Chemistry is in every thing

and every thing is in Chemistry

Contribution of Chemistry
Life saving drugs
Materials
Nano-technology
Textiles
Fertilizers
Pesticide
Insecticide
Herbicides
Energy
Achieved at the cost of Pollution
Toxic Release Inventory (TRI)
Green is a strong color. Green is the color of
chlorophyll and green is the color of money
(US dollar). Being green has long been a
battle cry of environmental activists and
being green has become an important
marketing tool for business.

And for chemists, it is becoming increasingly
important to be "green" by applying the
principles of green chemistry to all facets of
chemical sciences.
DEFINITIONS OF GREEN CHEMISTRY
Green Chemistry is the design of chemical products and
processes that reduce or eliminate the use and generation
of hazardous substances. It also refers to the discovery of
new chemistry and/or technology leading to prevention
and/or reduction of environmental, health and safety
impact at source. J H Clark
Green Chemistry is the utilization of a set of principles
that reduces or eliminates the use or generation of
hazardous substances in the design, manufacture and
application of chemical products. P T Anastas & J C
Warner (Green Chemistry: Theory and Practice, OUP)
Green chemistry efficiently utilises (preferably renewable)
raw materials, eliminates waste and avoids the use of toxic
and/or hazardous reagents and solvents in the manufacture
and application of chemical products. R A Sheldon
Green chemistry, also called sustainable chemistry, is a
chemical philosophy encouraging the design of products
and processes that reduce or eliminate the use and
generation of hazardous substances
Click chemistry is a chemical philosophy introduced by
K. Barry Sharpless in 2001 and describes chemistry
tailored to generate substances quickly and reliably by
joining small units together. This is inspired by the fact
that nature also generates substances by joining small
modular units.
Inspiration from Nature
Paul Anastas and John C. Warner developed 12 principles of green
chemistry, which help to explain what the definition means in
practice.

The principles cover such concepts as:
the design of processes to maximize the amount of raw material that
ends up in the product
the use of safe, environment-benign substances, including solvents,
whenever possible
the design of energy efficient processes; the best form of waste
disposal: not to create it in the first place.
The Principle
The Twelve Principles of Green Chemistry
1. Prevention of wastes
2. Maximization of the utilization of starting materials
3. Generation of non-toxic substances
4. Design of functionally efficient products
5. Minimization of the use of auxiliaries including solvents, use of
innocuous solvents
6. Minimization of energy requirements
7. Use of renewable raw materials
8. Avoidance of unnecessary derivatization, etc.
9. Use of catalytic reagents
10. Design and use of environmentally degradable chemicals
11. Adequate process monitoring and control
12. Chemical design to minimize potential accidents
Principle 1:
Prevent waste: Design chemical syntheses to prevent
waste, leaving no waste to treat or clean up.
In CASCADE reactions multiple chemical transformations take
place within a single reactant
In Multi-component reactions up to 11 different reactants form a
single reaction product.
In Telescopic synthesis one reactant goes through multiple
transformations without isolation of intermediates.
Many strategies exist in chemical synthesis that go beyond
converting reactant A to reaction product B.
A Cascade reaction or Tandem reaction or Domino
reaction is a consecutive series of intramolecular
organic reactions which often proceed via highly
reactive intermediates
Dr. L. F. Tietze
In chemistry, a multi-component reaction (or
MCR) is a chemical reaction where three or more
compounds react to form a single product.
Prof. Ivar Ugi
In chemistry a one-pot synthesis is a strategy to improve the efficiency of a
chemical reaction whereby a reactant is subjected to successive chemical
reactions in just one reactor (pot). This is much desired by chemists because
avoiding a lengthy separation process and purification of the intermediate
chemical compounds would save time and resources while increasing chemical
yield.
Basically, it is a sequential one-pot synthesis with reagents added to a reactor
one at a time and without work-up is also called a telescoping synthesis.
Telescopic Synthesis or One-pot Synthesis
Principle 2:
Design safer chemicals and products: Design
chemical products to be fully effective, yet have little
or no toxicity.
Chemicals include inorganic substances such as lead, mercury,
asbestos, hydrofluoric acid, and chlorine gas, organic compounds
such as methyl alcohol, most medications, and poisons from living
things.
Love Canal, in Niagara Falls, New York was used as the site for
chemical waste. Hundreds of suspected carcinogens were dumped.
The site was eventually closed, but a school and several apartment
homes were built. Heavy rains led to leaching and puddles of
chemical wastes formed in the neighborhood. Higher than normal
rates of miscarriage and birth defects were reported.

