Carbohydrates

Organic Chemistry for 12th grade

SMK – SMAK Bogor
Compiled by Nurul Hasanah, S.Si

1
Carbohydrates
1. Classification of Carbohydrates
2. Classification of Monosaccharides
3. D and L Notations from Fischer Projections
4. Structures of Some Important Monosaccharides
5. Cyclic Structures of Monosaccharides

Dwika Riandari, S.Si_SMAK Bogor 2

Objectives

Explain why carbohydrates are important

Define what a carbohydrate molecule is
Recognise and classify carbohydrate molecules
Define stereochemistry and explain its
importance in the structures of carbohydrates

3
Why Carbohydrates Important ?

4
Importance of Carbohydrates
Most organisms that live in air obtain energy
from the oxidation of carbohydrates
Glucose is most common simple carbohydrate
used as fuel
Important to consider structure of carbohydrates
Differences in molecular structure are often small
but critical to their function

5
Carbohydrates
 Most abundant organic compounds in
nature
 A major source of energy from our diet
 Composed of the elements C, H and O
 Also called saccharides, which means
“sugars”
 Produced by photosynthesis in plants

6
Classification of Carbohydrates
 Monosaccharides are the simplest carbohydrates
 Empirical formula = CH2O
 Disaccharides consist of two monosaccharides
 Polysaccharides contain many monosaccharides

Dwika Riandari, S.Si_SMAK Bogor 7

Classification of carbohydrates
 Monosaccharides
 Oligosaccharides
 Di, tri, tetra, penta, up to 9 or 10 monosaccharides
 Most important are the disaccharides
 Polysaccharides
 Homopolysaccharides
Examples :
Starch + H2O n. Glucose
Glycogen + H2O n. Glucose
Cellulose + H2O n. Glucose
Inulin + H2O n. Fructose

8
Classification of carbohydrates
 Heteropolysaccharides
Example :
Heparin + H2O n. Glucose + n. Amine
 Complex carbohydrates
Example :
Glycolipid + H2O n. Glucose + n. Lipid
Glycoprotein + H2O n. Glucose + n. Protein

9
Classification of
Monosaccharides
 Aldoses
 monosaccharides with an .................group (as carbon
number.....)
 Ketoses
 monosaccharides with a ....................group (as carbon
number........)
Aldose Aldose Ketose
CH2OH
CHO O
CHO
HO H HO H
HO H
H OH H OH
CH2OH
CH2OH H OH
CH2OH
OH 10
Classification of
Monosaccharides
CH2OH
O
CHO
CHO HO H
HO H
HO H H OH
H OH
CH2OH H OH
CH2OH
OH2OH
CH
triose tetrose hexose

11
 Sugars that are most common in
nature are indicated by boxes

The name mannose is derived from the Biblical word manna.12

Dwika Riandari, S.Si_SMAK Bogor 13
Learning Check
Which classification fits this sugar?

14
 Which classification fits this sugar?

Dihydroxyacetone

15
Which classification fits this sugar?

16
 Which classification fits this sugar?

Galactose
17
Which classification fits this sugar?

18
 Which classification fits this sugar?

Glyceraldehyde

19
Which classification fits this sugar?

20
 Which classification fits this sugar?

D-Threose 21
Which classification fits this sugar?

22
 Which classification fits this sugar?

Ketoheptose

Sedoheptulose 23
Monosaccharides (D-aldoses)

Dwika Riandari, S.Si_SMAK Bogor 24

Fischer Projections
 Using these rules the distinguishing
features of the 3D structure of
stereoisomers can easily and
accurately represented with 2D
drawings
 Fischer projection named after Emil
Fischer who established the molecular
structures of many sugars

25
Fischer Projections
 Used to represent carbohydrates (chiral carbons)
 Places the most oxidized group at the top
 Uses horizontal lines for bonds that come forward
 Uses vertical lines for bonds that go back

Dwika Riandari, S.Si_SMAK Bogor 26

D and L Notations
 By convention, the letter L is assigned to the
structure with the —OH on the left
 The letter D is assigned to the structure with
—OH on the right

27
D and L Monosaccharides
 The —OH on the chiral atom farthest from the
carbonyl group is used to assign the D or L
configuration
O O
C H C OH
CHO
H OH HO H
H OH
H OH HO H H OH
H OH H OH H OH
CH 2OH H OH HO H
D
D-Ribose CH2OH CH2OH
D LL-Galactose
D-Glucose
28
Learning Check
 Indicate whether each is the D or L isomer:

CH2OH
CHO
CHO O
HO H
H OH HO H
HO H
HO H H OH
HO H
CH2OH H OH
CH2OH
CH2OH
Ribose Threose Fructose

29
D-Glucose
 Most common hexose
 Found in fruits, corn
syrup, and honey
 An aldohexose with
the formula C6H12O6
 Known as blood sugar
in the body
 Building block for
many disaccharides
and polysaccharides
30
Blood Glucose Level
 In the body, glucose has a normal concentration of 70-90
mg/dL
 Depends on time since last meal (rise after eat; decrease
as used or stored)
 In a glucose tolerance test, blood glucose is measured for
several hours after ingesting glucose

Dwika Riandari, S.Si_SMAK Bogor 31

D-Fructose
 Ketohexose C6H12O6
 Differ from glucose at C1 and C2
(location of carbonyl)
CH2OH
 The sweetest carbohydrate (2x
sucrose) C O
 Found in fruit juices and honey HO C H
 Formed from hydrolysis of sucrose H C OH
 Converts to glucose in the body H C OH
CH2OH

D-Fructose32
D-Galactose
 Aldohexose
 Differ from D-glucose at C4 CHO
 Not found in the free form H C OH
in nature HO C H

 Obtained from lactose, a HO C H

disaccharide (milk H C OH

products) CH2OH

D-Galactose

33
Hemiacetal Review
 What is a hemiacetal?
 How is a hemiacetal formed?
O OH
+
H
CH3 C H + CH3OH CH3 C H

OCH3

 What if the alcohol and carbonyl are attached?

H
H
O O
O O
H+ O
= C
C C
HO H H
H
HOCH2
HOCH2
H
H
CH2OH O O
O O
H+ O
= C
C C
HO H H 34
H
Hexose hemiacetals
 Favor formation of 5- or 6-membered rings
 Hydroxyl group on C5 reacts with the aldehyde or ketone

 The Haworth structure can be written from the Fischer projection

 The cyclic structure of a D-isomer has the last CH2OH group located
above the ring
 The –OH group on the left (C3) is drawn up
 The –OH groups on the right (C2, C4) are drawn down 35
Rules for drawing Haworth
projections
 draw either a six or 5-membered ring
including oxygen as one atom
O O

 most aldohexoses are six-membered

 aldotetroses, aldopentoses, ketohexoses
are 5-membered

36
Rules for drawing Haworth
projections

 next number the ring clockwise starting next

to the oxygen 5
O O
4 1 4 1

3 2 3 2

 if the substituent is to the right in the Fisher

projection, it will be drawn down in the
Haworth projection (Down-Right Rule)

37
Conversion of Fischer’s to
Haworth’s

38
 and  Anomers for D-Glucose
 Anomers are isomers which differ in placement of
hydroxyl on C1
 The –OH is drawn down for the -anomer, and up
for the -anomer
CH2OH
O
CH2OH

O
OH
OH OH
OH OH OH
OH
 OH
-D-Glucose -D-Glucose
39
Mutarotation
 In solution, -D-glucose is in equilibrium with β-D-glucose
 Mutarotation involves the conversion of the cyclic anomers
into the open chain
 At any time, there is only a small amount of open chain

40
Cyclic Structure of Fructose
 As a ketohexose, fructose forms a cyclic
structure when the —OH on C5 reacts with
the ketone on C2
 Result is 5-atom ring
 Anomeric carbon is C2

CH2OH
C O CH2OH CH2OH CH2OH OH
O O
HO C H OH OH
H C OH OH CH2OH
H C OH OH OH

CH2OH
D-Fructose -D-Fructose -D-Fructose 41
Learning Check
Write the cyclic form of -D-galactose:

H O
C
H C OH
HO C H
HO C H
H C OH
CH2OH
-D-galactose 42
Physical Properties
 They are all sweet tasting, but their relative
sweetness varies a great deal
 They are polar compounds with high melting
points
 The presence of so many polar functional groups
capable of hydrogen bonding makes them water
soluble
 Unlike most other organic compounds,
monosaccharides are so polar that they are
insoluble in organic solvents like diethyl ether

43
Reactions of
monosaccharides
 Carbonyl reactions:
 Osazone formation
 Cyanohydrin reaction
 Reduction
 Oxidation
 Action of base
 Action of acid
 Ring chain tautomerism
 Alcohol reactions
 Glycoside formation
Treatment of a monosacccharide with an alcohol and acid
converts the hemiacetal into an acetal
 Ether formation
 Ester formation

