Harshada I. Patil et al.

/ Journal of Pharmacy Research 2011,4(12),4798-4804

Review Article
ISSN: 0974-6943

Available online through

www.jpronline.info

Green Chemistry: Why And How - For Sustainable Chemical Industry and
Environmentally Commendable Civilization
Harshada I. Patil*, Meera C. Singh 1, Preeti Gaikwad2, Kedar S. Lade 3, Nilam A. Gadhave 4, Sanjay D. Sawant5
Smt. Kashibai Navale College Of Pharmacy, Saswad Kondhwa Road, S. No 40/4, near Octroi post, Kondhawa (Bk), Pune 411048, Maharashtra, India.
Received on: 12-04-2011; Revised on: 18-05-2011; Accepted on:21-06-2011

ABSTRACT
Chemistry has provided valuable materials in the form of medicines, food products, cosmetics, dyes, paints, agrochemicals, biomolecules, and high-tech
substances like polymers, liquid crystals and nanoparticles. Chemists have used their knowledge and skill to prepare a large number of new materials which are
far better and more useful than the natural products, such as high-tech polymers, liquid crystals, tough ceramics, nonlinear optical substances, designer drugs,
genetic materials and new energy sources.The processes on industrial scale involve many chemical reactions using huge quantities and wider varieties of smaller
molecules, reagents, solvents, acids, alkali, etc. These chemical processes not only produce the required products but also large quantities of undesired and
harmful substances in the form of solids, liquids and gases and have become the biggest challenge that chemistry has to face. So, the pressing need for the
synthetic chemists is to minimize chemical pollution. During the last two decades much work has been going on in this direction.The term Green Chemistry
was coined in 1991 by Anastas. The purpose is to design chemicals and chemical processes during the manufacture and application of chemical products that
will be less harmful to human health and environment. Green chemistry protects the environment, not by cleaning up, but by inventing new chemical processes
that do not pollute. Principles of green chemistry, developments in this field and some industrial applications are discussed.

Key words: Needle free, Powder injection, Depot injection, liquid injection

INTRODUCTION[1-4]
During the twentieth century chemistry changed forever the way we live.
Perhaps the greatest perceived benefits, to the general public, have come from
the pharmaceuticals industry with developments of painkillers, antibiotics,
heart drugs and, more recently, Viagra.
Green chemistry is a revolutionary philosophy that seeks to unite government,
academic and industrial communities by placing more focus on environmental
impacts .This approach requires an open and interdisciplinary view of material
and product design, applying the principle that it is better to consider waste
prevention options during the design and development phase, rather than
disposing or treating waste after a process or material has been developed.
Environmentally benign alternative technologies have been proven to be
economically superior and function as well or better than more toxic traditional
options. When hazardous materials are removed from processes, all hazardrelated costs are removed as well, significantly reducing hazardous materials
handling, transportation, and disposal and compliance concerns. Green
Chemistry is the design, development, and implementation of chemical products
and processes to reduce or eliminate the use and generation of substances
hazardous to human health and the environment.
The term green chemistry was first used in 1991 by P. T. Anastas in a special
program launched by the US Environmental Protection Agency (EPA) to
implement sustainable development in chemistry and chemical technology by
industry, academia and government. In 1995 the annual US Presidential Green
Chemistry Challenge was announced.Their early definition of the subject is
still widely quoted: 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. However in practice
Green Chemistry is nowadays taken to cover a much broader range of issues
than the definition suggests. As well as using and producing better chemicals
with less waste, Green Chemistry also involves reducing other associated
environmental impacts, in particular reducing the amount of energy used in
chemical processes

*Corresponding author.
Harshada I. Patil
Smt. Kashibai Navale College of Pharmacy,
Saswad Kondhwa Road,
S. No 40/4, near Octroi post,
Kondhawa (Bk), Pune 411048,
Maharashtra, India.

Practitioners of green chemistry strive to protect the environment by cleaning

up toxic waste sites and by inventing new chemical methods that do not
pollute and that minimize the consumption of energy and natural resources.
Similar awards were soon established in European countries. In 1996 the Working
Party on Green Chemistry was created, acting within the framework of
International Union of Applied and Pure Chemistry. One year later, the Green
Chemistry Institute (GCI) was formed with chapters in 20 countries to facilitate
contact between governmental agencies and industrial corporations with
universities and research institutes to design and implement new technologies.
The first conference highlighting green chemistry was held in Washington in
1997. Since that time other similar scientific conferences have soon held on a
regular basis.
The terms Environmental Chemistry and Green Chemistry are two different
aspects of environmental pollution studies. The former is the study of chemical
pollutants in natural environment while the latter is an attempt to design
chemical products and processes to reduce the harm they cause to the
environment. Green chemistry seeks to reduce pollution at source, whereas
environmental chemistry focuses on the study of pollutant chemicals and
their effect on nature.On the other hand, environmental chemistry, as taught
today, is largely the study of what man has put into the environment and its
effect, as well as how to remediate contaminated sites.
The terminology green chemistry or sustainable chemistry is the
subject of debate. The expressions are intended to convey the same or very
similar meanings, but each has its supporters and detractors, since green is
vividly evocative but may assume an unintended political connotation, whereas
sustainable can be paraphrased as chemistry for a sustainable environment
A. The Role Of Pharmacist In Green Chemistry [6]
Chemists can use their knowledge of Green Chemistry and its benefits to
justify research into cleaner and greener processes. In most cases it is readily
demonstrable that a Green Chemistry approach involving reduction of waste,
materials and energy, will also lead to cost reductions and that this in turn will
have a positive effect on profitability. Although many of the technologies and
tools required to make chemical manufacturing more sustainable are available,
and indeed industry is already making significant progress, much more can be
achieved. In order to move forward chemists need to understand, and overcome,
the barriers, both real and perceived, that exist to innovation in this area.
In some cases a culture change may be required before the potential financial
benefits are fully appreciated. Professional chemists also have a major role in
helping to encourage all interested parties, including industry, customers, pressure
groups, governments, educationalists and researchers, to co-operate to ensure
a cleaner and more sustainable future.

