Chemistry of Carbohydrates 1

2022
Pharmaceutical
Chemistry-II
(Biochemistry)
Muhammad Wajid
Pharm-D, M.Phil, PhD (Scholar)
Assistant Professor
Gulab Devi Institute of Pharmacy, GDEC, Lahore.
[Type text] Page 0

Chemistry of
Carbohydrates
Muhammad Wajid, Assistant Professor, Gulab Devi Institute of Pharmacy, GDEC, Lahore Page 1
Carbohydrates:
Carbohydrates are the most abundant organic molecules in nature. They are primarily
composed of the elements carbon, hydrogen and oxygen. Some carbohydrates also contain
Sulphar, Nitrogen or Phosphorus. The name carbohydrate literally means “hydrates of
carbon”. The empirical formula of carbohydrates is (CH2O)n where n≤3. However, there are
several non-carbohydrate compounds (e.g. acetic acid (C2H4O2) and lactic acid (C3H6O3) and
some of the genuine carbohydrates (e.g. Rhamnohexose (C6H12O5) and deoxyribose
(C5H10O4) do not satisfy the general formula. Hence carbohydrates cannot be always
considered as hydrates of carbon.
“Carbohydrates may be defined as polyhydroxy aldehydes or ketones or compounds

which produce them on hydrolysis”.
OR
“Carbohydrates are defined chemically as aldehydes or ketone derivatives of the higher

polyhydric alcohols, or compounds which yield these derivatives on hydrolysis”.
Carbohydrates are often referred to as saccharides (Greek: sakcharon-sugar). The word

carbohydrates can be traced back to Germans, who calls them “Kohlenhydrates”. It was
termed carbohydrates in English.
CHO CH2OH
H OH O
HO H HO H
H OH H OH
H OH H OH
CH2OH CH2OH
D-Glucose D-Fructose
Functions of Carbohydrates:
Carbohydrates participate in a wide range of function. These functions are:
o Carbohydrates are the most abundant dietary source of energy (4 Cal/g) for all
organisms.
o They are precursors for many organic compounds (fats, amino acids).
o They are the components of cell membrane (glycoproteins and glyco-lipid) are
participate in cellular functions such as cell growth, adhesion and fertilization.
o Carbohydrates also serve as the storage form of energy (glycogen) to meet the
immediate energy demands of the body.
o Certain carbohydrate derivatives are used as drugs like cardiac glycosides/antibiotics.
o They are structural components of many organisms. These include the fiber
(cellulose) of plants, exoskeleton of some insects and the cell wall of microorganism.
Classification of Carbohydrates:
They are broadly classified into three major groups.
o Monosaccharides
o Oligosaccharides
o Polysaccharides
Monosaccharides:
Monosaccharides (Greek: mono-one) are the simplest group of carbohydrates and are often
referred to as simple sugars.
General formula: CnH2nOn
They cannot be further hydrolyzed. They contain 3-9 carbon atoms. They consist of carbonyl
group (aldehyde or ketone) and several hydroxyl groups.
Physical Properties of Monosaccharides:

o Most are called sugars because they taste sweet.
o Crystalline solids at room temperature.
o Because of the many –OH groups, they form hydrogen bonds with water molecules
and are extremely water soluble.
o Polar with high melting point (because of OH).
o Colorless.
Subdivision of Carbohydrates:
They can be subdivided further:
o Depending upon whether aldehyde (– CHO) or ketone (– CO) groups

o Depending upon the number of carbon atoms
Classification Based on Functional Group:
Aldose:
When the functional group in monosaccharides is an aldehyde (-CHO) group, they are known
as aldoses e.g. glyceraldehyde, glucose etc.
Ketoses:
When the functional group is a keto (-CO) group, they are referred to as ketoses e.g.
Dihydroxyacetone, fructose etc.
Classification Based on Number of Carbon Atoms:

Based on the number of carbon atoms, the monosaccharides are classified as:
o Trioses (3C)
o Tetroses (4C)
o Pentoses (5C)
o Hexoses (6C)
o Heptoses (7C) etc.
These terms along with functional groups are used while naming monosaccharides. For
instance, glucose is an aldohexose while fructose is a ketohexoses.
Sr. Monosaccharide Formula Aldoses Ketoses

