UNIT-I: Introduction to Green Chemistry page-2

UNIT-II: Microwave Assisted Synthesis page-10

UNIT-III: Ionic Liquids & Phase Transfer Catalysis page-26
UNIT-IV: Supported Catalysts or Biocatalysts page-32
UNIT-V Alternative Synthesis page-44
 Unit I
Introduction to green Chemistry
Introduction to green Chemistry
Green Chemistry designs the chemical processes and products that reduce or
eliminate the use and formation of hazardous substances. The main purposes of green
chemistry are mentioned.

Eco-friendly chemical technology: Green Chemistry aims to protect the

environment and also described as environmentally benign chemistry.
Replacement of organic solvent and to minimize the waste product: Green-
chemistry aims to devise greener reaction condition for the synthesis of chemicals
so that waste product formation can be minimized. It needs the replacement of
organic solvent by water or complete elimination of the use of solvent. It also needs
to minimize the formation of by-products.
Use of renewable feedstock’s: Green chemistry aims to develop the greener
synthesis of the required chemical products by using the renewable resources (e.g.
biomass rather than petrochemical feedstock’s). It reduces the consumption of non-
renewable resources(e.g. Crude oil).
To minimize the energy consumption: Green chemistry aims to develop the
greener conditions for the synthesis of chemical products so that energy
consumption can be minimized. For many existing chemical technologies, drastic
reaction conditions (like high temperature, high pressure, etc. which are energy
requiring), are applied. Greener synthesis aims to develop the mild or modest
conditions.
Use of more eco-friendly chemical products: Green chemistry aims to design
new chemical products to replace the existing hazardous chemical products
provided the new chemicals are having the same desirable properties of the existing
ones (example- development of new pesticide which is only toxic to the target
species and at the same time it biodegrades easily to harmless products).
Four R’s(4R’s) and integrated waste management: These four Rs' are:
Reduction, Recycling, Reuse and Recovery.

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The Twelve principles of Green chemistry:
1. Minimize the waste product formation: It is better to prevent the formation of
waste than to treat or clean up the waste after the formation.
The first principle aims to develop the zero-waste technology. In terms of
ZWT, in the chemical synthesis, waste product should be zero or minimum. It also
to use waste product of one system as the raw material for other systems. As one
example, bottom ash of thermal power station can be used as a raw material for
cement and brick industry; effluent coming out from cleaning of machinery parts
may be used as coolant water in thermal power station; municipal waste as a source
of energy etc.

2. Atom economy: During the synthesis of a chemical product, the methodology

should be designed in the way to maximize the incorporation of starting materials
into the desired final product. Thus, it demands to minimize the formation of by-
product. It can be mathematically calculated as:
𝐌𝐨𝐥𝐚𝐫 𝐌𝐚𝐬𝐬 𝐨𝐟 𝐏𝐫𝐨𝐝𝐮𝐜𝐭
Atom Economy = × 100%
𝐌𝐨𝐥𝐚𝐫 𝐌𝐚𝐬𝐬 𝐨𝐟 𝐚𝐥𝐥 𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭𝐬
If there is no side product being formed (ex-addition reactions), the atom
economy will be 100%. It is considered to be ideal for a green reaction.

3. To avoid the use and formation to toxic materials: If possible and the synthetic
methodologies should avoid the use and generation of toxic and environmentally
hazardous substances.
Illustration of the 3rd principle: This principle aims to develop the
methodologies that will minimize the use and formation of toxic and hazardous
substances .In other words, the synthetic methodologies should use and generate
the eco-friendly substances that no toxicity to human health and environment.

4. Use of nontoxic chemical products: Chemical products aims to be used in

different activities should have the efficacy to function but with reduced
environment.
In many chemical industries, not only the waste product but the starting
materials are also quite hazardous to the workers and environment. For example,
adipic acid is widely used in polymer industries. Benzene is the starting materials
for the synthesis of adipic acid but benzene is carcinogenic and benzene being a
VOC pollutes air.

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5. Minimum use of auxiliary substance: In a chemical synthesis, the use of
auxiliary substance like solvents, separating agents etc., should be avoided. If,
these are to be used, they should be eco-friendly.
This principle aims to use of green solvents (example- water, supercritical
CO2) in the place of volatile halogenated organic solvents example- CH3Cl3,
CHCl3, C2Cl4, CCl4 for chemical synthesis and other purposes. For example-
Claisen rearrangement.

6. Minimum energy consumption: In the synthesis of a chemical product, the

energy, the energy consumption should be minimized to make the process more
and more economic, Ideally, the synthetic methods be carried out at ambient
temperature and pressure.
To save energy, synthetic methodologies should need more and more
moderate conditions and the ambient temperature and pressure are the best choices.
It needs suitable catalysts that will accelerate the reaction rate even at lower
temperature. The biocatalysts can work at the ambient conditions.

7. Use of renewable sources: If it is technically and economically possible, then

the renewable resources (example- biomass) rather than the non-renewable
recourses (example- crude oil) should be used as the raw material or feed stock.
If encourages the use of starting material (example- raw material or
feedstock) which should be renewable, if technically and economically practicable.
In fact, continuous use of the non-renewable feedstock (example- petroleum
product, fossil fuel) will deplete the resource and future generation will be
deprived. Moreover, use of these non-renewable resources puts a burden on the
environment. On the other hand, use of sustainable or renewable resources
example- agricultural or biological products ensure the sharing of resources by
future generation. Moreover, this practice generally does not put much burden on
the environment. The products and wastes are generally biodegradable. The
practice of this principle has been illustrated in many cases like bio plastic and
biopolymer, biodiesel, CO2 feedstock in the manufacture of polycarbonate, greener
synthesis of furfural from biomass, greener synthesis of adipic acid and catechol
from biomass.

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8. Minimization of steps: The steps blocking groups, production/reproduction of
the group, temporary modification of physical and chemical processes etc.,
should be avoided as for as possible during the synthesis of a chemical product.
Thus, there should be a minimum of steps to synthesize a target product.
Specially in organic synthesis need very often protection of some functional
groups. Finally need their reproduction. It is illustrated in the example of synthesis
of m-hydroxybenzoic acid from m-hydroxybenzaldehyde.

9. Use of catalytic reagents: Selective catalytic reagents are superior to

stoichiometric reagents in a chemical synthesis, this shall save the energy and
reduce the burden of by-product.
This principle of green chemistry states that catalytic of the following
advantages-
(i) 100% atom economy because the true catalysts are fully recovered without
any change in their chemical and physical properties.
(ii) the catalysed reactions are faster so energy is saved.
(iii) reaction yields are better.
(iv) selective reaction products.
(v) maximum utilization of the starting material and minimum production of the
waste material.

10. Life time of a chemical product: At the end of function, the chemical products
(example- pesticides) should degrade easily to harmless products, i.e. after their
function, they should not persist in the environment. DDT is the best example. It
is an effective pesticide but its stability in the natural environment causes several
environment hazards.
It states that the waste product should degrade automatically to clean the
environment. Thus, the biodegradable polymer and pesticides are always preferred.
Sometimes, the polymers are to be made degradable photo-chemically so it should
be mentioned that the degraded products should not be toxic.

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11. Monitoring the generation of hazardous substance: Analytical methodologies
should be further developed to allow for real time in process monitoring and
control prior to the generation of hazardous substance in the synthesis of
chemical products.
Analytical methodologies should be developed or modified, so that
continuous monitoring of the manufacturing and processing units is possible. This
is very much important for the chemical industries and nuclear reactors. This
efficient monitoring is quite essential to avoid the accident.

