ABSTRACT

This project is a report about the

“BASICS OF GREEN CHEMISTRY”. Several reactions taught in
Pharmaceutical and medicinal chemistry laboratory today are
hazardous to environment and hence needs to be modified. With an
impetus from Pollution control act, Green Chemistry; a relatively
newer branch has originated. The article discusses basic concepts and
the implementation of various green chemical reactions. Basic
concepts of ionic liquids, supercritical fluids, and microwave assisted
organic synthesis, biocatalysts and their applications for chemical
reactions are discussed. It is the need of the hour to implement this
Green Chemistry in Pharmacy. I hope this project will help those who
interested to know about the “BASICS OF GREEN CHEMISTRY”
in a beginner level.
Contents:
INTRODUCTION
NEED AND GOALS OF GREEN CHEMISTRY
12 PRINCIPLES OF GREEN CHEMISTRY
LIMITATIONS OF GREEN CHEMISTRY
INTRODUCTION
Science based on research towards the development of
new sustainable process.

DEFINITION:-
It is defined as the invention, design and application of
chemical products and processes to reduce or to eliminate the use and
generation of hazardous substances.

FATHER OF GREEN CHEMISTRY:-

The term coined by Dr. Paul Anastasia known as the
“father of green chemistry”. He defined it as 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.

ACID RAIN
The massive emission of oxides of sulphur and Nitrogen
[SOx and NOx], from thermal power plants and industries, react with
moisture and other atmospheric constituents to form a cocktail of
sulphurous acid and nitric acid. Majority of the fuels, especially coal,
contain about 0.5 to 4% of sulphur and they are burnt in air and that
contain about 78 of Nitrogen and 21% of Oxygen, huge quantities of
SO2 and SO3 and NO2 are released.
 The super stacks and mammoth smelters at Ontario release
about 2500 tones of SO, everyday, these large stacks of the world
alone contributes about 1% of the total SO2 released. Acid rain affects
the nutrients in the soil, affects germination of plants, increases
concentration of heavy metal ions in water bodies, leaches buildings
and statues and marble monuments. In India, Mumbai and other
western parts have experienced acid rain. Taj Mahal, one of the
wonders of the world, is badly affected by SOx emission from
Mathura oil refinery and elsewhere and the damage is named as stone
cancer or stone leprosy. Acid rain has already caused severe damage
to the environment. About 100 lakes of USA, Canada and Sweden are
'dead' and about 1000 lakes are fishless, similarly 30% of West
Germany's forest cover is on the verge of vegetational death.

GLOBAL WARMING
Air pollutants such as CO2, N2O, CH4, SO2, SO3, O3, CFCs
(Chloro Fluoro Carbon’s) possess intense infra-red absorption which
could influence mean global temperature. UNEP (United Nation
Environmental Programme) has chosen the slogan 'Global Warming'
to alert the public on World Environment Day regarding the adverse
consequences of Global warming. It has been estimated that if earth's
temperature increases from 2 to 4.5°C, it will result in receding many
glaciers, melting of ice caps in Polar Regions over Greenland and
Antarctica and disappearance of deposits of ice on the globe.
 In hot tropical environment, an increase in CO2 content
will influence photosynthetic activities of the plants. As per official
estimate, it is expected that Green House Gas (GHG) would severely
affect climate stability on the earth, there by altering the earth's
delicate ecological balance. The only way to prevent the global
warming by Green House effect is to reduce the emission o f GHG
(Green House Gas). In Kyoto Protocol (1997), it was decided that the
developed countries that emit largely GHG should reduce emission of
CO2, CH4 and N2O. The implementation of Montreal Protocol will
reduce emission of another GHG that is CFC.
Bhopal Disaster
This disaster was most tragic in the history of mankind.
The chemical accident occurred on 2nd December in 1984 in Bhopal,
India at the Union Carbide factory (MNC of USA). In this accident
approximately 30 tonnes of MIC (methyl isocyanate, volatile liquid,
b.p. = 43°C), an extremely poisonous gas, was leaked, accompanied
with COCI2 (phosgene gas), killed several thousands of people &
disabled more than one lakh people. MIC was used as a feedstock to
the manufacture of sevin (carbaryl) a carbamate pesticide, as per the
reaction.
 And the probable cause of the accident is due to reactivity
MIC and safety measurement. The actual cause of explosion is not yet
identified. It is believed that somehow, water entered into the tank,
led to explosion. MIC being tremendously exothermically, reactive
with bimolecules having active hydrogen (-SH, -OH, -COOH,
CONH2 – NH2 etc) produced breathing troubles, irritation to the eyes,
chest congestion, cell fibrosis, massive secretion to clog the lungs
with fluid, thereby, caused extensive death & damage to the living
being. It is worth to note that the Indian Government is still fighting a
legal battle with Union Carbide, for claiming compensation for the
Bhopal victims, but alas it remains still a pipe dream.
 NEED AND GOALS OF GREEN CHEMISTRY

Need of green chemistry:-

Green chemicals either degrade to innocuous products or

are recovered for further use. The most important thing is to create

public awareness. Plants and animals suffer less harm from toxic
chemicals in the environment. Lower potential for global warming,
ozone depletion, and smog formation. Less chemicals disruption of
ecosystems.

