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CRITICAL REVIEW www.rsc.org/csr | Chemical Society Reviews

Green Chemistry: Principles and Practice

Paul Anastas* and Nicolas Eghbali
Received 9th September 2009
First published as an Advance Article on the web 20th November 2009
DOI: 10.1039/b918763b

Green Chemistry is a relatively new emerging field that strives to work at the molecular level to
achieve sustainability. The field has received widespread interest in the past decade due to its
ability to harness chemical innovation to meet environmental and economic goals simultaneously.
Green Chemistry has a framework of a cohesive set of Twelve Principles, which have been
systematically surveyed in this critical review. This article covers the concepts of design and the
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scientific philosophy of Green Chemistry with a set of illustrative examples. Future trends in
Green Chemistry are discussed with the challenge of using the Principles as a cohesive design
system (93 references).

I Introduction The most important aspect of Green Chemistry is the

concept of design. Design is a statement of human intention
Green Chemistry is defined as the ‘‘design of chemical and one cannot do design by accident. It includes novelty,
products and processes to reduce or eliminate the use and planning and systematic conception. The Twelve Principles of
generation of hazardous substances.’’1,2 This definition and Green Chemistry are ‘‘design rules’’ to help chemists achieve
the concept of Green Chemistry were first formulated at the the intentional goal of sustainability. Green Chemistry is
beginning of the 1990s nearly 20 years ago.3 In the years since, characterized by careful planning of chemical synthesis
there has been international adoption that resulted in the and molecular design to reduce adverse consequences.
creation of literally hundreds of programs and governmental Through proper design one can achieve synergies—not merely
initiatives on Green Chemistry around the world with initial trade-offs.
leading programs located in the U.S., United Kingdom, and The Green Chemistry approach strives to achieve sustain-
Italy.4 These have played a significant role in informing ability at the molecular level. Because of this goal, it is
sustainable design.5 Important early programs include the not surprising it has been applied to all industry sectors.
US Presidential Green Chemistry Challenge Awards established From aerospace, automobile, cosmetic, electronics, energy,
in 1995,6 the Green Chemistry Institute founded in 1997,7 and the household products, pharmaceutical, to agriculture, there are
publication of the first volume of the now well-established Green hundreds of examples of successful applications of award
Chemistry journal of the Royal Society of Chemistry in 1999.8 winning, economically competitive technologies.9
The concept of Green Chemistry has had this large impact
due to the fact that it goes beyond the research laboratory in
Center for Green Chemistry and Green Engineering at Yale, isolation and has touched industry, education, environment,
Yale Chemistry Department, 225 Prospect Street, New Haven, CT,
06511, USA. E-mail: paul.anastas@yale.edu; Fax: 1-203-436-8574; and the general public. The field of Green Chemistry has
Tel: 1-203-432-5215 demonstrated how chemists can design next generation

Paul T. Anastas is the Teresa Nicolas Eghbali earned a BS in

and H. John Heinz III Molecular Biology and a MS in
Professor in the Practice of chemistry from Bordeaux I
Chemistry for the Environment University (France). After
and the Director of the Center completing his PhD dissertation
for Green Chemistry and Green in 2007 under the supervision of
Engineering at Yale University. both Professors Chao-Jun Li
Trained as a synthetic organic and David Harpp at McGill
chemist, Dr Anastas received University, he joined the Center
his PhD from Brandeis for Green Chemistry and Green
University and is credited with Engineering at Yale, where
establishing the field of he worked as a post-doctoral
green chemistry in 1991. Dr research associate. His PhD
Anastas has published ten books work was centered on the
Paul Anastas and numerous papers on Nicolas Eghbali utilization of carbon dioxide
sustainability through science. and his current research inter-
ests range from green organic synthesis to material science and
biocatalysis.

