CHEMISTRY OF

CARBOHYDRATES
Miss Ayesha Shafi
CONTENTS

 Introduction
 Classification of carbohydrates
 Chemistry of carbohydrates
 Importance of carbohydrates
 introduction
 Carbohydrates are multiple aldehyde or ketone compound with multiple hydroxyl
groups.
 They are the most abundant biomolecules on earth; however in human being they
constitute almost about 1% of body weight.
 Carbohydrates Contain the Elements:
 Carbon
 Hydrogen
 Oxygen
 The formula for a carbohydrate is (CH2O)n
 Carbohydrates is also called as the hydrates of carbon because they have the
same ratio of carbon and hydrogen as that present in water.
 DEFINITION
 A carbohydrates is defined as a polyhydroxy aldehyde or polyhydroxy ketone or
compound that yield such derivatives upon hydrolysis.
 Classification of carbohydrates

 Carbohydrates are classified into 4 major groups

1. Monosaccharides
2. Disaccharides
3. Oligosaccharides
4. Polysaccharides
 monosaccharides

 Monosaccharides are also called as the simpler sugar because they cannot be
further hydrolyzed into simpler sugar.
 These simpler sugar also contains a single polyhydroxy aldehyde or polyhydroxy
ketone unit.
 Naturally occurring monosaccharides have three to seven carbon atoms;
 General formula : CnH2nOn
 Monosaccharides are further subdivided as:
 1. Depending upon whether aldehyde (– CHO) or ketone (– CO) groups
 Monosaccharides with an aldehyde carbonyl group are called as aldoses.
 Monosaccharides with a ketonic carbonyl group are called as ketoses.
 Monosaccharides (continue..)

Example

Example of aldoses and ketose sugar

Monosaccharides (continue..)
 2. Depending upon the number of carbon atom:
 Monosaccharides are also classified on the basis of no of carbon atoms
Monosaccharides (continue..)

Example
 Monosaccharides

 Some of the major properties of monosaccharides

are following:
 These are white crystalline solids
 They have a sweet taste.
 They are very soluble in water.
 Disaccharides
 Those sugar which yields two or more same or different types of monosaccharides upon
hydrolysis.
 General formula : Cn(H2O)n-1
 Examples
 Maltose yields 2 molecules of glucose on hydrolysis.
 Lactose yields one molecule of glucose and one molecule of galactose on
hydrolysis.
 Sucrose yields one molecule of glucose and one molecule of fructose on
hydrolysis.
 Lactulose a ketodisaccharide.
 Oligosaccharides and Polysaccharides

 Oligosaccharides : Those sugars which yield 3 to 10 monosaccharide units on hydrolysis, e.g.

Maltotriose.
 Polysaccharides : Those sugars which yield more than ten molecules of monosaccharides on
hydrolysis.
 General formula: (C6H10O5)n
 Polysaccharides are further divided into two groups:
 a. Homopolysaccharides (homoglycans):
 Polymer of same monosaccharide units.
 Examples—Starch, glycogen, inulin, cellulose, dextrins, dextran.
 b. Heteropolysaccharides (heteroglycans):
 Polymer of different monosaccharide units or their derivatives.
 Example—Mucopolysaccharides (glycosaminoglycans).
 Stereochemistry of carbohydrates
 Stereochemistry: The branch of chemistry that deals with the three dimensional
arrangement of atoms in space.
 The presence of asymmetric carbon atoms in a compound gives rise to the
formation of isomers of that compound.
 Asymmetric carbon: A carbon atom to which four different atoms or groups of
atoms are attached is said to be asymmetric.
 Stereoisomer: are the compounds that have the same molecular and structural
formula but differ in the orientation of the atoms in space.
 Example:
 Two such isomers of glucose exist i.e.
 D-Glucose and L-Glucose are mirror image of each other
Stereochemistry of carbohydrates

 D & L designations are based on the configuration about the single asymmetric carbon in
glyceraldehyde.
 If the OH group present at right side it is D-glyceraldehyde and if the OH group present at
the left side then it is designated as the L-glyceraldehyde.
 CONTINUE
 For sugars with more than one chiral center, D or L refers to the asymmetric carbon
farthest from the aldehyde or keto group.
 Most naturally occurring sugars are D isomers.
 It should be clearly understood that D
And L doesn’t signifies the dextrorotatory
And levorotatory but it only signifies the
Configuration (the arrangement of atoms in
relevant to space) of the sugar.
 Van’t Hoff’s rule of ‘n’

 The number of possible isomers of any given compound depends upon the number of
asymmetric carbon atoms the molecule possesses.
 According to Van’t Hoff’s rule of ‘n’; 2n equals the possible isomers of that compound,
where, n = represents the number of asymmetric carbon atoms in a compound.
 Optical activity and Optical Isomer
Some compounds rotate the plane polarized light toward left or right .These
compounds are called as the optical isomers and this property is known as the optical
activity.
Optical isomer are of two types
 Enantiomers
 Diastereomers
 ENANTIOMERS
 Enantiomers are stereoisomers that are non-superimposable mirror images of each other.
 D and L sugars are referred to as enantiomers.
 If two objects are superimposable,
it means you can not tell
them apart, they are identical.