No.
1. Trioses (C3H6O3) Glyceraldehyde Dihydroxyacetone
2. Tetroses (C4H8O4) Erythrose Erythrulose
3. Pentoses (C5H10O5) Ribose Ribulose
4. Hexoses (C6H12O6) Glucose Fructose
5. Heptoses (C7H14O7) Glucoheptose Sedoheptulose
Trioses:
The smallest monosaccharides, for which n=3, are dihydroxyacetone and D and L-
glyceraldehyde. Dihydroxyacetone is called a ketose because it contains a keto group,
whereas glyceraldehyde is called an aldose because it contains an aldehyde group.
Glyceraldehyde has a single asymmetric carbon and, thus, there are two stereoisomers of
this sugar. D-Glyceraldehyde and L-glyceraldehyde are enantiomers, or mirror images of
each other.
CHO CHO CH2OH
H OH HO H O
CH2OH CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde Dihydroxyacetone
Hexoses:
These contain six carbon atoms. They occur free, combined as oligo- and polysaccharides, or
forming the sugar part of glycosides.
D- Glucose:
Glucose is a monosaccharide. It is the one of the most important carbohydrates. Its chemical
formula is C6H12O6. Glucose is an aldoses- aldehyde group at one end. It exists in D and L
conformation. D-confirmation is the most abundant. It is commonly known as dextrose or
grape sugar. It is white crystalline solid which is soluble in water and insoluble in organic
liquids.
CHO CHO
CH2OH
H OH HO H
O H
H
HO H H OH
H
OH H
H OH HO H
OH OH
H OH HO H
H OH
CH2OH CH2OH
L-Glucose a- D-Glucose
D-Glucose
D- Galactose:
The galactose is an isomer of glucose, is also an aldohexose. Its formula is C6H12O6. It is an
epimer of glucose and differs in orientation of H and OH on carbon 4. It is not found in the
free form in nature.
CHO CHO
CH2OH
H OH HO H
O H
OH
HO H H OH
H
OH H
HO H H OH
H OH
H OH HO H
H OH
CH2OH CH2OH
L-Galactose a-D- Galactose

D-Galactose
D- Fructose:
It is a ketohexose and commonly called as fruit sugar, as it occurs free in fruits. It is very
sweet sugar, much sweeter than sucrose and more reactive than glucose. It occurs as a
constituent of sucrose and also of the polysaccharide inulin.
CH2OH CH2OH
O O
CH2OH CH2OH
O
HO H H OH
H OH
H OH HO H
H OH
H OH HO H H
OH
CH2OH CH2OH
D- Fructose L- Fructose a- D- Fructose

