Chapter-1

Introduction
Chapter 1 Introduction
The worldwide ketone market has been continuously expanding, propelled by demand
from a variety of important industries including chemicals, pharmaceuticals, cosmetics, food,
and agrochemicals. The biggest and fastest-growing regional market, accounting for
approximately 45% of worldwide market share due to increased industrialization, notably in
China and India. The need for ketones in textiles, chemicals, and medicines is a significant
driver. The worldwide ketone market was estimated at USD 4.2 billion in 2022, and it is
expected to rise at a 6.5% CAGR from 2023 to 2030. Ketones derived from biomass are
quickly expanding, driven by rising demand for environmentally friendly chemical
alternatives. In 2022, the bio-ketones market was estimated to be worth USD 500 million.
Key manufacturing methods include fermentation and enzymatic procedures that transform
agricultural waste and other organic materials into bio-ketones. Major applications include
medicines, cosmetics, and agrochemicals, all of which seek environmentally friendly
solutions.
Replacing petrochemical ketones with biomass-derived ketones has various benefits.
For starters, bio-ketones are derived from renewable resources, which reduces reliance on
fossil fuels and promotes sustainability. This transition reduces carbon emissions during
production, which helps to prevent climate change. Additionally, bio-ketones frequently have
reduced toxicity, making them safer for both consumers and the environment. Their usage is
consistent with a rising regulatory push for greener chemicals and customer desire for natural
products. Furthermore, adding bio-ketones can improve brand reputation and achieve
sustainability goals, offering enterprises a competitive advantage in markets focused on eco-
friendly solutions [1].
1.1. Biomass
Generally, lignocellulosic materials derived from wood stems comprise 40-55%
cellulose, 24-40% hemicellulose, and 18-25% lignin, whereas softwood stem-based products
contain 45-50% cellulose, 25-35% hemicellulose, and 25-35% lignin [2-5]. Lignocellulosic
biomass may be produced from agricultural and forest leftovers, industrial waste, animal
remains, and sewage wastewater as shown in Fig. 1.1. The benefits of using lignocellulosic
biomass include the fact that it is a very inexpensive renewable raw material that is widely
available and may be utilized to produce valuable biofuels, chemical compounds, power, and
heat. It will lead to improved energy, environmental, and economic performance by
developing biorefinery ideas. Biomass is generated globally at a pace of 170 billion metric
tons per year, making it the most abundant renewable resource.

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Chapter 1 Introduction

Fig. 1.1. Sources of biomass.

Traditionally, lignocellulosic biomass has been placed in landfills and burned;
however, the primary problems of this technique are the high cost of transportation and
incineration because of the high water content and the material's low calorific value. There
have been attempts to use agricultural and forest residues as animal feed, but large-scale
animal consumption of this material is uncommon. As a result, diverting rubbish to thorough
and imaginative green processes will add value to the waste while also helping to maintain
the ecosystem's natural resources.

1.1.1. Cellulose
Cellulose is a complex polysaccharide and one of the most prevalent organic
molecules on the planet, found predominantly in plant cell walls. The molecular structure
consists of long, linear chains of glucose units connected by β (1→4) glycosidic linkages.
Each glucose molecule in the chain comprises six carbon atoms, twelve hydrogen atoms, and
six oxygen atoms. A single glucose unit has the chemical formula C₆H₁₂O₆. The repeating
unit of cellulose, known as cellobiose, consists of two glucose molecules linked together,
resulting in a typical formula of (C₆H₁₀O₅)ₙ, where "n" reflects the number of repeating
units and can range from several hundred to over ten thousand is presented in Fig. 1.2.
The linear structure of cellulose allows for significant hydrogen bonding between
nearest chains' hydroxyl (-OH) groups, resulting in the development of microfibrils. These
microfibrils combine to form a rigid and crystalline structure, giving plants mechanical
strength and resistance to deterioration. Cellulose is insoluble in water and most organic
solvents, which helps to ensure its longevity and stability in plant tissues.

3
Chapter 1 Introduction

In addition to its main structure, cellulose may exist in a variety of crystalline forms,
with cellulose-I being the most prevalent in nature and cellulose-II frequently observed in
regenerated fibers such as rayon. The degree of polymerization (DP) of cellulose, which
refers to the number of glucose units in a chain, varies according on plant source and
processing processes. Understanding the chemical composition of cellulose is required for its
uses in different sectors, including textiles, paper, food, and biofuels, as well as researching
its potential in sustainable materials and biotechnological breakthroughs [2–8].

Fig. 1.2. Cellulose.

1.1.2. Hemicellulose
Hemicellulose is an important component of biomass, accounting for 20-35% of
lignocellulosic materials depending on the plant species and type of biomass. It is a complex,
branching polymer comprised of several sugar monomers, including pentoses (such as β-d-
xylose and α-l-arabinose), hexoses (such as β-d-mannose, β-d-glucose, α-d-galactose), and
uronic acids (such as glucuronic and galacturonic acids) as shown in Fig 1.3. The relative
quantity of these sugars varies by biomass source. For example, in hardwoods, xylans—
polymers largely composed of xylose—are the predominant kind of hemicellulose,
accounting for up to 20-30% of the biomass. Softwoods, on the other hand, have a higher
concentration of mannans, which are mannose-rich polymers that contribute considerably to
hemicellulose content. Agricultural wastes such as maize stover and straw are likewise high