12. Use of chemical safer substances: The substances to be used in a chemical

reaction should be selected in a way that they can minimize the occurrence of
chemical accidents, explosions, fires and emissions. In other words, the
substance to be used should not be hazardous.
The substance used in chemical industries should be in such forms so that the
possibility of accidents can be minimized. For example, if the chemical process
works with the gaseous substances, then the possibility of accidents including
explosion is relatively higher compared to the systems working with the non-
volatile liquid and solid substances. In the risk is minimum if the process works
with solid substance at every step.

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Use of safer reagents:
Green chemistry aims to replace the hazardous reagents. It is illustrated for the
methylation reaction which conventionally uses the hazardous reagents like CH 3X
(methyl halide), DMS (dimethyl sulphate), etc. The green alternative is DMC
(dimethyl carbonate).

Methylation of an active methylene group can be done by using the green reagents

The Conventional methylation process produces the hazardous toxic by product

while in the above methylation reaction, the reagents are green and the by products are
also green.

Disodium iminodiacetate is an essential reagent in manufacturing a herbicide.

Conventional route uses the hazardous chemicals like formaldehyde and HCN while
the green synthesis does not use any such hazardous substance.

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Di-ethanol Amine Green Synthesis

K2CO3 is also a green reagent that finds uses in the synthesis of different
heterocyclic compounds. It acts as a base and provides a solvent free condition in many
cases.
Conventional synthesis of polyurethanes needs the use of the toxic chemical like
phosgene gas. The green technique avoids the use of phosgene gas.

Use of Green Solvent:

The hazardous organic solvents need replacements. The eco-friendly reaction
media are water, polyethylene glycol, room temperature ionic liquids, supercritical
water, super critical carbon dioxide etc. microwave assisted organic reactions in such
green solvents are playing important roles in green chemistry. Organic synthesis in
aqueous media is becoming increasingly popular. Different organic reactions in
aqueous media coupled with microwave/ultrasonic irradiation have now been
established. Supercritical water in which organic compounds are more soluble
compound to water at ordinary condition is also a potential alternative.

Use of room temperature ionic liquids as green solvents:

Commonly used organic solvents are generally volatile organic compounds

(VOCs) that cause several environmental hazards including smog production in air,
ozone depletion, health hazards etc. The ionic liquids are the green alternatives. These
ionic liquids are generally organic salts like alkylammonium salts, N-alkyl pyridinium
salts, and N, N’-di alkyl imidazolium salts.

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 These non-volatile ionic liquids can be easily recovered after use. They can be
recovered and purified. The product can be isolated from the ionic liquid by using
some common solvent like either in a separating funnel.

Supercritical fluids as green solvents:

Use of supercritical CO2 fluids as green solvents: Use of supercritical CO2

emerging with a great substitute the VOC’s. The important uses of SO-CO2 are: dry
cleaning of clothes, polymerisation reaction etc.

Supercritical CO2 may be used to extract the organic pollutants like MTBE, PCBs,
DDT etc. present in water, soils and sediments.

Supercritical water (Tc=374oC) is too hot for many organic compounds. But near
critical water appears as a benign solvent for many organic reactions.

Use of greener catalyst:

Sometimes the used catalysts are toxic and these are accumulated in the industrial
waste product. For example, HF is the catalyst used in the production of linear alkyl
benzenes and it has been replaced by the greener catalyst i.e., fluorinated silica alumina
catalyst. Other example of greener catalyst are zeolites acting as acid catalysts in
Friedel crafts reaction, synthesis of oxime by titanium (IV)-silicate (TS-1) catalyst,
dehydration of organic molecules etc by ZSN-5 (used in the manufacture of synthetic
gasoline, TiO2 (used as a photocatalyst in removing water pollutants.

Biocatalysts are the most ideal, green catalysts and these are finding applications in
many biocatalytic transformations. These biocatalysts may be developed in the
genetically engineered bacteria.

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 Unit - 3
Ionic Liquids & Phase Transfer Catalysis
An ionic liquid is a salt in the liquid state. In some contexts, the term has been
restricted to salts whose melting point is below some arbitrary temperature, such as
100 °C. While ordinary liquids such as water and gasoline are predominantly made of
electrically neutral molecules, ionic liquids are largely made of ions and short-lived
ion pair. These substances are variously called liquid electrolytes, ionic melts, ionic
fluids, fused salts, liquid salts, or ionic glasses.

Properties of ionic liquids:

Ionic liquids also have a high thermal stability, which means they are more resistant to
changes in their chemical or physical structure.
They also tend to have high electrical conductivity, allowing electricity to flow through
them well, and have no vapor pressure which means they are not very reactive.
They also have a low viscosity, which means they flow easily.

Applications of ionic liquid:

Ionic liquids have many potential applications. Because of these unique properties,
ionic liquids have a number of useful applications. For example, because they have a
low volatility (that low vapor pressure mentioned before) and because they can
dissolve many different things, they have been used as 'green' solvents in different
industrial practices. Properties of ionic liquids make them useful for gas transport and
storage. Instead of using pressurized containers, gases can be dissolved into ionic
liquids and easily removed when needed. Ionic liquids can also be useful in recycling,
aiding in the separation of similar but different materials from one another. For
example, separating polymers from plastics.

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Application in alkylation:

Aldoximes react with α,β-unsaturated carbonyl and sulfonyl compounds in

organized aqueous media using dodecyl benzenesulfonic acid (DBSA) as surfactant to
generate N-alkylated nitrones, which undergo intermolecular cycloaddition in the same
pot with maleimides to give the desired cycloadduct in absence of any organic solvent
and catalyst. Divinyl sulfone was successfully used for both N-alkylation and
intramolecular cycloaddition, affording only one cycloadduct. This is a new example
of green chemistry and provides a new aspect of reactions in water.

Application in Hydroformylation:

Hydroformylation also known as oxo synthesis or oxo process, is an industrial

process for the production of aldehyde from alkene. This chemical reaction entails the
net addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon double
bond. This process has undergone continuous growth since its invention: Production
capacity reached 6.6×106 tons in 1995. It is important because aldehydes are easily
converted into many secondary products. For example, the resulting aldehydes are
hydrogenated to alcohol that are converted to detergents. Hydroformylation is also
used in chemical, relevant to the organic synthesis of fragrance and drugs.

Application in epoxidation:

Ethylene epoxides have many uses including generation of surfactants and

detergents. Epoxy-glues and structural materials are a result of epoxides reaction with
amines. These are used as a stabilizer in materials like PVC. These are also used in
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manufacturing of Epoxy resists which have low viscosity and without compromising
strength and physical properties. Epoxides are also used in insecticides, aerosols, resins
and chemical intermediates.

Synthesis of ether:

The most versatile method for making ethers is the Williamson ether synthesis,
named for English chemist Alexander Williamson, who devised the method in the
19th century. It uses an alkoxide ion to attack an alkyl halide, substituting the alkoxy
(―O―R) group for the halide. The alkyl halide must be unhindered or elimination
will compete with the desired substitution.

Friedel craft reaction:

The Friedel-Crafts reactions are a set of reactions to attach substituents to an

aromatic ring. Friedel-Crafts reactions are of two main types: alkylation reactions and
acylation reactions. Both proceed by electrophilic aromatic substitution. Friedel-Crafts
alkylation involves the alkylation of an aromatic ring with an alkyl halide using a
strong Lewis acid, such as aluminium chloride, ferric chloride, or other MX n reagent,
as catalyst. The general mechanism for tertiary alkyl halides is shown below.

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Diels-Alder reaction:
The Diels-Alder cycloaddition reaction between methyl acrylate and cyclopentadiene
has been investigated in a number of air and moisture stable ionic liquids. The
endo/exo ratio of the reaction has been used as an initial probe of the nature of the
solvents. Room temperature ionic liquids are used as solvents for regioselective Diels-
Alder reactions.

