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A Textbook of

Green Chemistry
A Textbook of

Green Chemistry
Sankar Prasad Dey, Ph.D. (J.U)
Associate Professor, Department of Chemistry (UG &PG),
Behala College, Parnashree, Kolkata-700060, India
Former Head and Associate Professor, Department of Chemistry,
Srikrishna College, Nadia, West Bengal, India
Former Post-Doctoral Fellow, Paul Sabatier University, France

Nayim Sepay, Ph.D. (J.U)

State Aided College Teacher, Department of Chemistry (UG & PG),
Lady Brabourne College, Beniapukur, Kolkata-700017, India
Former Post-Doctoral Fellow, Jadavpur University, Kolkata, India

TECHNO WORLD®
A Textbook of Green Chemistry
By Sankar Prasad Dey & Nayim Sepay

Published by:
TECHNO WORLD
90/6A, M. G. Road,
Kolkata - 700 007
((033) 2219 6116, 2257 1650
E-mail: technoworldcal@gmail.com
This book is sold subject to the condi on that
it shall not, by way of trade or otherwise, be lent,
Copyright resold, hired, hired out, or otherwise circulated
© 2021, Reserved by the Authors without the publishers' prior wri en consent in
any form of binding or cover other than that in
which it is published and without a similar
First Edi on: September , 2021
condi on including this condi on being
imposed on the subsequent purchase and
without limi ng the wrights under copyright
Printed by: reserved above, no part of this publica on may
D.G. Offset, Kolkata be reproduced, stored in or introduced into
retrieval system, or transmi ed in any form or by
Binding by: any means (electronic, mechanical, photocopy-
Standard Binding Works ing, recording or otherwise), without the wri en
permission of both the copyright owner and the
ISBN: 978-93-92145-03-2
authors of this book.
Informa on contained in this book work has
been published by Techno World and has been
obtained by its authors from sources believed to
be reliable and are correct to the best of their
knowledge. However, the publisher and its
Price: 395 authors shall in no event be liable for any errors,
omissions or damages arising out of this
informa on and specifically disclaim any implied
warran es or merchantability of fitness for any
par cular use.
 DEDICATED
To the fond memory of my parents - Sankar P. Dey,
To my Parents and brothers - Nayim Sepay
AND
To the people of the whole world who have died in Covid-19, a worst
pandemic in the history of more than 100 years
 ACKNOWLEDGEMENT
e authors have consulted various research journals and books on the green chemistry of
the previous authors to borrow the views, ideas and information for writing this book.
ey are indebted to those authors who have made remarkable contribution in this eld.

We are highly indebted to our parents who worked hard, took pain for the continuation of
our studies and always wanted us to do something.

Dr. Dey is proud of his daughter(Manideepa) and son(Archisman) for helping him in
different ways at the time of preparing hard and so copy of the manuscript. He is thankful
to his brother (Kinkar) for his constant encouragement. He is also thankful to his brother-
in-law, Mr. Subhasish Das who took his care and helped in different ways for saving from
serious illness. He is also grateful to his loving wife(Mousumi) for providing the moral
support in completing the book.

Dr. Sepay is thankful to his parents and brothers (Nasim and Nadir) for their constant
moral support and encouragement during work of the book.

ey express their thanks to Mr. Amiya Kumar Jana for checking some chapters and giving
valuable comments in regard of improvement of the book.

Finally, we are thankful to the M/S Techno World, Kolkata for publication of the book
during Covid-19 pandemic.

Sankar Prasad Dey

Nayim Sepay
 PREFACE
e book “A Textbook of Green Chemistry” is written as per the latest CBCS syllabus of
'Green Chemistry' of the UG and PG courses of all Indian Universities and Autonomous
Colleges.