Oligosaccharides:
Oligosaccharides (Greek: oligo-few) contain 2-10 monosaccharide molecules which are
liberated on hydrolysis. Based on the number of monosaccharide units present, the
oligosaccharides are further subdivided to disaccharides, trisaccharides etc.
Disaccharides:
Among the oligosaccharides, disaccharides are the most common. As it is evident from the
name, a disaccharide consists of two monosaccharide units (similar or dissimilar) held
together by a glycosidic bond. Maltose, isomaltose, and cellobiose are all homodisaccharides
because they each contain only one kind of monosaccharide, namely, glucose. They are
crystalline, water-soluble and sweet to taste.
Types of Disaccharides:
The disaccharides are of two types:
o Reducing disaccharides with free aldehyde or keto group e.g. maltose, lactose.
o Non-reducing disaccharides with no free aldehyde or keto group e.g. sucrose,
trehalose.
Reducing Disaccharides:
Maltose:
Maltose is composed of two α-D-glucose units held together by α (1→4) glycosidic bond.
The free aldehyde group present on C1 of second glucose due to which it has reducing
properties. On hydrolysis maltose yields two molecules of glucose.
Isomaltose:
In isomaltose, the glucose units are held together by α (1→6) glycosidic linkage. In
isomaltose, C-1 of one glucose is linked to C-6 of the other, and the configuration is α.
Cellobiose:
Cellobiose is another disaccharide, identical in structure with maltose, except that the former
has β (1→4) glycosidic linkage. Cellobiose is formed during the hydrolysis of cellulose.
CH2OH CH2OH
H O O H
H
H
OH H O H
OH
OH H OH
H OH H OH
-D- Glucose
(1 4) -D-Glucose
Cellobiose
Lactose:
Lactose is more commonly known as milk sugar since it is the disaccharide found in milk.
Lactose is composed of β-D-galactose and β-D-glucose held together by β (1→4) glycosidic
bond. The anomeric carbon of C1 glucose is free, hence lactose exhibits reducing properties.
Lactose of milk is the most important carbohydrate in the nutrition of young mammals. It is
hydrolysed by the intestinal enzyme lactase to glucose and galactose.
CH2OH CH2OH
OH O O OH
H
H
OH H O H
OH
H H H
H OH H OH
-D- Galactose
(1 4) -D-Glucose
Lactose
Non-Reducing Disaccharides:
Sucrose:
Sucrose (cane sugar) is made up of α-D-glucose and β-D-fructose. The two monosaccharides
are held together by a glycosidic bond (α1→β2), between C1 of α-glucose and C2 of β-
fructose. . The reducing groups of glucose and fructose are involved in glycosidic bond,
hence sucrose is a non-reducing sugar. Sucrose is the most abundant among the naturally
occurring sugars. It has distinct advantages over other sugars as a storage and transport form.
This is due to the fact that in sucrose, both the functional groups (aldehyde and keto) are held
together and protected from oxidative attack. It is sweeter than most other common sugars
(except fructose) namely glucose, lactose and maltose.
CH2OH
H O H CH2OH H
O
H H OH
OH
OH O CH2OH
OH H
H OH
-D-Glucose  (1 2) -D-Fructose
Sucrose
Polysaccharides:
Polysaccharides (or simply glycans) consist of repeat units of monosaccharides or their
derivatives, held together by glycosidic bonds. Polysaccharides are linear as well as branched
polymers. The occurrence of branches in polysaccharides is due to the fact that glycosidic
linkages can be formed at any one of the hydroxyl groups of a monosaccharide. The most
common constituent of polysaccharides is D-glucose, but D-fructose, D-galactose, L-
galactose, D-mannose, L-arabinose and D-xylose are also common. Common
monosaccharide derivatives in polysaccharides include the amino sugars (D-glucosamine and
D-galactosamine), their derivatives (N-acetylneuraminic acid and N-acetylmuramic acid),
and simple sugar acids (glucuronic and iduronic acids).
Types of Polysaccharides:
Polysaccharides are of two types:
o Homopolysaccharides / Homoglycans
o Heteropolysaccharides / Heteroglycans
Homopolysaccharides:
If a polysaccharide contains only one kind of monosaccharide molecule, or on hydrolysis
yield only a single type of monosaccharide units are called Homopolysaccharides /
Homoglycans. They are named based on the nature of the monosaccharide unit. Thus,
glucans are polymers of glucose whereas fructosan are polymers of fructose.
Starch:
Starch is a homopolymer composed of D-glucose units held by α-glycosidic bonds. It is
known as glucosan or glucan. Starch consists of two polysaccharide components-water
soluble amylose (15-20%) and a water insoluble amylopectin (80-85%). Chemically, amylose
is a long unbranched chain with 200-1,000 D-glucose units held by α (1→4) glycosidic
linkage. Amylopectin, on the other hand, is a branched chain with α (1→6) glycosidic bond
at the branching points and α (1→4) linkage everywhere else. Amylopectin molecule
containing a few thousand glucose units looks like a branched tree. 20 - 30 glucose units per
branch.
Glycogen:
Glycogen is the carbohydrate reserve in animals, hence often referred to as animal starch. The
structure of glycogen is similar to that of amylopectin with more number of branches.
Glucose is the repeating unit in glycogen joined together by α (1→4) glycosidic bond, and α
(1→6) glycosidic bond at branching point. Glycogens have a complex structure of highly
branched chains. A branch point occurs for every 12 to 18 glucose units. The molecular
weight (up to 1 x 108) and the number of glucose units (up to 25,000) vary in glycogen
depending on the source from which glycogen is obtained.
Dextran:
Dextran is a storage polysaccharide which are α (1⎯→6) linked polysaccharides of D-glucose
with branched chains. Because the main polymer chain is α (1⎯→6) linked, the repeating unit
is isomaltose. The branch points may be 1⎯→2, 1⎯→3, or 1⎯→4 in various species. When
starch is partially hydrolyzed by the action of acids or enzymes, it is broken down into a
number of products of lower molecular weight known as dextrins.
Inulin:
Inulin is a polymer of fructose i.e. fructosan and has a low molecular weight (MW = 5000).
It has β (1→2) glycosidic linkage between fructose residues and is levorotatory.
Polysaccharide is easily soluble in water. Inulin is not utilized by the body.
Cellulose:
The structural polysaccharides have properties that are dramatically different from those of
the storage polysaccharides, even though the compositions of these two classes are similar.
The structural polysaccharide cellulose is the most abundant natural polymer in the world.
Cellulose is composed of β-D-glucose units linked by β (1→4) glycosidic bond. Hydrolysis
of cellulose yields a disaccharide cellobiose, followed by β-D-glucose.
Chitin:
Chitin is composed of N-acetyl D-glucosamine units held together by β (1→4) glycosidic
bond. It is a structural polysaccharide found in the exoskeleton of some invertebrates e.g.
insects, crustaceans.
Heteropolysaccharides:
When the polysaccharides are composed of different types of sugars or their derivatives, they
are referred to as heteropolysaccharides or heteroglycans.
Chemically they are formed mostly of repeated disaccharides units that contain amino sugar
(N-acetyl glucosamine or N-acetyl galactosamine) uronic acid or glucuronic acid.
Mucopolysaccharides:
Mucopolysaccharides are heteroglycans made up of repeating units of sugar derivatives,
namely amino sugars and uronic acids. These are more commonly known as
glycosaminoglycans (GAG).
Some of the mucopolysaccharides are found in combination with proteins to form

