Green Chemistry
M.Sc. Chemistry-IV Semester
Dr. M. Seenivasa Perumal
Assistant Professor
Department Of Chemistry
Gandhigram Rural Institute
Gandhigram
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History of Green Chemistry
• Early 1900s, Chemistry grew from theories done in labs to an
industry done in factories. Example creating electricity in
power plants, making fuel for cars….
• Mid 1900s, the negative effects of the chemical pollution
were becoming apparent. Since then many countries around
the world began forming groups within their government to
combat the pollution.
• America formed the Environmental protection Agency
(EPA) in 1970. 3
History of Green Chemistry
• In 1990, the pollution prevention Act was passed, furthering
America’s policy for green chemistry.
• In 1991 “Green Chemistry invented by Paul Anstas.
• In 1998, Paul Anstas and John Warner published the book
“Green chemistry theory and Practice” this book includes 12
principles of green chemistry.
• In 1999 Royal Society of Chemistry formed the green
chemistry network and started the journal of Green
Chemistry. 4
Definition
Green Chemistry is the design of chemical products and
processes that reduce or eliminate the generation of
hazardous substances.
Green chemistry is the idea of making chemistry more
environmentally friendly as well as more sustainable.
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Green Chemistry is about….
Waste
Materials
Hazard
Risk
Energy
Cost
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Why do we need Green Chemistry ?
• Chemistry is undeniably a very prominent part of our
daily lives.
• Chemical developments also bring new environmental
problems and harmful unexpected side effects, which
result in the need for ‘greener’ chemical products.
• A famous example is the pesticide DDT.
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How green chemistry differs from
cleaning up pollution?
• Green chemistry reduces pollution at its source by minimizing or
eliminating the hazards of chemical feedstocks, reagents, solvents,
and products.
• This is unlike cleaning up pollution (also called remediation), which
involves treating waste streams (end-of-the-pipe treatment) or
cleanup of environmental spills and other releases.
• Remediation may include separating hazardous chemicals from
other materials, then treating them so they are no longer hazardous
or concentrating them for safe disposal. 8
How green chemistry differs from
cleaning up pollution?
• Most remediation activities do not involve green chemistry.
Remediation removes hazardous materials from the environment;
on the other hand, green chemistry keeps the hazardous materials
out of the environment in the first place.
• If a technology reduces or eliminates the hazardous chemicals
used to clean up environmental contaminants, this technology
would qualify as a green chemistry technology.
• One example is replacing a hazardous sorbent [chemical] used to capture mercury from the air for
safe disposal with an effective, but nonhazardous sorbent. Using the nonhazardous sorbent means
that the hazardous sorbent is never manufactured and so the remediation technology meets the
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definition of green chemistry.
How green chemistry differs from
cleaning up pollution?
• Green chemistry looks at pollution prevention on the
molecular scale.
• The Green Chemistry program supports the invention
of more environmentally friendly chemical processes
which reduce the generation of hazardous substances.
• This program works very closely with the twelve
principles of Green Chemistry.
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Principle#1
1. Prevention
It is better to prevent waste than to treat or clean up
waste after it has been created.
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Principle#1
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Principle#2
2. Atom Economy
Synthetic methods should be designed to maximize the incorporation
of all materials used in the process into the final product.
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Principle#2
The Boot ibuprofen synthesis
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Principle#2
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Principle#2
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Principle#3
3. Less Hazardous Chemical Syntheses
Wherever practicable, synthetic methods should be designed to use
and generate substances that possess little or no toxicity to human
health and the environment.
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Principle#3
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Principle#3
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Principle#4
4. Designing Safer Chemicals
Chemical products should be designed to affect their desired function
while minimizing their toxicity.
4,5-dichloro-2-octyl-4-isothiazolin-3-
one (DCOIT)
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Principle#4
4. Designing Safer Chemicals
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Principle#5
5. Safer Solvents and Auxiliaries
The use of auxiliary substances (e.g., solvents, separation agents, etc.)
should be made unnecessary wherever possible and innocuous when
used.
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Principle#5
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Principle#5
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Principle#5
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Principle#5
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Principle#6
6. Design for Energy Efficiency
Energy requirements of chemical processes should be recognized
for their environmental and economic impacts and should be
minimized. If possible, synthetic methods should be conducted at
ambient temperature and pressure.
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Principle#6
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Principle#7
7. Use of Renewable Feedstocks
A raw material or feedstock should be renewable rather than
depleting whenever technically and economically practicable.
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Principle#7
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Principle#8
8. Reduce Derivatives
Unnecessary derivatization (use of blocking groups, protection/
deprotection, temporary modification of physical/chemical
processes) should be minimized or avoided if possible, because
such steps require additional reagents and can generate waste.