http://www.epa.gov/history/topics/lovecanal/01.htm
Principle 3:
Design less hazardous chemical syntheses: Design
syntheses to use and generate substances with little
or no toxicity to humans and the environment.
Principle 4:
Use renewable feedstock: Use raw materials and
feedstock that are renewable rather than depleting.
Renewable feedstock are often made from agricultural
products or are the wastes of other processes;
CO
2
is renewable feed stock, oils and fats, glycerine.
depleting feedstock are made from fossil fuels (petroleum,
natural gas, or coal) or are mined.
Adipic Acid Synthesis
COOH
COOH
or
HNO
3
oxidation needed for conversion of ol/one
mixture
Not environmentally friendly
Biocatalysed Production of Adipic Acid
(Draths-Frost synthesis)
1. Highly choosy genetically engineered
microbe used
2. Avoids using carcinogenic benzene
3. Eliminates N
2
O formation
4. Uses glucose as a renewable source
GC Advantages of D-F Synthesis
An outstanding instance of biocatalysis. Although transition metal
based catalysts also may be effective, the above is an attractive
reaction. Commercially?
Production of methyl methacrylate by two
alternative routes
H
C N
H
3
C CH
2
O
C
H
H
N
H
3
C
O
CH
2
H
CH
3
O H
O
S
O
OH
OH
47% atom economy
H
3
C
CH
2
O
O
CH
3
H
3
C C CH + CO + H
3
C OH
Pd
100% atom economy
H
3
C
CH
2
O
O
CH
3
Replacement of a bad catalyst with a good catalyst
OH O
OH O
OH
OH
O
OH OH
OH
O
H
+
H
+
-pinene
verbenol verbenone
-pinene oxide isopinocamphenol isopinocamphenone
trans carveol trans sobrerol
1,2-pinanediol campholenic aldehyde
H
2
O/ Lewis acid
Reaction scheme of a-pinene oxidation
Product selectivity may be guided by catalysts used.
=
BIOMASS TO PRODUCTS VIA DEGRADED
MOLECULES
Biomass is firstly converted by gasification to synthesis
gas, which may then be converted to hydrocarbons or
methanol that are subsequently converted to
intermediate products and then to end products using the
classical synthesis routes developed for petroleum
feedstock.

Chemical Routes for the Transformation of
Biomass into Chemicals
Catalytic reactions can help to transform
carbohydrates, vegetable oils, animal fats, and
terpenes into valuable or potentially valuable
chemicals and fine chemicals.

Corma et al. Chem. Rev. 2007, 107, 2411-2502.

Platform molecules obtainable from biomass:
Lactic acid Succinic acid
3-Hydroxypropionic acid Itaconic acid
Glutamic acid
Organic Chemistry with Succinic Acid
CO
2
and biomass may be used to produce succinic acid.
Formation of valuable products from fats and oils
Summary of chemicals obtained from glucose oxidation
Principle 5:
Use catalysts, not stoichiometric reagents: Minimize
waste by using catalytic reactions. Catalysts are used
in small amounts and can carry out a single reaction
many times. They are preferable to stoichiometric
reagents, which are used in excess and work only
once.
ADVANTAGES OF CATALYSIS
Increases product yield
Lowers energy demand
Enhances productivity by ensuring faster
reactions
Enhances product selectivity