mucoproteins or mucoids or proteoglycans. Mucoproteins may contain upto 95%
carbohydrate and 5% protein. When carbohydrate content is > 4 per cent, they are called
Mucoproteins and when < 4 per cent they are called as Glycoproteins.
Classification:
Although there is no agreement on classification, the nitrogenous heteropolysaccharides
(mucopolysaccharides) are classified as follows:
MPS
Neutral Acidic
Sulphate Free Sulphate Containing
Acidic Sulphate free MPS:
Hyaluronic Acid:
Hyaluronic Acid is sulphate free mucopolysaccharides. It is composed of repeating units of
N-acetyl glucosamine and D-Glucuronic acid. On hydrolysis, it yields equimolecular
quantities of D-Glucosamine, D-Glucoronic acid and acetic acid.
COOH CH2OH
H H O
OH O O
H
H H O
H
H OH H
H OH H NHCOCH3
Glucoronic acid N-acetyl glucosamine
Chondroitin:
Chondroitin is another sulphate free acid mucopolysaccharides. It differs from hyaluronic
acid only in that it contains N-acetyl galactosamine instead of N-acetyl glucosamine.
COOH CH2OH
H OH O
OH O O
H
H H O
H
H H H
H OH H NHCOCH3
Glucoronic acid N-acetyl galactosamine
Chondroitin
Sulphate Containing Acid MPS:

Keratan Sulphate (Kerato Sulphate):
It is a sulphate containing acid MPS. It is composed of repeating disaccharide unit consisting
of N-acetyl glucosamine and D-galactose.
CH2OH CH2OSO3-
HO H O
OH O OH H O
H H O
H
H H H
H OH H NHCOCH3
D-Galactose N-acetyl glucsamine-6-Sulphate
Keratan Sulphate
Types of Keratan Sulphate:

Two-types have been described. They are found in tissues combined with proteins. They are:
o Keratan SO4 I
o Keratan SO4 II
Chondroitin sulfates:
Chondroitin sulfate (Greek: chondros-cartilage) is a major constituent of various mammalian

tissues (bone, cartilage, tendons, heart, valves, skin, cornea etc). Chondroitin sulfate consists
of repeating disaccharide units composed of D-glucuronic acid and N-acetyl D-
galactosamine.
If the sulfate group is found on C4 of N-acetyl galactosamine is called chondroitin 4-sulfat. If

the sulfate group is at C6 is called chondroitin 6-sulfate.
COOH CH2OH
H OSO3- O
OH O O
H
H H O
H
O H H H
H OH H NHCOCH3
D-Glucuronic acid N-acetyl galactosamine-4-Sulphate
Chondroitin 4-Sulphate
Dermatan sulfate:
The name dermatan sulfate is derived from the fact that this compound mostly occurs in the
skin. It is structurally related to chondroitin 4-sulfate. The only difference is that there is an
inversion in the configuration around C5 of D-glucuronic acid to form L-iduronic acid.
Heparin:
Heparin is an anticoagulant (prevents blood clotting) that occurs in blood, lung, liver, kidney,
spleen etc. Heparin helps in the release of the enzyme lipoprotein lipase which helps in
clearing the turbidity of lipemic plasma. Heparin is composed of alternating units of N-sulfo
D-glucosamine 6-sulfate and glucuronate 2-sulfat.
Fischer Projection:
The first system for doing this was developed by Fischer and Rosanoff around 1900. Fischer
first developed a method for drawing carbohydrates in two dimensions, and a convention
with respect to orientation, so as to indicate their three dimensional structure, so called
Fischer projection. The Fischer Projection consists of:
o The horizontal lines represented by the wedge bond

o The vertical lines represented by the dashed bond.
The point of intersection between the horizontal and vertical lines represents the central
carbon.
Vertical ines are going back behind the
plane of the page
Substituents
C
Carbon
Horizontal lines are comming out
of the plane of the page
D and L-isomers:
The orientation of the -H and -OH groups around the carbon atom just adjacent to the
terminal primary alcohol carbon e.g. C5 in glucose determines the series. When the – OH
group on this carbon is on the right, it belongs to D-series, when the –OH group is on the left,
it is a member of L-series. It may be noted that the naturally occurring monosaccharides in
the mammalian tissues are mostly of D-configuration. The enzyme machinery of cells is
specific to metabolize D-series of monosaccharides.
Haworth Projection:
Haworth in 1929 suggested that the six-membered ring forms of the sugars be called
pyranoses, because pyran possesses the same ring of 5 carbons and oxygen (6 membered
rings).
Similarly Haworth designated sugar containing 5-membered rings as the furanoses, because
furan contains the same ring. O
o Cyclization via intramolecular hemiacetal (hemiketal) formation