4
Chapter 1 Introduction
in hemicellulose, with varied amounts of pentoses and hexoses. Hemicellulose's branching
and amorphous shape, as opposed to cellulose's linear and crystalline structure, allows it to be
hydrolyzed more easily, increasing its reactivity in bioconversion processes. The polymer is
closely linked to cellulose and lignin in plant cell walls, providing a matrix that strengthens
and stabilizes the overall structure. However, this interaction makes it more difficult to
separate and remove hemicellulose during biomass processing. In biofuel production,
hemicellulose may be hydrolyzed into fermentable sugars, chiefly xylose, which can be
utilized to make bioethanol and other biochemicals. The complex structure of hemicellulose,
particularly the presence of side chains and various sugar units, poses challenges in
optimizing its conversion to simple sugars [9–11].

Fig. 1.3. Monomers of hemicellulose.

1.1.3. Lignin
Lignin is a very complex and irregular polymer made up mostly of three
phenylpropanoid units: p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S). These units are
formed from three distinct monolignols: p-coumaryl alcohol, coniferyl alcohol, and sinapyl
alcohol is presented in Fig.1.4. The ratio of these units varies by plant species, adding to the
variety of lignin structures observed in nature. Monolignols create a three-dimensional
polymer network through chemical bonding, including ether bonds (β-O-4) and carbon-
carbon bonds (β-β and β-5). Lignin also includes trace quantities of other components, such
as carbohydrates and proteins, which are usually included during its manufacture. This
structural complexity makes lignin more resistant to degradation and adds to its involvement
in strengthening [12].

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Chapter 1 Introduction

Fig. 1.4. Monomeric unit of lignin.

1.2. Conversion of biomass to carboxylic acids

The conversion of lignocellulose into carboxylic acids is a crucial area of research in
sustainable chemistry, as it offers the potential to produce valuable chemicals from renewable
biomass. Lignocellulosic biomass, which is abundant in agricultural residues, wood, and
energy crops, but their complex structure presents challenges for efficient conversion. The
process typically begins with pre-treatment methods aimed at breaking down the
lignocellulosic matrix to release fermentable sugars. Physical, chemical, and enzymatic pre-
treatments, such as steam explosion, dilute acid hydrolysis, and enzyme-based degradation,
are used to depolymerize cellulose and hemicellulose into simple sugars like glucose and
xylose. Once liberated, these sugars can undergo microbial fermentation to produce various
carboxylic acids. For example, acetic acid, one of the simplest carboxylic acids, can be
produced by the fermentation of sugars with acetic acid bacteria such as Acetobacter.
Similarly, lactic acid, an important platform chemical for biodegradable plastics, can be
synthesized by fermenting glucose using lactic acid bacteria like Lactobacillus. Succinic acid,
a key intermediate in bioplastics and pharmaceuticals, can be produced through fermentation
by engineered microbes such as Escherichia coli or Actinobacillus succinogenes. In addition
to fermentation, thermochemical conversion methods like pyrolysis and gasification can also
be used to convert lignocellulosic biomass into carboxylic acids. Pyrolysis involves heating
biomass in the absence of oxygen to produce bio-oil, which contains various organic acids,
including acetic and formic acids. Gasification, on the other hand, converts biomass into
syngas (a mixture of carbon monoxide and hydrogen), which can be catalytically processed
into acetic acid or other carboxylic acids through chemical reactions such as methanol
carbonylation. Anaerobic digestion is another biological route, where lignocellulosic biomass
is decomposed by anaerobic bacteria into volatile fatty acids like acetic, propionic, and
butyric acids, along with methane and carbon dioxide. This method is often employed in

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Chapter 1 Introduction
waste treatment processes, where organic matter is broken down in biogas plants. Each of
these approaches offers different advantages depending on the desired carboxylic acid and the
biomass source, but they all contribute to creating a circular bioeconomy. However, the
conversion of lignocellulose into carboxylic acids faces significant challenges. The complex
structure of lignin, which is a recalcitrant polymer, makes it difficult to break down, limiting
the overall efficiency of the process. Additionally, the variability in the composition of
lignocellulosic feedstocks requires process optimization to ensure consistent yields of
carboxylic acids. Enzymatic degradation and microbial fermentation are often hindered by
inhibitors formed during pre-treatment, necessitating careful selection of pre-treatment
conditions and robust microbial strains. Despite these challenges, advances in biotechnology,
catalysis, and process engineering are driving the development of more efficient and scalable
methods for converting lignocellulose into carboxylic acids, offering a sustainable alternative
to petroleum-based chemicals and reducing the carbon footprint of chemical
manufacturing [13–18]. Biomass can be transformed into carboxylic acids using several
methods. The main approaches include biochemical, thermochemical, and catalytic processes.

1.2a. Biochemical Conversion (Fermentation)

Biochemical methods primarily involve microbial fermentation, where specific
microorganisms convert sugars derived from biomass into carboxylic acids. Biomass is
pretreated to release fermentable sugars from cellulose and hemicellulose. Enzymatic
hydrolysis of cellulose yields glucose, and hemicellulose yields xylose and other sugars.
Microorganisms (bacteria, yeast, or fungi) convert these sugars into carboxylic acids. For
instance, Lactic acid is produced by Lactobacillus species through the fermentation of
glucose, Acetobacter species can produce acetic acid, and Succinic acid can be produced by
anaerobic bacteria like Actinobacillus and succinogenes. This method is energy-efficient but
may require advanced control of fermentation conditions and downstream processing to
recover pure acids [19–26].

