Green Chemistry Application for

Sustainable Development

Lecture 1

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Lectures
1. The principles of green chemistry. Principle 1 – Prevention. It is better to
prevent than to clean or to treat afterwards (waste or pollution)

2. Principle 2- Maximise synthetic methods, Atom Econοmy: All synthetic

methods used till now were wasteful and their yields between 70-90%.
Synthetic methods used by green chemistry can be designed in advance
to maximize the incorporation of all reagents used in the chemical process
into the final product, eliminating the need to recycling the by-products

3. Principle 3 - Less hazardous chemical syntheses. Green Chemistry must

strive, wherever practical, to design safer synthetic methods by using less
toxic substances as well as the products of the synthesis

4. Principle 4 - Designing safer chemicals. Chemical should be considered so

that to preserve all the qualities reducing as much toxicity

5. Principle 5 - Safer solvents and auxiliary substances. Solvents, separation

agents and auxiliary chemicals used in synthetic chemistry must be
replaced or reduced with less toxic chemicals.
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 6. Principle 6 - Design for energy efficiency. Energy consumption should be
minimized environmental impact. Synthetic methods should be conducted at
the ambient temperature and pressure

7. Principle 7 – Use of renewable raw materials and feedstocks. Green

chemists must change the manufacturing process by discovering renewable
chemicals

8. Principle 8 – Reduce intermediate derivatives. Chemists must aim for

reducing unnecessary derivatization (use of blocking groups,
protection/deprotection techniques and temporary modification of physical
and chemical processes) in the synthetic routes

9. Principle 9 - Catalysis, catalytic reagents. Catalytic reagents with great

selectivity can be superior to stoichiometric reagents. New catalysts and
more emphasis on catalytic processes is the future of green chemistry
techniques

10. Principle 10 – Design products which degrade easily. Green Chemistry

aims at designing products so that at the end of their useful life to break
down into innocuous materials
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11. Principle 11 – Real- time analysis for pollution prevention. Analytical
methodologies need to be further developed to allow for real time, in-
process monitoring and control prior to the formation of hazardous
substances

12. Principle 12 - Inherently safer chemistry for accident prevention. Green

Chemistry aims to stop the use of dangerous materials for the health and
safety of workers and the consumer

13. Green chemicals used by human: green plastic, colored green, green
solvents, etc.

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References lectures:
1. Albini A. Handbook for Synthetic Photochemistry. Wiley-VCH, West Sussex, UK, 2010.
2. Anastas PT, Levy IJ, Parent KE (Eds). Green Chemistry Education. Changing the Course
of Chemistry, ACS Publications, Washington DC, 2009
3. Ballini R (Ed). Eco-Friendly Synthesis of Fine Chemicals. RSC Green Chemistry Series,
Royal Society of Chemistry publications Cambridge, 2009
4. Dunkin IR. Photochemistry. In : Clark JH, Macquarrie D (Eds). Handbook of Green
Chemistry and Chemical Technology. Blackwell Science Ltd, Oxford, UK, 2007.
5. I. Haiduc, Chimia verde şi poluanţii chimici, Editura EFES Cluj-napoca, 2006
6. E. Lichtfouse, J. Schwarzbauer, D. Robert, Green Chemistry and Pollutants în
Ecosystems, Springer Veslag, 2005
7. Diana Cook and Kevin Prior, eds., Facilitating the Uptake of Green Chemical
Technologies, Crystal Faraday Partnership Ltd, Rugby, 2003
8. Anastas PT, Kirchhoff MM . Origins, current status, and future challenges of Green
Chemistry. Accounts Chem Res 35(9): 689-694, 2002
9. Clark, J., Macquarrie, D. Handbook of Green Chemistry & Technology, Blackwell
Science, 2002
World Commission on Environment and Development. Our Common Future. Oxford
University Press, Oxford, 1987
10. Matlack AS. Introduction to Green Chemistry. Marcel Dekker, New York, 2001
Boule P (Ed.) Environmental Photo-chemistry. The Handbook of Environmental Chemistry
2L. Springer-Verlag, Berlin, 1999
11. EPA. Green Chemistry Program. United States Environmental Protection Agency
(EPA), Office of Pollution Prevention and Toxics. Washington DC, (
http://(www.epa.gov/gcc), 1998
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12.Anastas, P. T., Warner, J. C., Green Chemistry, Theory and Practice. Oxford University
Press, Oxford, 1998
 Laboratories

1. Phenol isolation from aqueous matrix used liquid –liquid extraction

2. Phenol isolation from aqueous matrix used solid phase extraction

3. Ethanol- a challenge for new combustible

4. Catalyst in green chemistry

5. Biocatalyse – synthesis G penicillin, Bayer -Villiger reaction catalyzed

by yeast

6. Organics solvents in green chemistry. Supercritics fluids (FSC):

supercritic CO2, supercritic H2O, fluor biphasics solvents

7. Reactives on polymeric support

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 Seminars
1. Green chemistry application for analytical chemistry

