Carbohydrates

Team 1
Akshaya S
Arundhathi Alais Pushpavathi N
P Alexandra Susan
Harini M
Harini S
Kaniha Sudharshana U
V Kathryn Kiruba
Mohammad Shafiq I
Nivetha S
Dinadayalan C
Aswin A
Thamilarasu A T
Bragadeeswaran N
Bala Sakthi Kumar V
 DEFINITION

Carbohydrates:
A carbohydrate is a naturally occurring compound, or a derivative of such
a compound, with the general chemical formula Cx(H2O)y, made up of molecules
of carbon (C), hydrogen (H), and oxygen (O). Carbohydrates are the most
widespread organic substances and play a vital role in all life.

INTRODUCTION. Carbohydrates are of special importance because they are direct

products of photosynthesis and are therefore the primary energy storage compounds
and the basic organic substances from which most other organic compounds found
in plants are synthesized.
 Classification

Simple carbohydrates:
Simple carbohydrates are sometimes called "sugars" or "simple sugars." There
are 3 types of simple carbohydrates. They are classified depend on number of
simple sugars

Classification of carbohydrates:
1. Monosccharides
2. Oligosacharrides
3. Polysacharrides
Classification of carbohydrates
Epimers
And
Anomers
 Epimers
● Epimer specifies one of a pair of stereoisomers.
● Stereoisomers are isomeric molecules that possess the same constitution and
molecular formula, but vary in their three-dimensional orientation.
● A molecule may contain numerous stereocenters leading to several
stereoisomers.
● In other words, Epimers are carbohydrates which vary in one position for the
placement of the -OH group.
Epimerisation

● Epimerization refers to the conversion from one epimer of a molecule to

another.
● These processes can occur spontaneously Or can be catalysed with the
help of a group of enzymes called ISOMERASES.

Some of the examples of epimers :

Glucose and Mannose - C2 epimers
Gulose and Galactose - C3 epimers
 Anomers
● Anomers are cyclic monosaccharides or glycosides that are epimers,
differing from each other in the configuration of C-1 if they are aldoses or
in the configuration at C-2 if they are ketoses.
● The epimeric carbon in anomers are known as anomeric carbon or
anomeric center.

Anomerisation:

The phenomenon of converting the one form of anomer into another form is
known as anomerisation.
Configurations
Of Aldoses and ketoses
 Configurations of aldoses and ketoses

Fischer was the first person to devise a method of representing the

configuration of each chiral center in an unambiguous manner. He invented a
simple technique for drawing chains of chiral centers, that we now call the
Fischer projection formula.

At the time Fischer undertook the glucose project it was not possible
to establish the absolute configuration of an enantiomer. Consequently, Fischer
made an arbitrary choice for (+)-glucose and established a network of related
aldose configurations that he called the D-family. The mirror images of these
configurations were then designated the L-family.
 The last chiral center in an aldose or ketose chain (farthest from the
aldehyde or ketone group) was chosen by Fischer as the D / L designator site. If
the hydroxyl group in the projection formula pointed to the right, it was defined
as a member of the D-family. A left directed hydroxyl group (the mirror image)
then represented the L-family.
 if the carbohydrate has the hydroxyl group at the last chiral carbon towards the right side, it is denoted by the letter D
and if the hydroxyl group at the last chiral carbon lies towards the left side, it is denoted by the letter L.
The meaning of D and L configurations can be explained with the help of glyceraldehyde. Glyceraldehyde is
chosen as the standard for assigning D and L configurations to monosaccharides. It is the simplest carbohydrate as it
contains one chiral carbon and hence exists in two enantiomeric forms.The letters D and L represent the position of the
second last hydroxyl group in a carbohydrate.
An aldose is defined as a monosaccharide whose carbon skeleton has an aldehyde
group. They are primarily found in plants.
Ketose is a monosaccharide whose carbon skeleton has a ketone group. Only in the
presence of reducing sugar, they can isomerize to aldose. They are used in processed
food.

