Catalyst-free organic synthesis

410 Pages·2018·23.198 MB·English

by  Brahmachari, Goutam

Catalyst-free Organic Synthesis
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Green Chemistry Series
Editor-in-Chief:
James H. Clark, Department of Chemistry, University of York, UK
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2-F Series Editors:
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7 George A. Kraus, Iowa State University, USA
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0 Andrzej Stankiewicz, Delft University of Technology, The Netherlands
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7 Peter Siedl, Federal University of Rio de Janeiro, Brazil
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9/ Titles in the series:
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0.1 1: The Future of Glycerol: New Uses of a Versatile Raw Material
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oi: 2: Alternative Solvents for Green Chemistry
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or 4: Sustainable Solutions for Modern Economies
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s.rs 5: Chemical Reactions and Processes under Flow Conditions
ub 6: Radical Reactions in Aqueous Media
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p:// 7: Aqueous Microwave Chemistry
htt 8: The Future of Glycerol: 2nd Edition
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7 o 9: Transportation Biofuels: Novel Pathways for the Production of Ethanol,
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er 10: Alternatives to Conventional Food Processing
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m 11: Green Trends in Insect Control
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o 13: Challenges in Green Analytical Chemistry
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bli 15: Enantioselective Homogeneous Supported Catalysis
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17: Natural Polymers Volume 2: Nanocomposites
18: Integrated Forest Biorefineries
19: Sustainable Preparation of Metal Nanoparticles: Methods
and Applications
20: Alternative Solvents for Green Chemistry: 2nd Edition
21: Natural Product Extraction: Principles and Applications
22: Element Recovery and Sustainability
23: Green Materials for Sustainable Water Remediation and Treatment
24: The Economic Utilisation of Food Co-Products
25:BiomassforSustainableApplications:PollutionRemediationandEnergy
26: From C–H to C–C Bonds: Cross-Dehydrogenative-Coupling
27: Renewable Resources for Biorefineries
28: Transition Metal Catalysis in Aerobic Alcohol Oxidation
29: Green Materials from Plant Oils
30: Polyhydroxyalkanoates (PHAs) Based Blends, Composites
and Nanocomposites
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31:BallMillingTowardsGreenSynthesis:Applications,Projects,Challenges
32: Porous Carbon Materials from Sustainable Precursors
33: Heterogeneous Catalysis for Today’s Challenges: Synthesis,
Characterization and Applications
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1 37: Starch-based Blends, Composites and Nanocomposites
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8 38: Sustainable Catalysis: With Non-endangered Metals, Part 1
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9/ 40: Sustainable Catalysis: Without Metals or Other Endangered
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10 Elements, Part 1
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d Elements, Part 2
org | 42: Green Photo-active Nanomaterials
sc. 43: Commercializing Biobased Products: Opportunities, Challenges,
bs.r Benefits, and Risks
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p://p 44: Biomass Sugars for Non-Fuel Applications
htt 45: White Biotechnology for Sustainable Chemistry
on 46: Green and Sustainable Medicinal Chemistry: Methods, Tools and
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1 Strategies for the 21st Century Pharmaceutical Industry
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n 0 50: Fast Pyrolysis of Biomass: Advances in Science and Technology
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ed 51: Catalyst-free Organic Synthesis
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Catalyst-free Organic Synthesis
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12 Goutam Brahmachari
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8 Visva-Bharati University, India
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8 Email: [email protected]; [email protected]
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39/ GreenChemistrySeriesNo.51
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oi:1 PrintISBN:978-1-78262-412-7
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c. ISSN:1757-7039
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7 Preface
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oi: Since its first proposition in the 1990s, the topic of green and sustainable
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g | chemistry has grown considerably over the past 25 years and has become
or more popular among researchers working in all branches of chemical
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s.r science. Dedicated research endeavors have yielded innumerable green
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u products and processes so far, and over the past quarter century, well-
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p:// documented advances in the fields of green chemistry and green engin-
htt eering have framed a solid platform that motivates and empowers today’s
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7 o researchers to carry forward the flag with much enthusiasm and potential!
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0 The development of processes for the sustainable production of chemicals
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er and materials, innovations in green chemistry and engineering, at the
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e molecular, process, and systems levels, are being reported at an ever-
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No increasingrate.Hence,thenext25yearsofgreenandsustainablechemistry
n 06 are expected to become even more powerful and promising with the
o potential of finding many applications in the industrial sectors.
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he During the recent past, various greener alternatives to the traditional
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bli chemical syntheses and transformations have been described across a
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diverse field of chemistry, achieving sustainability through newer concepts
such as step- and atom-economy and E-factor. Greener features for de-
signinganalternativeprotocolforusefulorganicmoleculesand/ormaterials
include the use of bio-renewable resources, benign reaction media (use of
greenersolventsornosolvent),recyclablemagneticheterogeneouscatalysts
and minimization of byproducts or waste generation with the efficient
isolation of target products. Furthermore, consideration has been given to