o C1 becomes chiral upon cyclization called anomeric carbon
o Groups on the left of the Fischer projection are above the ring
Pyran
o Groups on the right of the Fischer projection are below the ring
o For cyclic form of D-glucose sugar the CH2OH group is always up. O
o Anomeric carbon contain –OH which may be α or β
o If -OH on C1 is Cis to -CH2OH group, it is a β-D sugar
o If -OH on C1 is trans to -CH2OH group, it is a α-D sugar
Furan
CHO 1 CHO
2
H OH H OH
H H OH H
HO H 3 6 1
HO H 5 4 3 2
4 HOH2C CHO
H OH H OH
OH OH H OH
H OH 5
H OH
CH2OH 6 CH2OH
Up on Down on
D-Glucose
the ring the ring
H
HOH2C
H
H CH2OH
O O
H O HO
H OH H
OH H
OH H
OH H
H OH
H OH
CH2OH
H O
H OH
OH H
H
OH
H OH
CH2OH CH2OH
O H H O OH
H
H H
OH H OH H
OH OH OH H
H OH H OH
-D-Glucopyranose -D-Glucopyranose
CH2OH 1 CH2OH
2
O O
3
HO H HO H H H OH O
6 5 4 2 1
4 3
H OH H OH HOH2C CH2OH
5
H OH H OH OH OH H
6
CH2OH CH2OH
D-Fructose
Up on Down on
the ring the ring
H H
CH2OH CH2OH O
O O
H OH
H OH
OH CH2OH
H CH2OH
OH H
OH H
CH2OH
O OH
H OH
CH2OH
H
OH H
CH2OH CH2OH
O CH2OH OH
O
H OH
H OH
H OH
H CH2OH
OH H
OH H
D-Fructofuranose
-D-Fructofuranose
Mutarotation:
Mutarotation is defined as the change in the specific optical rotation representing the
interconversion of α and β forms of D-glucose to an equilibrium mixture. Mutarotation is a
term given to the change in the observed optical rotation of a substance with time.
The α and β anomers of glucose have different optical rotations. The specific optical rotation
of a freshly prepared glucose (α anomer) solution in water is +112.2° which gradually
changes and attain equilibrium with a constant value of +52.7°. In the presence of alkali, the
decrease in optical rotation is rapid. The optical rotation of β-glucose is +18.7°.
The equilibrium mixture contains 63% β-anomer and 36% α-anomer of glucose with 1%
open chain form. In aqueous solution the β form is more predominant due to its stable
conformation. The α and β forms of glucose are interconvertible which occurs through a
linear form. The latter, as such, is present in an insignificant quantity.
o All reducing sugars exhibit mutarotation

o The phenomena of mutarotation occur slowly in aqueous medium.
CHO
CH2OH CH2OH
H OH
O H H O OH
H
HO HO H H
OH H OH H
H OH
OH OH OH H
H OH
H OH H OH
CH2OH
D-Glucopyranose D-Glucose -D-Glucopyranose
112.20
18.70
-D-Glucose Equilibriummixture -D-Glucose
112.20 52.70 18.70
Anomers:
Isomeric forms of monosaccharides that differ only in their configuration about the
hemiacetal or hemiketal carbon are called anomers. The hemiacetal (or carbonyl) carbon
atom is called anomeric carbon. The α and β cyclic forms of D-glucose are known as anomer.
In case of α anomer, the -OH group held by anomeric carbon is on the opposite side of the
group -CH2OH of sugar ring. The reverse is true for β-anomer. The anomers differ in certain
physical and chemical properties.
CH2OH CH2OH
H O OH O H
H
H H
OH H OH H
OH H OH
OH
H OH H OH
-D-Glucose -D-Glucose
Hemiacetal and Hemiketal:
The hydroxyl group of monosaccharides can react with its own aldehyde or keto functional
group to form hemiacetal and hemiketal. Thus, the aldehyde group of glucose at C1 reacts
with alcohol group at C5 to form two types of cyclic hemiacetal namely α and β.
O
OH
R' OH
R'' H
R'' H
OR'
Aldehyde Alcohol
Hemiacetal
OH
O
R' OH "R R"'

"R R"'
OR'
Ketone Alcohol Hemiketal
Acetals, Ketals, and Glycosides:
Hemiacetal and hemiketal can react with alcohols in the presence of acid to form acetals and
ketals. The pyranose and furanose forms of monosaccharides react with alcohols in this way
to form glycosides with retention of α or β configuration at the C-1 carbon. The new bond
between the anomeric carbon atom and the oxygen atom of the alcohol is called a glycosidic
bond. This reaction is another example of a dehydration synthesis.
R O H R' O
H
C R''-OH C H2O
R'
R' OH O R''
Hemiacetal
Acetal
R'''
R O R O
R''' H2O
C R''-OH C
O R"
R' OH R'
Hemiketal Ketal
Types of Glycosidic Bond:

Three types of glycosidic bonds are:
o O-glycosidic bond
o Alpha linkage
o Beta Linkage
o S-glycosidic bond
o N-glycosidic bond
Epimers:
If two monosaccharides differ from each other in their configuration around a single specific
carbon (other than anomeric) atom they are referred to as epimers to each other. For instance,
glucose and galactose are epimers with regard to carbon 4 (C4-epimers). They differ in the
arrangement of -OH group of glucose at C4. Glucose and mannose are epimers with regard to
carbon 2 (C2-epimer).
CHO CHO CHO CHO
H OH H OH H OH HO H
HO H HO H HO H HO H
H OH HO H H OH H OH
H OH H OH H OH H OH
CH2OH CH2OH CH2OH CH2OH
D-Galactose D-Glucose D-Mannose

D-Glucose
Enantiomers:
Enantiomers are a special type of stereoisomers that are mirror images of each other. The two
members are designated as D- and L-sugar. D-glucose and L-Glucose and D-galactose and L-
galactose are mirror images of each other. The term diastereomers is used to represent the
stereoisomers that are not mirror images of one another.
Chair conformations of sugars:

Often 6-membered monosaccharides can be represented by chair conformation. In this
representation bonds around stereogenic centers are drawn as equatorial and axial. The OH
group at the anomeric carbon may occupy the axial position this is α isomer, while if it is at
the equatorial this gives the β isomer. The rest of the substituent (-OH groups) occupy
equatorial positions this results in the most stable conformation.
H OH H OH
H O H O
HO HO
HO H HO OH
H OH H OH
H OH H H
-D-Glucose -D-Glucose
Mutarotation of fructose:
Fructose also exhibits mutarotation. In case of fructose, furanoses (five-membered) ring is
converted to the pyranoses ring (six-membered), till equilibrium is attained. And fructose has
a specific optical rotation of -92° at equilibrium. The conversion of dextrorotatory (+) sucrose
to levorotatory fructose.
Optical Isomerism
Presence of asymmetric C atom confers optical activity to the carbohydrates. When a beam of
plane polarized light is passed through a carbohydrate solution. It will rotate the light either,
to right DEXTRO ROTATORY (d) or (+) or to left LEVO ROTATORY (l) or (-)
Asymmetrical (chiral) carbon:

Having 4 different groups attached to the same carbon is called chiral carbon.
Chemical Reactions of Monosaccharides:

Oxidation:
Depending on the oxidizing agent used, the terminal aldehyde (or keto) or the terminal
alcohol or both the groups may be oxidize. These reactions produce different products
according to the reagent used:
Bromine water
It is a mild oxidizing reagent. It selectively oxidizes the -CHO group into -COOH, and
converts aldoses to the corresponding aldonic acids (Ruff Degradation).
COOH
CHO
H OH
H OH
Br2/H2O HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
CH2OH
D-Gluconic acid
D-Glucose
Nitric acid
It is a strong oxidizing agent. It oxidizes both the -CHO and terminal -CH2OH of an aldose to
-COOH groups and these dicarboxylic acids are known as aldaric acids
COOH
CHO
H OH
H OH
HNO3 HO H
HO H
H OH
H OH
H OH
H OH
COOH
CH2OH
D-Glucose D-Glucaric acid
Controlled oxidation
Controlled oxidation is carried out by first protecting the -CHO group, followed by oxidation
of the -CH2OH group, or in one step by the aid of a specific enzyme to give alduronic acid,
e.g. oxidation of glucose into glucuronic acid.
CHO
CHO
H OH
H OH
Controlled Oxidation HO H
HO H
H OH
H OH
H OH
H OH
COOH
CH2OH
D-Glucose D-Glucuronic acid
Reduction:
When treated with reducing agents such as sodium amalgam, the aldehyde or keto
group of monosaccharide is reduced to corresponding alcohol.
OH
CHO
H OH
H OH
HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
CH2OH
D-Glucose D-Sorbitol
The important monosaccharides and their corresponding alcohols are given below:
D-Glucose ----------------- D-Sorbitol
D-Galactose -------------- D-Dulcitol
D-Mannose --------------- D-Mannitol
D-Fructose ----------D-Mannitol + D-Sorbitol
D-Ribose --------------------- D-Ribitol
Reaction with Hydrogen cyanide:

Monosaccharides react with hydrogen cyanide at aldehyde group to form cyanohydrins of
corresponding monosaccharides.
CN
H OH
CHO
H OH
H OH
HCN HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
CH2OH
D-Glucose Cyanohydrin of glucose
Formation of Oxime:
Aldehyde or ketones react with hydroxylamine to form corresponding monosaccharides
Oxime.
H N OH
CHO
H OH
H OH
NH2OH HO H
HO H
H OH
H OH
H OH
H OH
CH2OH
CH2OH
Oxime of glucose
D-Glucose
Dehydration:
When treated with concentrated sulfuric acid, monosaccharides undergo dehydration with an
elimination of 3 water molecules. Thus hexoses give hydroxymethyl furfural while pentoses
give furfural on dehydration.
CHO
CHO
H OH
Conc. H2SO4 H
HO H O
3H2O H
H OH
H OH
CH2OH
CH2OH
D-Glucose Hydroxy Methyl Furfural
H H O
O
Conc. H2SO4
H OH
3H2O
H OH H O
H OH H
CH2OH H
D-Ribose Furfural
Osazone formation:
Phenyl hydrazine in acetic acid, when boiled with reducing sugars, forms osazones in a
reaction. The carbonyl group of an aldose reacts with phenyl hydrazine to give a
crystalline phenyl osazone.
CHO HC N-NH-C6H5
H OH N-NH-C6H5
HO H CH3COOH HO H
H2N-NH-C6H5 H OH
H OH
H OH H OH
CH2OH CH2OH
Glucosazone
D-Glucose
CH2OH HC N-NH-C6H5
O N-NH-C6H5
CH3COOH
H OH HO H
H OH H2N-NH-C6H5 H OH
H OH H OH
CH2OH CH2OH
D-Fructose
Glucosazone
Glycoside:
Glycosides are formed when the hemiacetal or hemiketal hydroxyl group (of anomeric
carbon) of a carbohydrate reacts with a hydroxyl group of another carbohydrate or a non-
carbohydrate (e.g. methyl alcohol, phenol, and glycerol). The bond so formed is known as
glycosidic bond and the non-carbohydrate moiety (when present) is referred to as
aglycone.
CH2OH Hemiacetal CH2OH
O H H O H
H
H H
OH H OH H
OH OH OH OH
H OH H OH
Alcohol
Hydrolysis Condensation
H2O
H2O
CH2OH CH2OH
O H H O H
H
H H
OH H OH H
O OH
OH
H OH H OH
Tautomerization or enolization:
The process of shifting a hydrogen atom from one carbon atom to another to produce
enediols is known as tautomerization. Sugars possessing anomeric carbon atom undergo
tautomerization in alkaline solution.
H H O
O
CH2OH
O HO H
H OH
HO H HO H
HO H
R R
R
D-Fructose D-Mannose
D-Glucose
H OH
OH
HO H
Enediol
Pharmaceutical Applications of Carbohydrates:
Starch:
o Starch is used pharmaceutically as an excipient
o As a diluents, starch is used for the preparation of standardized triturates of colorants

or potent drugs to facilitate subsequent mixing or blending processes in
manufacturing
o Starch is commonly used as tablet disintegrant
o Starch paste is used as binder in tablet granulation.
Glucose:
o Liquid glucose is used as a base in oral solutions and syrups and also as a granulating
and coating agent in tablet manufacturing
o Liquid glucose is also used as sweetener in confectionary products.
Lactose:
o Lactose monohydrates are used as a filler or diluents in tablets and capsules. It is also
used to prepare direct compression
o Anhydrous lactose is widely used in direct compression tableting application and as
tablet and capsule filler and binder
o Anhydrous lactose can be used with moisture-sensitive drugs due to its low moisture
contents.
Mannitol:
o Mannitol is widely used in pharmaceutical formulation and food products
o Primary used as diluents in tablet formulations
o Mannitol is commonly used as an excipient in the manufacturing of chewable
formulations because of its sweetness
o Mannitol has also been used to prevent thickening in aqueous antacid suspension of
aluminum hydroxide.
o Mannitol when given orally is not absorbed significantly from the GI tract, but in
large doses it can cause osmotic diarrhea
o It has been suggested as a plasticizer in soft-gelatin capsules, as a component of
sustained-release tablet formulations
Sorbitol:
o Diluent in tablet formulations
o Diluent in tablet formulation prepared by either wet granulation or direct compression
o It is particularly useful in chewable tablets owing to its pleasant, sweet taste and
cooling sensation
o Sorbitol has been used as plasticizer in different cosmetics and tooth paste
o In syrups it is effective in preventing crystallization around the cap of bottles
o Sorbitol may also be used analytically as a marker for assessing liver blood flow
o Sorbitol is therapeutically used as an osmotic laxative
o In liquid preparations Sorbitol is used as a vehicle in sugar free formulations and as a
stabilizer for drug, vitamin and antacid suspension
Sucrose:
o Binding agent for wet granulation
o Sucrose is used as a sweetener in chewable tablets
o Sucrose syrups are used as tablet coating agent
o Used as viscosity enhancer in suspension
o As an antioxidant
Cellulose:
o Primarily as a binder / diluents in oral tablet and capsule formulations where it is used
in both wet granulation and direct compression process
o Powdered cellulose is used as tablet diluents and hard gelatin capsule filler
o In soft gelatin capsules, powdered cellulose may be used to reduce the sedimentation
rates of oily suspension fills
Carboxy methylcellulose:
o Carboxy methylcellulose is used in pharmaceutical industry as a
 Binder
 Disintegrate
 Diluent
 Suspending agent
Microcrystalline cellulose:
o Microcrystalline cellulose is widely used in pharmaceuticals
 Binder
 Diluent
 Lubricant
 Disintegrate
Powdered cellulose:
o Powdered cellulose is used in pharmaceutical industry as a
 Diluent and capsule filler
 Reduce sedimentation rate
 Suspending agent
 Powder base in powder dosage forms
Xylan:
o Xylan is used for the production of micro- and nanoparticles for controlled drug
delivery system, and in film coatings
o Esterified Xylan has been used in the manufacturing of prodrug of Ibuprofen release
“Super gel” for wound dressing
Caramel:
o Caramel is obtained by heating glucose or sugar alkali or with mineral acids until
sweet taste of sugar is destroyed and uniform dark brown mass is formed
o Used pharmaceutically as Coloring agent
Fructose:
o Fructose Can be used pharmaceutically as
 Electrolyte replenisher
 Fluid nutrient
Dextrose:
o Obtained from the controlled hydrolysis of starch
o Pharmaceutically used as
 Nutrient
 Part of anticoagulant solution
 Sweeting agent
 Tablet binder
 Coating agent
Dextrin:
o Nutrient
o Adhesive for surgical dressing
o Binder
o Thickening agent