Green Chemistry is a fast developing and new area of chemistry. e subject of green
chemistry has developed tremendously in the last thirty to forty years to prevent or
minimize the harmful effects of various chemicals on the human health and the
environment. Green chemistry is now not only con ned within the students of chemistry.
Students of different other disciplines also need to know this subject. e book has been
written in a very systematic way in simple language and lucid style covering the whole
CBCS syllabus of the UGC to meet the requirements of the students in a desired way.
e book has been divided into twelve chapters to cover the full syllabus of the UG and PG
courses of green chemistry. e book covers introduction and the twelve principles of
green chemistry, metrics of green chemistry, use of green solvents, green catalysts, green
reagents, renewable energy sources (Microwave, Ultrasound and Light) in various types of
organic synthesis including solvent free synthesis, industrial applications and future
trends in green chemistry.
An added feature of the book is the inclusion of sufficient number of questions with their
answers at the end of each chapter for developing the skill of the students and familiar with
the various types of questions so that they can face the different examinations con dently.
In addition, a set of questions have been added under the head 'Exercise' to improve the
con dence level of the students to solve the unknown problems.
We hope the book will be immensely helpful to the students of chemistry of the UG and PG
courses of all the Indian universities. We are sure that in spite of our sincere effort, some
errors may have crept in. We shall be thankful to the learned readers if they bring these
errors to the notice of the authors. Following quotation may be mentioned here in regard of
errors in the book.
“A person who never made a mistake, never tried anything new”------ Albert Einstein
Constructive suggestion and comment from the readers will gladly be accepted for
improvement of the book.
Finally, we are thankful to the M/S Techno World, Kolkata for publication of the book
during Covid-19 pandemic.

5thJuly 2021, Kolkata

Sankar Prasad Dey
Nayim Sepay
 TABLE OF CONTENTS

Chapter 1 Introduction to Green Chemistry

Chapter 2 Metrics of Green Chemistry

Chapter 3 Twelve Principles of Green Chemistry

Chapter 4 Green Solvents in Organic Synthesis

Chapter 5 Solventless Reactions / Solid State Synthesis

Chapter 6 Alternative Sources of Energy in Organic Synthesis

Chapter 7 Catalysis and Green Chemistry

Chapter 8 Green Synthesis of Some Organic Compounds

Chapter 9 Applications of Some Green Reagents in Organic Synthesis

Chapter 10 Green Approaches to Some Organic Reactions

Chapter 11 Green Chemistry in Action: Some Real-World Cases

Chapter 12 Future Trends in Green Chemistry

 CONTENTS

Chapter 1 Introduction to Green Chemistry 01-10

 Origin of Green Chemistry .......................................................................................... 1
 What is Green Chemistry? ........................................................................................... 2
 Why green chemistry is called sustainable chemistry? ................................................ 3
 Need for green chemistry ............................................................................................. 3
 Goals of Green Chemistry ........................................................................................... 4
 Illustration of 4 R’s in the management of plastics ..................................................... 5
 Limitations/Obstacles of green chemistry ................................................................... 6
 Some questions with answers ...................................................................................... 7
 Exercise........................................................................................................................ 9
 References ................................................................................................................... 10

Chapter 2 Metrics of Green Chemistry 11-28

 Concept of Atom Economy or Atom Efficiency .......................................................... 11
 Atom Utilization ........................................................................................................... 11
 Atom Economy ............................................................................................................ 11
 Calculation of Atom Economy ..................................................................................... 11-17
Rearrangement Reaction, Addition Reaction, Substitution Reaction, Elimination Reaction, Single
Step Oxidation, Catalytic Process, Calculation of Atom Economy for Multistep Chemical
Synthesis
 Environmental Factor or E-factor................................................................................. 18
 Environmental Quotient (EQ) or Q-value .................................................................... 20
 Life Cycle Assessment or Life Cycle Analysis (LCA) ................................................ 21
 Some questions with answers ...................................................................................... 23
 Exercise........................................................................................................................ 28
 References ................................................................................................................... 28

Chapter 3 Twelve Principles of Green Chemistry 29-60

1. Pollution Prevention .................................................................................................... 29