1.2b. Thermochemical Conversion

Thermochemical methods involve breaking down biomass under heat and chemical
conditions to produce intermediates that can be further converted into carboxylic acids. In
the pyrolysis process, biomass is by high heat energy (207 to 434 KJ/Kg) in the absence of
oxygen to produce bio-oil [27,28]. This bio-oil contains a mixture of compounds, including
carboxylic acids (like acetic acid). However, the separation and purification of acids from the
bio-oil can be complex. Biomass is converted into syngas (CO and H₂) through partial

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Chapter 1 Introduction
oxidation at high temperatures in the gasification process. Syngas can then be used in
chemical processes (such as catalytic reactions) to synthesize carboxylic acids. In
hydrothermal liquefaction method, Biomass is treated with water at high temperatures and
pressures to produce a liquid mixture, from which carboxylic acids, especially acetic acid,
can be extracted. Other important method [29–32].

1.2c. Catalytic Conversion

Catalytic conversion of biomass or its intermediates into carboxylic acids is a growing area of
research. This method typically involves direct catalytic oxidation of Biomass-derived
compounds, such as alcohols or aldehydes, which are oxidized to carboxylic acids using
metal catalysts (e.g., copper, palladium, or platinum). For example, glucose can be
catalytically oxidized to gluconic acid. Another method, hydrolysis of esters and anhydrides
involves initially biomass can be converted into esters or anhydrides, which are then
hydrolyzed to carboxylic acids using acid or base catalysts [33–43].

1.2.1. Acetic acid

Acetic acid can be synthesized from biomass through various sustainable methods,
primarily involving fermentation and thermochemical processes. In fermentation,
microorganisms such as Acetobacter convert sugars derived from biomass (like corn,
sugarcane, or lignocellulosic materials) into acetic acid (Fig. 1.5), often yielding significant
quantities at lower temperatures and pressures. Alternatively, thermochemical methods
involve gasifying biomass to produce syngas, a mixture of hydrogen and carbon monoxide,
which can be chemically transformed into acetic acid through reactions like carbonylation.
Hydrothermal liquefaction is another promising approach, where biomass is treated with
high-temperature water, producing a liquid bio-oil containing acetic acid. Each method offers
the advantage of utilizing renewable biomass, thus reducing reliance on fossil fuels and
promoting carbon neutrality. However, challenges remain in economic viability, process
optimization, and feedstock variability. Overall, biomass-derived acetic acid represents a
sustainable pathway for acetic acid production, contributing to a greener chemical industry
and enhancing resource efficiency [44–62].

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Chapter 1 Introduction

Fig. 1.5. Schematic diagram of conversion of glucose to fine chemicals (acetic acid).

1.2.2. Propanoic acid

Propanoic acid, also known as propionic acid, is a short-chain fatty acid with the
molecular formula C₃H₆O₂. It is a valuable chemical used in various applications, including
food preservation, and animal feed, and as a precursor for the synthesis of various
pharmaceuticals and agrochemicals. The demand for propanoic acid is increasing, prompting
the exploration of sustainable production methods.
Traditionally, propanoic acid has been synthesized through petrochemical processes,
primarily from ethylene and carbon monoxide or through the hydrolysis of propionyl
chloride. However, these methods raise environmental concerns due to their reliance on fossil
fuels and the generation of greenhouse gases.
Biomass, composed of organic materials from plants, agricultural residues, and waste
products, can be converted into various bio-based chemicals, including propanoic acid,
through several biochemical and thermochemical pathways. The primary methods for
synthesizing propanoic acid from biomass include. Certain microorganisms, such as
Propionibacterium species, can convert sugars derived from biomass into propanoic acid
through anaerobic fermentation. This process involves the metabolism of carbohydrates to
produce organic acids, primarily propanoic acid, along with acetic and lactic acids.
Thermochemical processes like pyrolysis (thermal decomposition in the absence of oxygen)
and gasification (partial oxidation at high temperatures) can convert biomass into syngas (a
mixture of carbon monoxide, hydrogen, and carbon dioxide) [63–77]. Syngas can then be
catalytically converted into propanoic acid through various reactions, including Fischer-

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Chapter 1 Introduction
Tropsch synthesis and subsequent upgrading processes. Biomass-derived sugars or
lignocellulosic feedstocks can be chemically converted to propanoic acid through catalytic
pathways. This approach may involve the use of solid acid catalysts to facilitate the
transformation of sugars into carboxylic acids, including propanoic acid. Trance esterification
involves the reaction of triglycerides or fatty acids extracted from biomass with alcohol,
resulting in the production of fatty acid methyl esters and propanoic acid [78,79].