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B. Barriers to introducing Green Chemistry include:
1.
2.
3.

4.
5.
6.
7.
8.

[7]

Absence of a level playing field, i.e. the lack of global harmonization on regulation
and environmental policy
Rigid notification and authorization processes which hinder new product and novel
process development
The frequent need for speed and certainty of outcome caused by short-term planning
horizon Additional cost: although Green Chemistry is often financially beneficial
this is not invariably the case
Unsophisticated accounting practices, which do not encompass total costs
The difficulty of obtaining research and development funding
Insufficient guidance on best practice for Green Chemistry
The low profile of cleaner more sustainable chemistry in school and university teaching
A culture geared to looking at the product itself rather than the overall process and
life cycle.

Chemicals that behave like hormones, called endocrine disruptors, can violate
basic assumptions that underpin regulatory toxicology, with low doses causing
effects that are different and unpredictable from classic high dose experiments
that are the basis for setting current safe exposure levels.
Green chemistry is an approach to the design, manufacture and use of chemical
products to intentionally reduce or eliminate chemical hazards. The goal of
green chemistry is to create better, safer chemicals which choosing the safest,
most efficient ways to synthesize them and to reduce wastes. It aims to
eliminate hazards right at the design stage Over time green chemistry will
change chemistry as a whole, re-orienting societies toward an economy based
on sustainable feedstocks, renewable energy, bio-based production and green
jobs. The key is guiding the creative power of chemists with design criteria
that specify safety and sustainability at the outset.

2. NEED OF GREEN CHEMISTRY [1]

Chemical processes are as old as time, and over the centuries chemists have
been trying to understand natural processes to develop methods based on the
philosophies that are natures very own. However, there lies a difference in
that, while nature when working on any synthesis adopts methods following
routes that eliminate almost completely the use and generation of substances
hazardous to human health and the environment, chemists/do not seem to
rank the environment very high in their priorities. This is the reason why
natural processes are green while synthetic processes are often grey.
In fact, chemical technology has been rather malevolent in a number of cases.
Some of the most infamous examples are:

3. LITERATURE REVIEW:
Green Chemistry is the design, development of chemical products and processes
to reduce or eliminate the use and generation of substances. It is an innovative
approach toward sustainability .Green Chemistry challenges innovators to
design and utilize matter and energy in a way that increases performance and
value while protecting human health and the environment.

(a) DDT, an insecticide effective in controlling insect pests, was responsible

for causing a precipitous decline in the bald eagle population and is a suspected
carcinogen;

A national and international symposium for promoting green chemistry in

India,is developed.The main idea behind this to activate work toward green
chemistry for which involvement of academic, industrial, and governmental
and non-governmental bodies is needed collectively, which will help the designing
and development of environment-friendly chemistry practices in India.

(b) The chemical accident in Bhopal (India) in December 1984 that resulted
in the deaths of several thousand people.
The reason for this malevolence can be attributed to the fact that a number of
commonly used chemicals have high levels of intrinsic toxicity, and these
environmentally hostile chemicals often have their domains existing far beyond
the laboratories in which they are prepared or handled., for many of them paid
little attention to investigating, publicizing and protecting against the risks of
the chemicals which they produced or used. This should have been done since
neither Chemistry nor chemical-based products can be abandoned, because
they are essential
Looking at the global scenario, it becomes apparent that while the presentday chemistry is driven by an unparalleled social demand for better products
and services, there is also a growing sentiment that an undue exploitation of
resources must be minimized. However, with preservation of the environment
being a major concern, the chemical industry has to now seek to wean users
away from the conventional methodologies by driving towards those that are
more efficient and environmentally benign. In this there seems to be a
dichotomous challenge as, on the one hand, there is a requirement for increasing
synthetic efficiency in chemical transformations, while on the other, there is
a demand for minimizing environmentally hostile wastes. And thus, there lies
a responsibility on chemists and chemical technologists in the development of
a more sustainable chemistry, for the emergence and growth of a concept
which allows for improving the quality of life and environment.
Green Economic Innovation for the 21st Century: The Molecular
Revolution [2]
Cutting edge developments in two scientific disciplinesenvironmental health
science and green chemistryare revealing opportunities to stimulate economic
innovation with significant implications for disease prevention and lowering
the cost of health care. Discoveries in environmental health science are
confirming that some chemicals in widespread use have unanticipated
consequences for human health. Advances in green chemistry offer a path
toward new materials that are inherently benign.
Public health has been demonstrably imperiled by a range of chemical related
tragedies in childrens toys, human and pet food, medicines, and many materials
that make up the basis of our economy.
Current regulations and the way they are applied make it very difficult to
bring greener materials into the market
Modern chemicals have unintended consequences for human and ecosystem
health because potential toxicities and degradation pathways were not explored,
and indeed, often unknown, before the materials became widespread.
Some chemicals are capable of interacting with biological systems and altering
the genes of human, behave. These changes are causes diseases, including
cancers, infertility, learning and behavioral disorders, heart disease and type 2
diabetes.

In 2005, the ACS Green Chemistry Institute (GCI) and the global
pharmaceutical corporations developed the ACS GCI Pharmaceutical Roundtable
to encourage the integration of green chemistry and green engineering into
the pharmaceutical industry.