2. Atom Economy or Atom efficiency:............................................................................ 29
3. Use of less hazardous and toxic chemicals .................................................................. 30
4. Safer Products by design: ............................................................................................ 30
 5. Innocuous Solvents and Auxiliaries............................................................................. 31
6. Design for energy efficiency:....................................................................................... 31
7. Preferred use of renewable raw materials or feedstocks: ............................................. 32
8. Reduce derivatives or minimization of steps: .............................................................. 33
9. Use of Catalytic Reagents: ........................................................................................... 33
10. Design products for degradation or life time of a chemical product........................... 35
11. Real-time analysis for pollution prevention ................................................................ 36
12. Inherently safer processes for accident prevention or use of safer substances ........... 36
 Designing a Green Synthesis ...................................................................................... 37
 Inherent Safer Design (ISD) ....................................................................................... 45
 Subdivision of ISD .......................................................................................... 46
Minimization, Substitution, Moderation, Simplification
 Limitations of ISD ...................................................................................................... 48
 Bhopal Gas Tragedy (Safer route to carbaryl) ............................................................ 48
 Safer Route to Carbaryl .............................................................................................. 48
 Flixborough Accident ................................................................................................. 51
 Safer Route to Cyclohexanone ................................................................................... 51
 Strengthening/Development of some important techniques in chemical processes ... 51
 Some questions with answers ...................................................................................... 53
 Exercise........................................................................................................................ 58
 References ................................................................................................................... 59

Chapter 4 Green Solvents in Organic Synthesis 60-136

 Green Solvents ............................................................................................................. 60
 Supercritical fluids (SCFs)........................................................................................... 60
 Super Critical Water (SCW) ........................................................................................ 62
 Supercritical Carbon Dioxide (SC-CO2) ...................................................................... 64
 Discussion on some commercial applications of SC-CO2 ........................................... 66
1. Supercritical carbon dioxide (SC-CO2) in cleaning industry and
Micelle technologyCO2-Recycling System in Cleaning Industry .......................... 66
2. Decaffeination of Coffee Using SC-CO2: .............................................................. 68
3. SC-CO2 in Polymer and Plastic Industry:............................................................... 69
 Reaction in Supercritical Solvents ............................................................................... 69
 Reaction in Supercritical Water (SCW) ....................................................................... 69-71
 Pyrolysis of t-butylbenzene, Pinacol-pinacolone rearrangement, Beckmann rearrangement,
Diels-Alder reactions, Reduction of aromatic nitro compounds
 Reaction in Supercritical Carbon Dioxide ................................................................... 71-74
Diels-Alder reactions, Kolbe – Schmitt reaction, Friedel–Crafts reaction, Epoxidation reaction,
C-C coupling reaction, CO insertion reaction, Baylis-Hillman reaction
 Water as Solvent in Organic Synthesis ........................................................................ 74
 Hydrophobic Effect: .................................................................................................... 76
 Hydrogen bonding effect of water .............................................................................. 77
 Evidence in favour of hydrogen bonding effect in the rate acceleration of
Diels-Alder reaction .................................................................................................... 78
 Polarity Effect of Water ............................................................................................... 79
 Marcus trans-Phase H-Bonding ................................................................................... 80
 Reactions in water...................................................................................................... 80-85
1. ‘In water’ reaction, 2. ‘On water’ reaction, 3. ‘With water’ reaction
 Reaction in Micelle..................................................................................................... 86
 Surfactants and Micelle ............................................................................................... 86
 Micellar effects ........................................................................................................... 86
 Reaction under Micellar environment ......................................................................... 87-89
Hydrolysis reaction, Nucleophilicthiolation reaction, Hydroformylation reaction, Cycloaddition
reaction, Pauson–Khand reaction
 Ionic Liquid (IL) ........................................................................................................ 89
 Ionic liquid as designer solvent ................................................................................... 91
 General methods for the synthesis of ionic liquids (ILs) (Or RTILs) .......................... 97
1. Two Step Process: Alkylation followed by anion metathesis................................. 97
2. One-Pot Synthesis of ILs or RTILS ....................................................................... 97
3. Some other routes to ILs......................................................................................... 98
 Synthesis of some chiral ionic liquids ......................................................................... 99
 Organic reactions in ionic liquids ................................................................................ 99-105
Hydrogenation reaction, Friedel–Crafts reaction, Epoxide ring opening, Diels−Alder reaction,
Oxidation reaction, Aldol condensation, Knoevenagel condensation, Baylis-Hillman reaction,
Heck reaction, Suzuki reaction, Sonogashira reaction
 Task Specific Ionic Liquids (TSILs) ......................................................................... 105
 Classification of TSILs ................................................................................................ 106
 Reaction by TSILs ....................................................................................................... 107
  Fluorous biphasic solvents ........................................................................................ 108
 Application of fluorous biphasic solvent (FBS) in organic synthesis .......................... 110
 Reaction in FBS ........................................................................................................... 111-112
Hydroformylation reaction, C-C bond formation, Trans esterification, Alcohol oxidation, Heck
reaction
 Polyethylene Glycol (PEG) ........................................................................................ 112
 Reaction in PEG........................................................................................................... 114-118
Oxidation reaction, Hydrolysis reaction, Substitution reaction, Asymmetric aldol condensation
reaction, Baylis–Hillman reaction, Diels-Alder reaction, Williamson ether synthesis, Heck
reaction, Suzuki reaction, Synthesis of heterocyclic compounds, Synthesis of pyrrole, Synthesis
of benzimidazole, Synthesis of Quinoline, Synthesis of Quinoxaline, Synthesis of Chromene
 Some questions with answers ...................................................................................... 118
 Exercise........................................................................................................................ 130
 References ................................................................................................................... 134