Chemoselective:
A reaction that operates exclusively on one functional
group in the presence of other functional groups. This
NaBH4 reduction is chemoselective because the ketone is
reduced but the ester is unchanged. 32
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Principle#9
9. Catalysis
Catalytic reagents (as selective as possible) are superior to
stoichiometric reagents.
Catalytic Reduction
Stoichiometric Reduction
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Principle#10
10. Design for Degradation
Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do
not persist in the environment.
Degradation of Sodium Lauryl sufate by microbes
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Principle#10
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Principle#11
11. Real-time Analysis for Pollution Prevention
Analytical methodologies need to be further developed to allow for
real-time, in-process monitoring and control prior to the formation of
hazardous substances.
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Principle#12
12. Inherently Safer Chemistry for Accident Prevention
Substances and the form of a substance used in a chemical process
should be chosen to minimize the potential for chemical accidents,
including releases, explosions, and fires.
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Green Catalysis
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Indian College Environment
S. No Required Conditions Possibility Remedy
1. Inert Atmosphere No Air
2. Costly Solvents No H2O, EtOH..Etc
3. Costly Substrates No Benzaldehyde,
Acetyl acetone….Etc
Cheap chemicals
4. Safety (Fume Hood) No No Adverse effect
5. Purification (column No Recrystallization
Chromatography)
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Orgin of idea
“Who will cry? When onion dies”
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Ingredients of Onion
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Preparation of Water Extract of Onion
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Synthesis of Cis-β-Enaminone Derivatives
Classical Method
Non-Green component:
• Ni metal is used
• Reflux
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Synthesis of Cis-β-Enaminone Derivatives
Stereospecific: A reaction in which the stereochemistry of
the reactants controls the outcome of the reaction.
Green Method
Green component:
• Onion extract catalyst
• Room temperature
• Atom Economic 46
Solvent Optimization
Entry Solvent Time (h) Yield (%)
1 H2O 2 85
2 MeOH 2 91
3 EtOH 2 97
4 IPA 2 76
5 CHCl3 2.5 71
6 Acetone 2 69
7 CH2Cl2 2.5 97
8 ACN 2.5 69
9 DMSO 3 88
10 DMF 3 79
11 Hexane 2.5 65
12 Toluene 2 69 47
Catalyst Loading
Entry Quantity of onion Time (h) Yield (%)
extract (mL)
1 0.5 2 98
2 0.4 2 97
3 0.3 2 97
4 0.2 2 97
5 0.1 2 97
6 0.01 2 97
7 0 2 Traces
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Stereo/Regio specific Synthesis-β-
Enaminone derivatives
Intramolecular
Hydrogen bond
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Synthesis of Cis(Z)-β-Enaminone and
Enamino Ester Derivatives
1H NMR
The downfield shift of the NH proton
is in the range of δ value 8.9–12.5
ppm which indicates the
predominant formation of the Z-β-
enaminones
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Stereospecific Synthesis Trans-β-Enaminone
derivatives
1H NMR
The NH proton was found at 6.33 ppm
and 8.08 ppm which supports the
formation of E-isomer
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Regio-specific Synthesis Cis-β- Enaminone
derivatives
13C NMR : δ 188.7
13C NMR : δ 193.5
δ 188.7 δ 162.2
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Synthesis of Enaminone derivatives
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Synthesis of Cis-β-Enamino Ester derivatives
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Proposed Mechanism
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General Scheme for synthesis of
Knoevenagel Condenzation product
Green component:
• Onion extract catalyst
• Room temperature
• H2O as solvent
• Atom economic
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Optimization of reaction conditions
Optimization of reaction condition with various solvents
Optimization for catalyst quantity
Entry Solvents Yield (%)
Entry Onion extract (mL) Time (h) Yield (%) 1 H2O 70
2 MeOH 89
3 EtOH 98
1 0.1 2 57
4 2-PrOH 76
2 0.4 4 67
5 CH2Cl2 59
3 0.5 4 80
6 MeCN 77
4 1.0 3 88
7 DMF 74
5 1.5 3 93 8 DMSO 78