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products and processes so that they are profitable while being III The Twelve Principles
good for human health and the environment. Following the
scientific enthusiasm of Green Chemistry, teaching initiatives, The Twelve Principles of Green Chemistry were introduced in
governmental funding, and the establishment of Green 1998 by Paul Anastas and John Warner (Fig. 2). They are a
Chemistry Research Centers have multiplied in the past two guiding framework for the design of new chemical products
decades. Many universities now offer classes on Green and processes, applying to all aspects of the process life-cycle
Chemistry and Green Engineering. Some institutions offer from the raw materials used to the efficiency and safety of the
degrees in the field. Governmental funding has also increased transformation, the toxicity and biodegradability of products
in several countries around the world.10 and reagents used. They were summarized recently into the
more convenient and memorable acronym, PRODUCTIVELY.11
The following sections are intended to provide a general
II Framework of Green Chemistry knowledge about Green Chemistry. For the convenience of
the reader, technical examples are cited for each principle.
The three main points about the Green Chemistry framework
can be summarized as:
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1. Green Chemistry designs across all stages of the chemical

life-cycle.
2. Green Chemistry seeks to design the inherent nature of
the chemical products and processes to reduce their intrinsic
hazard.
3. Green Chemistry works as a cohesive system of principles
or design criteria.

The Twelve Principles of Green Chemistry are design criteria

or guidelines that provide the framework for sustainable design.
They constitute an overarching construct for the design of
safer chemicals and chemical transformations. Chemistry has
long been perceived as a dangerous science and often the
public associates the word ‘‘chemical’’ with ‘‘toxic.’’ There
are ways to reduce risk by using safety precautions such as
protective gear. When safety protections fail, the risk, which is
defined as a function of the hazard and exposure, increases
(Fig. 1). If the hazard is high and exposure controls fail,
the consequences can be catastrophic (injury or death). By
minimizing the hazard portion of the equation instead of
focusing only on exposure controls, the risk can be limited
even in cases of undesirable circumstances (accident, spills,
sabotage, etc. . .). Designing safer sustainable chemicals and
processes requires striving to reduce the intrinsic hazards to a
minimum and therefore limiting the risk of accident and
damage.1
The aim of Green Chemistry, to reduce hazards across all
the life-cycle stages, has been shown to be economically
profitable. Hazard is defined as the ability to cause adverse
consequence to humans or the environment. Intrinsic hazard
of a chemical substance or a chemical process can be designed
to be minimized at every level of a process, whether it is
toxicity, physical hazards (e.g., explosion, flammability) or
global hazards such as stratospheric ozone depletion. Risks
based on these hazards may rise from the nature of the
feedstock and raw materials that are used in the chemical
transformations as well as the final products that are made.
Careful design will reduce or eliminate intrinsic hazards within
chemicals and processes; a design based on the integration of
the Twelve Principles as one cohesive set.

Fig. 1 Risk is a function of hazard and exposure. Fig. 2 The Twelve Principles of Green Chemistry.

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1 Waste E-Factor dropped to 0.3 Kg of waste. The new process was

generating more than 16 times less waste than the original one,
Waste prevention is the first of the Twelve Principles of Green
eliminating the formation of waste water as well.15
Chemistry. It is better to prevent the formation of waste rather
When byproducts cannot be avoided, other innovative
than to clean it up after the fact. The generation of any
solutions should be considered and a productive one is to seek
material that does not have realized value or the loss of
an industrial ecology approach where waste can become a new
unutilized energy can be considered a waste. As mentioned
raw material with significant value for another process as it
above, waste can take many forms and may impact the
re-enters the life-cycle. This approach is currently being
environment differently depending on its nature, its toxicity,
applied to the production of biofuel (Fig. 3b).16
its quantity, or the way it is released.12 When large portions of
the initial raw materials used in a process are lost because of 2 Atom economy
the original design of the process itself then it will inexorably
generate waste which is by definition undesirable. In 1990 Barry Trost introduced the concept of synthetic
In 1992, the concept of what is now widely accepted as the efficiency: Atom Economy (AE) also called Atom Efficiency.17
E-Factor, or Environmental Impact Factor, was introduced by It refers to the concept of maximizing the use of raw materials
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Roger Sheldon.13 This metric helps to quantify the amount of so that the final product contains the maximum number of
waste generated per kilogram of product. It is a means to assess atoms from the reactants. The ideal reaction would incorporate
the ‘‘environmental acceptability’’ of a manufacturing process. all of the atoms of the reactants. The AE is measured as the
The environmental factor which has been adopted by many ratio of the molecular weight of the desired product over the
in the chemical industry underscores how inefficient certain molecular weights of all reactants used in the reaction (Fig. 4).
industrial processes have been and opened the door to creative It is a theoretical value meant to quickly assess how efficient a
solutions. One well-known example is the early synthesis of reaction will be.
ethylene oxide which was prepared through a chlorohydrin To illustrate this concept, a few examples such as the
intermediate (Fig. 3a). The E-Factor for the entire synthesis as Grignard reaction, A3 coupling and the Diels–Alder reaction
stated above was equal to 5. For each kilogram of product, are presented below. The Grignard reaction, which received
5 Kg of waste were to be disposed. This does not take into the recognition of the scientific community for its importance
consideration the waste water contaminated by chlorine
by-products.12–14 When the synthesis was modified to use
molecular oxygen, thus removing the need for chlorine, the