Knoevenagel condensation:

A Knoevenagel condensation is a nucleophilic addition of an active hydrogen to a

carbonyl group followed by a dehydration in which a molecule of water is eliminated.
The product is often an α,β-unsaturated ketone

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Wittig reaction:

The ionic salt [bmim][BF4] is an attractive solvent for Wittig reactions, allowing
both easier separation of alkenes from Ph3PO together with efficient reuse of the
solvent.

Phase-Transfer Catalyst:
PTC is a catalyst that facilitates the migration of a reactant from one phase into
another phase where reaction occurs. Phase-transfer catalysis is a special form of
heterogeneous catalysis. Ionic reactants are often soluble in an aqueous phase but
insoluble in an organic phase in the absence of the phase-transfer catalyst. The catalyst
functions like a detergent for solubilizing the salts into the organic phase. Phase-
transfer catalysis refers to the acceleration of the reaction upon the addition of the
phase-transfer catalyst. By using a PTC process, one can

achieve faster reactions,

obtain higher conversions or yields,
make fewer by-products,
eliminate the need for expensive or dangerous solvents that will dissolve all the
reactants in one phase,
eliminate the need for expensive raw materials and/or minimize waste problems.

Phase-transfer catalysts are especially useful in green chemistry. By allowing the

use of water, the need for organic solvent is reduced. Contrary to common perception,
PTC are not limited to systems with hydrophilic and hydrophobic reactants, they are
sometimes employed in liquid/solid and liquid/gas reactions as well. As the name
implies, one or more of the reactants are transported into a second phase which
contains both reactants.

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Synthesis of Phase transfer catalyst:

Most of the pharmaceuticals or agricultural chemicals are the result of organic

synthesis. Most of the syntheses require a number of steps in which additional reagents,
solvents and catalysts are used. In addition to the syntheses of the desired products,
some waste material is generated, the disposal of which causes problems and also
environmental pollution. In view of this, attempts have been made to use procedures
that minimise these problems. One of the most general and efficient methodologies
that takes care of the above problems is to use a phase-transfer catalyst (PTC).

Application of Phase transfer catalyst:

Phase-transfer catalysis (PTC) has been widely used for the synthesis of organic
compounds for more than three decades. The scope and mechanistic features of PTC
have been the aim of numerous studies. This review is approaching the subject by
focusing on the extraction-preconcentration-derivatization prior to analysis, reporting
recent progress made. Moreover, an attempt is made to approach the salient aspects of
PTC modes including a brief review of mechanistic pathways and kinetics pointing out
the potency of PTC in analytical chemistry. Optimization guidelines for PTC-based
analysis are given with respect to all parameters influencing the analytical method
under development, highlighting the capabilities and limitations of PTC reactions.

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 UNIT-IV
SUPPORTED CATALYSTS AND BIO-CATALYSTS

SUPPORTED METAL CATALYSTS

Supported metal catalysts are used for hydrogenation in organic solvent; however,
several metal species do not work for hydrogenation in supercritical carbon dioxide
solvent. Reverse water-gas shift reaction (CO2 + H2 → CO + H2O) proceeds over some
metal catalysts and Carbon monoxide molecules deactivate metal sites.

Catalyst support

In chemistry, a catalyst support is the material, usually a solid with a high surface
area, to which a catalyst is affixed. The activity of heterogeneous catalysts occurs at
the surface atoms. Consequently, great effort is made to maximize the surface area of
a catalyst.

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Example:

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TYPES OF CATALYSIS
Bio-catalysis:
Bio-catalysis is defined as the use of natural substances, like enzymes or cells, to
catalyse chemical reactions. An enzyme is simply a protein catalyst that helps the
digestion, produces vital nutrients, or moves muscles. biocatalyst are substances
(enzyme or hormone) that activates or speeds up biochemical reactions. For example,
digestive enzymes like pepsin, trypsin etc.

Homogeneous and Heterogeneous Catalysis:

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m-CPBA, meta-Chloroperbenzoic acid

m-CPBA is a strong oxidizing agent, which is comparable with other peracids.

Advantages of 3-chloroperbenzoic acid is its handling, because it is present as powder,
which can be kept in the refrigerator. Nevertheless, material of purity >75% is rarely
available commercially, since the pure compound is not particularly stable. Therefore,
the transport in airplanes with a content of > 72% is forbidden. Main pollution is 3-
chlorobenzoic acid (10%) as well as for safety reasons water.

m-CPBA is versatile applicable as peracid for use in laboratories.

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Baeyer-Villiger Oxidation

The Baeyer-Villiger oxidation is an organic reaction that forms an ester from a

ketone or a lactone from a cyclic ketone, using peroxy-acids or peroxides as the
oxidant. The reaction is named after Adolf von Baeyer and Victor Villiger who first
reported the reaction in 1899.

Uses of Mesoporous Silica

Zeolites and mesoporous silica nanoparticles are silicate or aluminosilicate

nanomaterials with well-defined pore networks. Zeolites are widely used in industry
for applications such as catalysis, separations and gas adsorption. Mesoporous silica
nanomaterials have not been as extensively applied relative to zeolites due to the cost
and reduced thermal stability, but are being intensively investigated for potential
environmental and biomedical applications. In this article, zeolite and mesoporous
silica nanomaterials are reviewed with emphasis on connections to the environment.
Specifically, the topics of greener syntheses, environmental applications and biological
toxicity will be addressed. Both of these materials are typically synthesized with a
template, which is then removed to produce the pore volume. Synthetic strategies for
the “greening” of the syntheses of zeolites and mesoporous silica will be discussed.
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Environmental applications including the adsorption of environmental contaminants
and environmental catalysis will also be presented. Finally, the toxicity of zeolite and
mesoporous silica nanomaterials will be considered.

Fermentation

Fermentation is the enzymatic decomposition and utililization of foodstuffs,

particularly carbohydrates, by microbes. Fermentation takes place throughout the
gastrointestinal tract of all animals, but the intensity of fermentation depends on
microbe numbers, which are generally highest in the large bowel.

Fermentation is a metabolic process that produces chemical changes in organic

substrates through the action of enzymes. In biochemistry, it is narrowly defined as the
extraction of energy from carbohydrates in the absence of oxygen. In the context of
food production, it may more broadly refer to any process in which the activity of
microorganisms brings about a desirable change to a foodstuff or beverage. The
science of fermentation is known as zymology.

In microorganisms, fermentation is the primary means of producing adenosine

triphosphate (ATP) by the degradation of organic nutrients anaerobically. Humans
have used fermentation to produce foodstuffs and beverages since the Neolithic age.
For example, fermentation is used for preservation in a process that produces lactic
acid found in such sour foods as pickled cucumbers, kombucha, kimchi, and yogurt,
as well as for producing alcoholic beverages such as wine and beer. Fermentation also
occurs within the gastrointestinal tracts of all animals, including humans.

For many years, man has worked to improve agricultural productivity by taking
advantage of the work of millions of soil microbes. These microbes can be cultivated
on a large scale and made to produce important biofertilizers, to assist plant growth;
and biopesticides, to control weeds, pests, and diseases. This process is known as
microbial fermentation.

Microbes function as both providers and defenders. They can contribute to plant
nutrition by converting important macromolecules into forms usable by plants, as
biofertilizers; or they can defend plants from other invasive, parasitic plants and pests,
as bioherbicides and bioinsecticides.

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Biofertilizers

Phosphate and nitrogen are important for plant growth. However, plants have a
limited ability to extract them from the environment, and thus need microbes to help
them absorb these nutrients at optimal concentration.

These same microbes are also involved in “nutrient recycling,” i.e. they help a plant
take up energy sources, while plants donate waste byproducts to microbes for food.
With this symbiotic relationship, plants develop stronger and bigger root systems. The
larger the plants’ roots, the more living space and food there is for the microbes to use.
In a way, microorganisms serve as biofertilizers.

