. This technology, which is still in its growth phase, has found widespread application predominantly exploiting the inexpensive unmodified household microwave (MW) ovens although the use of dedicated MW equipment has been rapidly gaining ground. Of special interest is the environmentally friendlier solventless approach that often involves exposure of neat reactants to MW irradiation or employs supported reagents on recyclable inorganic oxides or catalysts and has been adequately demonstrated in several MW-assisted condensation, deprotection, rearrangement, cyclization, reduction, and oxidation reactions. The rapid one-pot preparation of heterocyclic compounds from in situ generated reactive intermediates and the general application to multicomponent reactions, that are adaptable for building a library of compounds, have been accomplished using this MW technique. More recently, the strategy has been extended to combinatorial chemistry and the synthesis of a newer class of solvents, ionic liquids that are essentially molten salts with barely measurable vapor pressure. The salient features of these high yield protocols, namely, the selectivity, experimental ease of manipulation, and the enhanced reaction rates are discussed.
Microwaves in Organic Synthesis — If the source materials and products fail to withstand the usually long reaction times at high temperatures and decompose then this invariably reduces the yield. Yet the production of large amounts of waste means it is unacceptable from both an economic and an environmental standpoint. So-called green technologies are looking for alternative ways to allow clean and efficient chemical syntheses. It is against this background that microwave technology has increasingly developed into a powerful alternative that can be applied to practically the whole spectrum of organic synthesis. This volume provides those working in both research and industry with an indispensable source of information
Microwave-Assisted Organic Synthesis — This book demonstrates the underlying principles of microwave dielectric heating and, by reference to a range of organic reaction types, it’s effective use in synthetic organic chemistry. To illustrate the impact microwave assisted organic synthesis can have on chemical research, case studies drawn mainly from the pharmaceutical industry are presented.
http://www.amazon.com/exec/obidos/search-handle-url/103-4377871-0804610?url=index%3Dstripbooks%3Arelevance-above&field-keywords=Microwave+synthesis&Go.x=9&Go.y=8 — 系列有關Microwave Synthesis書籍的網頁,點選書籍後會有內容簡介。
Microwaves in Organic Synthesis — 推薦書籍。
Microwave Synthesis-Chemistry at the Speed of Light — 推薦書籍。update(2008.9.9)
Microwave-Enhanced Chemistry Fundamentals, sample Preparation, and Application — 推薦書籍。
   
Review Articles
Aqueous Microwave Chemistry: A Clean and Green Synthetic Tool for Rapid Drug Discovery — 以水為 solvent 的微波反應的 review。 New(2008.10.2)

ChemLin 中與 microwave chemistry 相關的內容 — This website shows the good research about microwave chemistry. One can know about the development of microwave chemistry, microwave assisted organic reaction enhancement (MORE) chemistry, microwave assisted organic synthesis (MAOS), microwave assisted various types of reactions such as Suzuki coupling, Heck reaction, microwave assisted ternary nitride synthesis, and microwave assisted coumarin synthesis and other synthesis. This website provides extensive review about microwave chemistry.

Microwave Assisted Medicinal Chemistry — A review describes how microwave can be useful in organic synthesis mainly in medicinal chemistry. They highlight microwave chemistry as an important tool for the fast development of molecules for rapid structure activity relationship in several programs related to various therapeutic areas.

Microwaves in Green and Sustainable Chemistry — Strauss CR, Varma RS Topics in Current Chemistry 266: 199-231 2006. Abstract: The various roles of microwave-assisted organic chemistry in green and sustainable chemistry are discussed beginning with the strategies, technologies, and methods that were employed routinely at the time the first reports of microwave applications for organic synthesis appeared. Applications of open-vessel microwave chemistry and closed-vessel microwave chemistry are presented, with sections on solvent-free methods, reactions in high-temperature water, technology for transposing reaction conditions.