Fig. 3 (a) Traditional preparation of ethylene oxide and the new

route relying on molecular oxygen. (b) Revalorization of biofuel
byproducts. Fig. 4 The Atom Economy AE and several illustrations.

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in organic synthesis, is unfortunately a relatively poor atom-

economical reaction due to the use of a stoichiometric amount
of metal reactant and the necessity to prepare the Grignard
reagent separately.18Fig. 4 presents a typical Grignard
reaction19 and an application of the Grignard reagent to build
a propargylic amine type structure.20 The values of the AE
respectively are 44 and 56% which reflect a loss of half of the
raw material. A solution in respect to the last example was
proposed by C.-J. Li et al. in 2002 through the A3 coupling
(Alkyne, Aldehyde and Amine).21 This one-step multi-
component coupling reaction is more efficient and conserves
atoms since 92% of the original atoms used are found in the
final product. The Diels–Alder reaction is also an excellent
example of an atom-economical reaction17 (Fig. 4). Its AE
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is equal to 100% since all atoms from the reactants are

incorporated into the final product. Diels–Alder type reactions
belong to the category of cycloaddition which is among the
greenest types of reactions in traditional chemistry.

3 Synthesis
As illustrated in Fig. 5, the synthetic toolbox of organic
chemists has been improved by a significant amount of
innovative work. Many of the new reactions that have been
developed in the past decade add to the already existing green
reactions that were discovered during the past century.
Reactions based on cycloaddition,17,22 rearrangement,23 or
multi-component coupling reactions24 were already known
and constitute one category of efficient reactions. Cascade or
tandem reactions,25 C–H activation,26 metathesis,27 and
enzymatic reactions28,29 are rather new approaches and
illustrate strong examples of cleaner, more efficient synthetic
tools available to organic chemists. The Grubbs catalyst, for
example, allows alkene metathesis through a mechanism
similar to Wittig-type reactions such as the Horner–
Wadsworth–Emmons reaction (formation of a four membered
ring as reaction intermediate, Fig. 5). It is an essential tool for
the construction of larger molecules. However, unlike the
Fig. 5 Examples of green reactions.
Wittig reaction, the metathesis reaction does not produce a
large amount of waste. The formation of phosphonium salts in
selectively without the need for any activating or directing
the case of the Wittig reaction is unfortunately unavoidable
groups. Those examples demonstrate the power of C–H
since it is part of the design of the reaction and is the main
activation in advancing Green Chemistry.
driving force.30
C–H activation is another relatively new area of chemistry
4 Molecular design
which holds great promise for the future.26 In traditional
coupling reactions, activated carbon–halogen bonds are While there has been significant focus on designing chemicals
usually used because of their high reactivity. Since halogenated for various functions ranging from medicines to materials,
molecules are rarely natural, it implies additional steps there has been a surprising lack of interest in taking into
to produce the precursor. The replacement of traditional consideration hazard in the design process. Understanding the
coupling reactions with C–H activation eliminates the need properties of a molecule that have an impact on the
for halogenated precursors and therefore the halogenated environment and the transformations that take place in the
waste byproduct generated. biosphere is essential to sustainability. Through a mastery of
Two famous examples of C–H activation were published in this understanding, chemistry will be able to genuinely design
1993 by Murai31 and in 2007 by Fagnou.32 In the first case, molecules that are safer for humans and the environment. Work
Murai et al. employed a ruthenium catalyst to couple the by Ariëns33 in 1984 and by Garrett and Devito in 1996 showed
inactivated substrates acetophenone and 2-methylstyrene. that designing safer chemicals is not only highly needed for the
This work was one of the first examples of C–H activation advancement of Green Chemistry, but is also possible.34
and represents a milestone in the field. In the second In recent decades, there has been a significant amount of
case, Fagnou and Stuart coupled two aromatic compounds work in the field of toxicology that has moved it from being a