An example is the fungus Penicillium bilaii, which allows plants to absorb

phosphates from the soil. It does this by producing an organic acid which dissolves
soil phosphates into a form which plants may use. A biofertilizer made from this
organism is applied either by coating seeds with the fungus (called inoculation), or
applying the fertilizer directly into the ground.

Another example is the bacterium Rhizobium. This bacterium lives on the plant’s
roots in cell collections called nodules. The nodules are biological factories that can
take nitrogen out of the air and convert it into an organic form that the plant can use.
Because the bacteria live within the roots, they transfer the nutrient directly into the
plant. Rhizobium works with legumes, such as beans, groundnut, and soybean.

Biofertilizers have been found to:

Increase crop yield by 20-30%.

Replace chemical nitrogen and phosphorus by 25%.
Stimulate plant growth.
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 Activate the soil biologically.
Restore natural soil fertility.
Provide protection against drought and some soil borne diseases.

Bioinsecticides
Insect pests of important crops can be difficult to control. Thanks to fermentation
methods, however, bioinsecticides have been developed, based on the insecticidal
proteins of bacteria, fungi, and viruses. Bacteria-based bioinsecticides

One of the most widely used bioinsecticides is a

naturally occurring soil bacterium called Bacillus
thuringiensis or Bt. Bt produces a protein which is
poisonous to insects. Within 15 minutes of being eaten,
the Bt toxin begins to create ulcers in the insect’s
stomach lining. The insect stops eating and eventually
dies. Researchers have identified between 500 and 600 strains, or types of Bacillus
thuringiensis. Bt is very selective — it affects only a specific species of insect pest
and does not harm humans, birds, fish, or beneficial insects.

Fungi-based bioinsecticides

Some fungi can cause disease in insects, and as many as 200 different insects are
known to be susceptible to such diseases. These fungi are thus used in fungi-based
bioinsecticides.

Inexpensive fermentation technology is used to mass produce fungi. Spores are

harvested and packaged so they can be applied to insect-ridden fields. When the spores
are applied, they use enzymes to break through the outer surface of the insects’ bodies.
Once inside, they begin to grow and eventually cause death.

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 bassiana fungus One bioinsecticide, Bb, is based on the action of Beauveria
bassiana, a fungus which is found worldwide in soils and plants. In China, over two
million hectares are sprayed with Bb annually to control forestry pests.

Bioinsecticides based on Bb have many advantages. The fungus does not grow in
warmblooded organisms (such as humans), nor does it survive long in water reservoirs
or rivers. However, its spores can withstand long periods of dryness and other harsh
environmental conditions. Studies to date have shown that the fungus also does not
harm plants and becomes inactivated by the sun’s ultraviolet rays in one to eight weeks.

Virus-Based Bioinsecticides

Insect pests are also susceptible to viral diseases, and virus-based insecticides
exploit this property in order to control the spread of pests.

An example currently being tested is the Baculovirus group. Baculoviruses affect

insect pests like corn borers, potato beetles, flea beetles, and aphids. One particular
strain is being used as a control agent for Bertha army worms. These worms attack
canola, flax, and vegetable crops, and have been known to clean out as many as one
million hectares of prairie crops at high infestation levels. Farmers used chemical
insecticides to control the worms in the past. Bioinsecticides do not persist long in the
environment, unlike synthetic pesticides. They also have shorter shelf lives and are
effective in small quantities, safer to humans and animals compared to synthetic
insecticides, and very specific, often affecting only a single species of insect. However,
bioinsecticides also have some disadvantages. They work slowly and the timing of
their application is relatively critical. Moreover, because most of these bioinsecticide
agents are living organisms, their success is affected by several factors like
temperature, pH, moisture, UV, soil conditions, and other microbial competitors
present in the environment.

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Bioherbicides

Weeds are a constant problem for farmers. They compete with crops for water,
nutrients, sunlight, and space; harbor insect and disease pests; clog irrigation and
drainage systems; undermine crop quality; and deposit weed seeds into crop harvests.
If left uncontrolled, weeds can reduce crop yields
significantly.

Farmers fight weeds with tillage, hand weeding,

synthetic herbicides, or a combination of all techniques.
Unfortunately, tillage leaves valuable topsoil exposed to
wind and water erosion, a serious long-term consequence
for the environment. For this reason, more and more
farmers prefer reduced or no-till methods of farming.

The use of bioherbicides is another way of controlling weeds without the

environmental hazards posed by synthetic herbicides. Bioherbicides are made up of
microorganisms and certain insects (for example- parasitic wasps, painted lady
butterfly) that can target very specific weeds. The microbes possess invasive genes that
can attack the defence genes of the weed, thereby killing it.

Due to better understanding of the genetics of both microorganisms and plants,

scientists have been able to isolate pathogens whose genes match particular weeds, and
which can cause fatal diseases in those weeds, and in those weeds alone. Some
bioherbicides contain such microorganisms, and they are sent out into the field when
weeds are most susceptible to illness. The specificity of the microbes for a specific
weed makes such bioherbicides very useful, since they can kill only certain weeds
without damaging important crops.

Bioherbicides can also survive in the environment long enough for the next growing
season, when there will be more weeds to infect. They are cheaper compared to
synthetic pesticides, and could essentially reduce farming expenses if managed
properly.

Baker’s yeast mediated reduction of 2-acetyl-3-methyl sulfolane

The baker’s yeast mediated reduction of 2-acetyl-3-methyl sulfolane 1 to provide

the corresponding alcohol 2 is described. Excellent efficiency and enantioselectivity
(>98%) have been achieved under these mild environmentally benign reaction

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conditions. In direct contrast, the chemical reduction of 1 proceeds with poor yield
(≤25%) and di-stereo control.

Application of baker's yeast

Baker's yeast has been widely used as a biocatalyst in organic synthesis, primarily
because it is inexpensive and readily available. The majority of studies on the
biotransformation capability of yeast deal with reductions of carbonyl groups and
carbon–carbon double bonds. Reactions involving carbon–carbon bond formation are
of great interest in chemical synthesis. Most of these biocatalytic reactions have been
carried out in aqueous media. The conversion of benzaldehyde and pyruvate to L-
phenylacetyl carbinol was one of the first commercial processes to utilize an enzyme
biotransformation step. During this biotransformation, a proportion of the
benzaldehyde is also reduced to benzyl alcohol. Recent studies on biocatalysis of
benzaldehyde and substituted benzaldehyde to benzyl alcohol by whole cells of wild-
type and mutant strains of baker's yeast in nonconventional media have established the
effects of organic solvents and substrate hydrophobicity on reaction performance.

Microbial polyesters synthesis

Production of microbial polyesters by fermentation and its complete carbon cycle.

Microorganisms isolated from nature are metabolically engineered to accumulate a
large amount of plastic with high yield and specific productivity. Biomass obtained
from carbon dioxide and sunlight is converted to fermentable sugars, and used as a
substrate for lab-scale fermentation for the examination of the performance and further
strain optimization. Once a high-performance microorganism is developed, industrial-
scale fermentation, after process optimization to give the highest possible yield and
productivity, is performed to produce large amounts of plastics. After fermentation,

42
polymers inside cells are purified and used to make articles that we use. When they are
disposed after use, they will be degraded to carbon dioxide (and methane under
anaerobic condition). Thus, the carbon cycle gets closed, providing environmentally
friendly sustainable way of producing plastics without using fossil oil.

43
 Unit-V
Alternative Synthesis
Green Solvents
The major application of solvents in human activities is in paints and coatings (46%
of usage). Smaller volume applications include cleaning, de-greasing, adhesives, and
in chemical synthesis Traditional solvents are often toxic or are chlorinated. Green
solvents, on the other hand, are generally less harmful to health and the environment
and preferably more sustainable.

Ideally, solvents would be derived from renewable resources and biodegrade to

innocuous, often a naturally occurring product. However, the manufacture of solvents
from biomass can be more harmful to the environment than making the same solvents
from fossil fuels. Thus, the environmental impact of solvent manufacture must be
considered when a solvent is being selected for a product or process.