ALDOSES
 ALDOTRIOSES:
The minimal number of carbons in a backbone required to make a carbohydrate molecule is three;
therefore, carbohydrates with three carbons are known as trioses.Glyceraldehyde is the sole aldotriose, containing one
chiral stereocenter and two potential enantiomers, D- and L-glyceraldehydes

There are two chiral centers and therefore, 2^2=4 stereoisomers are possible. These are the two pairs
ALDOTETROSES:
of enantiomers of threose and erythrose.
ALDOPENTOSES: Aldopentoses have three stereogenic centers, and therefore there are eight (2^3)
possible stereoisomers (four pairs of enantiomers). Four of the possible aldopentoses are D sugars,
while the other four have an L configuration:
 ALDOHEXOSES:
Aldohexoses have four stereogenic centers which means there are eight (24 = 16) possible
stereoisomers This corresponds to eight pairs of enantiomers-eight D aldohexoses,and eight L
aldohexoses
 KETOTRIOSES: A triose containing a ketone group, and in which the carbonyl group is
in the middle of the chain

KETOTETROSES: A monosaccharide having both a ketone (a ketose) and four carbons (a

tetrose). Only two ketotetroses are possible: the enantiomers of 1,3,4-trihydroxy-2-butanone,
also called erythrulose.

KETOPENTOSES: Any ketose having a chain of five carbon atoms in the molecule. Two
enantiomeric pairs of such compounds are possible, these being the d and l isomers of
ribulose and xylulose.

KETOHEOSES: A ketohexose is a ketone-containing hexose (a six-carbon monosaccharide).

Ketohexoses have three chiral centers, so 8 (23 = 8) different stereoisomers are possible
EXAMPLES
There are several ways to draw the structure of carbohydrate molecules.Mainly there
are 2 common ways of representing them they are as follows:

★ FISCHER PROJECTION

★ HAWORTH PROJECTION

★ CHAIR FORM
 FISCHER PROJECTION
❏ In a Fischer projection the carbohydrate is shown in its open chain form, rather than a
cyclical one.
❏ Carbon atoms in the main chain of the carbohydrate molecule are connected vertically,
whilst hydrogen atoms and hydroxyl groups are bonded horizontally.
❏ The horizontal lines illustrate the bonds which come out of the page, whereas the
vertical lines show bonds that are in the page. Carbon atoms may or may not be
shown in a Fischer projection.
❏ Fischer projections have one main advantage: it is easy to visually identify the
stereochemical properties of a carbohydrate and compare the difference between two
carbohydrates quickly and easily.
❏ For example, it is simple to tell the difference between two enantiomers (molecules
that are a mirror image of each other.)
❏ In most cases a Fischer projection is not an accurate representation of the actual
3D configuration of a molecule. It can be regarded as a projection of a modified
version of the molecule, ideally twisted at multiple levels along its backbone.

FISCHER PROJECTION FISCHER PROJECTION OF

OF D-GLUCOSE WITH D-GLUCOSE WITHOUT
CARBON ATOMS CARBON ATOMS
FISCHER PROJECTIONS OF OTHER ISOMERS OF GLUCOSE
 HAWORTH PROJECTION

❖ A Haworth projection differs from a Fischer projection in that it is

used to represent the carbohydrate in its cyclical form.
❖ This is especially useful for sugars which have a ring structure.
❖ It was devised by the English chemist Sir Norman Haworth who
expanded on the work of Fischer, characterizing many more
carbohydrates.
❖ The six membered cyclic form is generally refered to as the
“puranose”form,and the five -membered cyclic form is called the
“furanose” form.
PYRANOSE
FURANOSE
ALPHA AND BETA FORMS OF GLUCOSE
 RING CHAIN TAUTOMERISM IN GLUCOSE

1.The hydroxyl is nucleophilic; it possesses a lone electron pair that it can donate to the carbonyl carbon and
thus form a bond. The carbonyl carbon is amenable to such bond formation as its electrons experience a
pulling effect by the doubly-bonded oxygen. Oxygen can attract the bonding pair of electrons more strongly
than carbon; it is said to be more electronegative.