1.2.3. Pivalic acid

Pivalic acid (2,2-dimethylpropanoic acid) can be synthesized from biomass through
various biotechnological and chemical pathways, primarily leveraging fermentation and
thermochemical processes. One common approach involves the anaerobic fermentation of
carbohydrates derived from biomass, such as glucose or sucrose, using specific
microorganisms like Clostridium species, which can convert sugars into organic acids,
including pivalic acid. In this process, biomass undergoes hydrolysis to release fermentable
sugars, followed by microbial fermentation, where the sugars are converted into acids.
Another route is through the thermochemical conversion of biomass via pyrolysis, where heat
decomposes organic materials, yielding bio-oil that contains various organic compounds,
including pivalic acid. This bio-oil can be further refined through catalytic reactions or
chemical processing to isolate pivalic acid. Pivalic acid can also be produced from the
synthetic conversion of isobutylene, a byproduct of biomass processing, through
carbonylation reactions. These biomass-based methods for synthesizing pivalic acid not only
provide a renewable alternative to petrochemical routes but also contribute to reducing
greenhouse gas emissions and promoting sustainability in chemical manufacturing [80,81].

1.2.4. Benzoic acid

Benzoic acid is widely applied across several industries due to its antimicrobial,
preservative, and chemical properties. One of its primary uses is as a preservative in the food
and beverage industry, where it helps prevent the growth of mold, yeast, and bacteria. It is
particularly effective in acidic foods, such as carbonated drinks, fruit juices, pickles, and
sauces, often in the form of sodium benzoate. In the pharmaceutical sector, benzoic acid
serves as an antifungal and antimicrobial agent. It is commonly found in ointments and
creams designed to treat skin conditions like athlete’s foot and ringworm. It also acts as a pH
adjuster in various drug formulations, helping to maintain the stability of active ingredients. It
is also used in the cosmetic industry, where it serves as a preservative in products such as
shampoos, lotions, deodorants, and lipsticks, ensuring microbial safety and stability. In

10
Chapter 1 Introduction
industrial applications, benzoic acid is employed in the production of alkyd resins used for
paints, coatings, and varnishes. It is also a precursor for the production of benzoyl chloride,
which is essential in the synthesis of dyes, perfumes, and various chemicals. Moreover, in the
textile industry, benzoic acid functions as a mordant to fix dyes to fabrics. Benzoic acid’s use
extends to agriculture as well, where it is incorporated into fungicides to protect crops from
fungal infections. Its chemical versatility and preservative properties make it invaluable
across a broad spectrum of industries, including food, pharmaceuticals, cosmetics, and
manufacturing [82–84].

Benzoic acid can be synthesized from biomass by first breaking down lignocellulosic
material into aromatic compounds. One approach involves pyrolysis or catalytic
depolymerization of lignin, which yields a mixture of aromatic compounds, including
benzene derivatives (Fig 1.6.). These intermediates, such as toluene or benzyl alcohol, can be
oxidized to form benzoic acid. For example, toluene can be oxidized using oxidizing agents
like potassium permanganate (KMnO₄) or air in the presence of a catalyst (e.g., cobalt or
manganese-based catalysts). This biomass-to-benzoic acid conversion is a sustainable
approach to producing this important industrial chemical from renewable resources [85–91].

Fig. 1.6. benzoic acid synthesis from biomass.

1.2.5. Cyclohexane carboxylic acid
Hexanoic acid, a six-carbon carboxylic acid, has diverse applications across various
industries. It is primarily used as a flavoring agent in the food industry, as well as in the
production of esters for fragrances and cosmetics. Additionally, hexanoic acid serves as a key

11
Chapter 1 Introduction
intermediate in the synthesis of herbicides and surfactants. Synthesis from biomass involves
several methods, primarily fermentation and thermochemical processes. In fermentation,
sugars derived from lignocellulosic biomass, such as agricultural residues or food waste, are
converted by specific bacteria like Clostridium species into hexanoic acid under anaerobic
conditions. Alternatively, thermochemical processes like pyrolysis can decompose biomass at
high temperatures to produce bio-oil, which contains hexanoic acid along with other organic
compounds. This bio-oil can be further processed to enhance the yield of hexanoic acid,
making biomass a sustainable source for this valuable chemical.

1.3. Ketonization (ketones from biomass)

Ketonization is a clean process that makes it a useful synthetic method for producing
symmetrical and unsymmetrical ketones using carboxylic acids as starting materials. The first
example of ketonization was reported in 1858 by the French chemist Charles Friedel, who
synthesized acetone via distillation pyrolysis of calcium acetate, and until World War I this
reaction was the premier commercial method for its production. In 1856 however, two years
before Friedel, the Italian chemist Raffaele Piria reported the reaction between calcium
acetate and calcium formate to produce acetic aldehyde. This technique has gained
significance in recently as one of the possible environmentally benign techniques for
preparing various ketones by decarboxylating carboxylic acids. Ketonization is a more
suitable method in industry due to the possibility of producing ketones in continuous vapor
phase reactions. The ketonization gives a symmetrical ketone when self-decarboxylation of
acid and a combination of three products when two different carboxylic acids are used
namely the pair of matching symmetrical ketones, mixed ketone, along with byproducts
carbon dioxide and water as shown in Scheme 1.1.

