M.

Pharm Sem II Seminar Presentation

GREEN CHEMISTRY
PRESENTED BY GUIDED BY

ANKITA VASUDEO KHADE PROF. VASUNDHARA N. SAWANT

Roll No. 208 Assistant Professor
M.Pharm Sem -II

Department of Pharmaceutical Chemistry,

Smt. Kashibai Navale College of Pharmacy, Kondhwa (BK), Pune.
 CONTENT
 INTRODUCTION
 PRINCIPLE
 MICROWAVE ASSISTED REACTIONS
Merit and demerits of its use
Superheating effects of microwave
Increased reaction rates
Effects of solvents in microwave assisted synthesis
Mechanism
Microwave technology in process optimization
Its applications in various organic reactions and heterocycles synthesis
 ULTRASOUND ASSISTED REACTIONS
Types of Sono chemical reactions
Homogenous, heterogeneous liquid-liquid and liquid-solid reactions,
Synthetic applications
 REFERENCES
 INTRODUCTION
 Green chemistry is the design of chemical products and processes that reduce or eliminate
the use or generation of hazardous substances. Green chemistry applies across the life
cycle of a chemical product, including its design, manufacture, use, and ultimate disposal.
Green chemistry is also known as sustainable chemistry.
 Green chemistry looks at pollution prevention on the molecular scale and is an extremely
important area of chemistry it supports the invention of more environmentally friendly
chemical processes which reduce or even eliminate the generation of hazardous
substances.
 Green chemistry is about :
Hazard
Risk
Improve
Energy
Cost Renewabi
Waste lity
Reusabilit
Reduce y-ty
Toxicity
 PRINCIPL
 The twelve principles of green chemistry were introduced by Paul Anastas and John
ES
Warner in 1998. They are a guiding framework for the design of new chemical products
and processes. Green chemistry's 12 principles :
1. Waste Prevention
2. Atom Economy
3. Less Hazardous Chemical Synthesis
4. Designing Safer Chemicals
5. Safer Solvents & Auxiliaries
6. Design for Energy Efficiency
7. Use of Renewable Feed-stocks
8. Reduce Derivatives
9. Catalysis
10.Design for Degradation
11. Real Time Pollution Prevention
12.Safer Chemistry for Accident Prevention
1. Prevention: It is better to prevent waste than to treat or clean up waste after it has been
created.
2. Atom Economy: Synthetic methods should be designed to maximize the incorporation of all
materials used in the process into the final product.
3. Less Hazardous Chemical Synthesis: Wherever practicable, synthetic methods should be
designed to use and generate substances that possess little or no toxicity to human health and
the environment.
4. Designing Safer Chemicals: Chemical products should be designed to affect their desired
function while minimizing their toxicity.
5. Safer Solvents and Auxiliaries: The use of auxiliary substances (e.g., solvents, separation
agents, etc.) should be made whenever possible and innocuous when used.
6. Design for Energy Efficiency: Energy requirements of chemical processes should be
recognized for their environmental and economic impacts and should be minimized. If
possible, synthetic methods should be conducted at ambient temperature and pressure.
7. Use of Renewable Feed stocks: A raw material or feedstock should be renewable rather than
depleting whenever technically and economically practicable.
8. Reduce Derivatives: Unnecessary derivatization (use of blocking groups, protection/
deprotection, temporary modification of physical/chemical processes) should be minimized or
avoided if possible, because such steps require additional reagents and can generate waste.
9. Catalysis: Catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
10. Design for Degradation: Chemical products should be designed so that at the end of their
function they break down into innocuous degradation products and do not persist in the
environment.
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. Inherently Safer Chemistry for Accident Prevention: Substances and the form of a substance
used in a chemical process should be chosen to minimize the potential for chemical
accidents, including releases, explosions, and fires.
MICROWAVE ASSISTED REACTIONS
 Microwave have been used to speed up chemical reactions in the laboratories.
 Microwave-assisted synthesis is a kind of heating technique that uses microwave radiation
to accelerate chemical reactions and has been widely used in material synthesis.
 A microwave is a form of electromagnetic energy, which falls at the lower end of the
electromagnetic spectrum and is defined in a measurement of frequency as 300 to 300,000
MHz.
 The microwave region of the electromagnetic spectrum lies between infrared and radio
frequencies.
MERITS OF MICROWAVE ASSISTED
REACTIONS
 Rapid reactions
 High purity of products
 Less side-products
 Improved yields
 Simplified and improved synthetic procedure
 Wider usable range of temperature
 Higher energy efficiency
 Energy saving
 Uniform and selective heating
DEMERITS OF MICROWAVE ASSISTED
REACTIONS
 Sudden increase in temperature may led to distortion of
molecule