44
Oxidation reactions
 Aldoses may be oxidized to 3 types of acids
 Aldonic acids: aldehyde group is converted to a
carboxyl group ( glucose – gluconic acid)
 Uronic acids: aldehyde is left intact and primary
alcohol at the other end is oxidized to COOH
 Glucose --- glucuronic acid
 Galactose --- galacturonic acid
 Saccharic acids (glycaric acids) – oxidation at both
ends of monosaccharide)
 Glucose ---- saccharic acid
 Galactose --- mucic acid
 Mannose --- mannaric acid

45
Dwika Riandari, S.Si_SMAK Bogor 46
Fehling’s reaction to determine glucose levels in blood.

D-Glucose D-Gluconic acid

47
Fehling’s reaction

Dwika Riandari, S.Si_SMAK Bogor 48

Fehling solution
 Fehling solution (Attention: very corrosive)
is a solution to test for aldehydes, aldoses and
fructose in urine developed by Fehling (1850).
(More reducing substances react with F.S.
leaving a brick red precipitation).

 The deep blue solution is made by mixing 1 drop

of Fehling solution 1 ("Fehling 1") and 1
drop Fehling solution 2 ("Fehling 2").
"Fehling 1": 0,7 g blue copper sulfate dissolved in
10 ml water.
"Fehling 2": 3,4 g potassium sodium tartrate and
1.0 g NaOH in 10 ml water.
49
Tollens reaction

Ag+ ions react with OH- of aqueous ammonia to produce a

brown precipitate of AgOH which is dissolved on addition of an
excess of aqueous ammonia under the formation of [Ag(NH3)2]+.
The silver diamine complex is reduced by glucose to metallic silver.
Glucose is oxidized to gluconic acid.
50
Tollens reaction

51
“ Reducing sugar ?”

The Fehling and Tollens test are important in

carbohydrate for proof of structure.
The test is spesific for reducing sugar.
Fructose is also capable of reducing Fehling and
Tollens solution, and is thus classified a “reducing
sugar”. Under basic condition fructose is converted
into glucose.

52
Sugars Can Be Reducing
Agents
 Reducing Sugars - A sugar that will reduce
inorganic ions such as Cu++ (Fehling’s
reagent).

 All monosaccharides whether an aldose or

a ketose are reducing sugars.

 Most disaccharides are reducing sugars;

sucrose is a notable exception.

53
Glycosidic binds are between two
sugars
They can either be in the  or  configuration and
can be linked through the 1-2, 1-4 or 1-6 linkage

54
 Disaccharides

Disaccharides are linked by a glycosidic bond at

the anomeric carbon of one unit and a -OH group
of the other. Three important disaccharides are
maltose, lactose, and sucrose.

55
 .

Non-reducing sugar

Reducing sugar

Reducing sugar
56
Maltose:

Maltose is named after malt, the juice from sprouted barley and other cereal
grains.
Maltose consists of two molecules of D-glucopyranose joined by a -1,4-
glycosidic bond between carbon 1 (the anomeric carbon) of one unit and carbon
4 of the other unit. Maltose is a reducing sugar
Illustrated is -Maltose named so because the anomeric cabon of the glucose on
the right is beta. The alpha linkage between the two sugars is implied in the
name maltose.

Dwika Riandari, S.Si_SMAK Bogor 57

Lactose:

Lactose is the main sugar present in milk. It makes up about 5-

8% of human milk, 4-6% cow’s milk. It consists of D-
galactopyranose bonded by a -1,4-glycosidic bond to a carbon 4
of D-glucopyranose. Lactose is also a reducing sugar.

The enzyme needed to digest this beta glycosidic bond is lacking

in many people and, also, tends to disappear with age. This leads
to so-called lactose intolerance.
58
Sucrose:
Sucrose or table sugar is the most abundant disaccharide in the
natural world. Commercially, it is obtained from the juice of sugar
cane and sugar beets.
In sucrose, carbon 1 of -D-glucopyranose is joined to carbon 2 of
D-fructofuranose by an -1,2-glycosidic bond.
Note: glucose is a six-membered ring (pyranose) whereas fructose is
a five-membered ring. Because both of the anomeric carbons of the
monosaccharides are involved in the glycosidic bond, sucrose is a
non-reducing sugar.

Dwika Riandari, S.Si_SMAK Bogor 59