GREEN

CHEMISTRY
 Outline
Introduction :12 Principles of Green Chemistry with examples
Synthesis in benign solvents
(a) Water (b) ScCO2 (c) Ionic liquids (d) PEG
(e) Fluorous solvent
Synthesis in solid state
Alternate Energy sources:
(a) MW (b) US (c) Photo induced reactions
Synthesis using Green reagents
(a) Dimethylcarbonate (b) Polymer supported reagents (c) Polymeric
NBS
Synthesis using green catalyst: Types, Advantages and applications
(a) PTC (Phase transfer catalyst), (b) Crown ethers, (c) Green
Catalysts
(d) Polymer catalyst (e) Biocatalyst
Green synthesis of industrially important compounds
(a) Adipic acid, (b)Paracetamol, (c)Caprolatum, (d) Ibuprofen
(e)Methyl methacrylate,
Green transformations mechanism
Thalidomide
Definition
• Green chemistry is defined as environmentally benign chemical
synthesis.

• Green chemistry is a fundamental approach to designing

chemical products in very environmentally friendly way without
using toxic chemicals and solvents.

Objectives:
▷To minimize/eliminate the formation of hazardous substances.
By using this approach scientists have been able to reduce the
harmful impact of chemicals on environments
 Basic Principles of Green Chemistry

1. Prevention of waste/by-products.
2. Maximum incorporation of the reactants (starting materials
and reagents) into the final product.
3. Prevention or minimization formation of hazardous products.
4. Designing of safer chemicals.
5. Energy requirement for any synthesis should be minimum.
6. Selecting the most appropriate solvent.
7. Selecting the appropriate starting materials.
8. Use of the protecting group should be avoided whenever
possible.
9. Use of catalysts should be preferred wherever possible.
10. Products obtained should be biodegradable.
11. The manufacturing plants should be so designed as to
eliminate the possibility of accidents during operations.
12. Strengthening of analytical techniques
1. Prevention of Waste/By -Products

We should design a synthesis in which minimum waste product

should be formed.

Disadvantages…

1. Waste product causes Pollution of environment

2. It involves expenditure for cleaning of the waste products

Therefore prevention is always better than cure.

2. Atom Economy: Maximum Incorporation of the
Reactants (Starting Materials and Reagents) into the
Final Product

Synthetic process should be designed in such a way that output should

be maximum, i.e. maximum incorporation of reactants

Example:
A + B  C + D
desired by-product
MW ( C )
% Atom economy (A.E.)= ----------------------------- x 100
MW ( A + B )

In calculation of Atom economy molecular weight of by -product is not considered

Example 1
Consider the substitution reaction of ethyl propionate with methyl amine. In this
reaction, the leaving group (OC2H5) is not utilized in the formed amide. Also, one
hydrogen atom of the amine is not utilized.

MW=102 MW=31 MW=87 MW=46

Therefore, the % atom economy =

Example 2

Mw= 28

Mw= 54 Mw= 82

This is a 100% atom economical reaction, since all the reactants are
incorporated into the product.
3. Prevention or Minimization of Hazardous Products

Polyurethane can be synthesised replacing toxic hazardous phosgene by Carbon

dioxide.
Reactions involving use of safer reactants than the hazardous ones
RNH2 + COCl2  RNCO + HCl ROH  RNHCOOR (polyurethane)
phosgene (toxic)

RNH 2 + CO 2  RNCO + H 2 O  RNHCOOR

ROH
non-toxic
Non-hazardous chemical synthesis of Indigo-Dye
Replacing aniline by non hazardous amino acid tryptophan in presence of
enzyme as Aniline is a hazardous chemical. Indigo blue dye can be synthesised by
replacing aniline by Typtophan (amino acid).

Tryptophanase

Aniline / Tryptophan Indigo Dye

4. Designing Safer Chemicals

Example of an unsafe drug is thalidomide (introduced in 1961) for

lessening the effects of nausea and vomiting during pregnancy (morning
sickness). The children born to women taking the drug suffered birth
defects (including missing or deformed limbs). Subsequently, the use of
thalidomide was banned. It was replaced by a safer drug perinorm.

thalidomide (unsafe) perinorm (safer)

5. Energy Requirements for Synthesis

▷In any chemical synthesis, the energy requirements should be kept to a

minimum.

▷Use of a catalyst has the great advantage of lowering the energy

requirement of a reaction.

▷By replacing conventional means energy to a reaction can be supplied

by UV light, microwave (MW) or sonication.

▷These processes involve less energy and time.

6. Selection of Appropriate Solvent

▷Many solvents are volatile, that may damage human health and the
environment. If possible, the reaction should be carried out in aqueous
phase or without the use any of solvent.

