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M.Sc. III SEMESTER

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Paper Code CHEL-301B: Chemistry of Natural

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Products
Unit-4 Carbohydrates
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Seema Mishra
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Department of Chemistry
University of Lucknow, Lucknow
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 Carbohydrates

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 Compounds of C, H and O with H and O ratio 2:1 (i.e. composition
of water) are called carbohydrates.

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 The empirical formula of carbohydrates is Cn(H2O) n thus called as
hydrates of Carbon

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eg, C6H12O6 = C6(H2O) 6

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 Carbohydrates are the most abundant class of organic compound
in living organisms i.e. they constitute almost 50% of the weight
 They are mainly synthesized as a product of photosynthesis
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 They are also referred as saccharide because of the sweet taste of
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simpler members of sugars, It is derived from the Latin word
Sacchrum =sugar
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 Chemically carbohydrates are polyhydroxy aldehydes or

polyhydroxy Ketones or polymers of these
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 Classification

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Carbohydrate

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Monosaccharide Oligosaccharide Polysaccharide

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Simple sugars, Oligos=few (2-10) >10 subunits, can be
generally 4-10 C atom, subunits, can be hydrolysed to several

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cannot be hydrolysed hydrolysed to simpler simpler sugar units
further in simpler compounds
Homopolysaccharide;
compounds
Disaccharide; sucrose, Starch,
-Glucose a Maltose, Lactose Cellulose
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-Fructose Trisaccharide;
-Galactose Raffinose
Heteropolysaccharide;
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-Rubilose Tetrasaccharide; - Inuline

Stachyose.
-Xylose etc.

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 Classification

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Carbohydrate

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Sugar Non-sugar

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Monosaccharide Polysaccharide
Disaccharide

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are non-sugars
Have sweet taste

Reducing
Reduces Fehlings and
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Do not reduce Fehlings
Tollen’s reagents
and Tollen’s reagents
All monosaccharide
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and disaccharide
except Sucrose
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 Monosaccharide

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A polyhydroxy aldehyde or a polyhydroxy ketone. The polyhydroxy
aldehydes are called as aldoses and polyhydroxy ketone is are called

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ketoses.
They are classified according to the number of C atom

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For example

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Trioses 3 carbon Sugar
Tetroses 4C Sugar
pentoses a5C Sugar
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Hexoses 6C Sugar
Heptoses 7C Sugar
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Thus a 6 carbon polyhydroxy aldehyde is an aldohexose

Or a 6 carbon polyhydroxy Ketone is an ketohexose
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 Monosaccharide

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Glyceraldehyde is the only aldose whose name does not contain and
end ‘ose’ , it is an aldotriose

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Ald

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Triose

= Aldotriose
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 Monosaccharide

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Aldose

ketose

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Hexose Hexose

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= Aldohexose = Ketohexose
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 Configuration

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right left

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D & L configuration only indicate the configuration of the chiral
centre (like R,S configuration), it does not tell if the compound
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is dextrorotatory or levo.
For example , D-glyceraldehye is dextrorotatory
while D-Lactic acid is Levotrorotatory
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 Configuration

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right
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 Isomeric forms

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1. Constitutional isomerism:

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Differ in order of attachment of atoms or groups

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Glyceraldehyde (C3H6O3) Dihydroxyacetone (C3H6O3)
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 Isomeric forms

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2. Stereoisomerism:

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The order of attachment of atoms or groups are same
but they differ in spatial arrangement.

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Number of stereoisomers = 2n

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Glucose has 4 asymmetric C, thus 24 = 16 stereoisomers
i.e. 8 pairs of enantiomers
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Fructose has 3 asymmetric C, thus 23 = 8 stereoisomers
i.e. 4 pairs of enantiomers
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Stereoisomers of Aldoses Aldotriose

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Aldotetroses

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Aldopentoses

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Aldohexoses
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Stereoisomers of Ketoses

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Enantiomers:

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Non-superimposable mirror images

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 Diasteremers

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The stereoisomers that are not mirror images

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Diastereomers
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 Epimers

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The diastereoisomers that differ only in configuration about single C atom

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Epimers
The process used to change the conformation at one of the
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asymmetric C atom in compounds having more than one asymmetric

C without altering the rest of the molecule is called epimerization.
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 Anomers

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Isomers that differ at a new asymmetric C atom formed during ring

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closure

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anomeric C anomeric C
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α- D-Glucose β- D- Glucose
α- D-Glucopyranose β - D-Glucopyranose
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 Howorth projection of Aldoses

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Hemiacetal Hemiacetal

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Fischer Projection
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 Howorth projection of Ketoses

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Hemiketal

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+

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Furan

α-D- fructo furanose β-D- fructo furanose

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 formation of α and β anomers

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During cyclisation, the carbonyl oxygen atom may be pushed either up
or down, giving rise to two stereoisomers

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 Chair conformation of Aldohexoses

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C1 axial
α- D-Glucose

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β-D-Glucose a All equatorial
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The most common aldohexose 21
 Chair conformation of other Aldohexoses

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a β-OH
α-OH
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Anomers
D- Galactose is C4 epimer of D- Glucose
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 Chair conformation of other Aldohexoses

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Enantiomers

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Epimers
C2, C3 C2
C3
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C2,C3,C4 C2, C4
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C4
C3, C4

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 Glycosides and Glycosidic bond

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Sugars react with –OH of other compound (or another sugar) through

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the –OH group of anomeric C are called Glycosides.
In the reaction a water molecule is released

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Glycosidic bond
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The bond between anomeric C and the alkoxy oxygen is called

Glycosidic bond
 Nomenclature of Glycosides

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Glycosides of glucose are called glucosides and that of galactose are

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called galactosides…….
Similarly if pyranose or furanose name is used then they will be named
as payranoside or furanoside

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Such as..

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 Glycosides

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Reaction of single anomer with alcohol leads to formation of both α

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and β glycosides

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C2H5OH
OC2H5 +

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OC2H5
Ethyl Ethyl α

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This is because of formation of an SP2 hybridized oxacarbonium ion in
presence of acid
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 Glycosides

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.. ..
: .. H+ : - H2O
..

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2

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+

From top
C2H5ÖH
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From bottom
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Oxo carbonium ion
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OC2H5 +
OC2H5
Ethyl Ethyl α
 Sugar derivatives

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Sugar alcohol: Lack of aldehyde or ketone

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 Sugar derivatives

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Sugar Acids: The aldehyde at C1 or –OH at C6 or

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both are oxidized to a carboxylic acid

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D- gluconic D- glucuronic D- glucaric D- galactaric
acid acid acid acid
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 Sugar derivatives

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Amino Sugars : an –OH group is substituted by

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amino group

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-NH2 glucosamine

-NH CO CH3 a
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N- acetylglucosamine
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