St Francis Institute of Technology

Applied Chemistry II
GREEN CHEMISTRY

Green Chemistry

Chemistry and its development have given various products. Due to demand of these products,
industries are synthesizing these products in large quantity.

Chemical reaction involved in the production result in formation of by-products, which are harmful
for environment and causes pollution.

To prevent pollution and hazardous product formation, it is important to review and modify chemical
process. Today the chemists are profoundly interested in the sustainability of the world. It is important
to know how human action affects the health of our planet.

Green chemistry is the design of chemical products and process to reduce or eliminate the use
and generation of hazardous products.
It involves the development of chemical products and synthetic procedure which are
environmentally friendly and have reduced health risk. It is environmental chemistry.

The entire process is considered including, creating, manufacturing use and disposal products.

Goals / Objectives of Green Chemistry: -

1) To reduce environmental impacts by appropriate and innovative choice of material and their
chemical transformation.
2) To develop process based on renewable raw material.
3) To develop process that is less prone to toxic chemical release for explosion.
4) Redesign of reaction, to minimise by-products or to get better atom economy.
5) To develop less toxic substance.
6) To develop products that degrades rapidly.
7) To reduce use of hazardous solvent.
8) To improve energy efficiency.
9) To improve control, it is important to develop efficient monitor process.

Main goal is to design chemical process with respect to

a) Energy requirements
b) Chemicals used
c) Products used
d) By product generated
e) Waste generated
The philosophy of green chemistry tends to focus in industrial application where as environmental
chemistry focuses on chemical phenomenon in the environment.

Principles of green chemistry: -

A) Prevention of Waste: It is better to prevent waste than to treat or clean up waste after it is formed.

1) Preventing waste is better than treating or cleaning it after it is formed. The untreated material form
part of waste.
2) The waste or by products when discharged in atmosphere sea or land not only cause pollution
also require expenditure for cleaning up.

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3) It is especially important because in most of the cases the cost involved in the treatment and
disposal of the waste adds to overall production cost.
4) Thus green chemistry involved to design chemical synthesis in such away that the process
involves pathway to give products, leaving no waste to treat or clean up.

An example is the manufacture of phenol. It used to be made from benzene using sulfuric acid and
sodium hydroxide in a multi-stage process, which, overall, can be expressed as:

The chemical equation shows that 1 mol of benzene (78 g) should yield 1 mol of phenol (94 g). In
practice, the quantity of phenol produced is found to be about 77 g, giving a yield of 82%, which
may be regarded as quite good.
(Yield % = mass produced / mass expected x 100 %)
However, the calculation obscures the fact that the reaction also generates 1 mol (126 g) of sodium
sulfite for each mole of phenol produced. This may be acceptable if there is enough demand for
sodium sulfite, but if not, it presents a serious problem of waste management and adds significantly
to costs, meaning that this may not be the most suitable reaction for manufacturing phenol.

B) To Maximise atom economy: Synthetic materials should be designed to maximize the

incorporation of all materials used in the process into the final product.
1) When creating materials, it is important to maximize the incorporation of all the materials used
into the final products.
2) Many organic reaction release undesired products which along with unutilized material is
considered as waste product.
3) Green chemistry requires new process which should be designed in such away that most of the
starting material gets converted into products. It is known as maximizing atom economy.
Atom economy: describes the conversion efficiency of a chemical process in terms of all atoms
involved. It is just one way to evaluate a chemical process. In an ideal chemical process the amount of
starting material or reactants equals the amount of all products generated and no atom is wasted.

4) The reaction is considered to be green if there is 100 % (maximum) incorporation of reactant

and reagent in the final product.
Percentage atom economy = Mol. Weight of desired product x 100 / Mol. Weight of reactant

The concept of atom economy developed by B.M. Trost is consideration of “how much of the reactant
end up in the final product.”

For Rearrangement and addition reactions atom economy is 100% but for elimination and substitution
reaction it is lesser.

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Applied Chemistry II
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C) Less hazardous chemical reaction:-

1) Process should be such or should be designed to use and generate substances having little or no
toxicity.
2) The reaction which involves formation of toxic intermediate should not be used.
e.g. Methyl isocynate (CH3-NCO) is an intermediate in manufacture of agricultural pesticides
(Carbryl). It is highly poisonous so alternative pathway should be used for synthesis.

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e.g. synthesis of indigo:- It is the dye used to colour blue jeans.