 If two objects are

Non superimposable,
then you can always
distinguish them.
 ENANTIOMERS

 Enantiomers are said to be optically active.

because of the way they interact with plane-polarized light.

 An enantiomer that rotates plane-polarized light in a clockwise direction (to the right) is
said to be dextrorotatory (+) enantiomer.

 An enantiomer that rotates plane-polarized light in a counterclockwise direction (to the

left) is said to be levorotatory (-) enantiomer.
 DIASTEREOMERS
 Stereoisomers that are not mirror images of each other are
described as diastereomers .
superimposable objects are achiral
(a molecule that has a plane of symmetry
 RACEMIC MIXTURE

 When equal amounts of dextrorotatory and laevorotatory isomers are present, the
resulting mixture has no optical activity, since the activities of each isomer cancels
each other. Such a mixture is said to be Racemic.

 Resolution: The separation of optically active isomers from a racemic mixture is

called resolution.
Optical Activity
 Cyclic structures
 If the open-chain form of D-Glucose, which may be
called as Aldehydo-D-Glucose is taken, and
condense the aldehyde group on carbon-1, with the
alcoholic-OH group on carbon-5, two different forms
of glucose are formed. When the OH group extends
to right, it is called as α -D-Glucose and it extends to
left, it is called as β -D-Glucose.
 anomers
 Carbon-1, after cyclization has four different groups attached to it and thus it
becomes now asymmetric. The two cyclic compounds, α and β have different
optical rotations, but they will not be same because the compounds as a whole are
not mirror-images of each other. Compounds related in this way are called
anomers and carbon-1, after cyclisation becomes asymmetric is called now
anomeric carbon atom.
 For example, Glucose forms a six-membered ring with two anomeric forms:
 a-D-Glucoyranose
 b-D-Glucopyranose
 anomers (continue…)

 In glucose, the a-anomers has the —OH group of C-1 trans to the CH2OH group
attached to carbon 5.
 In glucose, the b-anomers has the —OH group of C-1 cis to the CH2OH group
attached to carbon 5.
 Mutarotation
 When an aldohexose is first dissolved in water and the solution is put in optical path so that plane
polarized light is passed, the initial optical rotation shown by the sugar gradually changes until a
constant fixed rotation characteristic of the sugar is reached. This phenomenon of change of rotation
is called as mutarotation.
 So Mutarotation is the change in specific rotation that accompanies the equilibration of a and b
anomers in aqueous solution.
 For example, a solution prepared by dissolving crystalline a-D-glucopyranose in water has a
specific rotation of +112°, which gradually decreases to an equilibrium value of +52.7° as a-D-
glucopyranose reaches equilibrium with b-D-glucopyranose.
 A solution of b-D-glucopyranose also undergoes mutarotation, during which the specific rotation
changes from +18.7° to the same equilibrium value of +52.7°.
 Mutarotation

 The equilibrium mixture of glucose consists of:

 64% (two-third) b-D-glucopyranose ,
 36% (one-third) a-D-glucopyranose and
 only a trace (0.003%) of the open-chain form.
 Mutarotation is common to all carbohydrates that exist in
hemiacetal forms.
 Epimers and epimerization
 Two sugars which differ from one another only in configuration around a single carbon
atom are termed Epimers.
 Examples
 Glucose and galactose are examples of an epimeric pairs which differ only with respect of
C4.
 Similarly, mannose and glucose are epimers in respect of C2.
 Epimerization: Process by which one epimer is converted to other is called epimerization
and it requires the enzyme epimerase, e.g. conversion of galactose to glucose in liver.
Epimers and epimerization
 Monosaccharides of biological importance