Chemistry of Carbohydrates 1

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Chemistry of Carbohydrates 1

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2022

[Type text] Page 0

“Carbohydrates may be defined as polyhydroxy aldehydes or ketones or compounds

“Carbohydrates are defined chemically as aldehydes or ketone derivatives of the higher

Carbohydrates are often referred to as saccharides (Greek: sakcharon-sugar). The word

General formula: CnH2nOn

Physical Properties of Monosaccharides:

o Depending upon whether aldehyde (– CHO) or ketone (– CO) groups

Classification Based on Number of Carbon Atoms:

Sr. Monosaccharide Formula Aldoses Ketoses

CH2OH CH2OH CH2OH

D-Glyceraldehyde L-Glyceraldehyde Dihydroxyacetone

L-Galactose a-D- Galactose

D- Fructose L- Fructose a- D- Fructose

-D-Glucose  (1 2) -D-Fructose

Some of the mucopolysaccharides are found in combination with proteins to form

Sulphate Free Sulphate Containing

Glucoronic acid N-acetyl glucosamine

Glucoronic acid N-acetyl galactosamine

Sulphate Containing Acid MPS:

D-Galactose N-acetyl glucsamine-6-Sulphate

Types of Keratan Sulphate:

Chondroitin sulfate (Greek: chondros-cartilage) is a major constituent of various mammalian

If the sulfate group is found on C4 of N-acetyl galactosamine is called chondroitin 4-sulfat. If

D-Glucuronic acid N-acetyl galactosamine-4-Sulphate

o The horizontal lines represented by the wedge bond

o Cyclization via intramolecular hemiacetal (hemiketal) formation

o All reducing sugars exhibit mutarotation

D-Glucopyranose D-Glucose -D-Glucopyranose

-D-Glucose Equilibriummixture -D-Glucose

112.20 52.70 18.70

R' OH "R R"'

Ketone Alcohol Hemiketal

Types of Glycosidic Bond:

CH2OH CH2OH CH2OH CH2OH

D-Galactose D-Glucose D-Mannose

Chair conformations of sugars:

Asymmetrical (chiral) carbon:

Chemical Reactions of Monosaccharides:

D-Glucose D-Glucaric acid

D-Glucose D-Glucuronic acid

D-Galactose -------------- D-Dulcitol

D-Mannose --------------- D-Mannitol

D-Fructose ----------D-Mannitol + D-Sorbitol

D-Ribose --------------------- D-Ribitol

Reaction with Hydrogen cyanide:

D-Glucose Cyanohydrin of glucose

D-Glucose Hydroxy Methyl Furfural

o As a diluents, starch is used for the preparation of standardized triturates of colorants

o Starch is commonly used as tablet disintegrant

o Starch paste is used as binder in tablet granulation.

 Reduce sedimentation rate

 Powder base in powder dosage forms

 Part of anticoagulant solution

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