Another factor to consider is the fate of the solvent after use. If the solvent is being
used in an enclosed situation where solvent collection and recycling is feasible, then
the energy cost and environmental harm associated with recycling should be
considered; in such a situation water, which is energy-intensive to purify, may not be
the greenest choice. On the other hand, a solvent contained in a consumer product is
likely to be released into the environment upon use, and therefore the environmental
impact of the solvent itself is more important than the energy cost and impact of solvent
recycling; in such a case water is very likely to be a green choice.

In short, the impact of the entire lifetime of the solvent, from cradle to grave (or
cradle to cradle if recycled) must be considered. Thus, the most comprehensive
definition of a green solvent is the following: "a green solvent is the solvent that makes
a product or process have the least environmental impact over its entire life cycle.

By definition, then, a solvent might be green for one application (because it results
in less environmental harm than any other solvent that could be used for that
application) and yet not be a green solvent for a different application. A classic
example is water, which is a very green solvent for consumer products such as toilet
bowl cleaner but is not a green solvent for the manufacture of polytetrafluoroethylene.

For the production of that polymer, the use of water as solvent requires the addition
of per-fluorinated surfactants which are highly persistent. Instead, supercritical carbon
44
dioxide seems to be the greenest solvent for that application because it performs well
without any surfactant In summary, no solvent can be declared to be a "green solvent"
unless the declaration is limited to a specific application.

Green chemistry addresses such challenges by inventing novel reactions that can
maximize the desired products and minimize by-products, designing new synthetic
schemes and apparatus that can simplify operations in chemical productions, and
seeking greener solvents that are inherently environmentally and ecologically

Plants and animals suffer less harm from toxic chemicals in the environment. Lower
potential for global warming, ozone depletion, and smog formation.

Less chemical disruption of ecosystems. Less use of landfills, especially hazardous

waste landfills. At the same time, green chemistry can save companies money by
reducing the need for costly chemicals, reagents and solvents, lowering insurance and
legal costs, reducing waste disposal costs .

45
Advantages of greener chemistry:
Prevention of unnecessary wastes; the avoiding of unnecessary waste in organic
synthesis can be reached by recyclability of most solvents, catalysts and
reagents;
Economy of matter (atoms): minimization of loss of precursors and intermediate
compounds during synthesis of final material;
Lower-hazard chemical reactions using little-toxic and safe chemical
substances;
Low-toxic and safe separation agents and solvents (water, natural compounds
as, for example, plant extracts);
Minimization of energy consumed (preferable/ideal conditions: normal pressure
and room temperature);
Renewable sources (raw materials);
Minimization of reagents to avoid unnecessary wastes (lesser number of reaction
steps and additional chemicals);
Use of most selective catalysts, allowing higher yields of reaction products;
Degradable reaction products, non-persisting in the environment;
Contamination prevention via permanent (real-time) analysis of reaction
intermediates when possible;
Small quantities of reactants to prevent accidents (explosions, releases, fire);
Green processes are cheaper and cost-effective, frequently resulting in products
with a better quality; and
green reactions allow avoiding problems with many environmental regulations
and laws.

Alternative methods for synthesis

1. Microwave Irradiation
This is a green source of heating both in organic and inorganic synthesis, based on
the conduction and dipolar polarization. A series of organic molecules have been
reported as obtained this economic, efficient, fast and clean way, now recognized as a
conventional synthetic chemistry tool, which has made a great contribution to organic
synthesis. MW energy is non-ionizing radiation, which does not influence on the
molecular structure of compounds. The MW coupling of a substance depends on its
dielectric constant, so N,N-dimethylformamide (DMF), methanol, acetone, water is
rapidly heated under MW irradiation, in a difference from CCl4, toluene or aliphatic
46
hydrocarbons. The electromagnetic energy, being transformed into heat, drives
interactions between compounds. MW irradiation and reaction components are in a
direct interaction, so a minimum of energy is needed for its heating, without expanding
the process to the furnace material. That is why the temperature profiles of
conventional and MW-heated simples are different (in the MW case, the interior is
hotter and the surface is cooler). The heating is uniform and takes place volumetrically,
in all the sample; the heat transfer requires lesser energy due to thermal conduction
inside the sample. The MW heating is almost instantaneous, very fast, due to the fast
transfer ‘MW energy-heat’, and can be stopped immediately by a simple turn-off of
the MW equipment. In addition, the MW heating is selective, since reagents possess
distinct capacity to be MW-heated, allowing, for example, the heating active points in
a sample instead of heating an entire sample.

MW heating has the following advantages, among others, being compared with
conventional heating: fast process speed, pure products, lesser heat loss, high heating
efficiency, less waste, low cost of operations, lesser possibility of side products.
Solvent-free (dry media) conditions of MW-assisted reactions are preferable, to avoid
fast uncontrolled solvent heating and violent explosions. Precursors can be adsorbed
on inorganic supports, transparent for microwaves (montmorillonite clays, zeolites,
ceramics, Al2O3, SiO2) or, on the contrary, possessing strong MW-absorbance (for
example, graphite). These supports can also contain additional reagents or catalysts.
MW assisted solvent-free reactions on inorganic supports at relatively low bulk
temperature have shown certain advantages in the processes of reduction and
oxidation, deprotection and protection, condensation, rearrangement, heterocyclic
synthesis, etc. leading to important products such as HCN, imines, nitroalkenes,
enamines, among others.

Modern apparatus for MW heating is well developed and covered in a

comprehensive review a commercial example is a reactor Monowave 50 [26]. For
simple experiments, modified domestic MW ovens are frequently used. Commercial
equipment includes SMC (apparatus with single-mode cavity, 0.2–80 ml volume of
sealed vessels), CEM MARS multimode MW reactor and Milestone Flowsynth
continuous-flow reactor, all with maximum pressure of 300 psi and temperature
300°C. Sometimes, ultrasmall particles (5-10 nm) can be formed due to very rapid
reaction time, although in some cases, larger particles can be also formed in
comparison with conventional synthesis. Crystallinity, defect concentration and
morphology can be different in MW-assisted and conventional synthesis. Shapes of
products can depend on MW power and irradiation time, as, for example, in MoS 2
47
synthesis, where the layer-, nanotube- and fullerene-like forms were observed
depending on the MW-treatment duration.

To carry out a successful MW-synthesis, all the reagents should ideally be good
absorbers, otherwise, it is necessary to looking for another material acting as a heat
source (susceptor) and converting MW energy to heat. The last case is not desirable at
scaling up processes, since this additional material is a contamination source. Also, the
substances, transparent for MW irradiation before certain temperature, can be
conventionally heated to reach it and then the MW-assisted process starts. The use of
MW-induced plasma, transferring energy between radiation and reagents and being, in
some cases, a source of reactive species, is also possible.

Green solid- and liquid(solution)-state MW-synthesis of inorganics includes the

formation of simple (in particular, yttria-stabilized ZrO2, α-Fe2O3 thin films) and
double oxides (i.e. Li, Cu, Co, Ni ferrites, BaTiO3 (from TiO2 and BaCO3), LaCrO3,
La1−xSrxCoO3, among others) during some minutes; chalcogenides (ZnS, CuS, Cu 2–
xTe, HgTe, Cu2SnSe4, Bi2Se3, CdSe, etc. sometimes from sulfates by carbothermal
reduction, but generally from elemental powders in vacuum, avoiding chalcogene
sublimation, without or with susceptors); borides (MgB2, ZrB2); carbides (SiC,
MgNi3C, CaC2, Mo2C, WC, etc. from metals or their oxides (Ta2O5 + C)); silicides
(Li21Si5, MoSi2, Mg2Si, CaAl1–xCuxSi, etc.); nitrides and other pnictides (TiN, Ta2N,
AlN, LiSi2N3, GaN, Li3Bi, Li3Sb); carbonitrides V1–x Tix(C, N), and oxynitrides (β′-
SiAlON).