Chapter 5 Solventless Reactions / Solid State Synthesis 137-172

 Classification of mechanochemical reaction methods/mechanochemical reactors ...... 137
1. Grinding with mortar and pestle method ...................................................................... 138
Synthesis of heterocyclic and carbocyclic compounds ................................................ 138-139
Dihydrofurans synthesis, Hantzsch synthesis, Synthesis of dihydropyridine
2. Planetary ball milling method ...................................................................................... 139-140
Knoevenagel reaction, Strecker reaction, Synthesis of triazoles
3. High speed vibration milling (HSVM) in a mixer mill method ................................... 140-141
Alkylation reaction, Ugi reaction, Synthesis of pyrazolones
4. Solid state reaction at room temperature ...................................................................... 141-142
Aldol condensation, Reformatsky reaction, Synthesis of quinoxaline derivatives .
5. Microwave assisted solid state reactions using solid support....................................... 142
Examples of some solid support synthesis ................................................................... 143-152
Protection and de-protection reaction, Oxidation of alcohols, Oxidation of arenes,
Reductionof carbonyl compounds, Rearrangement Reactions: Pinacol-pinacolone
rearrangement, Beckmann rearrangement, Benzil-benzilic acid rearrangement, Condensation
reaction: Knoevenagel condensation, Synthesis of heterocyclic compounds:Synthesis of
benzimidazole, Synthesis of oxazoles/thiazoles, Synthesis of oxadiazoles, Synthesis of N-
arylated pyrrole derivatives, Synthesis of isoxazoles, Synthesis of dihydropyridines, Synthesis
of quinolones, Synthesis of furans, Synthesis of Pyrimidinones, Synthesis of
benzopyranopyrimidinones, Synthesis of oxadiazinanone and triazinanone, Synthesis of
acridine derivatives, Synthesis of indoles, Synthesis of quinolones, Synthesis of flavones,
Synthesis of diazine, Synthesis of oxazoline, Synthesis of some heterocycles in solid state:
 Synthesis of tetrazoles, Synthesis of xanthenes, Synthesis of cyclopropane, epoxide and
aziridine derivatives
 Some questions with answers ...................................................................................... 152
 Exercise........................................................................................................................ 153
 References ................................................................................................................... 156