4. PRINCIPLES OF GREEN CHEMISTRY: [9 - 12]

Prof. Anastas and Prof. John C Warner have postulated twelve principles of
green Chemistry.
4.1. Prevention of Waste: It is better to prevent waste than to treat or clean
up waste after it is formed. It is most appropriate to carry out a synthesis by
following a pathway so that formation of waste is minimum or absent. One
type of waste product common and often avoidable is the starting material or
reagent that remains unreacted. In universities and colleges, the cost of disposal
of waste from chemical laboratory can be reduced by carrying out experiments
on a much smaller scale
4.2. Maximize Atom Economy: Atom Economy is a concept that evaluates
the efficiency of a chemical transformation, and is calculated as a ratio of the
total mass of atoms in the desired product to the total mass of atoms in the
reactants.
(Mol. wt of desired product)
% Atom Economy =

100
(Mol. Wt of all products)

Choosing transformations that incorporate most of the starting materials

into the product are more efficient and minimize waste,e.g., DielsAlder
reaction is 100% Atom Economy reaction as all the atoms of the reactants are
incorporated in the cycloadduct. If one mole of the starting material produces
one mole of the product, the yield is 100 %. However, such a synthesis may
generate significant amount of waste or by product which is not visible in the
above calculation. Such a synthesis, even though gives 100% yield is not
considered to be green synthesis. In order to find, if a particular reaction is
green, the concept of atom economy was developed. This considers the amount
of stating materials incorporated into the desired final product. Thus by
incorporation of greater amounts of the atoms contained in the starting
materials (reactants) in to the formed products, fewer waste by products are
obtained.
4.3 Less Hazardous Chemical Syntheses:. This principle focuses on
choosing reagents that pose the least risk and generate only benign by-products..
Wherever practicable, synthetic methodologies should be designed to use and
generate substances that posses little or no toxicity to human health and the
environment. Redesigning existing transformations to incorporate less
hazardous materials is at the heart of Green Chemistry.
Metathesis: Developed by Grubbs, Schrock and Chauvin, metathesis is a
major advance for green chemistry. It is a reaction in which double bonds are
broken and made between carbon atoms in ways that cause atom groups to

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change places, with the help of special catalyst molecules. It is used in the
development of pharmaceuticals and advanced plastic materials, and is a great
step forward for green chemistry, reducing hazardous waste through smarter
production.
4.4 Designing Safer Chemicals: New products can be designed that are
inherently safer for the target application. Pharmaceutical products often
consist of chiral molecules, and the difference between the two forms can be a
matter of life and death for example, racemic thalidomide when administered
during pregnancy, leads to horrible birth defects in many new borns. Evidence
indicates that only one of the enantiomers has the curing effect while the
other isomer is the cause of severe defects. That is why it is vital to be able to
produce the two chiral forms separately. Catalysts that can catalyse important
reactions that produce only one of the two mirror image forms are used.
Chemical properties of a molecule, such as water solubility, polarity etc. so
that they can manipulate molecules to the desired effects.
4.5 Safer Solvents and Auxiliaries: Widely used solvents in syntheses are
toxic and volatile alcohol, benzene (known carcinogenic),CCl4, CHCl3,
perchloroethylene, CH2Cl2. Purification steps also utilize and generate large
amounts of solvent and other wastes (e.g., chromatography supports). These
have now been replace by safer green solvents like ionic liquids.
a. Ionic liquids: Ionic liquid are liquids at RT and below. They are nonvolatile
and have no vapour pressure. They can serve as optimal replacements for
volatile organic traditionally used industrial solvents The reactions in ionic
liquids need no special apparatus and methodologies, and they can be recycled.
However, large-scale applications are still not known. They have many
attractive properties, such as chemical and thermal stability, non-flammability
and immeasurably low vapor pressure. eg: supercritical CO2 fluid, water or
supercritical water and also solvent-free systems that utilize the surfaces or
interiors of clays, zeolites, silica, and alumina.
b. Supercritical liquid: Supercritical CO2 fluid is another versatile green
solvent which has low viscocity and no surface tension. Supercritical CO2
fluid is now becoming an important commercial and industrial solvent for
chemical separation because of its low toxicity and non-inflammability. Its
stability and the relatively low temperature of the process allows most
compounds to be extracted with little damage and denaturation . Because CO2
is obtained as a byproduct of other industrial processes it is inexpensive and
being a gas it is easily evaporated leaving no residue.
c. Supercritical water: Organic substances are insoluble in water. Many
compounds are soluble in water when it becomes supercritical at 374 C and
218Atm.Hence, this clean and cheap solvent is used as a green solvent for
many synthetic reactions. The reactions in ionic liquids need no special
apparatus and methodologies, and they can be recycled.
d. Reactions in aqueous phase: The use of ordinary water for organic
reactions was unknown till the middle of the 20th century. However,
replacement of organic solvents with eco-friendly water has found success
with many reactions, some of which may occur at higher rates because of its
high polarity. Reactions carried out in aqueous medium include oxidations,
reductions, epoxidations, polymerizations (with or without catalysts) and
many named reactions.
e. Reactions in solid phase: Large number of reactions occurs in solid state
without the solvent, these reactions are simple to operate, economical and
solvent-related pollution is avoided. An auxiliary substance is one that helps in
manufacture of a substance, but does not become an integral part of the
chemical. Such substances are used in the manufacture, processing at every
step. Major problem with many solvents is their volatility that may damage
human health and the environment. Even processes like recrystalisation require
energy and substances to change the solubility. The problem of solvents has
been overcome by using such solvents which do not pollute the environment.
Such solvents are known as green solvents. Examples include liquid Even
reactions have been conducted in solid state. For example the condensation
reaction of orthoesters with o-phenylenediamines in presence of KSF clay
under solvent free conditions using microwave.
4.6 Use of Renewable Feedstocks: Chemical transformations should be
designed to utilize raw materials and feedstocks that are renewable.For green
synthesis, the feedstock should replace the traditional petroleum sources, e.g.,
benzene used in the commercial sythesis of adipic acid has been replaced to
some extent by the renewable and nontoxic glucose and the reaction is carried
out in water.
4.7 Use of Catalysts: Catalysts are used in small amounts and can carry out
a single reaction many times and so are preferable to stoichiometric reagents.