Controlled Microwave Heating in Modern Organic SynthesisAngew. Chem. Int. Ed. 2004, 43, 6250-6284. The nonclassical microwave heating technique is slowly moving from a laboratory curiosity to an established technique that is heavily used in both academia and industry. The efficiency of “microwave flash heating” in dramatically reducing reaction times (from days and hours to minutes and seconds) is just one of the many advantages. This Review highlights recent applications of controlled microwave heating in modern organic synthesis, and discusses some of the underlying phenomena and issues involved.
Microwave-assisted Organic Synthesis in Near Critical Water at 300°C - A Proof-of-Concept Study Eur. J. Org.Chem. 2005, 3672-3679.Microwave-assisted organic synthesis in near-critical water (NCW) in the 270–300 °C temperature range has been investigated in a dedicated multimode microwave reactor utilizing heavy-walled quartz reaction vessels. Several different known transformations such as the hydrolysis of esters or amides, the hydration of alkynes, Diels–Alder cycloadditions, pinacol rearrangements, and the Fischer indole synthesis were successfully performed in microwave-generated NCW without the addition of an acid or base catalyst.
The Impact of Microwave Synthesis on Drug Discovery — 2006年 Nature Reviews Drug Discovery 之回顧論文。
Microwave Assisted Organic Synthesis – A Review — 1998年 Tetrahedron review 關於原理。
Microwave Assisted Synthesis– A Critical Technology Overview — 本篇著重於微波領域之反應工程,討論包含了平行化與可量產的反應。在文章後段並以實例說明微波合成的實驗程序。
Focused Microwave-assisted Soxhlet Extraction: Devices and Applications (Talanta, Volume 64, Issue 3, 20 October 2004, Pages 571-577 )— 2004年Focused microwave-assisted Soxhlet extraction裝置與應用回顧。
Microwave-assisted Solvent Extraction of Environmental Samples (Trends in Analytical Chemistry, Volume 19, Issue 4, April 2000, Pages 229-248) — 2000年Microwave-assisted solvent extraction應用於環境樣品論文回顧。
   
Hot Articles
Development of Microwave-assisted Extraction Followed by Headspace Single-drop Microextraction for Fast Determination of Paeonol in Traditional Chinese MedicinesJournal of Chromatography A, 2006, 1103, 15-21.
Focused Microwave Aqueous Extraction of Chlorophenols from Solid Matrices and Their Analysis by Chromatographic Techniques — Journal of Chromatography A, Volume 1069, Issue 2, 1 April 2005, Pages 275-280
Determination of Residues of Quinolones in Pig Muscle: Comparative Study of Classical and Microwave Extraction Techniques — Analytica Chimica Acta, Volume 539, Issues 1-2, 10 May 2005, Pages 77-82
Determination of Dichlorvos by On-line Microwave-assisted Extraction Coupled to Headspace Solid-phase Microextraction and Gas Chromatography-electron-capture DetectionJournal of Chromatography A, 2002. 976(1/2), 349.
Determination of Chlorophenols in Soil Samples by Microwave-assisted Extraction Coupled to Headspace Solid-phase Microextraction and Gas Chromatography-electron-capture Detection.Journal of Chromatography A, 2003. 1012(2), 111.
Determination of Organochlorine Pesticides in Water Using Microwave Assisted Headspace Solid-phase Microextraction and Gas Chromatography.Journal of Chromatography A, 2003. 1012(2), 129.
Determination of Aniline in Silica Gel Sorbent by One-step in Situ Microwave-assisted Desorption Coupled to Headspace Solid-phase Microextraction and GC–FID — Talanta, Volume 64, Issue 3, 20 October 2004, Pages 650-654
   
News
Chemists Using Microwave Energy to Speed Chemical Reactions — This report provides how chemists using microwave chemistry to speed the chemical reactions. It also describes microwave facilities in University of Connecticut
Developments in Microwave Chemistry — 2005年4月Chemistry World月刊之報導。
   
重要網站
Alternative Chemical Synthetic Pathways — Solvent-Free Processes Using Mechanochemical Mixing or Supported Reagents; Accelerated Organic Syntheses via Activation by Microwave- and Ultrasound Irradiation in Eco-friendly Media. New(2008.10.2)
Greener and Expeditious Synthesis of Bioactive Heterocycles Using Microwave Irradiation — 介紹有關微波合成技術運用於生物活性的雜環化合物的網站。New(2008.10.2)
Center for Microwave and Analytical Chemistry (C/MAC) at DuquesneUniversity — This website describes information and advice regarding analytical sample preparation, trace analysis and microwave chemistry.