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descriptive science to one that has a large mechanistic

component,35 and even more recently progressively towards
the incorporation of an in-silico component.36 Because of
that transition, it has been possible to create correlations,
equations, and models that relate structure, properties, and
function. These approaches provide the basis for the work
being pursued in the development of a comprehensive design
strategy. For instance the existing understanding of medicinal
chemistry can already help establish some ground rules for
designing less toxic chemicals via incorporation of specific
design features that block their access into humans and many
animal organisms.37
Fig. 6 Pressure–temperature phase diagram showing the supercritical
5 Solvents region.
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Solvents are perhaps the most active area of Green Chemistry

research.38 They represent an important challenge for Green to be a versatile solvent, safe and easy to handle, as demon-
Chemistry because they often account for the vast majority of strated by the work of Poliakoff, Leitner, Jessop, DeSimone,
mass wasted in syntheses and processes.39 Moreover, many and others.45 What makes SCF so attractive in general and
conventional solvents are toxic, flammable, and/or corrosive. particularly scCO2 is the change of state that occurs when
Their volatility and solubility have contributed to air, water cooling down the vessel or reducing the pressure. Above
and land pollution, have increased the risk of workers’ critical points, CO2 will be a liquid in which reactions can be
exposure, and have led to serious accidents. Recovery and performed and below, it will be a gas. Degassing the system
reuse, when possible, is often associated with energy-intensive allows the complete removal of the solvent. ScCO2 has found a
distillation and sometimes cross contamination. In an effort to wide range of industrial applications with the most famous
address all those shortcomings, chemists started a search for being the decaffeination of green coffee beans and the
safer solutions. Solventless systems,40 water,41 supercritical replacement of perchloroethylene in dry cleaning.46
fluids42 (SCF) and more recently ionic liquids43 are some Supercritical fluids have proven to be one valuable alternative
examples of those new ‘‘green’’ answers. to traditional solvents.
Where possible, the ideal situation would be to not use any Another example of greener solvents would be ionic liquids
solvent because the decision to include an auxiliary always pioneered in modern times by Seddon.43 As their name high-
implies efforts and energy to remove it from a designated lights, ionic liquids, or sometimes called room temperature
system. Efforts have therefore been devoted to developing ionic liquids, are liquid salts at room temperature. They have
solventless systems.40 This idea was reinforced by the finding virtually no vapor pressure and very low flammability. What
that solvents account for most of the industrial waste.39 was discovered recently by Jessop et al. is a ‘‘switchable’’ ionic
Depending on the physical properties of the reagents used or liquid.47 A ‘‘smart-obedient solvent’’ generated in situ just like
the desired outcome of the transformation, the approach often the liquid scCO2. Addition of pressurized carbon dioxide into
requires a new or redesigned chemistry to allow the reaction to an organic mixture transforms it into an ionic liquid, generating
proceed without the original solvent. a safer solvent in situ. Releasing the pressure reverses the
Water is the most abundant molecule on the planet and is phenomenon and the ionic liquid is retransformed into the
sometimes referred to as a benign ‘‘universal solvent.’’41 Being original mixture, thus removing completely the solvent and
able to run a reaction in or on water therefore has significant eliminating tedious purification and extraction steps.
advantages. Water is safe and does not pose any hazards. It Another example based on the same concept is the
can be a useful solvent for large scale process chemistry. The development of fluorous biphasic catalysis advanced by
properties of water have even led to improved reaction rates Horvath.48 A fluorous phase or solvent containing a catalyst
through the hydrophobic effect44 and easier separation since a suited for the desired transformation is usually not miscible
lot of organic substances do not dissolve in water. The case of with organic reagents at ambient temperature. When heated,
an improved Diels–Alder reaction in water is one of the useful they form a single media, allowing the reaction to proceed.
examples illustrating the advantages of water as a solvent.17,41 Upon cooling the organic phase and the fluorous solvent
One drawback which may slow down industrial applications separate, simplifying the purification process. This is an
and has yet to be addressed is the risk of water contamination attractive approach with the restriction that fluorous solvents
that can be very energy intensive to clean. are expensive.
SCF are another alternative to traditional organic solvents These last examples are good illustrations of one of
and have been extensively studied in the past decades.42 They chemistry’s major challenges: separation. Apart from certain
are substances which have been simultaneously heated and solventless systems, the new improved green solvents remain
compressed above their critical points (see Fig. 6). auxiliaries and therefore must be isolated from the desired
Common SCF are generated from water, carbon dioxide, product. If their use cannot be avoided then the issue of
methane, methanol, ethanol or acetone. Carbon dioxide is one separation must be taken into consideration when choosing
of the most widely used SCF. The resulting scCO2 has proven the appropriate solvent.