2.When a single nucleophilic hydroxyl group in a sugar attacks an aldehyde or ketone, a product called a
hemiacetal or hemiketal, respectively, is produced. The prefix hemi- denotes the reversibility of the reaction .
They are also referred to as acetals or pyranoses.
KETO-ENOL TAUTOMERISM OF GLUCOSE:
 ALPHA AND BETA CONFIGURATION
➔ When the cyclic monosaccharide forms, there are two versions that can form,
called α(alpha) and β (beta) (see figure below). The arrow in the figure indicates
the anomeric carbon which it the location where the ring forms and where the
orientation of the −OH group can change.
➔ The orientation of the other −OH groups are fixed because they are determined
by the orientation of the −OH groups in the particular monosaccharide (compare
to the orientation of the −OH groups on the left and right sides of the Fischer
projections).
➔ Each monosaccharide can exist in either α or β vform and the two forms will
interconvert as the ring opens and closes.
➔ The α form occurs when the −OH group on the anomeric carbon is pointing
down and the β version exists when the −OH group on the anomeric carbon is
pointing up.
 SHORTCUT FOR CONVERTING FISCHER TO
HAWORTH PROJECTION

● FOR PYRANOSES:
● For C-2, C-3, and C-4, if the OH is on the right hand side of the
Fischer, it will be down in the Haworth. If it is on the left hand side
of the Fischer, it will be up in the Haworth.
● If the sugar is D, draw the C-5 CH2OH pointing up.
● For D-sugars, draw the C-1 OH pointing down for the alpha (and
up for the beta).
● FOR FURANOSES:
● The shortcut is essentially the same, but since the C4-OH is usually
forming the ring instead of C5-OH, the mnemonic right → down and left
→ up only applies for the two carbons adjacent to the carbonyl (usually
C2 and C3).
● So if the C4-OH is forming the ring, and if it’s on the right in the Fischer
(i.e. D, for a pentose), then the C5 will point up on the Haworth.
● Alpha and beta in a furanose are assigned by comparing the orientation
of the C1-OH with the C4 substituent (not the C5 substituent, as with a
pyranose).
Conversion of D-fructose to haworth with beta-furanose configuration
CONVERTING HAWORTH TO FISCHER PROJECTION
GLUCOSE
 GLUCOSE
INTRODUCTION :
● Glucose is a simple sugar with the molecular
formula C6H12O6.
● Glucose is overall the most abundant
monosaccharide,a subcategory of
carbohydrates.
● Glucose is mainly made by plants and most algae
during photosynthesis from water and carbon
dioxide, using energy from sunlight, where it is
used to make cellulose in cell walls
● It is the most abundant carbohydrate in the
world.
 Physical properties of GLUCOSE

● It is a color-less Crystalline Solid.

● It has less sweet than cane sugar .

● It’s Melting point - 146°C.

● It is readily soluble in Water.

● It is less soluble in Alcohol.

● It is almost insoluble in ether

 Preparation of GLUCOSE
LABORATORY METHOD:
● It is obtained by the hydrolysis of cane sugar and dilute
H2SO4.

INDUSTRIAL METHOD :
● It is obtained commercially by the hydrolysis of starch
with dilute HCL at high temperature and pressure.
 Uses of GLUCOSE

● It is used in the treatment of hypoglycemia (low

blood sugar).
● It produces carbohydrate calories.
● It is used as precision for the synthesis of
substances.
● It can be used to treat patients who are sick.
● It is used to store carbons and carbohydrates in a
solid or liquid state.
● It can be injected directly into the blood for a
speedy recovery.
● It can be used to produce energy in living
organisms.
 GLUCOSE - STRUCTURES AND CHEMICAL
PROPERTIES

Structure of Glucose
Glucose is an aldohexose.
❖ It is optically active with four asymmetric
carbons.
❖ Its solution is dextrorotatory and hence it is
also called as dextrose.
❖ Elemental analysis and molecular weight
determination show that the molecular formula
of glucose is C6H12O6.
 Cyclic structure of Glucose
Haworth projection
❖ It shows sugars in their closed chain form.
❖ The thicker bonds between carbon atoms represent those closet to the viewer,
and the hydrogen/hydroxyl bonds below the plane of the carbon atoms
represent those on the right in a fischer projection.
 Acyclic structure of Glucose
Fischer Projection (hemiacetyl formation)
❖ It shows sugars in their open chain form.
❖ The carbon atoms of a sugar molecule are connected vertically by solid lines,
while carbon-oxygen and carbon-hydrogen bonds are shown horizontally.
CHEMICAL PROPERTIES OF GLUCOSE
FRUCTOSE
 FRUCTOSE

● DEFINITION :

Fructose, or fruit sugar, is a ketonic

simple sugar found in many plants, where it is
often bonded to glucose to form the
disaccharide sucrose.