Chapter 6 Alternative Sources of Energy in Organic Synthesis 157-238

 A. Microwave Chemistry .......................................................................................... 158

1. Microwave Chemistry .................................................................................................. 158
2. Reaction Conditions .................................................................................................... 159
2.1. Choice of solvent ................................................................................................. 159
2.2. Reagents............................................................................................................... 160
3. Benefits of microwave irradiation ................................................................................ 160
4. Mechanism of “Microwave effect” .............................................................................. 161
Dipolar polarization, Conduction mechanism or Ionic polarization, Interfacial polarization
5. Nature of Interaction of microwave with materials ...................................................... 162-171
5.1. Thermal effect: Overheating, Hot spot, Selective heating: Solvents, Catalyst, Reagents:
Molecular Radiators, Susceptors: (a) Graphite, Diels–Alder Reaction, Ene Reaction, (b)Silicon
Carbide, Michael Additions, Claisen Rearrangement, Dimroth rearrangement (c) Other, Ionic
liquid, Alumina–magnetite
5.2 Non-thermal effect: Diels–Alder Reaction, [2+2] Cycloaddition, Metathesis reaction
6. Microwave Assisted Organic Synthesis (MAOS) ........................................................ 171
Microwave assisted organic synthesis in water: ..................................................... 171-174
Hoffmann elimination reaction, Hydrolysis reaction (Hydrolysis reaction, Hydrolysis Esters,
Hydrolysis ofbenzamide, Hydrolysis of N-phenyl benzamide), Oxidation oftoluene,
Oxidation ofAlcohol, Epoxide ring opening, Diels-Alder reaction
Microwave Assisted organic Synthesis in organic solvent: .................................... 174-179
Esterification reaction, Rearrangement reaction (Fries rearrangement), Pericyclic reaction
(Electrocyclic reaction, Cycloaddition reaction: [2+2]-cycloaddition reaction, Diels-Alder
reaction or [4+2]-cycloaddition reaction, Sigmatropic rearrangement: Claisen rearrangement,
OrthoesterClaisen rearrangement, Fisher indole synthesis), Synthesis of chromenes,
Decarboxylation reaction, Synthesis of imidazole, Pictet–Spengler Reaction
Microwave Assisted Solid State Reaction: .............................................................. 179-184
Deacetylation, Deprotection, Saponification of esters, Alkylation of reactive methylene
compounds, Reductions (Sodiumborohydride reduction of carbonyl compounds, Reduction
of carbonyl compounds using aluminium alkoxides, Reductive amination of carbonyl
 compounds), Synthesis of nitriles from aldehydes, Synthesis of anhydrides from dicarboxylic
acids, Synthesis of pyrimidines, Synthesis of pyridines, Synthesis of benzimidazoles
Miscellaneous microwave assisted organic reactions: ............................................ 184-187
Organometallic reaction, Condensation reaction (Aldol condensation, Knoevenagel
Condensation, Substitution reaction, Addition reaction (Michael addition, Reduction reaction,
Hofmann rearrangement, Cyclisation reaction, Quinazolinobenzodiazepine alkaloids
synthesis
 Some questions with answers ...................................................................................... 188
 Exercises....................................................................................................................... 193
 B. Ultrasound Chemistry .......................................................................................... 198
Instrumentation for ultrasonication ......................................................................... 198
i) Ultrasonic cleaning bath, ii) Direct immersion sonic horn, iii)Whistle reactor, iv) The Cup
Horn
Generation of ultrasound (or ultrasonic) waves ................................................ 199
1. The piezoelectric effect, 2. Magnetostriction method ........................................ 199
The physical aspects of sonochemistry: Acoustic Cavitation ................................ 200
Example of Effect of Ultrasound in Organic Synthesis ..................................... 203
Ullmann reaction
Sonoluminescence ………………………………………………………………… 204
Ultrasound Assisted Reactions (UAR) ................................................................ 205-215
Esterification reaction, Saponification reaction, Substitution reaction, Alkylation reaction: C-
alkylation, N-alkylation, O-alkylation, S-alkylation, Reduction reaction, Cannizzaro Reaction
reaction, Coupling reaction, Ullmann reaction, Heck reaction,Stecker Synthesis, Reformatsky
Reaction,Simmons-Smith Reaction, Diels-Alder reaction,Aldol reaction, Synthesis of keto-
lactones, Condensation reaction: synthesis of chromone, Synthesis of dihydropyrimidinone
 Some questions with answers ...................................................................................... 216
 Exercises....................................................................................................................... 221