 Microwave reactors are expensive and delectated

 Closed container is dangerous because it could be burst

MICROWAVE V/S CONVENTIONAL
THERMAL HEATING

 Traditionally, organic synthesis is carried out by conductive heating with

an external heat source (e.g., an oil hath o heating mantle). This is a
comparatively slow and inefficient method.
 In this temperature of the reaction vessel being higher than that of the
reaction mixture sometime due to overheating and causes decomposition
of product, reagent and substrate.
 In contrast, microwave irradiation produces efficient internal heating (in-
core volumetric heating) by direct coupling of microwave energy with
the molecules that are present in the reaction mixture.
 Microwave allows an increase in reaction rate, rapid reaction optimization, and rapid
analogue synthesis. It also uses both less energy and solvent, and it enables difficult
compound synthesis.
SUPER HEATING EFFECT AND REACTION RATE
 Microwaves interact directly with molecules of entire volume of solvent leading to sudden
and quick rise of temperature.
 Reaction time is reduced from hours to minutes when assisted by microwaves.
 Under microwave irradiations, high and intense temperature can be achieved very quickly
and liquids are super-heated and reaction rate also increased.

EFFECT OF SOLVENT IN MICROWAVE ASSISTED

SYNTHESIS
 Every solvent and reagent will absorb microwave energy differently. They each have a
different degree of polarity within the molecule, and therefore, will be affected either more
or less by the changing microwave field.
 In the case of the microwave-assisted reactions using (organic) solvents, the reactants are
usually dissolved in the solvent, which often couples effectively with microwaves and thus
acts as the energy transfer medium.
 water at elevated temperature is normally behave as a pseudo-organic solvent and is a
possible environmentally benign replacement for organic solvents.
MECHANISM
 All the materials are not susceptible to microwave heating as
response of various materials to microwave radiation is diverse.
Based on their response to microwaves, materials can be broadly
classified as follows:
(1) Materials that are transparent to microwaves, e.g. sulphur
(2) Materials that reflect microwaves, e.g. copper
(3) Materials that absorb microwaves, e.g. water
three main different mechanisms are involved for their heating namely:
1. Dipolar polarization,
2. Conduction mechanism and
3. Interfacial polarization
1. DIPOLAR POLARIZATION
For a substance to be able to generate heat when irradiated with microwaves it must be a dipole,
its molecular structure must be partly negatively and partly positively charged. Since the
microwave field is oscillating, the dipoles in the field align to the oscillating field. This
alignment causes rotation, which results in friction and ultimately in heat energy.

2. IONIC CONDUCTION
During ionic conduction, dissolved (completely) charged particles (usually ions) oscillate back
and forth under the influence of microwave irradiation. This oscillation causes collisions of the
charged particles with neighboring molecules or atoms, which are ultimately responsible for
creating heat energy.

3. INTERFACIAL POLARIZATION
The interfacial polarization method can be considered as a combination of both the conduction
and dipolar polarization mechanisms. It is important for heating systems that comprise a
conducting material dispersed in a non-conducting material.
MICROWAVE ASSISTED ORGANIC REACTIONS
AND HETER0CYCLES SYTHESIS
1. Hydrolysis :
Hydrolysis of benzyl chloride with water in microwave oven gives 97 % yield of benzyl alcohol
in 3 min. The usual hydrolysis in normal way takes about 35 min.

The usual hydrolysis of benzamide takes 1 hr. However, under microwave conditions, the
hydrolysis is completed in 7 min giving 99 % yield of benzoic acid.
2. Decarboxylation :
Conventional decarboxylation of carboxylic acids involve refluxing in Quinoline in presence of
copper chromate and the yields are low. However, in the presence of microwaves
decarboxylation takes place in much shorter time.

3. N-Acylation’s :
N-Acylation’s were carried out using secondary amines and isocyanate in dichloromethane
under microwave irradiation (8–10 min), yielding the product in 94% yield.
ULTRASOUND ASSISTED REACTIONS
 Sonochemistry involves the use of ultrasound technique to promote chemical reactions.
 Ultrasound is part of the sonic spectrum, which ranges from about 20 KHz to 10 MHz.
 The chemical effect observed during sonication (high intensity ultrasound waves) is accoustic
cavitation.
 Ultrasound enhances the reactivity of molecules towards many chemical reactions via the
process of acoustic cavitation which result in shortens the reaction times.