2. Principle 2 of green chemistry. Case study -Examples of atom economy

reaction: rearrangement reactions (Claisen rearrangement reaction, Fries
rearrangement reaction, Beckmann rearrangement reaction, the
rearrangement reaction of pinacol); addition reactions (Michael addition
reactions, enantioselective hydrogenation method for obtaining S -
naproxen); reactions Diels - Alder (obtain Aldrin by Diels-Alder reactions) –
4h

3. Principle 3 of green chemistry. Case study - Bhopal method for obtaining

carbaryl; green method to obtain adipic acid, Asahi method for obtaining
ciclohexanol

4. Principle 5 of green chemistry. Case study -Ionic liquid applications in green

chemistry

5. Principle 7 of green chemistry. Case study – Polylactic acid: a new source of

renewable raw materials

6. Principle 7 of green chemistry. Case study Hydrogen – ideal combustible for

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future
References labs and seminars:

1. Demirbas A. Biorefineries for Biomass Upgrading Facilities. Springer, Berlin & New York,
2009
2. Hester RE. Carbon Capture. Royal Society of Chemistry Green Chemistry Series, RSC
publishers, Cambridge, 2009
3. Gutsche B, Roβler H, Wurkerts A. Heterogeneous Catalysis in Oleochemistry. Wiley-VCH
Verlag GmbH, England, 2008
4. Clark JH, Deswarte EI. Introduction to Chemicals from Biomass. John Wiley & Sons,
England, 2008
5. Tundo P, Perosa A, Zachini F (Eds). Methods and Reagents for Green Chemistry: An
Introduction.(Lectures of the Summer School of Green chemistry). Wiley-VCH, West Sussex,
2007
6. Lankey RL, Anastas PT. Advancing Sustainability Through Green Chemistry and
Engineering. ACS publications, Washington DC, 2002
7. Tundo P, Anastas P, Black D StC, Breen J, Collins T, Memoli S, Miyamoto J, Polyakoff M,
Tumas W. Synthetic pathways and processes in green chemistry. Introductory overview.
Pure Appl Chem 72: 1207-1228, 2000
8. Anastas PT, Warner JC. Green Chemistry: Theory and Practice. Oxford Science
Publications, Oxford, 1998
9. Grieco PA. Organic Synthesis in Water. Blackie Academic & Professional, London, 1998
10. Ravindranath NH, Hall DO. Biomass, Energy, and Environment. Oxford University Press,
Oxford, 1995

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Chemistry is the science of matter.
Are you afraid of chemistry? Many people are and try to avoid it. But avoiding
chemistry is impossible. That is because all matter, all things, the air around us,
the water we must drink, and all living organisms are made of chemicals.

The practice of chemistry in a manner that maximizes its benefits while eliminating
or at least greatly reducing its adverse impacts has come to be known as green
chemistry.

Green chemistry can be defined as the practice of

chemical science and manufacturing in a manner that is
sustainable, safe, and non-polluting and that consumes
minimum amounts of materials and energy while
producing little or no waste material.

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 Sustainability
• Meeting the needs of the present generation without compromising the
needs of future generations
Is the goal

• Green chemistry: technologies of the invention, design and application

of chemical products and processes to reduce or to eliminate the use
and generation of hazardous substances and where possible utilize
renewable raw materials
is the means

Primary pollution prevention not remediation

Use of chemistry for improved environmental performance 10

As human beings --- we are part of the environment
The way in which we interact with our environment influences the quality of our
lives

Sustainable Industrial
development ecology
the goal

Green
Chemistry
A tool

Green chemistry, lies at the heart of the industrial ecology 11

Green chemistry, is called also Benign chemistry or clean
chemistry for sustainability

• Refers to the field of chemistry dealing with

1- Synthesis (the path to making chemicals)

2- Processing (the actual making of chemicals)

3- Use of chemicals that reduce risks to humans and

impact on the environment

Green chemistry education: A key to sustain the

development of new educational materials

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GREEN CHEMISTRY IS ABOUT:

• waste minimisation at source;

• use of catalysts in place of reagents;
• using non-toxic reagents;
• use of renewable resources;
• improved atom efficiency;
• use of solvent free or recyclable environmentally

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Some Aspects of Green Chemistry

Safer Reactions Catalysis

& Reagents
Solvent
Replacement
Separation
Processes
Green Use of
Chemistry Renewable

Energy Feedstocks

Efficiency Waste
Process Minimisation
Intensification

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 Areas of Research

• Feedstocks / Starting Materials

• Reagents or Transformations

• Reaction conditions

• Final product

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 Feedstocks / Starting Materials
• select and utilize more benign starting materials
– reduction in amount used
– reduction of intrinsic toxicity through structural modification /
replacement
• risks can be reduced through protective gear and control techniques,
but GC may be more cost effective and safer

- Alternative Synthetic Pathways Award

New process for 4 – aminodiphenylamine

-Academic Award
TAML™ oxidant activators: General activation of
hydrogen peroxide for green oxidation technologies

- Eliminate use of acids to break initial bonds

- Phosgene replacement

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 Alternative Reagents
• Assessment of the hazard of reagent,
• Evaluation of synthetic transformation associated with use of specific
reagents:
– determine product sensitivity
– reaction efficiency
• Improve reaction efficiency;
• Reduce needed quantity.