Goals of green chemistry:-

(i) Ecofriendly chemical technology:- Green chemistry aims

to protect the environment and this is what described as
environmentally benign chemistry.

(ii) Replacement of toxic organic solvent and to minimize the

waste product: Green chemistry aims to devise greener
reaction conditions for the synthesis of chemicals so that
toxic waste formation can be minimized. It requires the
replacement of toxic solvents by water or complete
elimination of use of solvent it is well documented that the
best solvent is no solvent.
(iii) Use of renewable feed stock: Green chemistry aims to
develop the green synthesis by using renewable resources,
that is, use of biomass rather than petrochemical feed
stock.
(iv) To minimize energy consumption
In most of the synthesis process, rigorous reaction
condition are applied (high temperature high pressure etc),
which require energy but greener synthesis aims to
develop modest or mild reaction condition.
(v) Use of Ecofriendly chemical products: Green chemistry
aims to design new chemical products to replace the
existing hazardous ones provided the new chemical, are
having same desirable properties of existing ones, but they
biodegrade themselves giving innocuous [means harmless]
products.
(vi) Four R's (4 R's) and Integrated Waste Management (IWM)
These four R's are
 Reduction (at source)
 Recycling [Green building]
 Reuse [Green product]
 Recovery [Green energy]
 It demands to reduce the amount of plastic waste. It aims
to reuse the waste product that means 'Waste to wealth generation'.
[That is value addition] The waste plastics may be recycled to
produce new plastics maintaining the properties comparable to these
of original plastic.

The plastic materials may be burnt with some combustible

materials in incinerators to generate electricity. Thus, the practices of
reuse recycling, recovery should be strictly followed during chemical
synthesis process.
12 RINCIPLES OF GREEN CHEMISTRY:-

1. It is better to prevent waste than to treat or clean up waste after

it is formed.
2. Synthetic methods should be designed to maximize the
incorporation of all materials used in the process into the final
product.
3. Whenever practicable, synthetic methodologies should be
designed to use and generate substances that possess littler no
toxicity to human health and the environment.
4. Chemical products should be designed to observe efficiency of
function while reducing toxicity.
5. The use of auxiliary substances (e.g. solvents, separation
agents, etc) should be made unnecessary wherever possible and
innocuous when used.
6. Energy requirements should be recognized for their
environmental and economic impacts and should be
minimized, synthetic methods should be conducted at ambient
temperature and pressure.
7. A raw material of feed stock should be renewable rather than
depleting wherever technically and economically practicable.
8. UnnecessaryaderivationA(blockingasgroup,protection/deprotec
tion,temporary modification of physical /chemical process)
should be avoided wherever possible.
9. Catalytic reagents (as selective as possible) are superior to
stiochio metric reagents.

10. Chemical products should be designed so that at the end of

their function they do not persist in the environment and break
down into innocuous (harmless) degradation product.

11. Analytical methodologies need to be further developed to allow

for real time, in process monitoring and control prior to the
formation of hazardous substances.

12. Substances and the form of a substance used in a chemical

process should be chosen so as to minimize the potential for
chemical accidents, including releases, explosions and fires.
1ST PRINCIPLE (PREVENT WASTE):-
 Design processes which minimize waste.

 Better to prevent waste than to clean and treat it, in other words,
prevention is better than cure.

 Waste if generated is discharged into the environmental, that

causes environmental they causes environmental pollution thus
they should be cleaned up.

E-Factor (Environmental factor):-

Environmental factor is defined as the ratio of the mass of waste per
mass of product.

E-factor = Mass of waste

Mass of product

E-factor tells about the actual amount of waste formed in the process
including solvent loss, acids, bases used in the work up.
A higher E-Factor means more waste and consequently, greater
negative environmental impact. The ideal E-factor is zero.
CALCULATION OF E-FACTOR:-
Oxidation of a secondary alcohol i.e. propan-2-ol by acidified
KMnO4, the E-factor is
2ND PRINCIPLE (ATOM ECONOMY):-
Synthetic methods should be designed to maximize the incorporation
of all the materials used in the process in the process into the final
product. The second principle demands to minimize the formation of
by product.

