Green Chemistry

By Mr. Shivaji Giram,

Associate professor at Indala Institute of Pharmacy
 Defination: Green Chemistry

• Green chemistry is the design of chemical compounds

(products) and processes that minimize or eliminate the use
and generation of hazardous substances.
• Green chemistry is also known as sustainable chemistry
• Any synthesis, whether performed in teaching,laboratories or
industries should create none or minimum by-productswhich
pollute the atmosphere
 importance\significance of Green Chemistry:
• Green chemistry helps in preventinig pollution at the molecular level.
• Applies innovative scientific solutions to real-world environmental
problems.
• Results in source reduction because it prevents the generation of pollution.
• Reduces the negative impacts of chemical products and processes on
human health and the environment.(Protects human health and the
environment.)
• Lessens and sometimes eliminates hazard from existing products and
processes. (reduces incident of accidents occurrence) e g bhopal gas
tragedy, green sythesis of carbaryl
• Lowers cost of production and regulation
• Green chemistry process are energy efficient (most of reaction carried out at
RT and normal pressure)
 12 Principles of Green Chemistry

1. Prevention (Prevent waste): It is better to prevent formation of

waste/ byproducts than to treat or clean up waste after it is formed
• Carry out a synthesis in such a way so that formation of waste
(by-roducts) is minimum or absent
• Cost involved in the treatment and disposal of waste adds to the
overall production cost.
• The unreacted starting materials also form part of the waste.
• If discharged causes pollution and requires expenditure for
cleaning-up
 12 Principles of Green Chemistry

2. Maximize Atom Economy: Synthetic methods should be

designed to maximize the incorporation of all the elements/atoms
present in reactant (Starting materials andreagents) used in the
process into the final disirable product.
• Ideal % atom economy of any synthesis should be as maximun
as possible that is 100 %.
• 100 % atom economy means all the atoms of reactant used in
the process are incorporated in to the final product and process
not genrates any byproduct (waste) and hence less problem of
waste disposal.
 12 Principles of Green Chemistry
• 2. Maximize Atom Economy:
• Formula for atom economy
•
• Atom economy = × 100
 12 Principles of Green Chemistry

The Atom Economy of this reaction is 49.81%, calculated using

the relative formula masses. This means that 49.81% of the mass
of the reactants ends up in the desired product. remaining 51 %
mass of the reactants incorporated into byproduct (waste)
formation.
 12 Principles of Green Chemistry

3. Design Less Hazardous Chemical Synthesis: Whenever

practicable, synthetic methodologies should be designed to use
and generate substances that possess little or no toxicity to human
health and the environment.
Risk=f(HAZARD, Exposure)
Eliminate the hazard, no need to worry about the exposure!
 12 Principles of Green Chemistry

3. Design Less Hazardous Chemical Synthesis:

 12 Principles of Green Chemistry

• Advantages
• diphenylcarbonate synthesized without phosgene
• eliminates use of COCl2
• higher-quality polycarbonates
 12 Principles of Green Chemistry
4. Design for enhancing energy efficiency:
• Energy requirements should be recognized for their environmental and
economic impacts and should be minimized.
• Synthetic methods should be conducted at ambient temperature and
pressure
• During chemical synthesis, the energy requirements should be kept to a
minimum.
• if the starting material and the reagents in reaction mixture has to be
heated to reflux for a required time, time required has to be kept minimum
for the minimum usage of energy.
• Use of a catalyst has the great advantage of lowering the energy
requirement of a reaction.
 12 Principles of Green Chemistry
4. Design for enhancing energy efficiency:
• In case the reaction is exothermic, sometimes extensive
cooling is required- adds to the overall cost.
• If the final product is impure, it has to be purified by
distillation, recrystallisation or ultrafiltration -All these steps
involves energy.
• By designing the process such that there is no need for
separation or purification, the final energy requirements can
be kept at minimum.
• Energy to a reaction can be supplied by photochemical
means, microwave or sonication
 12 Principles of Green Chemistry
• 5. Use safer solvents and auxiliaries: Avoid using solvents, separation
agents, or other auxiliary chemicals. If you must use these chemicals, use
safer ones.
• solvent selected not cause any environmental pollution and health
hazard.

• The reaction should be carried out in aqueous phase.