Simultaneously achieving the dual goals of
environmental protection and economic benefit.
Transition metal complexes as Homogeneous
catalysts for highly selective organic transformations.
Catalytic reactions carried out in absence of solvents
leads to the elimination of hazardous solvent wastes.
Supported catalytic reagents based on immobilization
of transition metal catalysts on nanoporous inorganic
solids. Heterogeneous catalysts
Biocatalyst
Advantages
ADVANTAGES OF CATALYSIS
The Jones Reagent (Stoichiometric)
3 PhCH(OH)CH
3
+ 2 CrO
3
+ 3 H
2
SO
4
3 PhCOCH
3
+ Cr
2
(SO
4
)
3
+ 6 H
2
O
Atom Economy = (360/860) 100 = 42%
Byproduct = Cr
2
(SO
4
)
3
undesirable
A Catalytic Route
Atom Economy = (120/138) 100 = 87%
Byproduct = H
2
O innocuous
Classical methods for forming alkyl aromatic derivatives from benzene
New and Improved Aromatic Chemistry
Alternatively, hydroquinone is produced (together with
catechol) by (TS-1)-catalysed hydroxylation of phenol
with aqueous hydrogen peroxide.
Zeolite-catalysed vs. classical Friedel-Crafts acylation
TS-1 CATALYZED OXIDATIONS WITH H
2
O
2
Heterogeneous catalysis
C
6
H
6
O + H
2
O
2
+ CH
3
OH + H
2
CO + 1/2 O
2
C
8
H
8
O
3
+ 3 H
2
O
Overall Reaction for Rhodia Vanillin Process
Vanillin
Importance of Heterogeneous Catalysis
S. Ratton, Chem. Today, March-April, 1998, p.33
Biocatalysis
Mild conditions ambient temperature and pressure,
physiological pH used
Fewer steps (no protection/deprotection) used
Largely avoids toxic/hazardous reagents & solvents
High chemo-, regio- and stereoselectivities
Involves the use of whole microbial
cells or an isolated enzyme to effect catalysis.
Advantages
In other chemical fields, such as organometallic catalysis, turnover
number (abbreviated TON) is used with a slightly different meaning:
the number of moles of substrate that a mole of catalyst can convert
before becoming inactivated.

An ideal catalyst would have an infinite turnover number in this
sense, because it wouldn't ever be consumed, but in actual practice
one often sees turnover numbers which go from 100 to a million or
more.
The term turnover frequency (abbreviated TOF) is used to refer to
the turnover per unit time, as in enzymology.
In enzymology, turnover number (also termed kcat) is defined as the
maximum number of molecules of substrate that an enzyme can
convert to product per catalytic site per unit of time.
For example, carbonic anhydrase has a turnover number of 400,000
to 600,000 s
-1
, which means that each carbonic anhydrase molecule
can produce up to 600,000 molecules of product (CO
2
) per second.
Catalytic Turnover number
herbicide intermediate
97% conv. / 96% sel.
Immobilized whole cells of P. chlororaphis B23
Catalyst consumption 0.006 kg/kg product
Higher conv./sel. than chemical process (MnO
2
cat. /130
o
C)
Nitrile Hydrolysis
Principle 6:
Avoid chemical derivatives: Avoid using blocking or
protecting groups or any temporary modifications if
possible. Derivatives use additional reagents and
generate waste.
Carbohydrate, nucleic acid, aminoacid, peptides
Principle 7:
Maximize atom economy: Design syntheses so that
the final product contains the maximum proportion
of the starting materials. There should be few, if
any, wasted atoms.
The actual amount of waste formed in a process, including
solvent losses, acids and bases used in work-up, process
aids, and, in principle, waste from energy production.
Can be derived from amount of raw materials purchased
/amount of product sold, i.e., from the mass balance:
E = [raw materials-product]/product
A good way to quickly show the enormity of the waste
problem. Lower value is always better.
The E Factor
(A concept developed by R A Sheldon)
The actual amount of waste formed in a process,
including solvent losses, acids and bases used in
work-up, process aids, and, in principle, waste from
energy production.
Can be derived from amount of raw materials
purchased /amount of product sold, i.e., from the
mass balance:
E = [raw materials-product]/product
A good way to quickly show the enormity of the
waste problem. Lower value is always better.
The E Factor
(A concept developed by R A Sheldon)
Sector E - Factor Product Tonnage
Oil Refining 0.1 10
6
- 10
8
Bulk Chemicals 1 5 10
4
10
6
Fine Chemicals 5 50+ 10
2
10
4
Pharmaceuticals 25 100+ 10 10
3
E - Factor = Total waste generated per kg of Product
Magnitude of Challenge
1. STOICHIOMETRIC BRNSTED ACIDS & BASES
Aromatic nitrations with H
2
SO
4
/ HNO
3
Acid promoted rearrangements, e.g., Beckmann (H
2
SO
4
)
Base promoted condensations, e.g., Aldol (NaOH, NaOMe)
2. STOICHIOMETRIC LEWIS ACIDS
Friedel-Crafts acylation (AlCl
3
, ZnCl
2
, BF
3
)
3. STOICHIOMETRIC OXIDANTS & REDUCTANTS
Na
2
Cr
2
O
7
, KMnO
4
, MnO
2
LiAlH
4
, NaBH
4
, Zn, Fe/HCl
4. HALOGENATION & HALOGEN REPLACEMENT
Nucleophilic substitutions
5. SOLVENT LOSSES
Air emissions & aqueous effluent
Origin of Wastes
Amount of Waste = amount of raw material amount of product
Atom Economy
Note that atom economy can be poor even when chemical
yield is near 100%