 C. Photochemistry ..................................................................................................... 225

Photo induced organic reaction .............................................................................. 225-228
Olefin isomerisation, Photoreduction: Benzopinacol formation, Pericyclic reaction, Aromatic
substitution reactions, Radical reactions, Arndt-Eistert reaction
o Norrish reaction................................................................................................. 228
o Norrish Type II reactions .................................................................................. 229
o Barton reaction .................................................................................................. 230
 Some questions with answers ...................................................................................... 231
 Exercises ...................................................................................................................... 231
 References ................................................................................................................... 233
Chapter 7 Catalysis and Green Chemistry ................................................. 239-280
 Catalyst and Catalysis .................................................................................................. 239
1. Homogeneous catalysis .......................................................................................... 239
2. Heterogeneous catalysis ......................................................................................... 240
 Catalysis in Green chemistry ....................................................................................... 241
i) Biocatalysis ............................................................................................................ 242
 Reactions using biocatalyst .......................................................................................... 243-247
Biocatalytic conversion of penicillin to 6-aminopenicillanic acid, Biocatalytic oxidation reaction,
Baeyer-Villiger oxidation, Biocatalytic hydrolysis reactions, Biocatalytic addition reaction
ii) Phase transfer catalysis .......................................................................................... 247
Quaternary ammonium or phosphonium salts, Crown ether and other cryptands
 Reactions using Phase Transfer Catalyst ..................................................................... 249
1. Quaternary ammonium salts ................................................................................... 249
Aromatic nucleophilic substitution reaction, Cyclopropanation reaction, Alkylation reaction,
Esterification reaction, Benzoin condensation,
2. Reaction using crown ethers .................................................................................... 251
Aromatic nucleophilic substitution reaction, Alkylation reaction(O-alkylation, C-alkylation, N-
alkylation)Oxidation reaction
3. Asymmetric catalysis .............................................................................................. 253
Reaction using asymmetric catalyst, Enantioselective alkylation reaction, Asymmetric annulation
reaction, Enantioselective reduction reaction
4. Photocatalysis ........................................................................................................... 255
Titanium dioxide (TiO2) as a green photocatalyst for destroying organic pollutants,
Some important photocatalytic applications of TiO2 ................................................... 258
1. Photocatalytic disinfection or sterilization: ......................................................... 258
2. Photocatalytic-cleaning and anti-soiling activities: ............................................. 258
Photo catalytic reaction, Oxidation reaction, Reduction reaction, Condensation reaction,
Coupling reaction
5. Polymer supported catalysis .................................................................................... 260
Reaction using polymer supported catalyst, Substitution reaction, Esterification reaction, Ether
formation reaction, Solid supported crown ether synthesis
 Use of other catalysis techniques in organic synthesis ................................................ 261
 Catalysis by solid acids and bases ............................................................................... 261
 Silica based solid acids ................................................................................................ 261
i. Reaction using silica supported aluminium chloride ........................................... 262
 Friedel–Crafts acylation reactions, Michael addition reaction
ii. Reaction using silica supported boron trifluoride ................................................ 262
iii. Reaction using silica supported sulfuric acid (SSA)............................................ 263
Synthesis of pyrrole fused coumarin............................................................................ 263
iv. Silica supported ionic liquids............................................................................... 264
v. Zeolite based solid acids ...................................................................................... 264
vii. Polymer based solid acid, Synthesis of xanthenes, Reduction reaction, Pinacol formation
reaction ....................................................................................................................... 265
viii. Solid supported base ............................................................................................ 264
ix. Catalysis by nano-particles ..................................................................................... 267
Reduction reaction, Multicomponent reaction (A3-condensation), Synthesis of furan, Synthesis of
flavones, C-Arylation reaction, Nano-porous TiO2 catalyzed reaction
 Catalysis by graphene oxide ........................................................................................ 269
 Graphene ...................................................................................................................... 269
 Some questions with answers ...................................................................................... 272
 Exercises ...................................................................................................................... 275
 References ................................................................................................................... 278