• The reaction should be carried out without the use a of solvent
(solventless reactions or aim for designing solvent free synthesis). For
example solid phase synthesis of benzilic acid from benzil. A better
method is to carry out reactions in the solid phase.
 12 Principles of Green Chemistry
5. Use safer solvents and auxiliaries:
Conventional / traditional method/ route:

• Alternate Green Procedure:

• Preparation of Benzilic Acid in Solid State under Solvent-free Condition:
• Green Context: O

• Solvent-free procedure O

Solid KOH
• Atom efficient HO
Grind in
mortar and
pestle
HO O

solid benzil benzilic acid

 12 Principles of Green Chemistry

5. Use safer solvents and auxiliaries:

• Immobilised solvents can be used
• The use of liquid or supercritical liquid CO2 should be
explored.
• The immobilised solvent maintains the solvency of the
material, but it is non-volatile and does not expose humans or
the environment to the hazards of that substance.
 12 Principles of Green Chemistry
• 6.Use of Renewable Feedstocks. Use renewable feedstocks:
Use starting materials (also known as feedstocks) that are
renewable rather than depletable whenever technically possible.
• The starting materials which can be obtained from agricultural or
biological products are referred to as renewable starting
materials
• Substances like carbon dioxide and methane gas are available
in abundance. These are considered as renewable starting
materials
• Examples: Synthesis of indigo dye from tryptophan and
synthesis of adipic acid from glucose (can sugar)
 12 Principles of Green Chemistry
• 7. Avoid chemical derivatives: Avoid using blocking or protecting
groups or any temporary modifications if possible. Derivatives use
additional reagents and generate waste.
• Unnecessary derivatization (blocking group, protection/deprotection,
temporary modification of physical/chemical processes) should be
avoided whenever possible
• 8. Use catalysts, not stoichiometric reagents: Minimize waste by
using catalytic reactions. Catalysts are effective in small amounts and
can carry out a single reaction many times. They are preferable to
stoichiometric reagents, which are used in excess and carry out a
reaction only once.
 12 Principles of Green Chemistry
• Catalysts performs transformation without consumed in the reaction and
without being incorporated in the final product hence is preferred
whenever possible.
• ADVATAGES
• Better yield
• Reaction becomes feasible
• Selectivity
• Advantage in energy requirement
• better utilization of starting materials and minimum waste product
formation.
 12 Principles of Green Chemistry

• 9. Design chemicals and products to degrade after use:

Chemical products should be designed so that at the end of their
function (use) they do not persist (accumulate) in the
environment and instead break down into innocuous degradation
products.
• Example: synthesis of Ibuprofen, adipic acid and Indigo dye by
green method.
 12 Principles of Green Chemistry
• 11. Analyze in real time to prevent pollution: Include in-
process, real-time monitoring and control during syntheses
to minimize or eliminate the formation of byproducts.

• 12. Minimize the potential for accidents: Design

chemicals and their physical forms (solid, liquid, or gas) to
minimize the potential for chemical accidents including
explosions, fires, and releases to the environment.
 1) Conventional and green route for synthesis of carbaryl (Sevin)
• Structure and uses of carbaryl (sevin): carbaryl is carbamate (urethane)
derivative. Carbamate are derived from carbamic acid
• General structure for carbamate (urethane) as follow
O
NH2
R3
O N HO

R1 R2 O
carbamic acid
• Structure of carbaryl: O

CH3
O N

• Use as insecticide.
 Conventional and green route for synthesis of carbaryl
(Sevin)
• Conventional (traditional) route for synthesis of carbaryl (Sevin): It is prepared by treating methyl
isocyanate (MIC) with alpha-naphthol (1-naphthol). methyl isocyanate (MIC) is prepared by reacting
methyl amine with phosgene. This process is carried out in Bhopal, Uninon Carbide where accidental
leakage of methyl isocyanate (MIC) gas take thousands of lives in 1984.
H O O

N + H3C + HCl
H3C H Cl Cl N Cl
methanamine phosgene
H
methylcarbamoyl chloride
(MCC)

N O + HCl
H3C C

methyl isocyanate (MIC) O

OH CH3
O N

H
N O
+ H3C C

1-naphthol methyl isocyanate (MIC)

carbaryl
 Conventional and green route for synthesis of carbaryl
(Sevin)
O
H
O
O Cl
• Green route for synthesis of carbaryl
O
(Sevin): green method involves
reaction of 1-naphthol with phosgene
+ Cl Cl
phosgene + HCl to yield chloroformate and then
1-naphthol
reacting chloroformate with
chloroformate mthaneamine to give carbaryl.
H