Use of visible light as reagent

- Alternative Synthetic Pathways Award
• Practical application of a biocatalyst in pharmaceutical
manufacturing
• Use of microbes as environmentally-benign synthetic
catalysts

- Academic Award
- TAML™ oxidant activators: General activation of
hydrogen peroxide for green oxidation technologies

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 Alternative Reaction Conditions
• Reduce or eliminate solvents used in reaction media, separations:
– use of supercritical fluids as solvents
– able to tune supercritical fluids by choosing critical region to
conduct chemistry
• Use aqueous solvent systems in place of organic solvents in chemical
manufacturing
• Use supercritical CO2 as a solvent
• Reduce operating temperatures
• Must evaluate impact on case by case basis
• Alternative Solvents and Reaction Conditions Award
The Development and Commercialization of ULTIMER®®: The First of a
New Family of Water Soluble Polymer Dispersions
• Alternative Solvents/Reaction Conditions Award
Novel Membrane-Based Process for Producing Lactate Esters.
Nontoxic Replacements for Halogenated and Toxic Solvents
• Alternative Solvents/Reaction Conditions Award
Dry View™ Imaging Systems
• Alternative Solvents/Reaction Conditions Award
The Development and Commercial Implementation of 100 Percent
Carbon Dioxide as an Environmentally Friendly Blowing Agent for the
Polystyrene Foam Packaging Market 18
 Alternative Products
• Identify part of molecule that is providing intended use and part of
molecule responsible for toxicity or other hazards
• Reduce toxicity w/o sacrificing efficacy of function
– eliminate toxic functional groups
– make molecule less bioavailable
• Pharmaceutical and pesticide manufacturing
• Change or replace products
• Designing Safer Chemicals Award
Designing an environmentally safe marine antifoulant
• Small Business Award
Coldstrip™, A revolutionary organic removal and wet
cleaning technology
• Designing Safer Chemicals Award
THPS Biocides: A new class of antimicrobial chemistry
• Designing Safer Chemicals Award
The invention and commercialization of a new chemical
family of insecticides exemplified by CONFIRM™ insecticide

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The principles of green chemistry

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 Principle 1 – Prevention

It is better to prevent than to clean or to

treat afterwards (waste or pollution)

Chemical
Process

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 Top 5 Environmental Disasters
5. On the night of March 24, 1989, the Exxon Valdez oil tanker ran aground on Bligh
Reef in the pristine waters of Alaska's Prince William Sound. The first of what would
turn out to be 10.8 million gal. of oil began to spew forth into the cold waters. It
would eventually spread almost 500 miles from the original crash site and stain
thousands of miles of coastline. Hundreds of thousands of birds, fish, seals, otters
and other animals would perish as a result, despite the mobilization of more than
11,000 people and 1,000 boats as part of the cleanup. While the Exxon Valdez oil
leak is considered to be the largest man-made environmental disaster in U.S.
history, the Gulf of Mexico spill may eventually surpass it in severity.

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4. Love Canal in Niagara Falls, NY a chemical and plastics company had used
an old canal bed as a chemical dump from 1930s to 1950s. The land was then
used for a new school and housing track. The chemicals leaked through a clay
cap that sealed the dump. It was contaminated with at least 82 chemicals
(benzene, chlorinated hydrocarbons, dioxin). Health effects of the people
living there included: high birth defect incidence and nervous disease among
the children.

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3. Saddam Hussein knew the war was over. He could not have Kuwait, so he
wasn't about to let anyone else benefit from its riches. As the 1991 Persian Gulf
War drew to a close, Hussein sent men to blow up Kuwaiti oil wells. Approximately
600 were set ablaze, and the fires — literally towering infernos — burned for seven
months. The Gulf was awash in poisonous smoke, soot and ash. Black rain fell.
Lakes of oil were created. As NASA wrote, "The sand and gravel on the land's
surface combined with oil and soot to form a layer of hardened 'tarcrete' over
almost 5 percent of the country's area." Scores of livestock and other animals died
from the oily mist, their lungs blackened by the liquid.