2. Photocatalysis
Photochemical reactions under UV-irradiation are considered as green chemistry
interactions and are based on the electronic excitation, which influences the chemical
reactivity of reagents in organic synthesis. A recent review on photocatalysis describes
generation of singlet oxygen and its role in the photo-oxygenation (incorporation of
molecular oxygen into molecules), combination of photochemical processes with
enzyme catalysis, application of continuous flows or microreactors for their
optimization. Some examples of such reactions are the synthesis of N-containing
heterocycles by photooxidation of furan derivatives, asymmetric oxidations catalysed
with enzymes, and preparation of several F-organic compounds by photocatalysed
trifluoromethylation of aromatics, using photocatalysis booth and reactors described .

48
3. Hydro(solvo)thermal synthesis
A solution reaction-based approach has been applied to synthesize compounds,
crystallize and grow single crystals and polycrystals at high pressures (normally up to
10 bar) and elevated temperatures (generally up to 300°C) in water or organic solvent
media. The equipment for hydro(solvo)thermal technique consists of an autoclave
(thick-walled steel cylinders, sometimes with protective inserts made of Teflon,
platinum, titanium, quartz, gold, etc.), containing solvent (water) and
dissolved/suspended precursors. For the past 20 years, a combined equipment
‘microwave-hydrothermal treatment’ has been frequently used in laboratories. The
main advantage of the hydrothermal method is the possibility of the formation of
crystalline phases, unstable at the melting point of the desired compound; the main
disadvantage is the necessity to have expensive equipment. Morphology control and
crystallinity for the formed materials can be made by changing pressure, temperature,
solvent, reaction time or precursors' ratio. Hydrothermal reactions in water are
considered as more suitable for green chemistry purposes, being environmentally
friendly, and are widely applied to fabricate a variety of materials. This method allows
minimum loss of reactants and frequently higher yields of products, being especially
useful to obtain classic and less-common nanostructures with desired shape and size
control: powders, films and especially one- to three-dimensional nanocrystals

4. Ultrasound-assisted (sonochemical) synthesis

Ultrasound-assisted (sonochemical) synthesis is only a solution-based approach

(since cavitation occurs only in liquids) working as a result of the phenomenon of the
acoustic cavitation (bubbles, appearing in a liquid, grow and implosively collapse,
leading to extreme local pressures of 1000 atm and temperatures of 5000 K) in a liquid
phase, without a direct affectation to the bond vibrational energy. Chemical reactions
can be started or intensified in these conditions, additionally to the formation of free
radicals and H2O2. Chemical composition, reactivity and surface morphology of
materials (frequently increasing surface area) can be considerably changed as a result
of these collisions. A variety of sonochemical reactions can be carried out in liquid
systems, solid–liquid and liquid–liquid interfaces (as well as sonocatalysis), useful for
the environment, for instance, destruction of halogenated aromatics. Ultrasound-
mediated organic synthesis and preparation of functional materials are classic
contributions, perfectly fitting to the green chemistry field, since they do not require
large energy consumption and hazardous chemicals; additionally, the cost of

49
equipment is normally low in the case of a simple ultrasonic cleaning bath (frequencies
20–40 kHz), with exception of high-power ultrasonic horns .

5. Magnetic field-assisted synthesis

Magnetic field-assisted synthesis is currently studied as an alternative to traditional

methods. because some of the traditional methods require the use of toxic solvents or
additional steps that need more energy and can generate unwanted residues. These
extra steps can be omitted using magnetic fields during the synthesis of the desired
material. The synthesis assisted by magnetic fields allows obtaining morphologies
different from those prepared by traditional methods. In addition, it is possible to
influence the orientations of the final product planes. Some synthesis techniques where
the assistance of magnetic fields can be used are the methods of coprecipitation,
solvothermal, electrospinning, etc. In addition, the magnetic field assistance can be
implemented directly in the solution to influence the growth of the crystals of the
desired material and can be applied for the formation of thin layers of some
composites. The synthesis assisted with magnetic fields has numerous advantages due
to its simplicity; however, it has some important limitations, derived from the
foundation of the technique, because it can only be applied to materials whose reactants
or products have magnetic properties; that is why the vast majority of reports in the
literature use magnetic iron oxides.

Iron oxides such as Fe3O4 can adopt different assisted morphologies with magnetic
field; for example, it is possible to obtain complex Fe3O4 nanorods by the solvothermal
technique. This is possible because, during the formation of nanorods, the growth of
the crystals of the metal oxide is oriented in a specific orientation due to the magnetic
field. If the magnetic field is applied in the Fe3O4 synthesis by thermal decomposition,
it is possible to obtain nanotubes of 250 nm, which are not formed in the absence of
the magnetic field; besides, it was observed that the speed in which these nanoparticles
of Fe3O4 are heated by hyperthermia is considerably higher in the oxides synthesized
in the presence of the magnetic field. Another example that can be mentioned of the
synthesis of Fe3O4 with the assistance of magnetic fields is a series of chains prepared
at a temperature of 90°C. These particles had an average size of 150 nm. This was
achieved due to the growth of the particles of uniaxial way by the influence of the
magnetic field, and it was observed that the intensity of the magnetic field during the
synthesis had a significant effect on the anisotropy of the resulting material.

The assisted syntheses with magnetic fields can also be applied to the synthesis of
some composites, as long as they comply with the characteristics mentioned above.
50
An example of this is the thin layers of reduced graphene oxide (rGO) with Fe 3O4
nanocrystals. The synthesis of this composite is quite simple, based on taking
advantage of the ferromagnetic characteristics of the nanocrystals of Fe3O4 that are
adhered to the surface of sheets of rGO. When applying the magnetic field on this
suspension, the particles agglomerate in one of the walls of the reactor and they adhere
to each other by the electrostatic interactions between the GO and the nanocrystals of
Fe3O4. Such techniques can support the synthesis of flexible electrodes for batteries of
new generation.

Some other materials reported to assist with magnetic fields are compounds
containing nickel, cobalt, bismuth and some of their alloys. This is due to the fact that,
as mentioned, it is necessary that the materials have ferromagnetic properties, this
being their only limitation. Although it is true that there are reports of iron oxides in
the literature, it is also possible to find reports, where assisted synthesis with
electromagnetic field has been made using other materials and compounds containing
nickel, cobalt, bismuth and some of their alloys with ferromagnetic properties. For
example, the synthesis of cobalt and cobalt carbide nanowires is known, using
magnetic field-assisted polyol synthesis. For comparison, both cobalt and cobalt
carbide synthesized by traditional methods in the absence of magnetic fields usually
have spherical morphologies. It is also possible to obtain thin films of cobalt
nanosheets using magnetic fields during the reduction in solution of the Co 2+–EDTA
complex, which opens a new methodology to create thin films of magnetic
nanocrystals with anisotropic forms.

The synthesis of bismuth by the solvothermal method assisted with a magnetic field
can also be used to generate nanowires. As it can be seen, the use of magnetic fields
has a particular influence on the orientation in the case of the formation of crystals of
ferromagnetic materials and in the order in which the composites assisted with
magnetic fields are accommodated. The use of this technique depends on the method
that is being complemented to be considered as a green synthesis. It is noteworthy that
this technique reduces waste and synthesis, helping to make it more efficient; in
addition, the application of the magnetic field does not generate any additional by-
product to the main technique used.