DARZEN’S REACTION:-

In the above Darzen’s synthesis, even through the product is a pure

liquid with 100% yields but it generates a lot of polluting gases . so, it
may not be considered as a green process.

Inorganic synthesis we meet with a no. of reactions like

(A) Addition reactions
(B) Substitution reactions
(C) Elimination reactions
(D) Elimination reactions
Some reaction produces with 100% yields, but it generates a lot of
byproducts.
3rdPRINCIPAL(LESS HAZADROUS CHEMICAL
SYNTHESIS):-
Whenever practicable, synthetic methodologies should be designed to
use and generate substance that possesses little or no toxicity to
human health and the environment.

POLYCARBONATE SYNTHESIS: PHOSGENE PROCESS

Traditional Route of Lexan making

Disadvantages:-
Phosgene is highly toxic, corrosive.
Polycarbonate contaminated with Cl impurities.
POLYCARBONATE SYNTHESIS: SOLID-STATE PROCESS

Advantage:-
(i) Diphenyl carbonate synthesized whiteout phosgene.
(ii) Higher quality polycarbonate.
4thPRINCIPLE (DESIGNING SAFER CHEMICALS):-
Chemical products should be preserve efficacy of function while
reducing toxicity.

For example, adipic acid is widely used in polymer industry for the
manufacture of nylon-6,6polyureathane, lubricants in which benzene
is the starting material, but benzene is carcinogenic and benzene
pollutes air. In green technology developed by Drath and Frost, adipic
acid is enzymatically synthesized from glucose.
5TH PRINCIPLE
(USE SAFER SOLVENTS/REACTION CONDITION):-
 The use of auxiliary substances (solvent separation agents etc)
should be made unnecessary whenever possible and when used,
innocuous.
 Solvent substitution.
 Water as a solvent.
 New solvents/green solvents
GREEN SOLVENTS

It has already been stated that most of the solvents as discussed

above are volatile [Volatile organic compounds, VOC] thus they pose
health hazard to living beings and hamper the ecosystem. Thus it is
desirable to use solvents which do not pollute the environment and
generate least waste; some of them are discussed here under:

(A) Super critical CO2 [sc CO2]

(B) Ionic liquids [IL] or RTIL [Room temperature ionic liquids]
(C) Super Critical Water [sc H2O]
(D) Water [H2O]
(E) P. E.G. [Poly ethylene Glycols]
(F) P.T.C. [Phase Transfer Catalysts]
(G) (G) Crown Ethers
(H) Immobilized solvent
(I) FBS
SUPER CRITICAL CO2

Carbon dioxide can exist in different states depending upon

temperature and pressure of its surrounding. At room temperature and
pressure (1 atm), it remains in gases state, at -56°C and 5.1 atm, CO2
exists as a gas, liquid and solid state which is denoted as (A) in the
phase diagram, is called as triple point, but at point (B), at 72.8 atm
pressure 31°C, (Tc) CO2 exists as a supercritical fluid. In the SCF
state. (SCF) the temperature is above Tc (T>Tc) and pressure is above
Pc (P> Pc), such that, an intermediate state of gas and liquid state is
attained. In this super critical state, the density is close to that of a
liquid state while viscosity is close to that of a gaseous state, thus
supercritical carbon dioxide (scCO2) possesses unique properties of a
solvent, and

 It is non-toxic, non-inflammable, and environmentally benign.

 It is a low cost material; it can be recovered after its use, which
will minimize the global warming.
IONIC LIQUIDS AS GREEN SOLVENT
Ionic liquids are the class og green solvents, made up two
components, the cation and the anion
Cation include

Anions Include
BF-4 (Tetraflouroborate ion)
PF-6 (hexaflucro phosphate ion)
SbF-6 ( hexaflucro antimonite ion)
SF3SO-2 (trifluoro methane sulphonate ion)

The ionic liquids have been described as designer solvents or

tunable solvents and this means that their properties can be adjusted
to suit the requirements of a particular process. Properties like
melting point, viscosity, density and hydrophobicity can be varied by
changing the structure of the ions. Considering the case of 1-alkyl-3-
methyl imidazolium tetrafluoroborate salts are miscible with water at
25°C where the alkyl chain length is less than 6, but at or above 6-
carbon atoms, they form a separate phase when mixed with water,
this kind of hydrophobic behavior can be utilized for solvent
extraction technique, or product separation, that is why they are
termed as designer solvents. The ionic liquids are the green solvents,
exhibit the following features like.
 they have low toxicity
 zero vapor pressure
 ease of recyclability, (do not cause disposal problem)
 easily removed from the product
 high boiling liquids,
 low odour,
 easily biodegradable and
 low reactivity with the target molecules.
Ionic liquids find enormous application in many organic
transformations like alkylation, allylation, hydroformylation,
epoxidation, Diels-Alder reaction, Knoevenagel reaction and many
more, some illustrations are given under.