Chapter 8 Green Synthesis of Some Organic Compounds ........................ 281-326

 Synthesis of Adipic Acid ............................................................................................. 281
 Synthesis of catechol ................................................................................................... 283
 Synthesis of Disodium Iminodiacetate (DSIDA)......................................................... 284
 Synthesis of Citral ........................................................................................................ 285
 Synthesis of BHT (Butylatedhydroxy toluene) ............................................................ 286
 Synthesis of Methyl Methacrylate (MMA) .................................................................. 287
 Synthesis of Urethane .................................................................................................. 288
 Synthesis of paracetamol (p-acetamido phenol) .......................................................... 289
 Synthesis of Furfural .................................................................................................... 290
 Synthesis of Acetaldehyde ........................................................................................... 291
 Synthesis of Ibuprofen ................................................................................................. 292
 Synthesis of Aromatic Amines (4-aminodiphenylamine) ............................................ 294
 Some questions with answers ...................................................................................... 296
 Exercises ...................................................................................................................... 301
 References ................................................................................................................... 303
Chapter 9 Applications of Some Green Reagents in Organic Synthesis .. 305-322
1. Dimethyl carbonate ..................................................................................................... 305
a. Selective methylation .............................................................................................. 305
i) Monomethylation of active methylene compounds ii) Monomethylations of amines
b. Solid-state polymerization of amorphous polymers using diphenyl carbonate ......... 307
2. Clayan........................................................................................................................... 308
3. Free radical bromination............................................................................................... 309
4. Tellurium (Te) ............................................................................................................... 310
Dehalogenation Reaction, C-C coupling reaction, Olefination Reaction, Reduction reaction,
Oxidation Reaction, Aldol Condensation
 Polymer supported reagents (PSRs) ............................................................................. 313
Polymer supported per acid, Polystyrene methyl sulphide, Polymeric S-chlorosulphonium
chloride, Poly-N-bromosuccinimide (PNBS)
 Some questions with answers ...................................................................................... 317
 Exercises ...................................................................................................................... 319
 References ................................................................................................................... 321

Chapter 10 Green Approaches to Some Organic Reactions ....................... 323-346

A. Green counter part of some common organic reactions .............................................. 323
 Aldol condensation reaction ........................................................................................ 323
 Green Approach
1. Reaction of silyl enol ethers with aldehydes in water ............................................ 323
2. Mukaiama reaction ................................................................................................ 324
3. Reaction in ionic liquid .......................................................................................... 325
4. Reaction in PEG: L-proline catalyzed direct asymmetric aldol reaction ............... 325
5. Reaction in surfactant ............................................................................................ 326
6. Microwave irradiation ............................................................................................ 326
 Friedal-Crafts reaction ................................................................................................ 327
 Green Approach
1. Friedal-Crafts alkylation in green solvents .......................................................... 328
2. Friedal-Crafts acylation in ionic liquid medium .................................................. 328
3. Ultrasound assisted Friedal-Crafts reaction ......................................................... 329
 Michael reaction .......................................................................................................... 329
  Green Approach
1. Reaction in Water (green solvent) .......................................................................... 330
2. Reaction under microwave irradiation ................................................................... 331
 Knoevenagel condensation reaction ............................................................................ 331
 Green Approach
1. Reaction using ionic liquid ....................................................................................... 332
2. Reaction under microwave irradiation ..................................................................... 332
3. Ball-milling Process................................................................................................. 333
 Cannizaro Raction ....................................................................................................... 333
 Green Approach
1. Ultrasound assisted Cannizaro reaction.................................................................. 333
2. Microwave assisted Cannizaro reaction ................................................................. 333
 Benzoin Condensation ................................................................................................. 334
 Green Approach
1. Reaction using thiamine hydrochloride ................................................................... 335
 Dieckmann condensation ............................................................................................. 336
1. Ultrasound assisted Dieckmann reaction ................................................................. 337
B. Rearrangement reactions by green approach ............................................................... 337
 Fries rearrangement ..................................................................................................... 337
 Claisen Rearrangement ................................................................................................ 339
 Baeyer–Villiger oxidation............................................................................................ 342
 Pinacol-pinacolone rearrangement............................................................................... 343
 Some questions with answers ...................................................................................... 344
 Exercises ...................................................................................................................... 345
 References ................................................................................................................... 346