 Trioses: Both D-glyceraldehyde and di hydroxy acetone occur in the form of phosphate
esters, as intermediates in glycolysis. They are also the precursors of glycerol, which the
organism synthesizes and incorporates into various types of lipids.
 Tetroses: Erythrose-4-P occurs as an intermediate in hexose monophosphate shunt which is
an alternative pathway for glucose oxidation.
 Pentoses: Two pentoses, ribose and deoxyribose, are extremely important because they are
used in the synthesis of nucleic acids (DNA and RNA).
 D-Ribose is a component of a variety of complex molecules, including ribonucleic acids
(RNAs) and energy-rich compounds such as adenosine triphosphate (ATP).
 2-Deoxy-D-ribose (along with phosphate groups) forms the long chains of
deoxyribonucleic acid (DNA).
 Monosaccharides of biological importance

 2-deoxyribose differs from ribose by the absence of one oxygen atom, that in the –OH
group at C2.
 Both ribose and 2-deoxyribose exist in the usual mixture of open-chain and cyclic hemi
acetal forms.
 Monosaccharides of biological importance

 Hexoses:
 D-Glucose
 Of the monosaccharides, the hexose glucose is the most important nutritionally and the
most abundant in nature.
 Glucose is present in honey and fruits such as grapes, figs, and dates.
 Ripe fruits, particularly ripe grapes (20%–30% glucose by mass), are a good source of
glucose, which is often referred to as grape sugar.
 Glucose is also known as blood sugar because it is the sugar transported by the blood to
body tissues to satisfy energy requirements.
 Monosaccharides of biological importance

 The normal concentration of glucose in human blood is in the range of 70 –100 mg/ dL.
 All tissues use glucose as a primary source of energy.
 Erythrocytes and brains cells utilize glucose solely for energy.
D-Galactose:
 D-Galactose is seldom encountered as a free monosaccharide.
 In the human body, galactose is synthesized from glucose in the mammary glands to
produce lactose (milk sugar).
 D-Galactose is sometimes called brain sugar because it is a component of glycoproteins
(protein–carbohydrate compounds) found in brain and nerve tissue.
 Monosaccharides of biological importance

 Like glucose, galactose is an aldohexose; it differs from glucose only in the spatial
orientation of the – OH group at carbon 4.
 Monosaccharides of biological importance

D-Fructose
 D-Fructose, often called levulose or fruit sugar, occurs in honey and many fruits.
 Aqueous solutions of naturally occurring D-fructose
rotate plane-polarized light to the left; hence the name
levulose.
 D-fructose is present in honey in equal amounts
with glucose.
 Monosaccharides of biological importance

 Fructose is sweeter than sucrose and is an ingredient in many

sweetened beverages and prepared foods.
 As a phosphate, it is an intermediate in glucose metabolism.
 Seminal fluid is rich in fructose and sperms utilize fructose for
energy.
 Important reactions of monosaccharides

 Iodocompounds:
 An aldose when heated with conc. HI loses all of its oxygen and is converted into an iodocompound.
 Acetylation or ester formation:
 The ability to form sugar esters, e.g. acetylation with acetyl chloride (CH3– COCl) indicates the
presence of alcohol groups. Due to alcoholic –OH groups, it can react with anhydrides and chlorides
of many organic and inorganic acids, like acetic acid, phosphoric acid, sulphuric and benzoic acids to
form esters of corresponding acids.
 Osazone formation:
It is a useful means of preparing crystalline derivatives of sugars. They are obtained by adding a mixture
of phenylhydrazine hydrochloride and sodium acetate to the sugar solution and heating in a boiling water
bath for 30 to 45 minutes. The solution is allowed to cool slowly (not under tap water) by itself. Crystals
are formed
 Important reactions of monosaccharides

 These are fine, yellow needles in fan-shaped aggregates or sheaves or crosses, typically
described as Bundle of Hay. Melting point = 204 to 205°C.
 Oxidation to produce the sugar acids:
 Monosaccharide oxidation can yield three different types of acidic sugars.
a) Aldonic acids
b) Aldaric acids
c) Alduronic acid
 The oxidizing agent used determines the product.
 Important reactions of monosaccharides

 Oxidation of the aldehyde end of

 an aldose with mild oxidizing agent
 such as bromine gives
 an aldonic acid.

 For example, the oxidation of the

 aldehyde end of D-glucose with
 bromine produces D-gluconic acid.
 Important reactions of monosaccharides

 Oxidation of both ends of an aldose (the aldehyde and the terminal primary alcohol group)
with Strong oxidizing agent such as nitric acid produces a dicarboxylic acid.
 Such polyhydroxy dicarboxylic acids are known as aldaric or saccharic acid.
 For glucose, this oxidation produces glucaric acid.
 Important reactions of monosaccharides

 In biochemical systems, enzymes can oxidize the primary alcohol end of an aldose such as
glucose, without oxidation of the aldehyde group, to produce an alduronic acid.