SUPER CERTICAL WATER (SCH2O)

SCF state is attained at or above the critical pressure (Pc) and

critical temperature (Tc), for

H2 O Tc : 374.10C
Pc: 217.7 atm
In SCF state, gaseous and liquid phase do not separate and its
properties lie between those of true liquid and true gas as per the
phase diagram.

So, at a temperature of 374°C and at a pressure of 218 atm,

water becomes supercritical. Most of the organic compouds are water
insoluble but become soluble in SCH2O. In constrast to scCO2, the
condition required to obtain scH2O are very drastic which prevents its
synthetic utility for most of the organic reaction. However organic
syntheses have been carried out in sub-critical but high temperature
water. The technique of super critical water oxidation (SCWO) has
potential use in remediation and waste treatment. It is pertinent to
mention that -refractory organics (non-biodegradable) like (Poly
chloro Biphenyls) dioxins, organochlorine insecticides, etc. present in
waste need special treatment, and these compounds can be oxidized
by air in super critical water.
WATER AS A SOLVENT

Water is an ideal solvent as it is environmentally benign and a

safe solvent. A large no of organic reactions have been carried out in
aqueous media, things can be better understood by taking the
following example of Diels - Alder Reaction.
Conventionally Maleic acid reacts with furan under reflux in
benzene, forms a [4+2] cyclo addition reaction.
USE OF P.E.G

Poly ethylene Glycol (PEG) and its solution are believed to be a

green reaction medium of the future. P.E.G. is denoted as HO-(CH2 –
CH2 -O)n -H, is available in a variety of molecular weights. A special
characteristics of PEG is that it has low flammability, low Volatility
and is biodegradable. It is stable to acids, bases and high temperature,
can be recovered and recycled. It has been used as a solvent for a
number of organic reactions like Heck reaction, asymmetric addol
reaction, Suzuki cross-coupling reaction, dihydroxylation of alkene,
Diels-Alder reaction etc, as given under.

P.T.C. [PHASE TRANSFER CATALYSTS]

These catalysts are used as devices for accelerating the reaction
between water insoluble organic compounds and water soluble
reagents. The most useful catalysts for this purpose are quaternary
ammonium salts, quaternary phosphonium salts, crown ethers and
polyglycolethers.
e.g. TEBA: Benzyl triethyl ammonium bromide or chlorides

ADVANTAGES OF USING A PTC

(i) It does not require rigorous condition
(ii) It does not require any expensive aprotic polar solvents
like DMSO (dimethyl sulphoxide), Dimethyl formamide
(DMF) etc.
(iii) The work-up procedure is easier
(iv) The energy requirements is kept at minimum)

CROWN ETHERS:
Crown ethers are powerful PTC [Phase Transfer Catalysts], they
are cyclic ethers. Crown ethers were first reported by Pederson etal.
(1987 nobel prize winners in chemistry) e.g. [18] - Crown - [6],
dibenzo [18] - crown- [6] Dicyclohexane [18] - Crown-[6], [12]-
Crown-[4], [21] - Crown - [7] etc.
IMMOBILIZED SOLVENTS

A major problem with many solvents in relation to human

health and the environment is their ability to volatile and thus has a
detrimental effect by exposing individuals and contaminating the air.
One solution that is being investigated is the use of immobilized
solvents. Immobilization has taken several forms but the goal of each
is the same, to maintain the solvency of a material while making it
non-volatile and unable to expose humans or the environment to the
hazards of that substance. In some cases this can be done by tethering
the solvent molecule to a solid support or by binding the solvent
molecule directly on to the backbone of a polymer. In some cases,
new polymer substances themselves are being developed that have
solvent properties and yet do not possess the properties that would
make them a hazard. This concept for solvent design and synthesis
offers the potential for significant source reduction in air and water
pollution, the following is an example developed by researches at
M.I.T. (USA).
6th PRINCIPLE (INCREASE EFFICIENCY):-
Energy requirements should be recognized for their environmental
and economic impacts and should be minimized synthesis methods
should be conducted at ambient temperature and pressure.