Chapter 11 Green Chemistry in Action: Some Real-World Cases ............. 347-382

1. Designing of Environmentally Safe Marine Antifoulant .............................................. 347
2. Rightfit Pigments: synthetic Azo-pigments to replace toxic pigments, Azo-pigments, Rightfit
pigments ....................................................................................................................... 348
3. Biopolymer .................................................................................................................. 356
An Efficient Green Synthesis of a Compostable and Widely Applicable Plastic (Poly-Lactic Acid,
PLA) from Corn ..................................................................................................... 357
Synthetic Method of Polylactic Acid (PLA) from Corn: ............................................. 357
 Advantages of polylactic acid over petrolium based polymers are: ............................. 358
4. Healthier Fats and Oils by Green Chemistry ................................................................ 358
Rancidification, Hydrogenation, Interesterification
5. Development of Fully Recyclable Carpet: Cradle to Cradle Carpeting ....................... 365
6. Surfactants for carbon dioxide-replacing smog producing and ozone depleting solvents with CO2
for precision cleaning and dry cleaning of garments ............................................. 366
 Some questions with answers ...................................................................................... 369
 Exercises ...................................................................................................................... 379
 References ................................................................................................................... 381

Chapter 12 Future Trends in Green Chemistry ........................................... 383-441

 A) Oxidation Reagents and Catalysts .......................................................................... 383
Tetra amido macrocyclic ligands (TAMLs)R.............................................................. 384
Some oxidation reactions by green oxidants and catalysts ......................................... 385
1. Oxidation using oxygen and catalysts ..................................................................... 385
2. Oxidation by singlet oxygen .................................................................................... 385
3. Oxidation using hydrogen peroxide: ....................................................................... 386
4. Oxidation of alkenes by peroxyacids: ..................................................................... 386
5. Oxidation of alcohols using Clayfen ........................................................................ 386
6. Oxidation of arenes using KMnO4 impregnated alumina ........................................ 387
7. Oxidation using nanoparticles ................................................................................. 387
8. Metal based catalytic reactions ................................................................................ 387
9. Reactions using phase transfer catalysts .................................................................. 389
10. Catalytic Oxidation ................................................................................................ 389
 B) Biomimetic, multifunctional reagents ..................................................................... 390
1. Biomimetic organic reaction,
Biochemical (microbial) oxidations ...................................................................... 391
2. Biochemical (microbial) reductions ....................................................................... 393
3. Biomimetic synthesis ............................................................................................. 394
4. Multifunctional reagents......................................................................................... 395
C) Combinatorial Green Chemistry ............................................................................. 397
Some example of combinatorial green chemistry ........................................................ 398
Condensation reaction, Diels Alder reaction, Multicomponent reaction
D) Proliferation of solventless reactions...................................................................... 398
 Aldol condensation, Solid supported acid catalyzed reaction, Benzil-benzilic rearrangement
Michael addition reaction, Friedel-Crafts reaction, Reformatsky reaction, Pericyclic reactions
E) Co-crystal controlled solid state synthesis (C3S3). .................................................. 404
F) Non-covalent Derivatization (NCD) ........................................................................ 408
G) Green chemistry in sustainable development .......................................................... 410
 Some questions with answers .............................................................................. 413
 Exercises .............................................................................................................. 416
 References ........................................................................................................... 418

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