They can enhance the selectivity of a reaction, reduce the temperature of a

transformation, reduce reagent-based waste and potentially avoid unwanted
side reactions leading to a clean technology . Apart from heavy metal catalysts
softer catalysts like zeolites, phase transfer catalysts, e.g., crown ethers, are
finding increasing industrial applications.
Biocatalysts Microorganisms and Enzymes: Enzymes are the most
efficient and commonest of the catalysts found in nature. The earliest
biocatalysed conversion known to mankind is the manufacture of ethyl alcohol
from molasses by the enzyme invertase. Enzymes have been used as important
tools in organic syntheses . In pharmaceutical industry, the largest scale
biocatalytic process is the conversion of the fermentation product of Penicillin
G into 6-amino penicillanic acid by enzyme penicillin acylase. Many chemically
modified penicillins, amino acids, vitamins, fructose syrup and many
biopharmaceuticals are obtained by this method. Biocatalysed reactions are
advantageous as they are performed in aqueous medium, all conversions are
single step, and protection of functional groups are not neceessary, reactions
are fast, stereo-specific. Such transformations are either impossible or
extremely difficult to achieve by conventional chemical methods.
4.8 Avoid Chemical 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 more waste. Instead, more selective
and better alternative synthetic sequences that eliminate the need for functional
group protection should be adopted.
4.9 Design Synthesis for Energy Efficiency: Energy requirements of the
chemical processes should be recognized for their environmental and economic
impacts.
i. Microwave irradiation: Reactions with microwave sources have been
carried out in a solid support like clay, silica gel, etc., eliminating the use of
solvents or with minimum amount of solvents. The reactions take place at a
faster rate than thermal heating. For example, Beckmann rearrangement of
oximes in the solid state with microwave irradiation gave quantitative yields
of the products without the use of acid catalysts.
ii. Sonochemistry (Ultrasound energy): Reactions using ultrasound energy
are carried out at RT with excellent yields. For example, Ullmanns coupling
which takes place at higher temperature giving low yields by conventional
method, gives increased yields at low temperature and in short duration with
ultrasound energy
4.10 Design for Degradation: Chemical products should be designed so that
at the end of their function, they do not accumulate and persist in the
environment but break down into innocuous hazardless substances. It is now
possible to place functional groups in a molecule that will facilitate its
biodegradation. Functional groups which are susceptible to hydrolysis,
photolysis or other cleavage have been used to ensure that products will be
biodegradable.
4.11 Inherently Safer Chemistry for Accident Prevention: Design
chemicals and their forms (solid, liquid, or gas) to minimize the chemical
accidents including explosions, fires and releases to the environment eg cancercausing benzene Nanoscience and nanotechnology is another important
contribution to green chemistry. Nanotechnology provides huge savings in
materials by development of microscopic and submicroscopic electronic and
mechanical devices. It has been found that in an attempt to recycle solvents
from a process (for economic reasons) increases the potential for a chemical
accident or fire.
4.12 Analytical methodologies: Development is further neded to allow for
real-time in-process monitoring and control prior to the formation of hazardous
substances.
5. THE HISTORICAL CONTEXT OF GREEN CHEMISTRY:
Green chemistry concerns the development of chemical technology and
processes that are designed to be incapable of causing pollution. During the
1990s, environmental protection forces have been enveloping the science of
chemistry with ideas and examples of green chemistry, and Paul Anastas coined
the term green chemistry
A few examples of recent initiatives and undertakings serve to illustrate the
historical growth and incalculable potential of green chemistry:[13]
In the United States, green chemistry was an official focus area by the EPA
at the beginning of the 1990s.
In 1995, the United States launched the Presidential Green Chemistry
Challenge Awards, which sought to provide visibility and recognition to those
companies and academic researchers with outstanding achievements in green
chemistry.