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6 Energy aspects of our consumer life and our economy. Turning towards
renewable feedstocks both for material and fuel has now become
Rising concerns over the depletion of petroleum feedstocks
more urgent. The major renewable feedstock on the planet both
and the increase in energy consumption have pushed the
for material and energy is bio-mass,58 the material available
development of more energy efficient processes and for the
from living organisms. This includes wood, crops, agricultural
search for renewable energies; non-depleting resources in a
residues, food, etc.59
time frame relevant to human scale.49
Examples of renewable material include cellulose, lignin,
As mentioned in the first section (first principle), unutilized
suberin and other wood compounds, polyhydroxyalkanoates,
energy may also be considered a waste. The design of chemical
lactic acid, chitin, starch, glycerol and oil.60 Lignin, for
reactions or systems that do not require intensive energy use is
instance, is a major waste of the pulp and paper industry. It
highly desirable. Reducing the energy barrier of a chemical
has been burned on the production site to provide energy for
reaction or choosing appropriate reactants so that the trans-
many years. In recent years it has found new applications as,
formation may proceed at room temperature is one example of
for example, dispersants, additives, and raw materials for the
what chemists can do to reduce energetic requirements, with
production of chemicals such as vanilin, DMSO or humic
all the direct and indirect benefits associated with it.1
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acid.61 Chitin is another abundant natural polymer that

Increasing the energy efficiency of a chemical system is
constitutes the exoskeleton of arthropods (e.g. crustaceans).
merely one part of the solution. Alternative energies are also
It is a major byproduct of the seafood industry and can be
needed. Several of those renewable energies have been identi-
transformed into chitosan by deacetylation.62 Numerous
fied in biofuels production,49,50 solar power (thermal and
applications of chitosan have been described from water
photovoltaic),49,51–53 wind power, hydro power, geothermal
purification, biomedical applications and other industrial
energy,49 and hydrogen fuel cells.49,54 Once again, green
uses.62,63 Reusing this waste of the bio-industries should
chemists have an important role to play in this new challenge
provide a large amount of raw materials to replace the current
as they have the ability to design both energy efficient trans-
petroleum feedstocks.
formations and materials or chemical systems that can be used
to harvest some of those renewable natural energies. 8 Derivatives
Solar energy, the primary sustainable energy source on
earth, is one of those alternatives to petroleum. Considerable Covalent derivatization is a ubiquitous technique in chemistry
efforts have been dedicated to understand and design chemical whether it is employed for organic synthesis or analytical
systems that can convert solar radiations into voltaic chemistry.64 In the early 1990s, an innovative concept surfaced
energy.53,55 Organic, inorganic and hybrid solar cells have called non-covalent derivatization, a derivatization that does
received interest although more focus has been placed on not rely on covalent bonding but rather on intermolecular
organic solar cells because of their higher efficiency. The interactions.65 The work by Warner was developed as a means
principle of those cells relies on the ability of the material to use little energy and less material to achieve chemical
used to absorb photonic energy from solar radiations. The modifications from the original system. An early example of
absorption leads to the formation of excited states that can be non-covalent derivatization is illustrated by the controlled
relayed and generate electronic current. Building materials and diffusion and solubility of hydroquinones used in Polaroid
polymers that can efficiently transform light into current films.66 Researchers at Polaroid sought to release hydro-
remain a challenge and are key to the success of this approach. quinones at elevated pH. Instead of relying on base-labile
Proton Exchange Membrane (PEM) fuel cells using hydrogen covalent protecting groups which would be the traditional
and oxygen gases could also provide another solution to the approach, they developed a non-covalent protecting group in
upcoming increase in energy demand (Fig. 7).54,56 PEM fuel cells the form of a co-crystal between hydroquinones and bis-(N,N-
have generated research interest, especially in the past decade dialkyl)terephthalamides (Fig. 8). This approach was successful
with the development of increasingly efficient catalysts such as
nanoparticles or even hydrogenase enzymes.57 An important
consideration in this approach is the hazard of handling
hydrogen gas, which is highly flammable and explosive.