N
H3C H
methanamine

CH3
O N
H

+ HCl

chloroformate
• Green chemistry principal involved in synthesis of carbaryl:
• Minimize the potential for accidents: green chemistry route
uses same feedstock (starting material) that is 1-naphthol,
methanamine and phosgene as conventional route but taken in
the different sequence to avoid formation of toxic methyl
isocyanate (MIC) responsible for Bhopal gas tragedy and
methylcarbamoyl chloride (MCC).
• Use of methanamine and phosgene needs to be avoided
because both are toxic chemicals.
 2) Conventional and green route for synthesis of Indigo dye
• Structure and uses of Indigo dye:
• Structure of Indigo dye :
O

H
N

N
H

• Use to color blue jeans

 Conventional and green route for synthesis of Indigo dye
• Conventional (traditional) route for synthesis of Indigo dye:
H
O HO O

H + Cl + HCl
N OH
Chloroacetic acid N
H
aniline H

Sodamide
NaNH2
OH O

Keto-enol
2 + H2O
tautomerization
N N
H H
Enol (1H-indol-3-ol or indoxyl) Keto (indolin-3-one)

Air, O2
O

H
N

N
H

O
 Conventional and green route for synthesis of Indigo dye
• Green route for synthesis of Indigo dye: O

OH
tryptophanase

NH2 enzyme
ctalysed
N removal of N
H side chain H
tryptophane 1H-indole

enzyme ctalysed naphthalene dioxygenase

hydroxylation of
indol ring

OH
H
Dehydration OH

removal of H2O
N
H H
N OH
H
H
Air, O2
O indoline-2,3-diol
H
N

N
H
O
 Indigo dye
• Green chemistry principal involved in synthesis indigo dye:
• Use of renewable feedstock: Naturally occurring renewable tryptophan is used as
starting material in green method.
• Design Less Hazardous Chemical Synthesis: aromatic amine (aniline) used in
conventional method is toxic and carcinogenic to human. Green method uses naturally
occurring tryptophan instead of aniline so green route is less hazardous.
• Green method has better yield compared to conventional method.
• Use catalysts, not stoichiometric reagents: First two steps of green methods are
enzyme catalyzed reactions. In green method instead of stoichiometric reagents like
chloroacetic acid and sodium amide, catalytic enzymes like tryptophanase and
naphthalene dioxygenas se are used.
• Prevention (Prevent waste): Conventional method compared to green method,
produces considerable amount of water and salt causing disposal problem.
 3) Conventional and green route for synthesis of Adipic acid
• Structure and uses of adipic acid:
• Structure of adipic acid (dicarboxylic acid) :

O OH
O

OH
adipic acid

• Uses: i) it is essential feedstock (starting material) for production of Nylon

(synthetic fiber)
ii) It is monomer of polyurethane.
iii) Use in pharmaceuticals
iv) Esters of adipic acid are used as plasticizer.
 Conventional and green route for synthesis of Adipic acid
• Conventional (traditional) route Raney nickel
for synthesis of adipic acid: (Ni / H2)

1) Reduction of benzene reduction of benzene

in to cyclohexane by Raney nickel benzene
in to cyclohexane
cyclohexane
catalyst (Ni / H2)
2) oxidation of cyclohexane in to O2 / CO (cobalt) oxidation of
cyclohexanol O2 / CO (cobalt) catalyst cyclohexane in to
cyclohexanol
catalyst.
3) oxidation of cyclohexanol in to OH
O

adipic acid by nitric acid and

ammonium metavanadate catalyst O OH
O HNO3 / NH4VO3
(HNO3 / NH4VO3) +
oxidation of
OH cyclohexanol in
to adipic acid cyclohexanol cyclohexanone
adipic acid (byproduct)

+ N 2O + HNO2 + H2O
nitrous oxide nitrou acid
 Conventional and green route for synthesis of Adipic acid
• A] Green route for synthesis of adipic acid:
• Reaction of cyclohexane with sodium tungstate in organic solvent aliquatt 336 gives adipic
acid