the energy-efficiency in performing a chemical reaction, by judicious
screeningof reaction conditionscapable ofcarrying out the transformation
at ambient conditions, or with the use of microwaves (MWs), ultrasound
(US), visible lights and mechanical mixings (ball-milling) as green tools for
alternative heating and activation of reactants. Besides the on-going
GreenChemistrySeriesNo.51
Catalyst-freeOrganicSynthesis
ByGoutamBrahmachari
rGoutamBrahmachari2018
PublishedbytheRoyalSocietyofChemistry,www.rsc.org
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viii Preface
progress with all of these views, a somewhat challenging concept has also
beenemerginginrecenttimesconcerningwhetheracertaintransformation
could be attained efficiently without the aid of any catalyst or additive by a
careful selection of reaction conditions. If so, then it would be very inter-
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0 esting with many levels of benefits. Designing catalyst-free synthetic pro-
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F cesses is a step forward toward safe, cost-effective, waste-free, simple, and
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8 sustainable environment. The concept of the present book originated from
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1 this perception with an aim to summarize the key advances developed in
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8 recent times in this field of topical interest.
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8 ThebookCatalyst-FreeOrganicSynthesisisthefirstattempttoofferrecent
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9/ cutting-edge advances in developing organic synthetic protocols achieved
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10 without the aid of any catalyst or additive, and it features an in-depth and
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1 thorough coverage of a huge number of such organic synthetic protocols.
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d This book is unique in its authoritative, thorough, and comprehensive in-
org | clusion of a wide variety of more than 130 comprehensively screened cata-
sc. lyst-freeorganicsyntheticmethodsforthegenerationofcarbon–carbonand
bs.r carbon–heteroatom bonds, which result in a wide spectrum of chemical
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p://p compounds — aliphatic, aromatic, alicyclic and heterocycles. Clearly struc-
htt turedforeasyaccesstotheinformation,eachselectedreactionisdiscussed
on in a very compact manner through point-wise discussion covering all pos-
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1 sibleaspects.Thisbookconsistsofsixchapters.Chapter1isanintroductory
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er chapter that focuses on the essence of catalyst-free organic synthesis and
mb offers an overview of the topics covered in the book as well as guiding the
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v readersonhowtouseit.Thefivetechnicalchaptersareclassifiedbasedon
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6 their varying reaction conditions. Chapter 2 presents catalyst-free organic
n 0 transformations occurring under room-temperature conditions, while
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ed Chapter 3 covers those catalyst-free organic reactions accomplished with
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blis conventional heating. Catalyst-free organic transformations performed by
Pu means of the applications of microwave irradiation, ultrasound irradiation
and ball milling are summarized in Chapter 4, 5 and 6, respectively.
Greenchemistryischangingthepracticeofchemistrywithinindustryand
academia.Whatisalsoanequallyimportantandessentialtaskforeducators
of chemistry is to infuse the green chemistry advances into the existing
chemistry curriculum so that these new discoveries can be disseminated to
thefuturegenerationofmolecularinnovatorswhowilleventuallytacklethe
up and coming challenges in the fields of sustainable chemistry and en-
gineering. Proper training and nurturing of the future generations of
chemists,byeducatingthemaboutthesenewconcepts,arecrucialforfuture
innovations in research and industrial applications that will be needed to
meet society’s growing demand for sustainable products and processes. Al-
though notable progress has been made toward infusing green chemistry
concepts, strategies and tools into the modern chemistry curriculum, there
is still some way to go.
The book successfully integrates research advances in designing catalyst-
free reaction procedures for useful organic transformations which satisfy
several green chemistry principles and their feasibility into industrial
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Preface ix
applicationsandprocessdevelopments.Awidespectrumofsuchimportant
synthetic methodologies involving carbon–carbon and carbon–heteroatom
bondformingreactionsdealtwithinthisbookwouldsurelymakethework
of much interest to the scientists deeply engaged in organic synthesis and
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0 relatedfields.Thistimelyvolumealsoservesthepurposeasanoutstanding
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F sourceofinformationwithregardtotheindustrialapplications.Itwillserve
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8 not only as a valuable resource for researchers in their own fields, but will
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1 also motivate young scientists and advanced chemistry students in the dy-
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8 namic field of organic synthesis and practice of green chemistry.
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8 I would also like to express my deep sense of appreciation to all of the
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9/ editorialandpublishingstaffassociatedwiththeRoyalSocietyofChemistry
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10 fortheirkeeninterestinproducingthework,aswellastheirall-roundhelp
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1 toensurethatthehigheststandardsofpublicationhavebeenmaintainedin
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d bringing about this book. My effort willbe successfulonly when it is found
org | helpful to the readers at large. Every step has been taken to make the
sc. manuscripterror-free;inspiteofthat,someerrorsmayhavecreptinandany
bs.r such error is, of course, my own. Constructive comments regarding the ap-
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p://p proach of this book from the readers will be highly appreciated.
htt Finally, I should thank my wife and my son for their understanding and
on for allowing me enough time throughout the entire period of writing;
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1 without their support, this work would not have been successful.
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mb Goutam Brahmachari
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d To my most beloved sister KAMALA who lives with me at all times!
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