Conventional method involves use of toxic amine (aniline) and produces salts which can cause
disposal problem where as greener route involve use of an amino acid (L-Tryptophan)

Conventional route:-

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D) Design safer chemicals and products:-

1) Chemical products should be designed to function well but by reducing toxicity.
2) Reducing toxicity reduces hazards to people and environment.
3) In place of toxic insecticides (DDT, Gamaxene) biological pesticides should be used.Spinosad is
important biodegradable insecticide.
4)Use of thalidomide used by mothers to reduce nausea during pregnancy led to birth defects in
children.
5)MTBE is better to use in gasoline as antiknocking agent inplace of harmful TEL.
6) Underlying the concept of green chemistry we need to produce chemicals that are both safe for us
to use and safe for the environment. Safety refers to both flammability and toxicity. For example,
polymers have been developed which are much less flammable but also retain properties such as
toughness. They must be able to absorb severe impacts without cracking and breaking. One such
polymer is polyphenylsulfone which has the formula:

Polyphenylsulfone is now widely used for the interior panels of aircraft and has been introduced
into underground trains where it is also so important to use non-flammable materials.

E) Less Use of Auxillary Substances: The use of auxiliary substances (solvents, separation agents,
etc.) should be made unnecessary whenever possible and, when used, innocuous.

1) Whenever possible the use of additional Auxillary substances like solvent and separating agent
should be avoided.
2) When these substances are required they should be non toxic.
3) Highly inflammable solvents like benzene, acetone, these should be avoided.
4) CCl4, CHCl3 these type of solvents, because of health problem should be avoided.
5) Water is a very good solvent.
6) Eco-friendly solvents which don’t cause smog formation or don’t affect ozone layer can be used.
7) Wherever possible alternative solvents are used which are not harmful, one example being
the development of water-borne paints, which are replacing paints that use volatile organic
compounds such as the hydrocarbons which are harmful to the atmosphere.

Supercritical (liquid) carbon dioxide is widely used as a solvent in the extraction of caffeine from
coffee beans .Toxic solvents like perchloroethenes (used for dry cleaning) is replaced by liquid CO2

F) Energy efficiency : Energy requirement should be recognized for their environmental and
economic impacts and should be minimized.
1) Energy efficiency should be considered when designing and producing a product. All
manufacturing processes need energy to convert raw materials into useful products. In the chemical
industry it is used to heat reactants and in processes such as distillation, product drying, electrolysis,
and treatment of waste.
2) The energy requirement should be minimized since they impact the environment and raise cost.
3) When possible process should be conducted at room temperature and pressure.

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4) The aim is to increase energy efficiency, it can be done by:-
a) Proper heat transfer.
b) By reducing wastage of energy during the process.
Catalyst can be used to increase energy efficiency.
5) Fossil or gaseous fuels should not be used to provide energy as it releases solid or gaseous
pollutants.
6) For the processes require less energy, sunlight, microwave or ultrasound radiations (sonication) are
used.
7) Fermentation process is also suitable as the energy requirement is low and products formed are
less harmful.
8) Green fuel power alcohol and Biodiesel should be utilized more.
9) Waste often has energy content, and it may be possible to convert this to a useful fuel. Waste
solvents from the manufacture of paints, varnishes, adhesives, inks, cleaning fluids and so on are
made into a liquid fuel for use by the cement-making industry. A solid fuel is also made from
shredded carpets, packaging, furniture, plastics and paper,

G) Use of Renewable Feed stock:A raw material or feedstock should be renewable.

i) When possible the feedstock or raw material should come from renewable resources.
ii) Research is being done to make chemicals out of product like corn instead of coal or oil.
iii) A new method is developed to prepare adipic acid.
a) Traditional pathway: - involves use of benzene (byproduct of petrochemical industry) which is
byproduct of petrochemical industry(Non renewable energy source)

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b) Greener pathway :-uses glucose (natural,biomolecule)which is renewable feedstock and safe.

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H) Reduce Derivatization:Unnecessary derivatization (blocking group, protection /deprotection,
temporary modification of physical / chemical processes) should be avoided whenever possible.

i) Chemical derivatives are used to cause a temporary effect in process.

ii) This can be a chemical which protects a certain part of the substance that is later removed.
iii) During chemical synthesis unnecessary derivatisation (like blocking / protecting group /
modification) should be avoided.
iv) Use of these Derivatives increases reaction steps and increases waste formation. It results in lesser
atom economy of the reaction.
.
For e.g. Incase of Ibuprofen synthesis in green synthesis less steps are used to increase atom –
economy.
Traditional way: - Due to use of blocking agents, derivatives are formed which increases number of
steps .More no. of steps atom economy reduces .Atom economy = 40 %

Greener Route: Alternate way for synthesis without forming derivatives ,increases atom economy.

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I) Use of catalyst:-
1) A special advantage of use of catalyst is better utilization of starting material and minimum waste
product formation.
It enable alternative reactions to be used which have better atom economy and thus reduce waste.it is
possible to control reaction pathways more precisely, reducing unwanted side products and making it
easier to separate and purify the required product.