● PREPARATION :

It can be prepared by hydrolysis of sucrose

in presence of invertase or dilute sulfuric acid. It
is a laboratory method of preparation of
fructose.
 PREPARATION OF LEVULOSE

❖ Fructose is separated from glucose by crystallization using

alcohol. As glucose is only sparingly soluble in alcohol so
it gets separated first in the form of crystals.

❖ Commercial production of fructose is done by using

glucose. An aqueous solution of glucose is prepared which
is then converted into D – glucosone.

❖ Now by chemical hydrogenation process D – glucosone is

converted into pure fructose.
 PHYSICAL PROPERTIES
Fructose is an important ketohexose that is
obtained by hydrolysis of disaccharide sucrose.
Physical properties of fructose are listed below ;

❖ Its molar mass is 180.156 g.mol.

❖ Its melting point is 103 °C.

❖ It is the most soluble sugar in water.

❖ It is sweet in taste. This is the reason it is used in

beverages and foods as a sweetening agent.
 PHYSICAL PROPERTIES

❖ It is a white crystalline solid at room temperature.

It is an odorless sugar.It is sticky.

❖ It has great hygroscopicity, ie; the ability to

absorb moisture from surrounding elements. It
quickly takes in moisture and slowly releases out
compared to other sugars.

❖ It is has great humectant, ie; moisture

withholding. It can also retain the moisture
absorbed.
 USES OF C6H12O6
❖ It is used in plastics as well.

❖ It is used to increase the shelf life of foods like

nutrition bars and cookies.Corn syrup is
produced by using fructose.

❖ It is used in infant feeding formulas. It is used

as a food for diabetics.

❖ It has a low glycemic index and results in a

moderate release of insulin to the
bloodstream relative to glucose and fructose.
 USES OF FRUCTOSE
❖ As it can be converted into
hydroxymethylfurfural (“HMF”) so it can be
used as diesel fuel additives and diesel fuel
itself

❖ Large scale applications of fructose involve

its use as a sweetener.
CHEMICAL PROPERTIES OF FRUCTOSE:

STRUCTURE:
● Since fructose consists of both ketone
and alcohol groups,therefore it shows
the chemical properties of both
functional groups.
REDUCTION REACTION:
Reduction of fructose in the presence sodium amalagam gives the
mixture of sorbitol and mannitol,where -CO- is converted into
asymmetrical carbon atom
OXIDATION REACTION:
MILD OXIDATION:
● In this process ,no reaction takes place
and the ketone group remains
unchanged.
● MILD oxidising agents doesn't
completely oxidise the alcohol into
carboxylic acids
STRONG OXIDATION:
● Strong oxidizing agents breaks the
molecular bond and converts ketone
group into carboxylic acids with less
number of atoms
STRONG OXIDATION REACTION:

FORMATION OF CYANOHYDRIN:
Fructose reacts with HCN to form cyanohydrin.
FORMATION OF OXIME:
Fructose reacts with hydroxyl
amine to form oxime.
ACTS AS AN REDUCING AGENT:
Ketose can be oxidised easily hence it acts as a strong
reducing agent ,which can reduce tollen’s reagent,fehlings
reagent,and benediction reagent
ACIDIC CHARACTER:
Fructose behaves weakly acidic and forms salt when it
is treated with weak alkali

ESTER FORMATION:
Fructose when treated with acetic anhydride in the
presence of sulphuric acid or zinc chlorideforms
acetyl derivatives
ETHER FORMATION:
Fructose reacts with dimethyl sulfate in the
presence of alkali to form penta-o-methyl derivatives
 ASCENDING IN CARBOHYDRATE SERIES:

1. KILIANI FISCHER SYNTHESIS

2. IMPROVED KILIANI FISCHER SYNTHESIS

3. WOLFROM METHOD

4. SOWDON METHOD
 1. KILIANI FISCHER SYNTHESIS:

● The Kiliani–Fischer synthesis lengthens the carbon chain of carbohydrates by adding one
carbon to the aldehyde group of an aldose.
● D-arabinose can be converted into D-glucose.
● In the first part of the Kiliani–Fischer synthesis, we have an addition reaction of the cyanide
to the aldehyde forming a cyanohydrin.This is when a new carbon is added to the
carbohydrate chain.
● The nitrile group is a good electrophile that can further be reacted with a variety of
nucleophiles such as Grignard or Organocuprate nucleophiles.
● The nitrile group is reduced to an imine using H2 and Pd-BaSO4 catalyst, and in the last
step, we only need to convert the imine to an aldehyde by an acidic hydrolysis.
 2. IMPROVED KILIANI FISCHER SYNTHESIS:

● D-Arabinose is converted into D-Glucose.

● In the first step, D-arabinose is treated with hydrogen cyanate to
form cyanohydrin of glucose.
● Then, it is reduced with Pd/BaSO₄ in the presence of water to give
imine.
● In the last step, the imine this formed is hydrolyzed to form an
aldohexose (D-Glucose).
 Wolfram method

● Aldose is treated with bromine water to form Aldonic

acid, which in turn is treated with acetic anhydride
and thionyl chloride
● The product obtained is treated with CH2N2 to add
an extra carbon and is then treated with AcOH and
Barium hydroxide to form aldose with extra carbon
atom.
 Sowden Method

Aldose is treated with nitro methane in sodium

methoxide,an intermediate is obtained and is reacted
with concentrated sulphuric acid which produces
aldose with extra carbon
 Descending in carbohydrate series

● Ruff’s degradation method

● Wohl’s degradation method
● MacDonald’s method
 Ruff's degradation method:
• The ruff's degradation method is a method for shortening a carbohydrate
chain by a single chain.
• In the first step , the aldehyde is selectively oxidized to a carboxylic acid by
bromine (Br2) and water. (Note : The secondary and primary alcohos are
oxidized here).
•The next step involves an adding an iron (III) salt [ Fe2(SO4)3] with
hydrogen peroxide , which involves the loss of carbon dioxide and oxidation
of the adjacent C2 -OH to an aldehyde.
 Wohl’s degradation method:
● Aldose is treated with hydroxylamine to give corresponding aldoxime.
● The resulting aldoxime acetylated by acetic anhydride in presence of ZnCl2 or
sodium acetate giving acetylated aldonitrile .
● Sodium nitrate act as a base and convert acetylated oxime in to nitrile by
elimination.
● Nitrile is the cyanohydrin of the next lower aldose which on treatment with a base
( methoxide ion) undergo transesterification to form the aldose with the loss of
HCN.
MACDONALD’S METHOD

● In this reaction aldoses is made to react with ethyl

thiol to form mercaptol
● Then it is treated with peroxyprionic acid (used
mainly to release O2) to form disulphone
● Then the disulphone is reduced by ammonium
hydroxide to give the next lower aldose
 CONVERSION OF ALDOSE TO
ISOMERIC KETOSE
● Aldose is treated with excess of phenyl hydrazine
to form osazone
● Osazone is then hydralysed to osone by HCl and
phenol
● Osone is then reduced to ketose with the help of
Zn/acetic anhydride
 SYNTHESIS:KETOSE TO ISOMERIC ALDOSE

A ketose can be converted to its isomeric aldose in following steps

● Reduction using Hydrogen and nickel :In this step the carbonyl group
(C=O) present in the ketose gets reduced to an alcoholic group
● Oxidation of CH2OH to CHO using hydrogen peroxide in Ferric
sulphate
 KETOSE TO ISOMERIC ALDOSE

● Reduction using Hydrogen and nickel :In this step the carbonyl group
(C=O) present in the ketose gets reduced to an alcoholic group
● Oxidation of primary alcoholic group to carboxylic acid using HNO3
● Lactone of corresponding acid is obtained by heating
● Lactone is reduced to aldose using CO2 and sodium amalgam
 ALDOSE TO ITS EPIMER

The following reactions can be used to convert aldose to its epimer

● Via lactone formation
● Lobry de Bruyn van Ekenstein rearrangement
Via Lactone formation
LOBRY DE BRYUN VAN EKENSTEIN REARRANGEMENT
Dissolving monosaccharides in aqueous base causes them to undergo a series of enolizations and keto–enol tautomerizations that lead to
isomerizations.