Scheme 1.1. Cross-ketonization of acetic acid and propanoic acid

1.3a. Bulk ketonization
Carboxylic acids can be transformed into ketones using two different methods. Oxides
with low lattice energies or very high basicity, such as alkali, alkali earth, and rare earth
oxides (e.g., Bi2O3, MgO, CaO, BaO, SrO, CdO, La2O3, Pr6O11, and Nd2O3), interact strongly
with carboxylic acids, forming bulk carboxylate salts that decompose under thermal treatment

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Chapter 1 Introduction
to produce ketones, water, and CO 2. The reaction between alkali oxides is bimolecular and
occurs in the liquid phase, where reactants are more mobile.
1.3b. Surface ketonization
Amphoteric oxides, such as TiO 2 and ZrO2, are commonly used for surface
ketonization reactions. However, it has also been proposed for basic oxides (e.g., MgO) under
particular reaction circumstances, highlighting the complexity of the coupling reaction and
the ongoing debate over reaction intermediates and routes. Since its discovery, several
surface processes have been hypothesized, including concerted, acid anhydride, ketene, and
β-ketoacid mechanisms. Our present understanding of ketonization shows that the β-ketoacid
pathway is the most possible.

1.3.1. Cyclohexyl phenyl ketone

Cyclohexyl phenyl ketone (CHPK) is an organic compound characterized by the
presence of both a cyclohexyl and a phenyl group attached to a carbonyl (ketone) functional
group. It is represented by the chemical formula C₁₃H₁₈O and is a member of the class of
compounds known as ketones. This compound has garnered significant interest in various
fields, including organic chemistry, materials science, and pharmaceuticals, primarily due to
its unique structural properties and diverse applications.
The synthesis of cyclohexyl phenyl ketone typically involves the Friedel-Crafts
acylation of cyclohexanone with phenylacetyl chloride or similar reagents, which facilitates
the formation of the ketone linkage between the cyclohexyl and phenyl groups. This reaction
is favored due to the reactivity of the carbonyl group, enabling subsequent modifications that
enhance the compound's utility. It is not very friendly to the environment and therefore does
not meet the requirements of green chemicals. Cyclohexyl phenyl ketone exhibits interesting
physical properties, including a moderate melting point and solubility in organic solvents,
which are advantageous for its application in various chemical processes.
One of the notable applications of cyclohexyl phenyl ketone is as a photo initiator in
UV-curable coatings and inks. Its ability to absorb UV light and initiate polymerization
reactions makes it an essential component in the formulation of high-performance coatings,
adhesives, and printing inks. The use of CHPK in these applications not only improves the
efficiency of the curing process but also contributes to the development of more durable and
environmentally friendly products. In addition to its role in photoinitiation, cyclohexyl phenyl
ketone has potential applications in the pharmaceutical industry, where it may serve as an
intermediate in the synthesis of biologically active compounds. Its structural features make it

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Chapter 1 Introduction
a valuable building block for the development of new drug candidates, particularly in the
search for novel therapeutic agents. CHPK can be explored for its performance in polymer
science, where it may influence the mechanical and thermal properties of polymeric
materials. Its unique combination of cyclohexyl and phenyl moieties could enhance the
material properties of polymers, leading to improved performance in various applications
[92–99]
.

Fig. 1.7. CHPK chemical transformation

1.3.2. Pinacolone
Pinacolone, also known as 3,3-dimethyl-2-butanone, is an organic compound with the
chemical formula C₆H₁₄O and a molecular weight of 102.18 g/mol. It belongs to the ketone
family and is structurally characterized by a branched carbon chain featuring a carbonyl
(C=O) group. Pinacolone is derived from the pinacol rearrangement of pinacol, which is a
vicinal diol, highlighting its importance in organic synthesis and its relevance in various
industrial applications. The synthesis of pinacolone typically involves the acid-catalyzed
rearrangement of pinacol, where the hydroxyl groups of pinacol are transformed into a
ketone. This process not only emphasizes the utility of pinacol as a precursor but also
showcases the reactivity of carbonyl compounds in organic reactions. The resulting
pinacolone is a colorless liquid with a pleasant minty odor and a boiling point of 130 °C,
making it suitable for various applications in chemical manufacturing and formulation [100].

Pinacolone finds significant applications in the synthesis of pharmaceutical

compounds and fine chemicals. It serves as an important intermediate in the production of

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Chapter 1 Introduction
various biologically active molecules, contributing to the development of therapeutic agents.
Due to its branched structure, pinacolone exhibits unique chemical properties, which make it
valuable for further transformations in organic synthesis. For example, it can undergo
condensation reactions to form larger molecules or be used in the synthesis of esters,
aldehydes, and other functionalized compounds.
Moreover, pinacolone has been explored for its potential applications in the
production of solvents and plasticizers. Its compatibility with a range of organic solvents
enables its use in formulations requiring specific solvent characteristics. Additionally,
pinacolone can serve as a building block in the manufacture of polymers, enhancing the
material properties and performance of various plastic products. The compound also holds
interest in the fragrance and flavor industry, where its pleasant odor can be utilized in
perfumery and flavoring agents. Its minty scent contributes to the sensory experience of
various products, further diversifying its applications [101–106].

Fig. 1.8. Applications of pinacolone

1.3.3. Diethyl ketone
Diethyl ketone (3-pentanone) is a colourless liquid organic compound with the
chemical formula C5H10O. It belongs to the class of ketones, which are characterized by a
carbonyl group (C=O) bonded to two alkyl groups. In this case, the two alkyl groups are ethyl
groups, making it a simple dialkyl ketone. Diethyl ketone has a mild, pleasant odor and is
moderately soluble in water. It is primarily used as a solvent in various industrial
applications, such as in the production of resins, lacquers, and coatings, as well as in the
extraction of oils and fats. Its volatility and ability to dissolve both polar and nonpolar

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Chapter 1 Introduction
substances make it a versatile solvent in organic synthesis and laboratory work. Although it is
relatively less common compared to other ketones like acetone or methyl ethyl ketone
(MEK), diethyl ketone’s unique properties make it valuable in specialized processes. It is also
used as an intermediate in organic chemical reactions, contributing to the synthesis of various
compounds.