7 Renewable materials
It has been estimated that the vast majority of our manufacturing
products are derived from petroleum feedstock or natural
gas.1,49,58 The depletion of those resources will touch many

Fig. 8 Hydroquinones protected by non-covalent interactions with

Fig. 7 General concept of a hydrogen fuel cell. bis-(N,N-dialkyl)terephthalamides.

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and viable for the industrial process. It solved the problem

without modification of the original hydroquinone structures
and minimized waste material and energy.

9 Catalysis
In many cases, the formation of waste is linked to the
traditional use of a stoichiometric amount of reagents.67
Switching from stoichiometric methodologies to catalytic
processes is perceived as one major way to improve the
efficiency of the synthetic toolbox. Catalysis can improve the
efficiency of a reaction by lowering the energy input required,
by avoiding the use of stoichiometric amount of reagents, and
by greater product selectivity. This implies less energy, less
feedstock and less waste.68 Moreover, it often opens the door
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to innovative chemical reactions and bring unconventional

solutions to traditional chemical challenges. Fig. 10 Integrating biodegradability in the design of surfactants.
Oxidation and reduction reactions illustrate this concept.
Reduction employing DIBAL-H as the hydride donor is a that there were examples where ‘‘water tended to foam when
well-established procedure used by organic chemists.69 It coming out of the tap.’’73,74 The public outcry prompted the
generates a significant amount of waste since a stoichiometric industry to seek an immediate solution and it was found that
amount of reducing agent is needed to complete the reaction. replacing the methyl branched chain of TPPS by a linear
Switching to catalytic hydrogenation like the Noyori hydro- carbon chain reduces the biopersistence (Fig. 10). A common
genation70 eliminates the need for stoichiometric reagents and example is the replacement of TPPS by linear alkylbenzene
in consequence decreases the amount of feedstock needed and sulfonate (LAS).
the amount of waste generated (Fig. 9). Designing biodegradable materials and chemicals is not
Beyond efficiency, catalysis can allow for otherwise a simple task as illustrated by continuing problems of
unfavorable reactions to be realized. This was the case for environmental pollution. Trends have emerged following
the metathesis reaction and the development of the Grubbs decades of data collection. Certain chemical structures such
catalyst.27 As illustrated in Fig. 5, the development of a as halogenated moieties, branched chains, quaternary carbons,
metathesis catalyst allowed a groundbreaking approach to tertiary amines, and certain heterocycles may possess
the formation of unsaturated compounds. The environmental enhanced persistence and are avoided. On the other hand,
benefit was significant and the innovation was important. integrating functional groups such as esters or amides which
Biocatalysis is yet another example of ‘‘green’’ chemistry as are recognized by ubiquitous enzymes may help the design of
it is a biomimetic approach relying on natural or modified environmental degradable products.73,75 This strategy was
enzymes.28–29,71 It usually refers both to the direct use of applied to surface-active quaternary ammonium compounds
purified enzymes and the transformations accomplished by used as household fabric softeners.76 Until the 1990s, long
engineered living organisms. Reaction conditions are relatively chain ammonium salts such as di(hydrogenated)tallow
mild as the transformation can be performed in water at dimethyl ammonium chloride (DHTDMAC) were released
atmospheric pressure and ambient temperature. Moreover, into the environment. It was then discovered that their rate
enzymes have proven to be more chemo-, regio- and stereo- of biodegradation in aqueous sediment was low and the
selective. intrinsic ecotoxicity, high. In response, hydrolyzable amide
10 Biodegradation or ester linkages were introduced. The new ammonium salts
have proven to be more biodegradable as illustrated in
The problem of persistence has been known for a long time Fig. 10; DHTDMAC was replaced by di(ethyl-ester) dimethyl
and became apparent in the early stages of industrial ammonium chloride (DEEDMAC) which was followed by a
development.72,73 In the 1950s for instance, tetrapropylene 70% increase in the biodegradability.
alkylbenzene sulfonate (TPPS) was used as a surfactant for
laundry detergents and accumulated into the water supply due 11 Analysis
to an incomplete degradation. The situation was so critical
It is the goal of green analytical chemistry to measure
chemicals without generating waste.77–79 The environmental
issues associated with analytical chemistry are usually linked
to the analytical approach itself. Real time direct analysis is
unfortunately not systematic as many methodologies still
require a pre-treatment of the sample or rely on what one
may call ‘‘ex situ analysis.’’ Process analytical chemistry79 is
defined as the ability to monitor a transformation and act
immediately upon it to prevent unwanted outcomes. It is not
Fig. 9 Comparison between stoichiometric and catalytic reduction. always possible, and therefore waste may be generated when