6. Solvents and catalysis in green processes

For the organic synthesis, where hazardous solvents are mostly used, the 12 rules
of green chemistry can be successfully applied maximal atom economy (avoiding by-
products and wastes, in particular by solvent-less techniques, i.e. dry media), safe and
51
non-hazardous chemical routes without harmful chemicals, use of renewable
precursors (i.e. plants instead of fossil fuels), catalysts in small amounts (non-harmful
and preferably solids in order to be renewable), safer chemicals and solvents (water,
ILs) or better their absence, biodegradable substances, as well as avoiding energy
waste, preventing pollution and minimizing possibility of accidents.

Solvents represent a major source (80–90%) of pollution in organic (and not only)
chemical processes. Conventional organic solvents, derived from oil, are toxic and
possess bad health, environmental and safety impacts. So, the solvents to be used as
green media for organic synthesis need to possess biodegradability, low toxicity, high
boiling point, easily recyclable and non-miscible with water. Upon these conditions,
the water, ILs, polyethylene glycols (PEGs) and some SC fluids are most appropriate.
In this respect, nontoxic and biodegradable glycerol, which is the principal side product
in the fabrication of biodiesel, is quite suitable for green synthetic organic synthesis
and even called ‘organic water’. Its advantages are great availability, biodegradability,
low cost, low vapour pressure, high boiling point; in addition, glycerol is immiscible
with aliphatic hydrocarbons, highly polar, capable to form hydrogen bonds and
solubilizes both inorganic and organic compounds. The review describes a host of
reaction schemes (metal-free, metal- and bio-catalysed transformations) with glycerol
use.

7. Supercritical green solvents

Among other greener solvents, non-flammable, non-toxic and environmentally

friendly SC CO2 is known from long ago as a good alternative solvent for the synthesis
of polymers. SC water has been also used as a green solvent. Currently, the
technologies based on the supercritical fluids (SCFs), in particular SC water or CO 2,
contribute to the green chemistry in the nano-materials synthesis (for example, in
semiconductors' fabrication using SC CO2), solving some environmental problems.
The SCF technologies have been used in materials synthesis processes such as
extraction, cleaning, fractionation, drying, polymerization, hydrothermal reactions,
plating, biomass conversion, dyeing, among others, providing solvent-free media,
simplicity and recyclability, high yields, absence of wastewater and secondary
pollution, etc.

In the case of SC water (above critical pressure 22.1 MPa and critical temperature
646 K), it can be mixed with organic and inorganic substances forming homogeneous
phase. The reactions in SC H2O can occur by different routes due to the changes in
thermal conductivity, diffusion coefficient, density of molecules and viscosity.
52
Additionally, the dielectric constant of water (78 at room temperature (r.t.)) decreases
to values typical for polar organic solvents around the critical point. Metal oxides can
be hydrothermally produced in SC water, sometimes with H 2O2 addition to create
oxidizing atmosphere. A considerable decrease in their solubility near the critical point
was observed and considered as a good advantage. Resulted green reactions have led
to the fabrication of a variety of metal oxides, suitable for applications in the catalysis
(for example, nanoparticles of TiO2), as sensors, coatings, semiconductors, devices for
solar energy and batteries (in that number, LiMn2O4, LiFePO4 and LiCoO2), ceramics,
as well as for distinct medical applications. These methods are indeed green due to the
use of water and especially because they lead to the fabrication of lower-cost
sustainable nanomaterials. Metal oxide nanoparticles, modified with organic
functionalities, can be also obtained in these conditions, providing good dispersibility
in water or organic solvents. Other examples of SC-hydrothermally obtained materials
are hybrid materials based on inorganic nanoparticles and polymers, possessing
properties of both counterparts (high electrical resistance, mechanical strength, and
thermal conductivity, light weight, etc.). Also, recycling materials (plastics) can also
be made in SC water and EtOH; in these conditions, their decomposition or
depolymerization occurs to form monomers. Recovery of materials from wastes is also
available, in particular by hydrolysis of plastics in SC water or by SC oxidation of
wastewater.

ILs, some of the best solvents after water for green chemistry goals, are indeed salts
(ionic compounds, ‘constructed’ of ions and short-lived ion pairs), which are in a liquid
state at 100°C and below (usually at room temperature). In their composition, mostly
used cations are N-alkyl pyridinium, 1-alkyl-3-methylimidazoium, PR4+, NR4+, typical
anions are [PF6]−, [BF4−], [CF3SO3−], tosylate, alkylsulfate, [CH3COO−], NO3−, Cl−,
etc., common alkyl chains are ethyl, butyl, hexyl, octyl and decyl. IL molecules have
a significantly lower symmetry in comparison with classic ionic compounds. In a
difference with water, where hydrogen bonds act between molecules, and organic
solvents with van der Waals interaction, in ILs, the Coulomb interactions are main
forces. These solvents are generally thermally stable, electrically conducting fluids,
highly viscous and highly powerful solvents with low vapour pressure (approx. 10−10
Pa at 25°C); some of them are magnetic, for instance 1-butyl-3-methylimidazolium
tetrachloro-ferrate. The solubility of chemical compounds in ILs depends on the ability
of hydrogen bonding and polarity. In addition to a solvent's role in chemical processes,
ILs are used for gas handling, coal processing, fabrication of pharmaceuticals, nuclear

53
fuel reprocessing and cellulose processing, among several other uses. Currently, about
1000 ILs are known, including 300 commercially available products.

The catalysts in organic synthesis are used in the homogeneous and heterogeneous
catalysis, acting in the same (normally in liquid phase) or different phase (typically
solid/gas, liquid/gas or solid/liquid) in the reaction mixture, respectively. In the first
case, the active sites of catalysts are separated from each other. In the second case,
phase separation ‘product-catalyst’ is easier, since no extraction or distillation is
needed, thus contributing to the green chemistry. In addition, solid hazardous catalysts
(for example, polluting and corrosive catalysts) can be substituted by greener zeolites
or clays. Catalyst-free organic synthesis as the best greener alternative occurs for
several reasons, limiting catalyst use, for instance, lower selectivity, longer synthesis
duration, higher catalyst amounts, toxicity, insolubility, high cost, etc.

8. Dry media

In organic synthesis is obviously a great contribution to the green chemistry in the

conditions of solvent-free interaction of reagents, which can react directly or be
incorporated in alumina, silica, zeolites or clays. Physical treatments described above
(heating, UV-irradiation, ultrasound or microwaves) can be also used in these
reactions. The processes are shorter, with reduced contaminations, economic and
frequently scalable.

As examples of replacing dangerous procedures with greener methods [50], we

note, for example, use of Na2CO3 and Zn instead of fusing metallic Na with organic
substances for organic qualitative analysis, use of LiOH instead of NaOH in the
synthesis of dibenzal propanone from acetone, benzaldehyde and EtOH, solvent
(EtOH)-free preparation of benzylic acid, bromination of trans-stilbene in EtOH
instead of chlorinated solvents, etc.

Biological methods
Biological methods, being compared with conventional chemical and physical
methods, could be a preferable synthesis route due to environmentally friendly
conditions, despite their lower speed of metal reduction. However, their studies are
currently relatively limited, especially those establishing key factors of the
biosynthesis, so this method is only developed in laboratory scale, although bacteria
could be applied for industrial recovery of silver. The biological synthesis of
nanoparticles does not require further stabilizing agents: the microorganisms or

54
extracts themselves act as stabilizing and capping agents. Other advantages of the
biological routes are no necessity of toxic chemicals and contaminants, possibility to
control shapes and sizes, low cost, biocompatibility and numerous precursors
(microorganisms and plants). So, biological methods perfectly fit to the green
chemistry, in particular to nano-chemistry, resulting in biologically produced
nanoparticles, which are non-toxic, stable, environmentally friendly and cost effective.
Frequently, the nanoparticles, prepared by biological methods, expose a higher
antimicrobial activity (being compared with those synthesized by conventional
chemical methods), related with the fact that the stabilization and capping by proteins
is more effective. Main recent reviews in this area are described.