PRINCIPLE AND MECHANISM

Sound waves generates compressions and rarefactions, thus micro-bubbles are formed in
the rarefaction regions. These micro-bubbles grow , at one point it will become highly
unstable and collapse violently producing shock waves (temperature of around 5000°C
and pressure of 500 atmospheres during a few microseconds). The process of rapid
growth and implosive collapse of bubbles is known as cavitation which produce chemical
effect.
 TYPES OF SONOCHEMICAL REACTIONS

HETEROGENOUS HETEROGENOUS
HOMOGENOUS LIQID- LIQUID LIQID- LIQUID
REACTIONS REACTIONS REACTIONS

1. HOMOGENOUS REACTIONS
Bond breaking and radical formations takes place.
Homogeneous systems which proceed via radical or radical-ion intermediates. This implies that
sonication is able to effect reactions proceeding through radicals and further that it is unlikely to
effect ionic reactions.
Hydrolysis of nitrile in acidic and basic condition :
Hydrolysis of nitriles in acidic or basic conditions as hydrolysis of benzonitriles under thermal
or ultrasound using 2M HCl or 2M NaOH with improvement of reaction time from 8h. to
45min.

2. HETEROGENOUS LIQID- LIQUID REACTIONS

In heterogeneous liquid /liquid reaction cavitation collapse at or near the interface will Causes
disruption and mixing resulting in the formation of very fine emulsions.
Ultrasound generates extremely fine emulsions from mixtures of immiscible liquids.
3. HETEROGENOUS LIQID- SOLID REACTIONS
Acoustic cavitation can produce dramatic effects on solid in liquid imperfection Or trapped gas
can act as the nuclei for cavitation bubble formation on the surface collapse Can the lead to
shock waves break the particle apart.
cavitation bubble collapse in the liquid Phase near to a particle can produce force into rapid
motion.

SYNTHETIC APPLICATION :
1. Esterification : -
The esterification is generally carried out in the presence of catalyst like sulphuric acid.
Reaction requires longer time, and yields are very low. A simple procedure for the esterification
of a variety of carboxylic acids with different alcohol at ambient temperature using ultrasound is
reported.
2. Saponification: -
Saponification can be carried out under milder conditions using sonification. Thus, methyl 2,4-
dimethyl benzoate on saponification (20 KHz) gives the corresponding acid in 94% yield,
compared to 15% yield by the usual process of heating with aqueous alkali (90 min).

3. Synthesis of Pyrroles:-
Synthesis of substituted pyrroles using zirconium chloride-catalyzed under ultrasound irradiation
provides as easy access to various substituted pyrroles in good to excellent yields with short
reaction times compared to known methods.
4. Ulmann coupling reactions :-
The Ulmann-type coupling reaction occurs at a lower temperature and shorter time in almost
quantitative yield with probe sonication.
REFERENCES
1. Green Chemistry: Principles, Applications, and Disadvantages. Chem Methodol. 2020 Jun
1;4(4):408–23.
2. Abdussalam-Mohammed W, Qasem Ali A, O. Errayes A. Green Chemistry: Principles,
Applications, and Disadvantages. Chem Methodol. 2020 Jul 1;4(4):408–23.
3. Ahluwalia, V.K. & Kidwai, M. 2004. New trends in Green Chemistry Microwave Induced
Green Synthesis. Anamaya Publishers, New Delhi 264.
4. Grewal, A.S., Kumar, K., Redhu, S. & Bhardwaj, S. 2013, MICROWAVE ASSISTED
SYNTHESIS: A GREEN CHEMISTRY APPROACH, International Research Journal of
Pharmaceutical and Applied Sciences (IRJPAS) vol. 3. по 5 278 – 285.
5. Surati, M.A., Jauhan, S. & Desai, K.R. 2012. A brief review: Microwave essintod organic
reaction, Scholars Research Library, vol. 4, no. 1 645 – 661.
6. Sonochemistry (Application of ultrasound in chemical Synthesis and reactions): A Review
part I; Az. J. Pharm Sci. Vol. 53, March, 2016.
7. Sonochemistry Advantages and Application A Review. Research gate publication.
8. James Clark And Duncan Macquarrie. Handbook of green chemistry technology:2002;
372-393.
THANK
YOU