3) The catalytic reagents which are selective are preferred over stoichiometric reagents as catalysts are
used in small amount and carry out a single reaction many times but stoichiometric reagents are used
in excess of work only once.
4) Catalytic reaction is faster.
5) Reactions of energy efficient.
6)Zeolite is a green catalyst.

J) Design Products to degrade: Chemical product should be designed that at the end of their
function they do not persist in the environment and break down into innocuous degradation products.
i) Design should be for proper disposal of items.
ii) The product that is made should break down into nontoxic substances after it has been used so that
the product will not remain and build up in the environment.
iii) Packaging material like plastic/ polystyrene are non biodegradable and cause solid waste.
iv) Biodegradable plastic having cellulose and packing pellets of starch can be used.
v) Different types of insectisides are used to protect crop from insects . More widely used insectisides
are organophosphate, carbamates and organo chloride (DDT). Organochloride are more persistent in
environment and tend to bio accumulate in plants. It incorporates into food chain.
Biological insectisides should be used. It is possible to have a molecule which may possess functional
group that facilitate it’s biodegradation. Specific functional group should be susceptible to hydrolysis
photolysis or other cleavage.

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K) Advance analytical method:-

i) Analytical technique should be so designed that they require minimum usage of chemicals.
ii) The placement of accurate sensor to monitor the generation of hazardous by products during
chemical reaction is also advantageous.
For e.g. during preparation of ethylene glycol, if reaction conditions are not monitored perfectly, toxic
substances are produced at higher temperature.

L) Safer chemistry for accident prevention: or Minimise the potential for accident:-
Substances and the form of substances used in a chemical process should be chosen to minimize the
potential for chemical accidents, including chemical releases, explosion and fire.

Applications / Examples of green chemistry:-

A) Bio-diesel application:-
Biodiesel refers to a non -petroleum based diesel fuel consisting of short chain alkyl ester, typically
made by trans esterfication of veg oil or animal fat which can be used in unmodified diesel engine
vehicles.

Professor Supper proposed the system of converting waste glycerol obtained from biodiesel to
produce propylene glycol.
Use of copper chromite catalyst was able to lower required temperature of conversion (with increase
in efficiency)

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Propylene glycol produced in this way is cheap and can be used in place of toxic ethylene glycol
which is used as automobile antifreeze.

B) Benzimidazole

Benzimidazole is a heterocyclic aromatic organic compound.

It is an important pharmacophore and privileged structure in medicinal chemistry.

It plays a very important role with plenty of rational therapeutic activities such as antiulcer,
antihypertensive, analgesic, anti-inflammatory, anti-viral, antifungal, anticancer, and antihistaminic.
Because of its importance, the methods for their synthesis have become a focus of Synthetic Organic
Chemists.

Historically, the first benzimidazole was prepared in1872 by Hoebrecker, who obtained 2, 5 –

dimethyl benzimidazole by the reduction of 4- methyl-2-nitro- acetanilide .

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Hoebrecker Reaction: traditional Method

Lab Method: Preparation of benzimidazoles practically starts with benzene derivatives possessing

nitrogen-containing functions ortho to each other i.e. the starting material o –Phenylenediamines (OPD)

react readily with most carboxylic acids to give 2-substituted benzimidazoles , usually in very good

yield. The reaction is carried out usually by heating the reactants together on a steam bath, by heating

together under reflux or at an elevated temperature, or by heating in a sealed tube.

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Lab Method by using o-phenlinediamine(OPD)

Green Synthesis of Benzimidazole:

Davood A., in 2010 Synthesised benzimidazoles by condensation of o-phyneline diamine

promoted by acetic acid under microwave. They concluded that a mild, manipulatable procedure, eco-

friendly and green aspects avoiding hazardous solvents, shorter reaction times and high yields of the products are the

advantages of this method.

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Kabeer A. Shaikh et al., 2012 have been efficiently synthesized Benzimidazoles in high yields by

treatment of 1, 2- diamine with aldehydes using the metal coordinate complex K4[Fe(CN)6] as a

catalysis. The method was carried out under solvent free condition via oxidation of carbon-nitrogen

bond which is green, mild and inexpensive process.

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Saberi in 2015 ,synthesised Benzimidazole by using Zeolite as a catalyst in solvent free

environment and by using grinding techniques.

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Conclusion:

Benzimidazoles are been used in many fields and are very essential for human kind and it is most

important nuclei in many drugs. In conventional method of synthesis the yield was less and the

chances of environmental pollution were more, but in greener methods the yields are higher which

reduces byproducts. Even though green methods are available for the synthesis of benzimidazoles

there is a necessity for the development of further more effective methods as the utilization of

benzimidazole derivatives is high not only in the field of pharmacy but also in other viz polymer industry.

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