GREEN CHEMISTRY

Prof. (Dr.) Animesh Pramanik

Department of Chemistry, University of Calcutta
92, A.P.C. Road, Kolkata- 700 009, India

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 Chemical products
Modern civilization depends on chemical
products which come from chemical industries.
1. Organic polymers such as (a) Polyvinyl chloride (PVC),
(b) Polystyrene (PS), (c) Nylon, (d) Teflon (polytetra-
fluoro ethylene), (e) Thermoplastic polyurethanes
(TPU)
2. Insecticides, Pesticides, Chemical fertilizers
3. Paints and Dyes
4. Drugs and Medicines
5. Cosmetic and Beauty products
6. Glass and ceramic products

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 Industrial Pollutions: A + B Product + WASTE
1. The wastes are thrown into the environment in the form of
gas, liquid or solid. In all cases either the air or water or
land is polluted due to dumping of wastes.
2. Due to industrial activities, a variety of poisonous gases like
NO, SO2, NO2, SO3, Cl2, CO, CO2 etc. volatiles
chemicals, dust etc. liberated into the atmosphere causing
acute pollution problem.
3. Many of the above poisonous gases causes depletion of
ozone layers, creation of ozone hole, green house effect,
global warming, acid rain etc.
4. Some products are non-degradable like polymers. Some
pesticides have long life-time (like DDT), causes several
environmental hazards. Sometimes we are also to use the
hazardous substances.
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 To prevent or minimize the formation and use of such
hazardous substances the chemists are required to develop
the novel technologies. This need has inspired the
generation of the new branch of chemistry called GREEN
CHEMISTRY which follows the principle, PREVENTION
IS BETTER THAN CURE.
Green Chemistry is the designing of the chemical
processes and products that reduce or eliminate the use
and formation of hazardous substances. Green Chemistry
is defined as environmentally benign chemical synthesis.
The following basic principles of green chemistry have
been formulated.
BASIC PRINCIPLES OF GREEN CHEMISTRY
1. Prevention or minimization of waste/by-products as much
as possible
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Four R’s (4R’s) and integrated waste management
(IWM): These four R’s are – reduction (at source),
recycling, reuse and recovery.

Reduction (at source)

Reuse

IWM

Recovery Recycling

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2. Maximum incorporation of the reactants (starting
materials and reagents) into the final products.
A+B Product + Waste
It minimizes the formation of by-products/waste
3. Prevention or minimization of hazardous/toxic
products.

4. Designing of safer chemicals.

5. Energy requirement for any synthesis should be

minimum.
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6. Selecting the most appropriate solvent.
Replacement of organic solvent by water or complete
elimination of the use of solvent (solid state
reactions).
7. Selecting appropriate starting materials. Use of
renewable starting materials.
8. Use of the protecting groups should be avoided
whenever possible.
9. Use of catalysts should be preferred whenever
possible.
10. Products obtained should be biodegradable or
degradable.
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The concept of Atom Economy in Chemical
Synthesis
A+B Product + Waste

Formula weight of the

desired product
% of Atom Economy = X 100
Sum of formula weight
of the all reactants (A+B)

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Some representative reactions with 100% atom
economy (totally green reactions without
formation of by-products)
Ni-Cat
CH3-CH=CH2 + H2 CH3-CH2-CH3
(Propene) (Propane)

Diels-Alder Reaction:

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Substitution Reaction:
CH3-CH2-CO-OC2H5 + CH3-NH2
(Ester) (Amine)

CH3-CH2-CO-NHCH3 + C2H5OH
(Amide) (Alcohol)
Reactants Product by-product
Formula FW Formula FW Formula FW
C5H10O2 102.132 C4H9NO 87.106 C2H5OH 46.07
CH5N 31.057
C6H15NO2 133.189
(Total)
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Therefore,
87.106
The % of atom economy = X 100 = 65.40
133.189

Higher is the value of % of Atom Economy

greener is the reaction

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 Environmental Factor or E-factor
It is a parameter which gives a measure of the green credential of a
reaction for industrial application.
A + B Product + Waste

Mass of wastes (gm)

E-factor =
Mass of product (gm)

Mass of raw materials (gm) – Mass of products (gm)

=
Mass of product (gm)
gm
= < 1
gm
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• Lower is the value of E-factor greener is the
process

• Generally E-factor should be less than 0.5

• A value around 0.3-0.2 indicates good green

credential

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Some important techniques and directions in practicing
green chemistry
1. Green starting materials(renewable feedstock)
2. Green Chemical Products (degradable waste,
degradable polymers, degradable pesticides)
3. Use of green reagents and catalyst (Bio-catalysts)
4. Use of green solvents (Water, solid state reactions)
5. Employ green reaction conditions (save energy, high
atom economy and low E-factor)
6. Use of unconventional energy sources (Micro wave
induced green synthesis, Ultrasound Assisted green
synthesis)

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Synthesis Involving Basic Principles of Green Chemistry
Synthesis of Urethane:
Urethane is required in large quantities for the manufacture
of polyurethanes, a class of important polymers which are
used for a number of commercial applications.
Urethane was synthesized earlier using phosgene, an
extremely hazardous chemical.
R-NH2 + COCl2 R-N=C=O + 2HCl
Amine Phosgene Isocyanate
R’OH
RNHCOOR’
Urethane
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Monsanto company has developed a method for the
synthesis of urethanes eliminating the use of
phosgene.

R-NH2 + CO2 R-N=C=O + H2O

R’OH

RNHCOOR’
Urethane

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Synthesis of Methyl Methacrylate (MMA): MMA is used
in large quantity for manufacture of polymer. It was
earlier synthesized as shown below.

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A very convenient and green synthesis of MMA,
developed by the Shell Corporation is given
below.

Propyne

MMA

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The new synthesis employs a palladium catalyst and enjoy 100%
atom economy compared to the conventional synthesis, which
besides using an extremely poisonous HCN enjoys only 47%
atom economy.

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Poly(methyl methacrylate) is produced by free‐radical
polymerization of methyl methacrylate in mass (when
it is in sheet form) or suspension polymerization

Free radical polymerization

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 Adipic Acid

Adipic acid is required in large quantities (about 1 billion

kg a year) for synthesis of nylon, plasticizers and
lubricants. Conventionally, adipic acid is made from
benzene, a non-renewable source (petroleum feedstock).

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 Conventional Industrial Synthesis of Adipic Acid

Here adipic acid is obtained from benzene, which is

carcinogenic and is a petroleum feedstock (nonrenewable
source). In addition in this synthesis nitrous oxide (N2O) is
generated as a by-product, which contributes to the (i)
green house effect as well as (ii) destruction of ozone layer

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Green Synthesis of Paracetamol

Paracetamol (p-acetamidophenol) is widely

used to treat pain and fever.

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Conventional route to prepare paracetamol

This conventional route produces a huge amount of

industrial waste
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Green synthesis of paracetamol

p-hydroxyacetophenon

Oxime

Titanium (IV)-silicte(TS-1) catalyses the controlled oxidation

of NH3 by H2O2 in the micropores to generate NH2OH
(hydroxylamine) in situ: NH3 + H2O2 NH2OH
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 Green synthesis of paracetamol involves two steps:

(i) TS-1 catalysed oxime formation which is very

economic step and it gives a minimum burden of
waste product on the environment
(ii) The second step is a molecular rearrangement step
enjoying atom economy 100%. Thus the second step
does not produce any waste or by-product

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