Diethyl ketone is synthesized using various methods like Catalytic cross-coupling

reactions of ethyl halides, catalytic dehydration of secondary alcohols such as 3-pentanol, and
ketonization of propanoic acid, diethyl ketone can also be prepared through Friedel-Crafts
acylation of ethane using a suitable acyl chloride. The ketonization of propanoic acid method
highly sustainable process and no hazardous to the environment [107–120].

1.3.4. Propiophenones
1.3.4a. propiophenone
Propiophenone is an organic compound classified as an aryl ketone, consisting of a
phenyl group attached to a carbonyl group, which is further connected to an ethyl chain. Its
chemical formula is C₉H₁₀O, and it appears as a colourless to pale yellow liquid with a faint,
sweet odor. Propiophenone is a versatile chemical intermediate used primarily in the
synthesis of pharmaceuticals, fragrances, and agrochemicals. In the pharmaceutical industry,
it serves as a precursor in the synthesis of compounds like ephedrine, amphetamine, and
cathinone, which are used in medications for the treatment of conditions such as asthma,
nasal congestion, and ADHD. It is also employed in the production of certain sedative drugs.
In perfumery, propiophenone contributes to the development of various fragrances and
flavors due to its mild odor profile. The chemical can be synthesized through the Friedel-
Crafts acylation of benzene with propionyl chloride or by the oxidation of 1-phenyl-1-
propanol. Additionally, it is an important intermediate in the production of UV stabilizers and
certain polymer additives. While its use is widespread in chemical manufacturing,
propiophenone must be handled with care as it can be an irritant to the eyes and skin and is
harmful if ingested or inhaled. Due to its potential as a precursor for controlled substances, its
production and distribution are subject to regulatory oversight in various regions. Overall,
propiophenone is a key building block in organic synthesis, valued for its reactivity and role
in producing a variety of industrial and pharmaceutical products [121–130].

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Chapter 1 Introduction

Fig. 1.9. Propiophenone applications in medicinal chemistry.

1.3.4b. 3'-Chloro propiophenone

3'-Chloropropiophenone (m-CPP) is an organic compound that belongs to the class of
aryl ketones, specifically a derivative of propiophenone where a chlorine atom is substituted
at the meta-position of the benzene ring. Its chemical formula is C 9H9ClO, and it consists of a
phenyl group attached to a three-carbon chain that includes a carbonyl group (C=O) and a
chlorine atom on the aromatic ring. 3'-chloropropiophenone is a colorless to pale-yellow
liquid at room temperature, with moderate solubility in organic solvents and low solubility in
water. This compound has found applications in organic synthesis and pharmaceutical
intermediates due to its reactivity and functional groups. It serves as a starting material or an
intermediate in the synthesis of various compounds, including pharmaceuticals,
agrochemicals, and fine chemicals. The chloro and carbonyl functionalities provide reactivity
that enables further chemical modifications, such as halogen exchange, nucleophilic
substitution, and condensation reactions, making it a versatile building block in chemical
manufacturing. Moreover, it has been explored for use in chemical studies related to
polymerization and in the development of specialized compounds with biological activity.
Due to its reactive nature, safety precautions are essential when handling 3'-
chloropropiophenone, as exposure may irritate the skin, eyes, and respiratory system. Proper
storage in a well-ventilated area, away from direct sunlight and sources of ignition, is
recommended to prevent degradation and maintain its stability. In summary, meta-chloro
propiophenone is an important intermediate in organic chemistry, valued for its utility in the
synthesis of more complex molecules and compounds across various industries [131–138].

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Chapter 1 Introduction
1.3.4c. 3'-Methoxy propiophenone
3'-Methoxy propiophenone is an organic compound belonging to the class of aryl
ketones, characterized by a methoxy group (-OCH₃) attached to the meta position of a
benzene ring and a propiophenone backbone (a phenyl group bonded to a propionyl group).
Its molecular formula is C10H12O2, and it is used primarily as an intermediate in the synthesis
of various pharmaceuticals and fine chemicals. The presence of the methoxy group in the
meta position relative to the carbonyl group influences the compound's reactivity, especially
in electrophilic substitution reactions. 3'-methoxy propiophenone is commonly synthesized
through Friedel-Crafts acylation, where a propionyl chloride reacts with anisole in the
presence of a Lewis acid catalyst, such as aluminium chloride. It serves as a precursor in the
production of more complex organic molecules, including compounds with biological
activity. This compound is also useful in organic chemistry research for studying reaction
mechanisms and properties of ketones. Due to its aromatic structure and functional groups,
3'-methoxy propiophenone finds applications in the creation of fragrances, agrochemicals,
and other specialty chemicals. In addition to its synthetic versatility, the methoxy group
imparts a degree of electron-donating character, which can impact the compound's chemical
behaviour in various reactions. Safety and handling considerations include avoiding
prolonged exposure, as it can irritate the skin and eyes. Its widespread utility in chemical
synthesis makes 3'-methoxy propiophenone a valuable compound in both academic and
industrial settings [139–144].
Table. 1.1. Physical Properties of propiophenone
Property Value Value Value
Chemical name Propiophenone 3'-Cloro 3'-Methoxy
propiophenone propiophenone
Chemical formulae C9H10O C9H9ClO C10H12O2
Mass 134.17 g·mol−1 168.62 164.20 g/mol
Appearance Colourless White to Yellow -
liquid
Solubility in water Insoluble Insoluble Slightly soluble
Density (at STP) g/mL 1.0087 1.100 1.016
Boiling point (ºC) 218 °C 43.0 259 ºC
Melting point (ºC) 18.6 °C 124.0 3.6 ºC
Vapor pressure mmHg 1.3±0.5 0.0±0.5 0.0±0.5