Na2WO4, H2O O OH
O
Aliquatt 336(organic solvent),
KHSO4
cyclohexene OH
adipic acid
• Green chemistry principal involved in synthesis:
• Design Less Hazardous Chemical Synthesis: aromatic compound (benzene) used in conventional
method is toxic and carcinogenic to human. Green method uses safer and non toxic cyclohexene as
starting material instead of aniline, so green route is less hazardous.
• Maximize Atom Economy: percent (%) atom economy of green and conventional methods are 67 %
and 55 % respectively.
• Design for enhancing energy efficiency: number of steps involved in green method are less than
conventional method, so less energy is required for production of adipic acid by green route.
• Prevention (Prevent waste): Conventional method compared to green method, produces considerable
amount waste (cyclohexanone as byproduct in second step, a nitrous oxide and nitrous acid are
produced in third step) causing disposal problem. nitrous oxide gas is greenhouse gas.
• Minimize the potential for accidents : Conventional rout has risk of fire hazard because oxidation of
cyclohexanol with air leads to uncontrolled reaction which has potential for explosion.
 Conventional and green route for synthesis of Adipic acid
• B] Green route for synthesis of adipic acid:
• Step1: Conversion of glucose to 3-hydroxyl HO
COOH
schikimate by E. Coli
• Step2: Conversion of 3-hydroxyl schikimate
HO
to muconic acid by E. Coli O E. Coli
• Step3: Reduction of muconic acid to adipic Bacteria
acid by Pt / H2 HO OH
O OH

OH
OH
Shikimate
Glucose

E. Coli

COOH COOH
COOH Pt / H2 COOH

Adipic acid muconic acid

• Green chemistry principal involved in synthesis:
• Design Less Hazardous Chemical Synthesis: aromatic compound (benzene) used in conventional
method is toxic and carcinogenic to human. Green method uses safer and non toxic glucose as starting
material instead of aniline, so green route is less hazardous.
• Prevention (Prevent waste): Conventional method compared to green method, produces considerable
amount waste (cyclohexanone as byproduct in second step, a nitrous oxide and nitrous acid are
produced in third step) causing disposal problem. nitrous oxide gas is greenhouse gas.
• Minimize the potential for accidents : Conventional rout has risk of fire hazard because oxidation of
cyclohexanol with air leads to uncontrolled reaction which has potential for explosion.
• Use of renewable feedstock: Naturally occurring renewable glucose is used as starting material in
green method. glucose is obtained from can sugar.
 4) Conventional and green route for synthesis of Ibuprofen
• Structure and uses of Ibuprofen:
O

CH3 2-methylacetic acid

HO

Benzene ring

H3C
isobutyl (i-Bu)

CH3

• Uses: Over-the-counter (OTC) pharmaceutical product used as pain killer

 Conventional and green route for synthesis of Ibuprofen
H
• Conventional (traditional) route for synthesis of step 1:
O
O
friedel crafts acylation
Ibuprofen: +
O O
+ HO
+
1) Acetylation of isobutylbenzene by acetic O
AlCl3
HCl

unhydride ans AlCl3 +

hydrated forms of Al

2) Formation of epoxide by reaction of 4- isobutylbenzene

byproduct/waste
4-isobutylacetophenone
isopropylacetophenon with sodium ethoxide and C2H5ONa
Cl COOEt step 2:
ethyl 2-chloroethanoate. O
O
COOEt
3) Hydrolysis of epoxide H

4) Formation of oxime by reaction of carbonyl C2H5OCOOH +

H , H2O
+ C2H5OH + NaCl
step 3:
compound and ammonium hydroxide. byproduct/waste byproduct/waste

5) Formation of Nitrile from oxime:

6) Conversion of Nitrile to carboxylic acid :Nitriles NH4+OH-
ammoniumhydroxide step 4:
get hydrolysed with water in presence of acid or
alkali to yield corresponding carboxylic acid or salt. step 5:

N
N
step 6:
H OH

O
HO
 Conventional and green route for synthesis of Ibuprofen

• Green route for synthesis of H O

Ibuprofen: O
step 1:
1) Acetylation of isobutylbenzene by O O acylation
+ + HO
using acetic unhydride and HF as
AlCl3
catalyst. O
byproduct/waste
2) Reduction of ketone to secondary
alcohol by using Raney Nickel catalyst.
3) Conversion of secondary alcohol to isobutylbenzene

carboxylic acid by Cobalt (CO), 4-isobutylacetophenone

O
palladium (Pd) catalyst Raney Ni Catalyst Ni , H2 step 2:

HO HO

Co , Pd
No waste genration No waste genration
step 3:
• Green chemistry principal involved in synthesis:
• Maximize Atom Economy: percent (%) atom economy of conventional and green methods are 40 %
and 77 % respectively.
• Design for enhancing energy efficiency: number of steps involved in green method are less than
conventional method, so less energy is required for production of adipic acid by green route.
• Prevention (Prevent waste): Conventional method compared to green method, produces considerable
amount waste (HCl and hydrated aluminium as byproduct in first step, a ethanol and NaCl are
produced in step 2, C2H5OCOOH in step 3 and ammonia in step 4) causing disposal problem. HCl is
corrosive compound. Hydrated Aluminium are non degradable and causes soil pollution. Ammonia is
toxic.
• AlCl3 is not true catalyst in the process it is converted in to a hydrated Aluminium (Al) and HCl.
Incontract HF (hydrogen fluoride) is true catalyst which can be recovered and reused.
 5) Conventional and green route for synthesis of benzimidazole
• Structure and uses of Ibuprofen:

H
N

• Uses: used as antiviral, antifungal etc

 Conventional and green route for synthesis of benzimidazole
• Conventional (traditional) route for synthesis of benzimidazole:
1) Benzimdazole is prepared by condensation reaction of orthophenylenediamine (OPD) with organic
acid like formic acid. In acidic condition salt of benzimdazole is obtained which is converted to
benzimidazole by 10 % NaOH.
. NH H
2 O N
+ + 2 H2O
2 Hrs reflux
H OH N
NH2
formic acid
OPD H
salt of benzimdazole

NaOH
H
N
+ NaCl
N
benzimdazole
 Conventional and green route for synthesis of benzimidazole
• Green route for synthesis of benzimidazole:
1) Benzimdazole is prepared by condensation reaction of orthophenylenediamine (OPD) with aldehyde
like formaldhyde in presence of boric acid in water at room temperature (RT).

NH2 H
O N
RT
+ + 2 H2O
Boaric acid
H H N
NH2
formaldehyde
OPD
• Green chemistry principal involved in synthesis:
• Design for enhancing energy efficiency: Energy is not required for formation of benzimidazole by
green method. Reaction occurred at RT.
• Prevention (Prevent waste): Conventional method compared to green method, produces considerable
amount waste (NaCl) causing disposal problem.
• Yield of green method is good compared to conventional method.
 Biodiesel
• Biofuel definition: Biofuel referee to the solid, liquid, gaseous fuel
that are derived from living organism and their waste products. A
wide verity of fuel such as methanol, ethanol, biodiesel can be
obtained from biomass (organic waste material produced by living
things)
• Biodiesel: biodiesel is produced by the process of
transesterification of animal or vegetable oil such as sunflower
seed oil, palm oil, soya bean oil, mustard oil etc.
• The transesterification process involves treatment of triglyceride
in these oil with excess of methanol (alcohole) in presence of
catalyst (KOH, potassium hydroxide) to give monomethylester
of long chain fatty acid (biodiesel) and glycerine (glycerol).
 Biodiesel
H O
• The mixture is allow to settle down by
H C O C (CH2)16CH3
gravity at the bottom of reaction tank O H
through gravity separation method and H C O C (CH2)16CH3 + 3 H C O H

then byproduct crude glycerin (glycerol) H

H C O C (CH2)16CH3
is removed from bottom of vessel. after Methanol
Excess
H O
refining of crude glycerin it can be uses triglyceride
for preparation of triglyceride. from vegetable oil
KOH Transesterification

• Excess methanol in crude H

monomethylester of long chain fatty acid H O

H C OH

(biodiesel) is removed by distillation or 3 H C O C (CH2)16CH3 +

H C OH
flash evaporation and used for H
Monomethylester of long chain fatty acid
production of next batch of biodiesel. (biodisel) H C OH

H
Triglycerol
Biodiesel
 Biodiesel

7. Less emission sulfur compounds (sulphur oxides) which is responsible for acid rain, so no acid rain.
9. Reduction in methane emission.
10. Reduction in particulate matter emission.
The disadvantages of biodiesel are:
1. Higher amount of nitrogen oxides are produced.
2. The energy content of biodiesel is low
3. Degradation during long term storage.