6 2.0 2.5 98 9 Hexane 74
10 AcOH 71
7 0 3 Trace
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Synthesis of Knoevenagel product
13C NMR
1H NMR
δ 162.4
δ 155.0
δ 8.268 δ 115.4
CN
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Optimization of reaction conditions for
pyrimidine-2,4,6(1H,3H,5H)-trione
Optimization for catalyst quantity Optimization of reaction condition with various
solvents
Entrya Onion extract (mL) Time (h) Yield (%)b
Entrya Solvents Yield (%)b
1 H2O 90
1 0 4 43
2 MeOH 87
2 0.5 4 53 3 EtOH 83
4 2-PrOH 80
3 1 3.30 72
5 CHCl3 42
4 1.5 2.45 85 6 DCM 59
7 ACN 74
5 2 1.15 88
8 DMF 83
6 2.5 1.15 90
9 DMSO 88
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Synthesis of Knoevenagel product
1H NMR 13C NMR
H-C=C
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Proposed Mechanism
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General Scheme for synthesis of
Benzimidazole derivatives
Type-I
Type-II
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Green component:
• Onion extract catalyst
• Room temperature
• EtOH/H2O as solvent
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Optimization of reaction conditions for 2-
substituted benzimidazole
Entry Substrate (eq) Solvent Cat. (mL) Temp (oC) Time Product (eq)
a (h) Yield (%)b
Amine Aldehy 2-substituted 1,2-disubstituted
de
1 1 2 DMF (5 mL) 3 90 12 67 28
2 1 2 EtOH (5 mL) 3 70 12 53 24
3 1 1 EtOH (5 mL) 3 70 12 77 10
4 1 1 EtOH (5 mL) 1.5 70 16 89 5
5 1 1 EtOH (15 mL) 0.5 RT 18 93 -
6 1 1 EtOH/H2O 0.5 RT 24 62 10
(2:1) (15 mL)
a Unless otherwise mentioned, all the reactions were carried out using o-phenylenediamine (1 eq), 4-bromo benzaldehyde (1 eq) in various solvent and onion extract.
b The yields are all isolated.
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Synthesis of 2-substituted benzimidazoles
1H NMR 13C NMR
δ 151.7
δ 13.00
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Optimization of reaction conditions for 1, 2-
substituted benzimidazole
Entry.a Substrate (eq) Solvent Cat. Temp (oC) Time Product (eq)
(mL) (h) Yield (%)b
Amine Aldehy 2-substituted 1,2-
de disubstituted
1 1 2 EtOH 0.1 RT 12 32 55
2 1 2 EtOH 2 RT 24 31 66
3c 1 2 EtOH 2 RT 24 22 68
4 1 2.5 EtOH 2 70 12 24 73
5 1 2.5 EtOH/ H2O (2:1) 2 RT 12 09 81
6 1 2.5 EtOH/ H2O (1:2) 2 RT 36 18 43
7 1 2.5 H2 O 2 RT 12 26 51
a Unless otherwise mentioned, all the reactions were carried out using o-phenylenediamine (1 eq), 4-bromo benzaldehyde (2.5 or 2 eq) in
different solvent and onion extract at room temperature. bThe yields are all isolated yields. C Where the catalyst onion extract was added
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after 3 h.
Synthesis of 1,2-disubstituted benzimidazole
1H NMR 13C NMR
δ 48.39
δ 5.46
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Synthesis of isomeric 2-substituted and 1,2-
disubstituted benzimidazole
1H 1H NMR
NMR
OCH3 (δ3.79 & 3.78)
N-H ( δ12.6 & 12.5) CH3 (δ2.48 & 2.43)
CH3 (2.42 & 2.41)
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Proposed Mechanism
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Optimization of reaction conditions for 2-
substituted benzimidazoles
Optimization of Solvents
Optimization of catalyst loading
Entry Solvents (mL) Yield (%)
1 EtOH 95
Catalyst 2 MeOH 94
Entry Time (h) Yield (%)
(mL) 3 IPA 87
1 0.1 24 73 4 ACN 86
5 DMSO 82
2 0.5 24 89
6 DMF 88
3 0.8 24 91
7 DCM 85
4 1 24 95
8 Water 78
5 1.5 24 96
9 Toluene 81
6 0 24 No reaction 10 Hexane 89
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Synthesis of 2-substituted benzimidazole
derivatives
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Proposed Mechanism
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Major advantages of PTC in industrial applications are
listed below.
•elimination of organic solvents
•elimination of dangerous, inconvenient, and expensive reactants (NaOH,
KOH, K2CO3, etc. in-stead of NaH, NaNH2, t-BuOK, R2NLi, etc.)
•high reactivity and selectivity of the active species
•high yields and purity of products
•simplicity of the procedure
•low investment cost
•low energy consumption
•possibility to mimic counter-current process
•minimization of industrial wastes
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Acknowledgment
Research Group
Funding Agencies
SERB
UGC
Dr. K. Prabakaran E. Rajendran
DST-FIST
R. Santhiya
UGC-SAP (DRS-II)
Dr. M. Sivakumar S. Loganathan 88
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