The Green Chemistry Technical Blog — This blog is linked to my site www.microwavechemportal.org . Itself specifically related to Microwave-assisted chemistries... This technical blog's objective is to put that technology and others into context of the wider-picture, with insights, their impacts within the world in general such as in Economics, Society and potential Environmental impacts. The associated sciences will be highlighted also, with appropriate discussion and links to further information...

Microwave Chemistry 有很多微波的相關網頁可以連結。
About Microwave Synthesis — 介紹微波合成及列出一些微波相關的reviews、articles 和 books
Microwave Chemistry — 介紹微波化學的網站。
References for Microwave-Assisted Synthesis — 介紹微波相關的book、 monographies 和 review articles (authored by C.O. Kappe)
Microwave Chemistry Highlights Microwave Chemistry Highlights 此期刊列出2004-2006年在此期刊中有關微波在合成上的實例。
Microwave-Assisted Organic Synthesis (MAOS) Webpages The MAOS Websites were created in 2000 as a general web resource guide for scientists working in the broad area of "microwave chemistry". These pages are here to provide chemists with an overview of microwave-assisted chemistry. The use of Microwaves in Organic Synthesis (MAOS) has experienced an exponential growth rate, both in industry and academia, but large numbers of scientists are still unaware of its benefits. Information on current literature, upcoming conferences, workshops and exhibitions is collected and updated regularly on these pages. Links to the websites of instrument vendors and other MAOS related organizations are also provided.
Association for Microwave Power in Europe for Research and Education — AMPERE (Association for Microwave Power in Europe for Research and Education) is an "European" non-profit association devoted to the promotion of microwave and radio frequency heating techniques for research and industrial applications. Despite the fact that AMPERE is a European association, it has a world-wide membership domain which comprises industrialists, academics and consultants.
Environmental Analysis and Microwave Chemistry Laboratory 利用微波的綠色化學實驗室網頁。
Experimental Summary 與綠色化學與微波有關的網頁,主要在介紹一些教學式的實驗。
Microwave Synthesis Web article
Microwave Synthesis Web article
微波儀器提供廠商 Microwave Instruments
微波儀器提供廠商Microwave Instruments
微波儀器提供廠商Microwave Instruments
Microwave-Enhanced Synthesis Services from Librarion This website describes the cost effectiveness of microwave enhanced highly-efficient synthesis. This information about Librarion’s Operations Director, Dr Bernard Wathey, is a recognized expert in the application of microwave-enhanced synthesis.

Chemspeed In this website they are describing about chemspeed instruments. Chemspeed is a global leader in the development of innovative instruments and consumables for scientists working in research and development laboratories including a line of fully automated parallel synthesizers, instruments for high throughput solid dispensing and liquid handling, and workstations for process research and development. Chemspeed is a premier provider of products and services that reduce time-to-market schedules, increase productivity, and lower costs in research and development.

   
Databases/Expert System
Microwave Chemistry
Biotage
Chemlin
全國碩博士論文 關於微波合成的查詢。
   
演講之Powerpoint檔案/ Summer School之資料
MAOS User Group Meeting Presentation 可下載演講內容,需成為會員。

Microwave-Mediated Synthesis: A Green Chemistry Technology Pfizer 公司 Global R&D – Cambridge Labs 之M. Pollastri 於2004年10月5日在 Microwave Assisted Organic Synthesis Symposium 會中發表演講

11th International Travelling Summer School on Microwaves & Lightwave 2001 介紹此次Summer School 的內容
Microwave-Mediated Synthesis: A Green Chemistry Technology 介紹微波的合成應用,並說明微波是一種達到綠色化學的科技。
優點與原理
   
Conferences

Microwave-Assisted Organic Synthesis (MAOS) Congress This website provides information about chemistry conference congress related to microwave assisted organic synthesis (MAOS).

3rd International Conference on Microwave Chemistry
4th International Microwaves on Chemistry Conference
Microwave Technology & Applications in Medicinal Chemistry