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In August 1996, IUPAC approved the formation of the Working Party on
Green Chemistry under Commission III.
The First International Green Chemistry Conference in Venice was held in
September 1997 under the IUPAC sponsorship. The same year, the Green
Chemistry Institute was founded.
5.1 The emergence of green chemistry [14]
Since its initial introduction in the early 1990s, green chemistry has spread
throughout all aspects of the international chemical enterprise. There has
been general recognition that green chemistry affects all of the various sub
disciplines of chemistry .
Currently, around the world there are conferences, research funding programs,
national awards, and recognition and educational programs devoted to green
chemistry. In recent years, a number of research institutes like Green Chemistry
Institute have been established in the United States, Italy, China, Japan,
Australia, Sweden, the United Kingdom, Germany, Spain, Taiwan, and other
nations as well. The chemical literature on green chemistry has been expanding
through books,journals, and direct Internet publishing.IUPAC is uniquely
positioned to play a major role, in supporting and advancing economic and
environmental benefits through scientific innovation in green chemistry.
Through the vehicle of green chemistry, IUPAC can engage and is engaging
the international community in issues of global importance to the environment
and to industry. By virtue of its status as a leading and internationally
representative scientific body, IUPAC is able to collaborate closely in furthering
individual national efforts as well as those of multinational entities.
6. AREAS OF DEVELOPMENT:
The areas for the development of green chemistry have been identified as
follows:
6.1. Use of alternative feedstock : [15] The use of feedstocks those are
renewable rather than depleting and less toxic to human health and the
environment. The synthesis and manufacture of any chemical substance begins
with the selection of a starting material from which the final product will be
built.In many cases the selection of a starting material can be the most
significant factor. If the substance itself does not pose any hazard to human
health or the environment, for example, but the retrieval and/or isolation of
the substance causes significant risk to either, then this factor must be taken
into account in the selection.
6.2 Use of innocuous reagents: [16] The use of reagents that are inherently
less hazardous and are catalytic whenever feasible. Certainly, a first-level
assessment of any starting material must be whether or not the substance itself
poses a hazard in the form of either toxicity, accident potential, possible
ecosystem damage, or another form.
6.3. Employing natural processes: [16] Use of biosynthesis, biocatalysis, and
biotech-based chemical transformations for efficiency and selectivity.
Biocatalysis harnesses the catalytic potential of enzymes to produce building
blocks for the pharmaceutical and chemical industry. While fermentations use
the carbon source for de novo product synthesis, biocatalytic processes employ
a different strategy
6.4 Use of alternative solvents: [17] The design and utilization of solvents
that have reduced potential for detriment to the environment and serve as
alternatives to currently used volatile organic solvents, chlorinated solvents,
and solvents that damage the natural environment.
6.5 Design of safer chemicals or use of enzymes: [17] Use of molecular
structure designand consideration of the principles of toxicity and mechanism
of actionto minimize the intrinsic toxicity of the product while maintaining
its efficacy of function. Enzymes play important roles in food and beverage
industry and have already been recognized as valuable catalysts for organic
transformations and production of fine chemicals and pharmaceuticals.
Enzymes catalyze reactions in a selective manner, not only regio- but also
stereo selectively and have been used both for asymmetric synthesis and
racemic resolutions.
6 . 6 M i n i m i z i n g e n e r g y c o n s u m p t i o n : The design of chemical
transformations that reduce the required energy input in terms of both
mechanical and thermal inputs and the associated environmental impacts of
excessive energy usage.
6.7 Renewable resources 18]: In addition to the direct hazard associated with
a particular chemical substance, the implications of using a renewable versus a
depleting feedstock need to be included in the selection of that substance as a
starting material in a synthetic transformation.. To ensure a high degree of

product safety for consumers and the environment, renewable resources have
often been shown to have advantages
Oleochemistry is a branch of chemistry that uses vegetable oils and fats as
renewable resources. Together with carbohydrates and proteins, fatty oils are
important renewable resources compared to fossil and mineral raw materials.
Light is another emerging feedstock in a broad sense, a safe alternative to
toxic catalysts in many synthetic transformations. Beside UV light, the most
renewable and environmentally ideal energy source is sunlight.
6.8 Solve other environmental problems: Selection of a starting material
should be assessed not only for any hazards that the substance might or might
not possess, but also for existing environmental problems that its use as a
starting material might assist in solving. Utilization of waste biomass as a
chemical feedstock in chemical manufacturing processes can alleviate if not
completely eliminate such waste problems. The sequestering of carbon dioxide
is another example of how the selection of a starting material can help solve
an existing environmental problem. It is well known that carbon dioxide is
among the most potent of greenhouse gases that have been found to
contribute to global warming. Research is currently being conducted in the
design of new materials that could be used in applications that sequester carbon
dioxide during manufacturing processes.
6.9 Benign reagents/synthetic pathways: [ 18] As in the selection of a starting
material, the selection of a reagent must include an evaluation to identify
what the hazards associated with a particular reagent are. This evaluation
should include an analysis of the reagent itself, as well as an analysis of the
synthetic transformation associated with the use of that reagent (i.e., to
determine product selectivity, reaction efficiency, separation needs, etc.).
In addition, an investigation should be undertaken to determine if more
alternative reagents are available that either are themselves more
environmentally benign.
6.10 Generates less waste: An important consideration and benefit associated
with the use of a particular reagent is whether it is responsible for the generation
of more or less waste than other reagents. Not only amount but type of any
waste generated must also be assessed.
In this regard, it is obvious that oxidation reactions involving oxygen and
hydrogen peroxide will be of outstanding priority, as they produce water as a
by-product. Green oxidation reactions require the use of nontoxic solvents
(water or CO2) and mild reaction conditions. Hydrogen peroxide is a clean
reagent, with water the only by-product formed, and a very high selectivity
can be obtained. However, the use of hydrogen peroxide for fine chemical
production is currently limited by its poor reactivity and its ease to undergo
radical decomposition. Therefore, there is a great effort to develop systems
able to selectively activate oxygen and hydrogen peroxide for oxidative
transformations.
6.11 Selective Reagents: [19] Utilizing a reagent that is more selective means
that more of the starting material is going to be converted into the desired
product. Both high selectivity and high conversion must be achieved in order
for a synthetic transformation to generate little or no waste
6.12 Catalytic Reactions: [19] If a catalyst is necessary, it should be used in
actually catalytic amount. In fact, if a reagent can be utilized and yet not
consumed in the process, it will require less material to continuously effect the
transformation. This implies that catalysis has to be as efficient (not only
effective) as possible, involving a high turnover number.
6.13 Synthetic transformations: [14] The various reaction types most
commonly used in synthesis can have different degrees of impact on human
health and the environment.
Addition reactions, for example, completely incorporate the starting
materials into the final product and, therefore, do not produce waste that
needs to be treated, disposed of, or otherwise dealt with.
Substitution reactions, on the other hand, necessarily generate stoichiometric
quantities of substances as by-products and waste.
Elimination reactions do not require input of materials during the course of
the reaction other than the initial input of a starting material, but they do
generate stoichiometric quantities of substances that are not part of the final
target molecule. As such, elimination reactions are among the least atomeconomical transformations.
For any synthetic transformation, it is important to evaluate the hazardous
properties of all substances necessarily being generated from the transformation,
just as it is important to evaluate the hazardous properties of all starting
materials and reagents that are added in a synthetic transformation. Freeradical chemistry has shown a magnificent development over the last 30