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the sample is analyzed. Green chemists must take into industry has been adapting to the new challenges of Green
consideration the functional requirements of analytical Chemistry.
methods since it will be counterproductive if the chosen As a first example, a greener synthetic pathway which was
methods contribute to further environmental problems. Green attributed to Eastman for its enzymatic esterifications.85 This
analytical chemistry can be defined as the use of analytical biocatalytic process runs under mild conditions, minimizes the
procedures that generate less waste and are safer to human formation of byproducts and saves energy, resulting in
health and the environment.79 This definition includes both increased efficiency. Overall hundreds of litres of organic
aspects of ‘‘live’’ monitoring of a chemical transformation and solvents were eliminated from the previous process.
the environmental shortcomings associated with traditional In 2008, researchers at Dow AgroSciences were rewarded
analysis. In situ monitoring of a reaction has significant for the design of green pesticides. While trying to understand
advantages in terms of Green Chemistry. When action can the structure–activity relationships of natural biopesticides in
be taken quickly, it may prevent accidents, save energy, and/or an effort to predict analogues that would be more active,
prevent the formation of significant amounts of by-products they designed Spinetoram. The company expects that the
that would otherwise require additional purifications. production of this new pesticide will eliminate ‘‘about 1.8
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When it comes to the analytical methods themselves, most million pounds of organophosphate insecticides during its first
of them share two problems linked to the two major steps five years of use.’’86
of a method: a pretreatment of the sample which includes In 2006, Merck developed a greener synthetic pathway for
extraction, separation or even sometimes chemical modification Sitagliptin, a chiral b-amino acid derivative used for the
of the sample, and a signal acquisition step.79 Since the treatment of type 2 diabetes.87 The approach was based on a
pretreatment step usually calls for large volumes of solvent, novel asymmetric catalytic hydrogenation of unprotected
it has been the center of analytical chemists concerns. If the use enamines which avoided the need of excessive derivatization
of solvents can not be avoided for an extraction step, benign (Fig. 11).88 Merck presented a three-step synthesis, claiming
alternatives such as Accelerated Solvent Extraction (ASE) or an increase in the overall yield. Implementing the new route on
SCF extraction should be considered.79,80 a manufacturing scale showed a significant reduction in the
Material used in the manufacture of analytical apparatus amount of waste, making the new process a more cost-effective
should be taken into consideration. Both green chemists and option.
green engineers building new sensors should be aware of the In 2004, BMS developed a new approach to Paclitaxel, the
toxicity and any potential environmental problems related to active ingredient in the anticancer drug Taxols.89 Paclitaxel is
the material they handle. Mercury electrodes, for example, commercially produced from the naturally occurring precursor
are often used for electrochemistry. Replacing them with 10-deacetylbaccatin III (10-DAB) through an 11 step synthesis.
carbon-based electrodes such as nanotubes or nanofibers has This ‘‘semisynthetic route’’, which was first developed as an
proven to be an effective solution.81 economically viable approach to the molecule, was not
without certain environmental concerns. A more sustainable
12 Accident prevention process was therefore investigated by BMS using the latest
Dangerous substances and processes have multiplied in our biotechnological advances. Instead of synthesizing Paclitaxel
working environment. According to the ‘‘Chemical accident from a precursor, the active compound was extracted directly
prevention and the clean air act amendments of 1990,’’ from plant cell cultures. This method eliminated all organic
preventing accidents starts by identifying and assessing the solvents, hazardous reagents, and additional steps associated
hazards.82 All types of hazards whether it is toxicity, physical with the previous process. BMS is now manufacturing
hazards such as explosivity or flammability, and global Paclitaxel using only plant cell cultures.
hazards should be addressed in the design of chemicals and
processes in order to prevent accidents such as Bhopal or the
Love Canal incident.83
A recent and shocking illustration of these dangers and
hazards can be found in the UCLA accident that occurred in
January 2009.84 Handling of the very common and highly
flammable butyllithium reagent resulted unfortunately in a
terrible outcome with the death of the research assistant
involved. This accident should be a strong reminder to the
scientific community that many chemicals we still use present
serious hazards and should be replaced by safer alternatives to
prevent accidents wherever possible.