Conventionally we have been carrying out reactions by heating wire

gauge, in oil bath using glycerol, dibutyl phthalate, paraffin oil, poly
ethylene glycol, silicon oil, most often causes oil spillage problems
consumes a lot of electrical energy. Heating with metal bath using
woods metal, rose’s metal which are highly expensive.

In all of the above cases, a lot of electrical energy is required as there

action completion time is very high due to prolonged heating
procedure, thus it puts heavy burden on the environment. For example
coal based thermal power plants; generate energy, releasing SOX and
NOX gases (SO2, NO2) which are responsible for global warming and
acid rain, which turns dangerous effects on agriculture crops.

It is now possible that the energy to a chemical reaction can be

supplied by using microwaves (MWI) and sound wave (sonication
technique).
USE OF MICROWAVES:-
7TH PRINCIPLE
(USE OF RENEWABLE FEED STOCKS):-
A raw material or feedstock should be renewable rather than
depleting whenever technically and economically practical.

Raw material from renewable resources:-

The bio-fine process:-

8TH PRINCIPLE
(REDUCE CHEMICAL DERIVATIVES):-
Unnecessary derivation (blocking group, protection/de protection, and
temporary modification of physical/chemical processes) should be
avoided whenever possible.

 Reduces atom economy.

 Increases wastes.
9TH PRINCIPLE (USE CATALYSTS):-
Catalytic reagents as selective as possible are superior to
stoichio metric reagents.
 Readily regenerated, separated.
 Recyclable.
 Mild conditions.

TYPES OF CATALYSIS
These are two types of catalysis
(1) Homogeneous catalysis
(2) Heterogeneous catalysis

HOMOGENEOUS CATALYSIS
If the catalyst is present in the same phase as the reactants, it is
called a homogeneous catalyst
Oxidation of sulphur Dioxide to sulphur trioxide in presence of
Nitric oxide as catalystin Lead chamber process for the manufacture
of H2SO4.

HETEROGENEOUS CATALYSIS
If the catalyst is present in a different phase than that of the
reactants, then it is called as heterogenes catalyst and this catalysis
type of catalysis is called heterogeneous.
(i) Synthesis of ammonia from N2 and H2 by Haber - Bosch
process using 'Fe' as catalyst.

Here reactants are in gaseous phase where as catalysis is in solid phase.

(ii) Manufacture of sulphuric acid using V2O5 as catalyst

[Contact process]
 ADVANTAGES AND DISADVANTAGES OF
HOMOGENEOUS AND HETEROGENEOUS CATALYSTS.

In homogeneous catalysis processes, mild reaction

conditions required, they are often highly selective, they are
associated with ease of heat transfer from a solution. The
disadvantages are separation of product, recycling of catalysts, most
often product gets contaminated. But in heterogeneous catalysis
systems, product separation is easier and straight forward with
continuous processing. Heat transfer problem lies with heterogeneous
systems but-one attractive feature is that many of the solid catalysts
are robust at high temperature and therefore make available in a wide
range of operating conditions.

10TH PRINCIPLE (DESIGN FOR DEGRADATION):-

Chemical products should be designed so that at the end of
their function they do not persist in the environmental and instead
breakdown into innocuous degradation products.
 CFCs, DDT
 Biodegradable polymers.
11TH PRINCIPLE
(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.
12TH PRINCIPLE (INHERENTLY SAFER
CHEMISTRY FOR ACCIDENT PREVENTION):-
Substance and the form of a substance used in a chemical
process should be chosen so as to minimize the potential for chemical
accidents, including releases, explosions, and fires.

Various industrial accidents.

Example:-Bhopal gas tragedy.
LIMITATIONS OF GREEN CHEMISTRY:-
One of the most pressing problems faced by the human beings
world over is environmental pollution. To reverse the trends of
environmental damage, it is most imperative to follow the principles
of green chemistry, strictly in the true spirit. In the context of green
chemistry, pollution means chemical pollution. The release of toxic
pollutants to the air, water and soil is harmful to human health and
environment. Environmental laws are in place with a view to control
the environmental pollution. This approach has yielded some results,
but still, the quality of air, water and soil has impaired. The limiting
factor in fixing the upper limit of various chemical pollutants into
various segment of the environment are the unknown characteristics
of the pollutants whether the substance is of high toxicity, unknown
toxicity, carcinogenicity or chronic toxicity, mutagenicity or
teratogenicity. Due to these unknown characteristics of the pollutants,
it becomes problematic, if not impossible to fix appropriate levels that
the human beings and the environment can tolerate.