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years. In the past, radicals were generally thought to be too reactive to be
controlled and unlikely to produce synthetic applications. Now, the view is
that they are useful and selective intermediates.
Two methods for effecting radical reactions in an environmentally friendly
way are presented:
(i)The Tetrathiafulvalene (TTF)-mediated radical-polar crossover reaction
converts are nediazonium salts to aryl couple with TTF+ to afford sulfonium
salts which, in turn, undergo solvolysis to alcohols, ethers, or amides. The
method provides the key step in a synthesis of ()-aspidospermidine;
(ii) Hypophosphite salts and hypophosphorous acid, on the other hand, form
CC bonds with reductive termination. These economical reagents give radicals
efficiently from alkyl halides and allow a very easy separation of products
from by-products.
6.14 Solvents/reaction conditions: [20] The use of solvents in the chemical
industry and the chemical related industries is ubiquitous. With increasing
regulatory pressure focusing on solvents, there is significant attention being
paid to the use of green chemistry alternatives to traditional solvents.
Less toxic solvents have been developed. The earliest and most obvious
hazards that were recognized in solvent molecules were their ability to explode
or ignite. With the greater understanding of the health and environmental
effects that could be caused by a large number of solvents, new designer
solvents are being scrutinized for other hazards as well Human health.
6.15 Products/design of safer chemicals: [21] The design of safer chemicals
is a process that utilizes an analysis of the chemical structure to identify what
part of a molecule is providing the characteristic or property that is desired
from the products and what part of the molecule is responsible for the toxicity
or hazard. By knowing this information, it is possible to maintain efficacy of
function while minimizing the hazard..
Mechanism of action: In cases where a mechanism of action is known, there
is the greatest potential to design a chemical that is safer from the perspective
of toxicity or other hazard to human health and the environment. Simply
stated, if the pathway toward toxicity is known, and then if any step within
that pathway can be prevented from occurring, then the toxic endpoint will be
avoided.
Structureactivity relationships: Although mechanisms of action may be
unknown, there are often detailed correlations, by way of structureactivity
relationships, that can be used to design a safer chemical. As an example, if it
is known that the methyl-substituted analog of a substance has very high
toxicity, and that the toxicity decreases as the substitution moves from ethyl
to propyl, etc., it would be reasonable to increase the alkyl chain length to
design a safer chemical.
Elimination of toxic functional group: A class of chemicals is often defined
by certain structural features, such as functional groups like aldehydes, ketones,
nitriles, or isocyanates. If one doesnt have any information about the specific
variations in toxicity with structural modification or in the mechanism by
which it produces that toxicity, the assumption that certain reactive functional
groups will react similarly within the body or in the environment is often a
good one.
7. ADVANCES IN GREEN CHEMISTRY:
7.1 Supercritical Fluids (SCF) : A Supercritical Fluids (SCF) is defined as a
substance above its critical temperature and critical pressure. The critical
point represents the highest temperature and pressure at which the substance
can exist as a vapor and liquid in equilibrium. Supercritical fluids (SCF) are
highly compressed gases which combine properties of gases and
liquids.Supercritical fluids are suitable as a substitute for organic solvents in a
range of industrial and laboratory processes. Carbon dioxide and water are the
most commonly used supercritical fluids, being used for decaffeination and
power generation, respectively.
The use of Supercritical CO2 (scCO 2) as an environmentally acceptable
alternative to conventional solvents for reaction chemistry, so called Clean
Technology. In addition, supercritical fluids can lead to reactions which are
difficult or even impossible to achieve in conventional solvents. Fluids such as
supercritical xenon, ethane and carbon dioxide offer a range of unusual chemical
possibilities in both synthetic and analytical chemistry.
7.1.1 Properties of Supercritical Liquids:
There is no surface tension in a supercritical fluid, as there is no liquid/gas
phase boundary. By changing the pressure and temperature of the fluid, the
properties can be tuned to be more liquid- or more gas-like. One of the most