18
Chapter 1 Introduction
1.4. Aims and objectives
The present thesis work aimed to design and development of heterogeneous catalyst
that can employed to synthesize of industrial applicable ketones from biomass-derived
carboxylic acids. The thesis works mainly focused on the preparation of cyclohexyl phenyl
ketone, pinacolone, propiophenone, 3-methoxy propiophenone, and 3-chloro propiophenone.
 Design and synthesis of high basic and high lattice energy metal oxides-based catalysts
for the synthesis of cyclohexane phenyl ketone from benzoic acid and cyclohexane carboxylic
acid.
 Synthesis of a supported La2O3 and Mn3O4 containing metal oxide catalysts for the
preparation of cyclohexyl phenyl ketone.
 Understanding the role of the basic and acidic nature of catalysts for the cross-
ketonization of carboxylic acids.
 Preparation of high basic La2O3 and MgO along with high lattice energy ZrO 2 catalysts to
synthesize pinacolone from pivalic acid with acetic acid through the cross-ketonization
method.
 Understand the activity of the catalysts by changing the acidic and basic strength of the
catalysts for the ketonization reaction.
 Design of Al2O3 containing mixed oxide catalysts with various acidic and basic metal
oxides for the synthesis of propiophenone and substituted propiophenones.
 Investigation of catalyst stability and establishment of reasons for stability and/or
deactivation.
 Evaluation of reaction parameters to attain high conversion and yield for the targeted
catalytic transformations at optimized reaction conditions.
1.5. Thesis organization
The thesis comprised seven chapters. The chapters are as follows:
Chapter 1. This chapter gives a detailed introduction to synthesizing ketones from carboxylic
acids through the ketonization process. The biomass source of carboxylic acids and its synthesis
process are also discussed in this chapter. The various types of ketonization reactions are
covered. Detailed information regarding the synthesis, physical and chemical properties, and
application of cyclohexyl phenyl ketone, pinacolone, propiophenone, 3-methoxy
propiophenone, and 3-chloro propiophenone are covered with all details.
Chapter 2. This chapter describes an overview of the research work carried out on the synthesis
and characterization of simple metal oxides, supported metal oxides, and mixed metal oxide
catalysts. The possible reaction mechanism with acidic and basic metal oxide utilized for

19
Chapter 1 Introduction
ketonization reactions were discussed. This chapter provides an outline of the catalytic systems
utilized in the synthesis of ketones through the ketonization method.
Chapter 3. his chapter presents the experimental details used to synthesize catalysts and the
characterization techniques to analyze their physiochemical properties. The elaborated
information on the characterization techniques for the catalysts includes N 2-physisorption study
(BET), powder X-ray diffraction (XRD), H 2 temperature-programmed reduction (H2-TPR),
temperature-programmed desorption of CO2 (CO2-TPD), temperature-programmed desorption
of NH3 (NH3-TPD), Raman spectroscopy, Fourier transform infrared spectroscopy (FT-IR),
Thermogravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS) are explained
in detail. The experimental methods used for the synthesis of fine chemicals and their analysis
process were also explained in detail.
Chapter 4. This chapter presents the synthesis of cyclohexyl phenyl ketone from benzoic acid
with cyclohexane carboxylic acid. It is further divided into two sections. Section 4.1 presents
the cross-ketonization of benzoic acid with cyclohexane carboxylic acid to cyclohexane phenyl
ketone over lanthanum oxide impregnated on alumina catalysts. Section 4.2 described the cross-
ketonization of benzoic acid with cyclohexane carboxylic acid to cyclohexane phenyl ketone
over manganese oxide impregnated on alumina catalysts
Section 4.1. This section describes the cross-ketonization of benzoic acid with cyclohexane
carboxylic acid to cyclohexyl phenyl ketone using lanthanum oxide supported on alumina
catalysts. A series of lanthanum oxide supported on alumina catalysts were prepared and
characterized by techniques like N2-physisorption, XRD, H2-TPR, CO2-TPD, NH3-TPD, TGA,
FT-IR, and XPS to learn about their surface and structural properties. The role of acidity and
basicity and other characteristics of catalysts on the ketonization of benzoic acid and
cyclohexane carboxylic acid was explained. The catalytic activity was studied at different
reaction parameters like varying lanthanum oxide loading on alumina, temperature, Feed mole
ratio of reactants, and GHSV. The time on stream analysis of the catalyst is also studied for 24
hours, and the stability of the catalyst is confirmed by post-reaction characterization.
Section 4.2. This section describes the cross-ketonization of benzoic acid with cyclohexane
carboxylic acid to cyclohexyl phenyl ketone using manganese oxide supported on alumina
catalysts. A series of manganese oxides supported on alumina catalysts were prepared and
analyzed by characterization techniques like N 2-physisorption, XRD, H2-TPR, CO2-TPD, NH3-
TPD, RAMAN, and XPS to learn about their surface and structural properties. The role of
acidity and basicity and other characteristics of catalysts on the ketonization of benzoic acid and
cyclohexane carboxylic acid was explained. The catalytic activity was studied at different