 For D-glucose, such an oxidation produces D-glucuronic acid.

 Important reactions of monosaccharides

 Oxidation reactions are often used as a test for the presence of an aldehyde group in a
carbohydrate.
 Benedict’s test and Fehling’s test both employ a solution of Cu 2+ ions in aqueous base.
 When the carbohydrate is oxidized, the blue Cu2+ ion is reduced to Cu2O, which forms a
brick red precipitate.
 Important reactions of monosaccharides

 Reduction of suger to alcohol:

 The monosaccharides may be reduced to their corresponding alcohols by reducing agents
such as Na-Amalgam. Similarly, ketoses may also be reduced to form keto alcohol.
 For example, the reduction of D-glucose gives D-glucitol.
 D-Glucitol, also known by the common name D-sorbitol, is used as the sweetener.
 D-Sorbitol accumulation in the eye is a major factor in the formation of cataracts due to
diabetes.
Important reactions of monosaccharides
 Important reactions of monosaccharides

 The sugar alcohols formed from mannose, fructose and galactose are:
 D-Mannose D-Mannitol
 D-Fructose D-Mannitol + D-Sorbitol
 D-Galactose D-Dulcitol
 D-Xylose D-Xylitol
 Mannitol is frequently used medically as an osmotic diuretic to reduce
cerebral edema.
 Important reactions of monosaccharides
 Actions of acids on carbohydrates: Polysaccharides and the compound carbohydrates in
general are hydrolyzed into their constituent monosaccharides by boiling with dilute
mineral acids (0.5 to 1.0 N) such as HCl or H2SO4.
 • With conc. mineral acids the monosaccharides are decomposed.
 • Pentoses yield the cyclic aldehyde “furfural” .
 Important reactions of monosaccharides

 Glycoside formation:
 Cyclic monosaccharides (hemiacetals and hemiketals) readily react with alcohols in the
presence of acid solution to form acetals and ketals, which are called glycosides.
 A glycoside produced from glucose is called a glucoside, that from galactose is called a
galactoside, and so on.
 For example, glucose reacts with methanol to produce methyl glucoside.
Important reactions of monosaccharides
 Important reactions of monosaccharides

 The bond between the anomeric carbon atom of the monosaccharide and the oxygen atom
of the –OR group is called a glycosidic bond.

 Disaccharides and polysaccharides form as a result of glycosidic bonds between

monosaccharide units.
 Important reactions of monosaccharides

4. Phosphate Ester Formation

 The hydroxyl groups of a monosaccharide can react with acids and derivatives of acids to
form esters.
 The phosphate esters are particularly important because they are the usual intermediates in
the breakdown of carbohydrates to provide energy.
 Phosphate esters are frequently formed by transfer of a phosphate group from ATP to give
the phosphorylated sugar and ADP.
 For example, specific enzymes in the human body catalyze the esterification of the
hemiacetal group (carbon 1) and the primary alcohol group (carbon 6) in glucose to
produce the compounds glucose 1-phosphate and glucose 6-phosphate, respectively.
Important reactions of monosaccharides
 disaccharides
 Disaccharides are sugars composed of two monosaccharide units linked together by the
acetal or ketal linkages.
 They can be hydrolyzed to yield their monosaccharide building blocks by boiling with
dilute acid or reacting them with appropriate enzymes.
 In disaccharide formation, one of the monosaccharide reactants functions as a hemiacetal,
and the other functions as an alcohol.
 disaccharides
 Three important naturally occurring disaccharides are:
1. Maltose
2. Lactose
3. Sucrose
 They illustrate the three different ways monosaccharides are linked:
 By a glycosidic bond in the a orientation (maltose),
 A glycosidic bond in the b orientation (lactose), or
 a bond that connects two anomeric carbon atoms (sucrose).
 Maltose

Occurrence
 Maltose, often called malt sugar, is present in fermenting grains and can be prepared by
enzyme-catalyzed degradation of starch.
 In the body, it is produced during starch digestion by a-amylase in the small intestine and
then hydrolyzed to glucose by a second enzyme, maltase.
Chemistry
 Chemically, maltose consists of two D-glucose units, one of which must be a-D-glucose.
 The glycosidic linkage between the two glucose units is called an (1 → 4) linkage.
Maltose
 Maltose

 Maltose has one free hemiacetal group. Consequently, maltose exists in

three forms:
 a-maltose,
 b-maltose, and
 open-chain form.
 In solution, maltose exists as an equilibrium mixture of all the three forms.
 In the solid state, the b form is dominant.