▷Replacement of CCl4, CHCl3 by water and other safer solvents like: PEG
(polyethylene glycol) and Inorganic Liquids (ILs)
7. Selection of Starting Materials
▷Petrochemicals are mostly obtained from petroleum, which is a non-
renewable source in the sense that its formation take millions of years
from vegetable and animal remains.
▷Petroleum reactants must be replaced by natural compounds
▷Substances like carbon dioxide and methane gas (obtained from natural
sources such as marsh gas) are available in abundance. These are
considered as renewable starting materials.
▷Synthesis of Succinic acid
7 Glucose + 6 CO2  12 Succininc Acid
(C6 H 12 O 6 )
renewable starting
material
8. Use of Protecting Groups

▷Protecting the functional group in organic reactions should be avoided.

▷In case an organic molecule contains two reactive groups and you want to
use only one of these groups, the other group has to be protected, the
desired reaction completed and the protecting group removed.

▷Since protecting groups are not incorporated into the final product, their
use is less atom-economical. Hence the use of protecting groups must be
avoided whenever possible.
9. Use of Catalyst
▷It is well known that use of a catalyst facilitates transformation without the catalyst
being consumed in the reaction and without being incorporated in the final product.

▷Therefore, use of catalyst should be preferred whenever possible. Advantages:

▷Better yields.
▷Shorter reaction time

No reaction occurs without the PTC catalyst

10. Products Designed Should be Biodegradable

▷It is possible to have a molecule (e.g. insecticide) which may possess

functional groups that facilitate its biodegradation. The functional groups
should be susceptible to hydrolysis, photolysis or other cleavage.

dibenzoylhydrazines
(non-biodegradable) (biodegradable)

Fenozides
Bz – NH – N- Bz
11. Designing of Manufacturing Plants

.
▷The hazards posed by toxicity, explosions, fire etc. must be looked into.

▷The manufacturing plants should be so designed to eliminate the

possibility of accidents during operation.
12. Strengthening of Analytical Techniques

To monitor and control generation of hazardous by products during

chemical reaction by placement of accurate sensors.

▷Analytical techniques should be so designed that they require minimum

usage of chemicals, like:
Recycling of some unreacted reagent (chemical) for the
completion of a particular reaction.
 With the advancement of science, green
chemistry has changed our life style. Some of
its important applications are described.

Dry Cleaning of Clothes

 Perchloroethylene (PERC), C12C=CC12 is
commonly being used as a solvent for dry
cleaning. It is now known that PERC
contaminates ground water and is a suspected
human carcinogen.

 Micell technology has also evolved a metal-

cleaning system that uses carbon dioxide and a
surfactant, thereby eliminating the need of
halogenated solvents.
 Versatile Bleaching Agent
 The use of chlorine removes all the lignin (to
give good quality white paper) but causes
environmental problems.

 Bleaching agents like hydrogen peroxide,

ozone or oxygen also did not give the desired
results.
 H2O2 and TAML act as a good bleaching and
oxidizing agent.
 These bleaching agents also find use in laundry
and result in lesser use of water.
 The use of chlorofluorocarbons (CFCs) and
hydrochlorofluordcarborns (HCFCs) as solvents creates
environmental problems. The CIO radical formed, can react with an
oxygen atom to form an oxygen molecule and regenerate a
chlorine radical.
 CF2Cl2 + UV -> CF2Cl + Cl*
 O3 + Cl* -> O2 + ClO*
 ClO* + O -> Cl* + O2
 The overall reaction is the conversion of ozone into oxygen.
 O3 + O -> 2O2
 This results in depletion of the ozone layer and so the harmful
ultraviolet radiations reach the surface of the earth
 A harmless blowing agent viz. carbon dioxide has been developed.
The advantage of C02 is that it does not deplete the ozone layer,
does not form smog, is economical, handling is easier and is
nonflammable.
 2NO2 + H2O -> HNO2 + HNO3
 Acid rain is detrimental to plants and aquatic life. In some extreme
cases, when the pH falls below 4.5, acid rain is responsible for
making lakes devoid of aquatic life.
 In order to carry out the transformation of selected feedstock
into the target molecule the criteria of efficiency, availability
and effect of the reagent used must be kept in mind. Some
of the green reagents are as follows.
Dimethylcarbonate
 Conventional methylation reactions employ methyl halides or
methyl sulfate which are toxic. Tundo, developed a method
to methylate active methylene compounds selectively using
dimethylcarbonate (DMC) in which no inorganic salts are
produced.
Polymer Supported Reagents
 Besides DMC, there are a group of reagents which though
are ordinary reagents, are bound to polymer support. The
main advantage of using these reagents is that any excess
of the reagent can be recovered by filtration and used
again. Also, the isolation of the product is very easy. Some
of such reagents are given as follows:
Polymer Supported Peracids
 These are used for epoxidations of alkenes in good yields.
Green Catalysts
 The function of catalyst is to reduce the consumption
of energy by decreasing activation energy. Green
catalyst are safer catalyst as compared to conventional
catalyst