important properties is the solubility of material in the fluid. Solubility in a

supercritical fluid tends to increase with density of the fluid (at constant
temperature). Since density increases with pressure, solubility tends to increase
with pressure. The relationship with temperature is a little more complicated.
At constant density, solubility will increase with temperature. However, close
to the critical point, the density can drop sharply with a slight increase in
temperature. Therefore, close to the critical temperature, solubility often
drops with increasing temperature, and then rises again. All supercritical fluids
are completely miscible with each other so for a mixture a single phase can be
guaranteed if the critical point of the mixture is exceeded.
7.1.2 Applications Supercritical Liquids:
A. Supercritical fluid extraction: The advantages of supercritical fluid
extraction (compared with liquid extraction) are that it is relatively rapid
because of the low viscosities and high diffusivities associated with supercritical
fluids. The extraction can be selective to some extent
B. Inhalable compounds : One of the most promising applications of gas
type supercritical processing is in the development of inhalable pharmaceutical
compounds where it has been shown that a supercritical fluid product has the
potential for rapid systemic delivery and reduction in the dose. A current
example using an anti-solvent technology is an inhaled migraine relief
pharmaceutical, which is currently in phase II development.
C. Sterilization of biomedical materials: Recent studies have proved SCCO2 is an effective alternative for terminal sterilization of biological materials
and medical devices. Moreover, this process is gentle; as the morphology,
ultrastructure, and protein profiles of inactivated microbes are maintained.
D. Catalysis: Another area of potential is catalysis in supercritical fluids,
where it is claimed that supercritical reactions occur at significantly faster
rates than in conventional solvents. This technology has been reported to
have been used to form of drug-drug co-precipitates.
E. Refrigeration: Supercritical carbon dioxide is also an important emerging
natural refrigerant, being used in new and low-carbon solutions for domestic
heat pumps.
7.2 Ionic liquids: [24, 25]
Ionic liquids, originally known as liquid electrolytes, ionic melts, ionic fluids,
fused salts, liquid salts, or ionic glasses, is a term generally used to refer to
salts that form stable liquids. Among other reasons, these liquid salts are of
particular interest due to their extremely low- saturated vapor pressures.The
entities comprising an IL are predominantly ions and ion-pairs. Ordinary table
salt (sodium chloride) consists of sodium cations (Na+) and chloride anions
(Cl ); when heated to several hundred degrees C, it melts (undergoes a phase
change) into a liquid of mostly ions. The term ionic liquid includes all
classical molten salts, which are composed of more thermally stable ions, such
as sodium with chloride or potassium with nitrate Ionic liquids are often
moderate to poor conductors of electricity, non-ionising (e.g. non-polar),
highly viscous and frequently exhibit low a vapour pressure. Their other
properties are diverse: many have low combustibility, excellent thermal stability,
wide liquidus regions, and favourable solvating properties for a range of polar
and non-polar compounds. Properties, such as melting point, viscosity, and
solubility of starting materials and other solvents, are determined by the
substituents on the organic component and by the counterion. Many ionic
liquids have even been developed for specific synthetic problems. For this
reason, ionic liquids have been termed designer solvents.
Applications of Ionic Liquids:
a. Natural Product Extraction: Ionic liquids are proving superior to
conventional solvents in the extraction of specific natural compounds from
plant biomass for pharmaceutical, nutraceutical and cosmetic applications.
b. Waste Recycling: Ionic liquids can be developed for the recycling of
synthetic goods, plastics and metals. They offer the specificity required to
separate similar compounds from each other, such as in the separation of
polymers from plastic waste streams.
c. Hydrogen Storage: Ionic liquids have several properties that make them
viable options for hydrogen storage systems. For instance, the vapor pressure
of ionic liquids is very low and is negligible in most situations. In addition,
ionic liquids are able to act as solvents for a wide variety of compounds and
gases, they also have weakly coordinating anions and cations which are able to
stabilize polar transition states.

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d. Cellulose Processing: Cellulose is the earths most widespread natural
organic chemical and thus, highly important as a bio-renewable resource. A
more intensive exploitation of cellulose as a bio-renewable feedstock has to
date been prevented by the lack of a suitable solvent that can be used in
chemical processesMaking cellulosic fibers from so-called dissolving pulp
currently involves the use, of great volumes of various chemical auxiliaries,
esp. carbon disulfide (CS2). These processes can be greatly simplified by the use
of ionic liquids, which serve as solvents and are nearly entirely recycled.
8. FUTURE PERSPECTIVES
8.1 Future challenges and opportunities for the chemical profession
and the science of chemistry [26]
Green chemistry has major contributions to make to the quality of life, human
welfare, and sustainable development. However, before green chemistry can
contribute fully to these areas, it must be integrated into the discipline of
chemistry itself. This requirement presents a number of major challenges to
the chemical profession:
Chemists will need to integrate into pure chemistry the questions of why or
why not, on environmental protection grounds,.
It is vital that green chemistry not become a fad, in which chemistry that is
not really green gets paraded as such before the scientific community and
the world.
Certain of the largest sustainability issues, where chemists have so much to
offer, will require new approaches that can only be built with long-term
commitment.
8.2 Green chemistry education [27]
In order to allow for the full potential of green chemistry to explore the
scientific and economic advances the scientific community needs to provide
educational opportunities to train chemists of the future. Since green chemistry
requires the same skills and abilities of traditional chemistry, students of all
ages can learn fundamental concepts in ways that are more environmentally
benign.
This educational endeavor can take several forms, including traditional courses
in chemistry for students at primary, secondary, and university levels, as well
as professional training for practicing chemistry in industry . In addition,
nonscience students and professionals (especially those involved in the business/
finance communities) need to be aware of the recent developments and advances
green chemistry
[28]

9. GREEN CHEMISTRY IN PHARMACEUTICAL SCIENCES:

After numerous Acts and Rules, the current economic situation is forcing
managements to re-think their stand on Environmental, Health & Safety
(EHS) policies of how pharmaceutical companies can go green
After a long struggle pharma manufacturers have recognized the economic
and environmental value of Green Chemistry. Although various Act and Rules
such as
i.The Environmental (Protection) Act, 1986 and Rules.
ii. The Water (Prevention & Control of Pollution) Act, 1974 and Rules.
iii. The Air (Prevention & Control of Pollution) Act, 1982 and Rules.
have been introduced by the Indian government, these have been followed for
compliance and for obtaining licenses rather than realising the importance
and value of Green Chemistry. The importance and self realisation has now
come to mean economic value also. Pharma companies have to take
responsibility for two major issues: energy efficiency and solvent reduction.
9.1 Energy efficiency: (HVAC, Boilers and Cogeneration), improving energy
efficiency should be a strategic goal for the pharma industry today. Not only
can energy efficiency reduce overall manufacturing cost, it usually reduces
environmental emissions, establishing a strong foundation for a corporate
green house gas management programme.
9.2 Solvent reduction a good place to start:. About 80 percent of pharma
waste results from solvent use, with the remainder related to reagents and raw
materials. High vapour pressure of the solvent in the air increases the likelihood
of breathing of solvent vapours by the people close to it. The solvents are
highly toxic and can damage an exposed living organism.eg,replacement of
organic solvents with safer available aqueous solvents in tablet coating to
protect the environment and health as well as industrial safety.
9.3 Increasing incentives to go green: One of the solutions is to teach
green principals at the earliest stages of chemistry education.In this connection
Green Chemistry Network Centre, Delhi University is playing an important
role.Another step should be setting up of a special department under the
concerned ministry in line with Department of Scientific & Industrial Research