Atom economy is just one way to evaluate a chemical process.
Other criteria can include energy consumption, pollutants
released and price.
Examples of Atom Efficient Reactions
ATOM ECONOMY

Atom Economy Table






% Atom Economy = (FW of atoms utilized/FW of all reactants)
X 100 = (137/275) X 100 = 50%

Principle 8:
Use safer solvents and reaction conditions: Avoid
using solvents, separation agents, or other auxiliary
chemicals. If these chemicals are necessary, use
innocuous chemicals. If a solvent is necessary, water
is a good medium as well as certain eco-friendly
solvents that do not contribute to smog formation or
destroy the ozone.
Current Approach
No solvent
Water
Carbon dioxide (Super critical)
Ionic liquids
Lactate esters
Fluorous phase reactions
Water
Acetone
Ethanol
2-propanol
Ethyl acetate
Isopropyl acetate
Methanol
Metyl ethyl ketone
1-Butanol
t-Butanol
Preferred
Cyclohexane
Heptane
Toluene
Methylcyclohexane
Methyl t-butyl ether
Isooctane
Acetonitrile
2-MethylTHF
Tetrahydrofuran
Xylenes
Dimethyl sulphoxide
Acetic acid
Ethylene glycol
Usable Undesirable
Green Chem., 2008, 10, 31-36
Solvent Selection Guide
Pentane
Hexane
Di-isopropyl ether
Diethyl ether
Dichloromethane
Dichloroethane
Chloroform
Dimethyl formamide
N-Methylpyrrolidinone
Pyridine
Dimethyl acetate
Dioxane
Dimethoxyethane
Benzene
Carbone tetrachloride
Principle 9:
Increase energy efficiency: Run chemical reactions
at ambient temperature and pressure whenever
possible.
Principle 10:
Design chemicals and products to degrade after use:
Design chemical products to break down to
innocuous substances after use so that they do not
accumulate in the environment.
Example: Biodegradable or photodegradable materials
Principle 9:
Analyze in real time to prevent pollution: Include in-
process real-time monitoring and control during
syntheses to minimize or eliminate the formation of
byproducts.
Principle 10:
Minimize the potential for accidents: Design
chemicals and their forms (solid, liquid, or gas) to
minimize the potential for chemical accidents
including explosions, fires, and releases to the
environment.
PRINCIPLES OF GREEN
CHEMISTRY
PRINCIPLES OF GREEN ENGINEERING
P
Prevent wastes
I
Inherently non-hazardous and safe
R
Renewable materials
M
Minimize material diversity
O
Omit derivatization steps
P
Prevention instead of treatment
D
Degradable chemical products
R
Renewable materials and energy inputs
U
Use safe synthetic methods
O
Output-led design
C
Catalytic reagents
V
Very simple
T
Temperature, Pressure ambient
E
Efficient use of mass, energy, space & time
I
In-Process Monitoring
M
Meet the need
V
Very few auxiliary substances
E
Easy to separate by design
E
E-factor, maximize feed in product
N
Networks for exchange of local mass & energy
L
Low toxicity of chemical products
T
Test the life cycle of the design
Y
Yes its safe
S
Sustainability throughout product life cycle
M. Poliakoff et al., Green Chem., 2008, 10, 268
The 24 Principles of Green Chemistry and Green Engineering
PRODUCTIVE IMPROVEMENTS
Environmental Science and Green Chemistry

# Both areas of study seek to make the world a better place

# These two are complementary to each other.

# Environmental Science identifies sources, elucidates
mechanisms and quantifies problems in the earths
environment

# Green Chemistry seeks to solve these problems by
creating alternative , safe technologies

# Green Chemistry is NOT Environmental Chemistry

# Green Chemistry targets pollution; prevents at the source
during the design stage of a chemical process and thus
prevents pollution before it begins
Carbon Footprint is a measure of the impact our activities have on the
environment.Global warming and climate change are directly a result of
an increase in fuel consumption and subsequent release of Carbon
Dioxide (CO2) in the air. Approximately 225 kgs of CO2 is emitted for
about 1200-1500 kms of air distance.

To help reduce your Carbon Footprint when you fly, a small donation
you make to Seva Mandir, an NGO that works in the field of
afforestation in Rajasthan, will lead to more trees being planted. For
every tree planted, more that 20 kgs of CO2 is absorbed yearly.

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