Acid Catalysts
 Microencapsulated Lewis acids have replaced
traditional corrosive monomeric Lewis acids in the
reactions like Michael, Friedel Crafts, Mannich etc.
Oxidation Catalysts
 The most important application of titanium silicates
(TS-1) is the hydroxylation of phenol, giving mixtures
of hydroquinone and catechol. The process is clean,
giving excellent conversion to product with very little
waste.
Phase-Transfer Catalysis in Green
Synthesis
 The phase transfer catalyst facilitates the reaction between water
insoluble organic compounds and water soluble reactants (reagent).
 The basic function of PTC is to transfer the anion (from the reagent)
from the aqueous phase to the organic phase.
 As a typical example, the reaction of 1-chlorooctane with NaCN in
water does not give 1-cyanooctane even if the reaction mixture is stirred
for several days. However, if a small quantity of an appropriate PTC
(quaternary ammonium salts and quaternary phosphonium salts) is
added the product is formed in about 2 hr giving 95% yield
 The mechanism of the PTC reaction is well known and
is described
 Types of Phase transfer catalyst:

 Quaternary salts containing nitrogen and phosphorous atoms.

 Benzyl tributyl ammonium chloride, C6H5CH2 (n-C4H9)3 N+ Cl"
 Benzyl triphenyl phosphonium iodide, C6H5CH2(C6H5)3P+I“
 Aliquat 336: methyl trioctyl ammonium chloride, N+CH3 (CgH17)3Cl~ act as etc.

 Crown ethers: Cyclic ethers are known as crown eithers.

 The aqueous solution of KMNO4 does not oxidized toluene.
 KMNO4 dissolves in benzene in presence of crown eithers and readily oxidizes toluene
into benzoic acid.
C6H5CH3 KMNO4/Crown either C6H5COOH

[18] crown-6
 Williamson’s Ether Synthesis
 The PTC technique provides a simple method for conducting Williamson ether
synthesis. Use of excess alcohol or alkyl halide, lower temperature and larger
alcohol (e.g. CgH,7OH) give higher yields of ethers
 Attempts to prepare ethers from alcohols by reacting with dimethyl sulphate in
aq. NaOH or even by the use of alkali metal alkoxide have been unsuccessful.
However, use of PTC (e.g. tetrabutyl ammonium salts) gives high yield of
ethers.

 The Wittig Reaction

 The usual Wittig reaction consists in the treatment of a phosphonium salt with
a base (e.g. NaH) to give an ylide, which can react with aldehydes or ketones to
give alkenes
Microwave Induced Green
Synthesis
Advantages
 High yield
 High purity of compound
 Shorter reaction time
 Moderate reaction conditions

 Conventional heating is slow thus conduction, while

Microwave heating is direct.
 Hydrolysis of Benzyl Chloride

Conventional 1 hr

 Oxidation of Toluene

Conventional 10-12 hr
 Deacetylation
Ultrasound Assisted Green
Synthesis
Advantages
 Excellent yields
 High purity of compound
 Shorter reaction time
 Moderate reaction conditions
 Esterification

 Saponification

94%

Conventional yield 15%, 90 mins

 Coupling Reactions

 Cannizaro Reaction
Aqueous Phase Reactions
 Diels-Alder Reaction

 Pinacol Coupling
 What is Supercritical CO 2

When CO2 is compressedat 73 bar pressure and 310 C

temperature it is converted to supercritical state.
It exists both as gaseous and liquid state.
Properties

▷Non-toxic environmentally benign solvent

▷It is used for dry cleaning of clothes and dying
▷Used in extraction of caffeine
▷Solvent for many organic reactions
▷Very good solvent for organic, inorganic and
polymeric reactions
Reactions
▷Diels-Alder Reaction

+ Sc CO2
CO2Me CO2Me
Carboxilation

Sc CO2

▷Fridel crafts reaction

Sc CO2
Versatile Ionic Liquids
What are ionic liquids
▷They are low melting point salts.M.Pt. < 100 0C.
Properties
▷No vapour pressure
▷Reduced toxicity
▷They dissolve wide range of organic compounds

▷They are designer solvents, means they can be designed

for particular application. Their properties can be changed
by changing anionic or cationic part.

[I.L.] BF4 ------------------- hydrophilic

[I.L.] PF6 ------------------ hydrophobic

▷They can be recycled.