(DSIR) for recognising and rewarding those industries which are investing
money and time towards Green Pharma.
Similarly the government of India should introduce special incentives under
Income Tax Act on the similar lines of section 35 A(B) for deduction on
capital and revenue expenditures for the amount spent on implementing the
12 principles of Green Pharma as discussed above. This will provide suitable
economic incentives and motivation to companies in SEM as well as large
sectors to go ahead and make long term investments. The apex bodies can also
form special committees to educate and guide industries on the front.
10. GREEN GUIDELINES FOR TEACHERS AND STUDENTS IN
LABORATORY[28]
It is most appropriate to carry out a synthesis by following a pathway so that
formation of waste is minimum or absent. In universities and colleges, the cost
of disposal of waste from chemical laboratory can be reduced by carrying out
experiments on a much smaller scale. Many do not have such a scheme so that
all this goes in the sewage untreated
If you dont use a chemical, you dont have to buy it and you cant lose it.
Green chemistry need not be expensive. If the whole chemical process is
rethought and modified, the result may be cheaper. It may be not be possible
to green every step of the process at once.
1. Experiments should involve the use of alternative reagents which are not
only eco-friendly but also be easily available at very cheap price. They should
not preferably invo lve the use of organic solvents ethanol and methanol.
2. Modified Experiments, if possible should not involve sophisticated
instrumentation techniques like high -pressure system, evacuated system, inert
atmosphere using argon, etc.
3. Experiments should avoid tedious experimental procedure like longer reaction
time, reaction at high temperature etc.
4. All organic chemistry experiments should preferably be conducted in semimicro or micro-scale. Thin-layer chromatography (TLC), spectroscopic
techniques (UV, IR and NMR) should be methods of choice for determining
purity, functional groups and structure elucidation.
5. One can use ethyl chloroformate as a substitute for PCl 5, PCl3, POCl3 or
SOCl2. The acid is converted to anhydride which can be used for the same
purpose
A. Inorganic Analysis
The conditions of the laboratories for doing inorganic analysis by conventional
methods in the under graduate level are at all not eco -friendly. The gases are
toxic causing health-hazards. Sometimes experiments are carried out in
closed doors in hot, humid conditions. Students often fall victim of this
infrastructure. The acid fumes, which are toxic, pollute the atmosphere. So, a
change in outlook must be brought about with the existing systems.
Inorganic analysis mainly deals with the detection and estimation of basic and
acid radicals. For the detection of radicals Spot -tests may be introduced.
B. Physical Chemistry Experiments
1. In distribution experiment, the use of chemicals like carbon tetrachloride,
benzene should be avoided and can be substituted by toluene or acetic acid in
butanol.
2. Experiments involving conductometry, polarimetry, potentiometry,
pHmetry, colorometry, polarography, spe ctrophotomery, requires chemicals
in very low concentrations and have no negative influence on the health or
environment, hence these expt. may not need any change or alterations.
3. If possible, instrumental methods may be introduced from the UG level.
11. EXAMPLES OF IMPLEMENTATION OF GREEN CHEMISTRY
PRINCIPLES INTO PRACTICE: [35]
In some industrial chemical processes, not only waste products but also the
reagents used for the production, may cause a threat to the environment. The
risk of exposure to hazardous chemical compounds is limited in daily work by
protective equipment such as goggles, breathing apparatus, face-guard masks,
etc. According to the principles of green chemistry, a threat can be eliminated
in a simpler way, by applying safe raw materials for production process.
Following is one such case study.
Large amounts of adipic acid [HOOC(CH2)4COOH] are used each year for the
production of nylon, polyurethanes, lubricants and plasticizers. Benzene a
compound with convinced carcinogenic properties is a standard substrate
for the production of this acid. Chemists from State University of Michigan
developed green synthesis of adipic acid using a less toxic substrate. Furthermore,
the natural source of this raw material glucose is almost inexhaustible. The

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glucose can be converted into adipic acid by an enzyme discovered in genetically
modificated bacteria. Such a manner of production of this acid guards the
workers and the environment from exposure to hazardous chemical compounds

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1.
2.

OH

3.
4.
3 H2

O2

5.

HNO3

Cata
O

N2O

6.
COOH
CO OH

7.
8.
9.

COOH

OH

H2

HOOC

10.
Pt

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E.coli

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13.

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CONCLUSIONS:
In conclusion, the practicing of green chemistry in India is a necessity rather
than an option. The future of green India is in the hands of young researchers
and students, as the practice of green chemistry is a moral responsibility for
them. Government agencies should enforce the laws strictly to practice green
chemistry. Industries should also understand their moral responsibility toward
the fragile environment.
The research and development and the science and technology agencies that
are responsible for the funding of scientific activities in the country must
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Source of support: Nil, Conflict of interest: None Declared

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