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2. Around midnight on Dec. 2, 1984, an accident at a Union Carbide pesticide plant
in Bhopal, India, resulted in 45 tons of poisonous methyl isocyanate escaping from
the facility. Thousands died within hours. More followed over subsequent months —
about 15,000 in all. In total, about half a million people were affected in some way.
Many of those who survived suffered blindness, organ failure and other awful bodily
malfunctions. A shockingly high number of children in the area have been born with
all manner of birth defects. In 1989, Union Carbide paid out about half a billion
dollars to victims, an amount the afflicted say is not nearly enough to deal with the
decades-long consequences. Bhopal remains the worst industrial disaster ever.

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1. The worst nuclear-power-plant disaster in history. On April 26, 1986, one of the
reactors at the Chernobyl power plant in Ukraine exploded, resulting in a nuclear
meltdown that sent massive amounts of radiation into the atmosphere, reportedly
more than the fallout from Hiroshima and Nagasaki. That radiation drifted westward,
across what was then Soviet Russia, toward Europe. Since then, thousands of kids
have been diagnosed with thyroid cancer, and an almost 20-mile area around the
plant remains off-limits. Reactor No. 4 has been sealed off in a large, concrete
sarcophagus that is slowly deteriorating. While the rest of the plant ceased
operations in 2000, almost 4,000 workers still report there for various assignments.

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Definition of Sheldons environmental acceptability E and E values
of industrial chemical processes
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 Classic Route to Ibuprofen (1960)
H C l, A c O H , A l W a s te HCl AcO H

A c 2O H 2O / H +
C lC H 2 C O 2 E t
A lC l 3
NaO Et

COCH3

E tO 2 C
O OHC

N H 2O H

H 2O / H +

N OHN
H O 2C

Six steps syntheses consuming chemicals and

NH3 energy with lower yield of final product (40%) 28
and 60 % waste
 Hoechst Route To Ibuprofen
(1990)
AcOH

HF H2 / Ni CO, Pd
Ac2O

O HO HO2C

Three steps syntheses increased efficiency. The atoms of the starting chemicals
are incorporated into the products of the reactions and waste is minimised. A
catalyst of Nickel (Raney nickel) was used thus decreasing substantially the steps
of the synthesis. The yield 77% and waste 1% 29
30
Adipic acid
- most important dicarboxylic acid (2.5 billion kilograms are produced annually),
mainly as a precursor for the production of nylon;
- medicine: incorporated into controlled-release formulation matrix tablets to obtain
pH-independent release for both weakly basic and weakly acidic drugs;
- food: used as a flavorant and gelling aid.

The “traditional route” for the synthesis of adipic acid and the new “greener” method,
with less waste and recycling. In the second method W salts are used which can be
recycled. [Aliquat 336 (Stark's catalyst) is a mixture of octyl C8 and decyl C10 chains
with C8 predominating. It is a quaternary ammonium salt used as a phase transfer
catalyst and metal extraction reagent able to dissolve metal complexes]. 31
 Principle 2:
Maximise synthetic methods, Atom Econοmy

All synthetic methods used till now were

wasteful and their yields between 70-90%.
Synthetic methods used by green chemistry can
be designed in advance to maximize the
incorporation of all reagents used in the
chemical process into the final product,
eliminating the need to recycling
the by-products

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The Efficiency of the “Green” Method of Adipic Acid

A. The “old”, traditional method for the adipic acid with

cyclohexanone/cyclohexanol oxidation by Nitric acid in the presence of catalyst
copper/vanadium [Cu(0.1-05% & V (0.02-0.1%)]

Negative aspect - release of nitrogen oxides.

Yield or Mass efficiency of the reaction

Product mass = (6C)(12) (10H)(1) (4O)(16) = 146 g
Reactant mass = (6C)(12) (14Η)(1) (7Ο)(16) (2Ν)(14) = 226 g
ratio of product/reactants X 100 = (146/226) X 100 = 64.60 %

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B. The new “greener” method. The preparation from cyclohexene oxidized by
H2O2 in the presence of the catalyst Νa2WΟ4x2Η2Ο (1%) with solvent Aliquat 336
[CΗ3(ν-C8Η17)3Ν] ΗSΟ4 (1%) ].

The new “greener” method do no produce toxic waste.

Yield or Mass efficiency of the reaction

Product mass = (6C)(12) (10H)(1) (4 O)(16) (2N)(14)=146 g
Reactant mass = (6C)(12) (18H)(1) (8 O)(16) = 218 g
Reaction Mass efficiency = 146/218 X 100 = 67%.

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 Hydroquinone synthesis
Uses
- reducing agent that is soluble in water. It is a major component in most
photographic developers for film and paper;
- human medicine - topical application in skin whitening to reduce the color of skin;
- Food industry - beer and coffee.

The classical route to

hydroquinone

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The new Upjohn route to hydroquinone
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The atom-economy of various reaction types

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