▷Acetylation

I.L.
▷Diels-Alder Reaction

I.L.
▷Heck Reaction
POLYETHYLENE GLYCOL

▷Low toxicity, low volatility

▷Biodegradable
▷Stable in acid/ base
▷Not effected by O2 and H2O
▷Can be recycles
▷Used in oxidation reactions
▷Diels-Alder Reaction

PEG
Water

▷H 2O can also be used as a synthesis

▷Properties
○Abundantly available
○Cheap
○Non-volatile
○Readily recycles
Aqueous Phase Reactions
▷ Diels-Alder Reaction

▷Pinacol Coupling
Organic Synthesis in Solid
State

▷Simply by grinding

▷Without solvent

▷On solid support (Al2O3 / silica)

▷Beckmann Rearrangement
Photo -induced organic
reactions
▷Diels-Alder Reaction

+ hν
Synthesis Involving Basic
Principles of Green Chemistry:
Some examples
▷Synthesis of Styrene
▷The chemical industry consumes styrene, the monomer used for
the manufacture of polystyrene in large quantities each year. The
commonly used industrial method for making it converts benzene
into styrene by a Friedal-Crafts alkylation followed by
dehydrogenation
▷Synthesis ofCatechol

▷Synthesis of Adipic Acid

▷Green Synthesis ofParacetamol
▷Conventional Synthesis ofParacetamol
Green Chemistry in
Sustainable Development
▷The green chemistry revolution provides an enormous number of
opportunities to discover and apply new synthetic approaches using
alternative feedstocks; ecofriendly reaction conditions, energy
minimizations and the design of less toxic and inherently safer
chemicals.
▷The origin and basis of green chemistry for achieving
environmental and economic prosperity is inherent in a sustainable
world.
▷One important element of sustainable chemistry is commonly
defined as the chemical research aiming at the optimization of
chemical processes and products with respect to energy and
material consumption, inherent safety, toxicity, environmental
degradability, and so on.
▷Industrial Interest in Green Chemistry
▷Many forward -looking companies are embracing green chemistry,
not only to protect the environment and to create good public
relations, but also because it isoften'beneficial to the bottom line
▷It is estimated to cost US industries between $ 100 and $ 150
billion per year to comply to environmental regulations.

▷Green Chemistry in Education

▷Hosting a green chemistry speaker.
▷Organizing an interdisciplinary green chemistry workshop on
campus.
▷Working with a local company on a green chemistry project.
▷Developing a Green Chemistry activity with a local school.
▷Converting a current lab experiment into a greener one.
▷Organizing a Green Chemistry poster sessions on campus.
▷Distributing a Green Chemistry Newsletter to the local
community.
▷Designing a Green Chemistry web page.
▷Energy Conservation
▷Energy generation and consumption has long been known to
produce a major environmental effect. Chemistry and chemical
transformations play a major role in capturing and converting
substances into energy as well as converting existing sources of
energy into a form that is usable to society. Microwave irradiation in
the solid state12 is a technique that is being utilized to effect
chemical transformations rapidly, in contrast to those that have
classically been conducted in liquid solutions. Solvent -free
microwave assisted reactions13 provide an opportunity to work
with open vessels, thus, avoiding the risk of high pressure and
increasing the potential for scale up of such reactions.

▷Ultrasound is a relatively new way of introducing energy into

chemical systems.20 It has been used to enhance reaction rates21 in a

large number of classical organic reactions

▷Bio-based Renewables

▷The growth of green chemistry over the course of the past decade
needs to increase at an accelerated pace if molecular science is to
meet challenges of sustainability.
▷It has been said that the revolution of one day becomes the new
orthodoxy of the next Green chemistry is applied and must involve
the successful implementation of more environmentally friendly
chemical processes and product design.
▷Most importantly we need the relevant scientific, engineering,
educational and other communities to work together for
sustainable future through Green chemistry.
▷Green Engineering Education for Sustainability for Developing
Countries
▷Zujang et al. presented a paper of existing philosophy, approach,
criteria and delivery of environmental engineering (EE) education
(E3) for developing countries.

▷In general EE is being taught in almost all major universities in

developing countries, mostly under civil engineering degree
programmes. The main component of E 3 in near future will remain
on basic sanitation in most developing countries, with special
emphasis on the consumer-demand approach.
▷The concept, principles and methodologies of green chemistry and
green engineering are fundamental in integrating sustainability
throughout the system of our chemical enterprise.
▷In order to substantially overcome environmental problems in
developing countries, E3 should include integrated urban water
management, sustainable sanitation, appropriate technology,
cleaner production wastewater minimization and financial
framework.