IV Accomplishments by industry
There are numerous examples of successful industrial changes
using Green Chemistry.85 The following section is not
intended to present an exhaustive list of the awards winners
but rather introduce a few key examples to show how the Fig. 11 New synthesis of Sitagliptin.

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V Future challenges
The accomplishments in the field of Green Chemistry thus far
are impressive due to the scientists in academia, industry,
and research institutes around the world. However, the
accomplishments achieved thus far are a prelude to the grand
challenges still to be addressed by the field. A few notable
challenges are mentioned below.

Twelve Principles as a cohesive system

The design framework of the Twelve Principles of Green
Chemistry has been a template for many advances in the field,
however, the Twelve Principles were not meant to be twelve
Fig. 12 New synthesis of sertraline.
independent goals but rather an integrated cohesive system of
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design. Only through the applications of all principles can one

hope to achieve a truly sustainable process. By seeking out
In 2002, Pfizer developed a new greener synthetic pathway
the mutually reinforcing aspects of the principles, systemic
for the redesigned synthesis of sertraline, an active ingredient
sustainable design is possible and can facilitate transformative
used to treat depression (Fig. 12).90 The new process offered
innovation rather than incremental improvement.
substantial environmental benefits while improving the
overall efficiency and selectivity of the synthesis. Specifically,
a three-step sequence in the original manufacturing process Multi-functional catalysts
was streamlined to a single one.91 Raw material use was Catalysis has made significant progress during the past two
significantly cut and the process was optimized so that decades. However, even today, most catalysts are designed to
all steps could be performed in ethanol. This last change act on one transformation only and little is known about
eliminated the need to use, distill, and recover four toxic multi-functional catalysts, defined as the ability of one
solvents (methylene chloride, tetrahydrofuran, toluene, and catalytic system to act on a series of transformations. If the
hexane). same catalyst could be used for various independent reactions
One final noteworthy example is the work accomplished in or achieve an entire synthesis in one pot, it will bring chemistry
1998 by Solutia, Inc. on the elimination of chlorine from the to a new level as more complex molecules could be made with
synthesis of 4-aminodiphenylamine (Fig. 13).92 Researchers at higher material and energy efficiency.
the company explored new routes to a variety of aromatic
amines, including 4-aminodiphenylamine (4-ADPA), in order Mastering weak forces for synthesis and properties
to eliminate the formation of aqueous waste streams containing
high levels of inorganic salts. There were also concerns about Non-covalent and weak-force interactions are likely to play
the hazard associated with storage and handling of large an increasingly important role in the future of chemistry.
quantities of chlorine gas. The solution came with a new Imparting properties through weak-forces and guiding
synthetic pathways in the same manner while minimizing the
synthesis to 4-ADPA that utilizes the base-promoted, direct
amount of bond breaking and bond forming can result in
coupling of aniline and nitrobenzene.93 The environmental
significant advantages. These include reducing the amount of
benefits were significant and included a dramatic reduction in
energy needed, suppressing the amount of waste, and an
waste generated.
increase in efficiencies. Mastering the weak forces in the same
way that the field of chemistry has mastered covalent forces
holds great potential to help in reaching sustainability at the
molecular level.

Integrative systems thinking

The traditional approach to scientific investigation has been
largely based on the reductionist approach. This approach has
brought about a depth of understanding and discovery that
have made the things of modern life—from communication to
transportation to medicine—possible. It has also resulted in
tremendous unintended and unforeseen consequences that
have had a damaging impact on humans and the environment.
By thinking in terms of systems, Green Chemistry can pursue
significant innovations while avoiding unintended results.
Fig. 13 Differences between the chlorine-based and chlorine-free Coupling reductive and integrated thinking can result in truly
processes for the preparation of 4-ADPA. transformative innovations.

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