20
Chapter 1 Introduction
reaction parameters like varying manganese oxide loading on alumina, temperature, Feed mole
ratio of reactants, and GHSV. The time and stream analysis of the catalyst is also studied for 24
hours, and the stability of the catalyst is confirmed by post-reaction characterization.
Chapter 5. This chapter presents the synthesis of pinacolone from pivalic acid with acetic acid
using the ketonization method. It is further divided into two sections. 5.1 explains the cross-
ketonization of pivalic acid with acetic acid to pinacolone over La 2O3-ZrO2 mixed oxide
catalysts. Section 5.2 described the cross-ketonization of pivalic acid with acetic acid to
pinacolone over MgO-ZrO2 mixed oxide catalysts
Section 5.1. This section describes the cross-ketonization of pivalic acid with acetic acid to
pinacolone using La2O3-ZrO2 mixed oxide catalysts. A series of La-Zr mixed oxides were
prepared with changing molar ratios and calcination temperatures and analyzed by
characterization techniques like N2-physisorption, XRD, H2-TPR, CO2-TPD, NH3-TPD, TGA,
and XPS to learn about their surface and structural properties. The role of acidity/basicity and
other characteristics of catalysts on the ketonization of pivalic acid and acetic acid was
explained. The catalytic activity was studied at different reaction parameters like varying
lanthanum oxide mole ratio, calcination temperature reaction temperature, feed mole ratio of
reactants, and WHSV. The time on-stream analysis of the catalyst is studied for 20 hours to
know the catalyst's stability and reusability.
Section 5.2. In this section, a series of MgO-ZrO2 mixed oxide catalysts were prepared with
various mole ratios with varying calcination temperatures and explored for cross-ketonization of
pivalic acid with acetic acid to pinacolone. The characteristics of the catalysts were established
through various characterization techniques. The effect of MgO-ZrO 2 molar ratios on the cross-
ketonization reaction was established. The catalytic activity was studied at different reaction
parameters like varying magnesium oxide mole ratio, calcination temperatures, reaction
temperatures, feed mole ratio of reactants, and WHSV. The time on-stream analysis of the
catalyst is studied for 24 hours to know the catalyst's stability.
Chapter 6. This chapter describes the study on alumina containing various metal mixed oxide
catalysts. MgO-Al2O3 mixed oxide catalysts synthesis with varying molar ratios and explore for
the cross ketonization of benzoic acid, 3-methoxy benzoic acid, 3-chloro benzoic acid with
propanoic acid to propiophenone, 3-methoxy propiophenone, and 3-chloro propiophenone
respectively. The characteristics of the catalysts were established through various
characterization techniques like N 2-physisorption, powder XRD, CO2, NH3-TPD, TGA, and
XPS analysis. The catalytic activity was studied at different reaction parameters like varying
magnesium oxide mole ratio, reaction temperatures, feed mole ratio of reactants, and WHSV.

21
Chapter 1 Introduction
The time on-stream analysis of the catalyst is studied up to 20 hours to know the catalyst's
stability.
Chapter 7. This chapter describes the summary of the work carried out in the thesis work
“studies on heterogeneous catalysts for ketonization of carboxylic acids to ketones” and the
important conclusions drawn from the results obtained in this work. The scope for the future
work is also highlighted.

1.6. Highlights of thesis work

 Lanthanum oxide supported on Al2O3 catalysts provides a moderate basic site along
with acidic alumina support leading to the ketonization of BA with CHCA to CHPK.
 A high amount of lanthanum oxide leads to the formation of La2O2CO3 which
provides a high basic nature and reduces the conversion of BA to CHPK.
 Manganese oxide supported on Al2O3 catalysts in which a high amount of manganese
oxide leads to the formation of basic Mn2O3 and Mn3O4.
 The combination of the basic and acidic nature of Mn3O4/Al2O3 catalysts showed
a high conversion of BA with CHCA to CHPK.
 Cross-ketonization of pivalic acid with acetic acid to produce pinacolone was studied
over ZrO2 containing La2O3 and MgO mixed oxide catalysts.
 The formation of mixed oxide with changing lattice structure and creation of oxygen
vacancies advantage for the conversion of PA and AA to synthesis pinacolone.
 The creation of moderate basic and acidic properties of La 2O3, MgO along ZrO2
enhances the ketonization reaction.
 The ketonization of meta-substituted benzoic acid with propanoic acid to generate
propiophenones with MgO-Al2O3 catalyst was studied by varying mole ratio,
temperature, and WHSV etc.
 Various metal oxides like (La2O3, CeO2, MgO, MnO2, Fe2O3, and ZrO2) mixed with
Al2O3 with a 1:3 mole ratio prepared and studied for ketonization of BA with Pr. Acid
to propiophenone.
 The relationship between the structural properties of the prepared catalysts and their
catalytic performance on cross-ketonization was evaluated.

22
 Chapter 1 Introduction
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