Biology-based green chemistry methods consist of the use of bacteria, viruses,

yeasts, plant extracts, fungi and algae, among which we consider plant extracts as most
frequent and popular green routes, as it will be shown below especially for the
synthesis of nanoparticles, not only those of noble metals, but also carbon dots, metal
sulphides, oxides, etc. This area, phyto nanotechnology (use of plants) is scalable and
medically applicable. Microorganisms represent natural nano factories, capable to
adsorb, accumulate and reduce toxicity of heavy metals, where enzymes are able to
reduce metal ions to cero-valent nanoparticles. In the case of bacteria use for
nanoparticle preparation, the techniques include the use of bacteria-containing
biomass, as well as supernatant and derived components. Myco synthesis (use of fungi)
allows an easy, stable and possibly scaled-up biosynthesis of nanoparticles. Viruses,
whose feature is dense and highly reactive surface (for instance, the surface of tobacco
mosaic virus contains 2130 capsid protein molecules), were used to produce several
inorganic nanoparticles, such as CdS, ZnS, Fe2O3 and SiO2, important for
semiconductor and quantum dot (QD) applications. In addition to conventional 0D
nanoparticles, the nanotubes and nanowires can also be produced by virus action. The
use of yeasts led the preparation of CdS and PbS QDs, Au and other metal
nanoparticles. The use of algae is rare, generally for Au, Pd and Pt nanoparticles. Thus,
in the case of algae use, the tetrahedral, decahedral and icosahedral Au nanoparticles,
as well as bimetallic Ag/Ag nanoparticles, can be formed due to the action of proteins
as stabilizing agent, shape-control modifier and reductant at the same time.

Inorganic micro- and nanosized materials can be prepared via intracellular- and
extracellular-microorganism-assisted synthesis. The formation of nanoparticle is
considered (but not yet fully understood) as a bottom-up process due to redox
processes with participation of metal ions and biological molecules (proteins, sugars
and enzymes), provided by the microorganism, whose interaction with metal ions
55
depends on its type and can vary, also depending on temperature and pH
(environmental factors), as well as metal salt concentration, leading to a particular
morphology and size of nanoparticles. In the intracellular methods, several additional
stages are needed, such as ultrasonication to destroy cell wall, washing, centrifugation,
etc. which are absent in the extracellular techniques.

Biosynthesis processes of fabrication of homogeneous-size nanoparticles with

certain reproducible morphology is carried out by size and shape control of critical
factors, such as temperature (maximum possible for fast growth of microorganisms),
pH (one of the most important factors, ranged generally from 3 to 10; acidic pH
contributes to the agglomeration of nanoparticles due to the higher ion binding), salt
concentration, choice of biological source, temperature, redox conditions, synthesis
duration and incubation period, irradiation and aeration.

As it was noted, the use of plant extracts are common preparation procedures for a
variety of nanoparticles of metals, non-metals and several of their compounds. Plant
extracts contain polyphenols, terpenoids, proteins, enzymes, peptides, sugars, phenolic
acids, bioactive alkaloids as a driving force for nanoparticle formation. Using plant
extracts, the following nanoparticles have been obtained: Au, Ag (a host of reports),
Cu, CuO, TiO2, ZnO, In2O3, Fe, Fe2O3, Pb and Se. A large number of their final
morphologies have been reported: spheres, triangles, cubes, pentagons, hexagons,
wires, rods, etc., for example, Au triangles (reduction of HAuCl4 with Aloe vera), Ag
nanowires (reduction of Ag+ with Cassia fistula leaf). Nanoparticle sizes can vary
considerably, for example, CdS (from ultrasmall 2–5 nm to large 200 nm), Ag (5–400
nm), Au (5–85 nm) or magnetite (20–50 nm). Factors influencing their size and shape
are as follows: plant extract and metal salt concentrations, temperature (25–95°C), pH
(lower pH—larger particles), reaction time (normally from minutes to several hours).

Different metals have distinct capacity to be reduced by plant extracts; easiest

processes correspond to noble metals, especially silver. Typical disadvantages in plant-
assisted reduction of metals are difficulties in separation of formed metal nanoparticles
from the biomass and accompanying purification processes in reaction systems in the
case of long-term reduction. So, the low or practically no cost of plant extracts can
cause an imagination about apparent scalability for these processes; however, necessity
of additional separation steps can result a negative conclusion on potential pilot-plant
or major fabrication of metal nanoparticles.

A huge number of reports are dedicated to Ag 0, Au0 monometallic and Ag0/Au0

bimetallic nanoparticles, obtained by biological methods and reviewed in . Silver
56
nanoparticles have been biologically obtained by all possible methods , including
bacteria-assisted bio-reduction (in particular, using Escherichia coli, Bacillus
licheniformis, B. subtilis, among others), fungi (Aspergillus fumigatus, Fusarium
acumina-tum, Penicillium fellutanum, among others), yeast (yeast strain) and
numerous plant extracts containing polyphenols as reductants (pennyroyal—Mentha
pulegium L., Platanus orientalis, thyme—Thymus vulgaris L. , carum carvi L. seeds ,
black and green tea, lemon grass, grape wastes, orange wastes, Magnolia kobus,
marshmallow flower (Althaea officinalis L.), geranium, etc.). Au and Ag nanoparticles
can be obtained with the use of actinomycetes (microorganisms with some properties
of bacteria and fungi) and leaves of Passiflora edulis. Sometimes additional
microwave treatment and capping agents were applied to complete metal formation
process. Using microorganisms, metal ions (for instance, Au+) can be reduced on cell
membranes and walls in the intracellular reduction as a result of releasing enzymes
from cell membrane. At the same time, the proteins can take a capping role. In the
extracellular reduction, nitrate reductase enzyme can be a driving force for metal ion
(Au+, Ag+) reduction according to the electron transfer mechanism and further
stabilization by proteins.

Dimethyl Carbonate (DMC)

It is an organic compound with the formula OC(OCH3)2. It is a colourless,
flammable liquid. It is classified as a carbonate ester. This compound has found use as
a methylating agent and more recently as a solvent that is exempt from the restrictions
placed on most volatile organic compounds (VOCs) . Dimethyl carbonate is often
considered to be a green reagent.

Methylating agent

Dimethyl carbonate methylates anilines, phenols, and carboxylic acids, but many of
these reactions require the use of an autoclave.

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 Dimethyl carbonate's main benefit over other methylating reagents such as
iodomethane and dimethyl sulphate is its low toxicity. Additionally, it is
biodegradable. Unfortunately, it is a relatively weak methylating agent compared to
these traditional reagents.

Friedel-crafts reaction

The Friedel-Crafts reaction, a widely used reaction in both industrial and academic
laboratories, produces several byproducts which must be handled as pollutants. An
alternative which involves the photochemically-mediated reaction of an aldehyde with
a quinone is described.

Supercritical carbon dioxide (sCO2)

It is a fluid state of carbon dioxide where it is held at or above its critical temperature
and critical pressure.

Carbon dioxide usually behaves as a gas in air at standard temperature and pressure
(STP), or as a solid called dry ice when cooled and/or pressurised sufficiently. If the
temperature and pressure are both increased from STP to be at or above the critical
point for carbon dioxide, it can adopt properties midway between a gas and a liquid.
More specifically, it behaves as a supercritical fluid above its critical temperature
(304.13 K, 31.0 °C, 87.8 °F) and critical pressure (7.3773 MPa, 72.8 atm, 1,070 psi,

73.8 bar) expanding to fill its container like a gas but with a density like that of a liquid.

Supercritical CO2 is becoming an important commercial and industrial solvent due to

its role in chemical extraction in addition to its low toxicity and environmental impact.
The relatively low temperature of the process and the stability of CO2 also allows most
compounds to be extracted with little damage or denaturing. In addition, the solubility
of many extracted compounds in CO2 varies with pressure permitting selective
extractions.

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Uses of supercritical CO2

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