Chapter 7

Carbohydrates

Chapter Objectives:
• Learn how to classify carbohydrates.
• Learn how to recognize molecules with chiral centers and draw Fischer projections.
• Learn how to classify the monosaccharides, and learn their chemical and physical
properties.
• Learn about the disaccharides and oligosaccharides.
• Learn the major types of polysaccharides and their structural and biological features.

Mr. Kevin A. Boudreaux

Angelo State University
CHEM 2353 Fundamentals of Organic Chemistry
Organic and Biochemistry for Today (Seager & Slabaugh)
www.angelo.edu/faculty/kboudrea
Monosaccharides

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 Classification of Monosaccharides
• The monosaccharides are the simplest of the
carbohydrates, since they contain only one
polyhydroxy aldehyde or ketone unit.
• Monosaccharides are classified according to the
number of carbon atoms they contain:
No. of Class of
carbons Monosaccharide
3 triose
4 tetrose
5 pentose
6 hexose

• The presence of an aldehyde is indicated by the

prefix aldo- and a ketone by the prefix keto-.
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 Classification of Monosaccharides
• Thus, glucose is an aldohexose (aldehyde + 6 Cs)
and ribulose is a ketopentose (ketone + 5 Cs)
O H
C CH2OH
H C OH C O
HO C H H C OH
H C OH
H C OH
H C OH
CH2OH
CH2OH ribulose
a ketopentose
glucose
an aldohexose
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 Examples: Classifying Monosaccharides
• Classify the following monosaccharides:

CH 2OH CHO
CH2OH CHO
C O HO H
C O HO H
H OH HO H
H OH HO H
HO H H OH
CH2OH CH2OH
CH 2OH CH2OH

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 The Family of D-aldoses
(L-forms not shown)
CHO
H OH Aldotriose
CH2OH 21 = 2
D-glyceraldehyde

CHO CHO
H OH HO H
Aldotetroses
H OH H OH 22 = 4
CH2OH CH2OH
D-erythrose D-threose

CHO CHO CHO CHO

H OH HO H H OH HO H
H OH H OH HO H HO H Aldopentoses
H OH H OH H OH H OH 23 = 8
CH2OH CH2OH CH2OH CH2OH
D-ribose D-arabinose D-xylose D-lyxose 29
 The Family of D-aldoses
(L-forms not shown)

CHO CHO CHO CHO CHO

H OH HO H H OH HO H H OH

H OH H OH HO H HO H H OH
Aldohexoses
H OH H OH H OH H OH HO H 24 = 16
H OH H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH CH2OH

D-allose D-altrose D-glucose D-mannose D-gulose

CHO CHO CHO

HO H H OH HO H
H OH HO H HO H
HO H HO H HO H
H OH H OH H OH
CH2OH CH2OH CH2OH
D-idose D-galactose D-talose
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 The Family of D-ketoses
(L-forms not shown)
CH2OH
O Ketotriose
CH2OH
20 = 1
Dihydroxyacetone

CH2OH
O
Ketotetroses
H OH 21 = 2
CH2OH
D-erythrulose

CH2OH CH2OH

O O

H OH HO H Ketopentoses
H OH H OH 22 = 4
CH2OH CH2OH
D-ribulose D-xylulose 31
 The Family of D-ketoses
(L-forms not shown)

CH2OH CH2OH CH2OH CH2OH

O O O O

H OH HO H H OH HO H
Ketohexoses
HO H
H OH H OH HO H 23 = 8
H OH H OH H OH H OH

CH2OH CH2OH CH2OH CH2OH

D-Psicose D-Fructose D-Sorbose D-Tagatose

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 Physical Properties of Monosaccharides
• Most monosaccharides have a sweet taste (fructose
is sweetest; 73% sweeter than sucrose).
• They are solids at room temperature.
• They are extremely soluble in water:
– Despite their high molecular weights, the
presence of large numbers of OH groups make
the monosaccharides much more water soluble
than most molecules of similar MW.
– Glucose can dissolve in minute amounts of water
to make a syrup (1 g / 1 ml H2O).

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Physical Properties of Monosaccharides
Table 7.2 The relative sweetness of sugars
(sucrose = 1.00)

Sugar Relative Type

Sweetness
Lactose 0.16 Disaccharide
Galactose 0.22 Monosaccharide
Maltose 0.32 Disaccharide
Xylose 0.40 Monosaccharide
Glucose 0.74 Monosaccharide
Sucrose 1.00 Disaccharide
Invert sugar 1.30 Mixture of glucose and fructose
Fructose 1.73 Monosaccharide
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 Chemical Properties of Monosaccharides
• Monosaccharides do not CH2OH
usually exist in solution in H
their “open-chain” forms: H
C O
an alcohol group can add H O
C
into the carbonyl group in OH H C
the same molecule to form HO
C C H
a pyranose ring containing
a stable cyclic hemiacetal H OH
or hemiketal. D-glucose
CH2OH CH2OH

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

a pyranose ring H OH cyclic H OH

-D-glucose hemiacetals -D-glucose
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-up -down
 Glucose Anomers
O H
CH2OH C CH2OH
1
H C OH OH
O O
OH HO C H OH
1 1
H C OH
OH OH OH
H C OH
Haworth OH OH
structures CH2OH
-D-glucose D-glucose -D-glucose
36% 0.02% 64%
• In the pyranose form of glucose, carbon-1 is chiral,
and thus two stereoisomers are possible: one in
which the OH group points down (-hydroxy group)
and one in which the OH group points up (-
hydroxy group). These forms are anomers of each
other, and carbon-1 is called the anomeric carbon. 36
 Fructose Anomers
• Fructose closes on itself to form a furanose ring:
H
CH2OH O
O O
OH
CH2OH
a furanose ring

OH
D-fructose
-hydroxy
CH2OH CH2OH CH2OH OH
O O
HO HO

OH -hydroxy CH2OH
OH OH
-D-fructose -D-fructose 37
 Drawing Furanose and Pyranose Rings
• Monosaccharides are often represented using the
Haworth structures shown below for furanose and
pyranose rings.
• The remaining OH groups on the ring point up or
down depending on the identity of the sugar.

always above ring

for D-saccharides
CH2OH
CH2OH
O O

Furanose Pyranose
ring ring
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 Examples: Anomers
With Friends Like These, Who Needs Anomers?

• Identify the structures below as being the - or -

forms, and draw the structure of their anomers:

CH2OH OH CH2OH
O OH O
OH

OH
OH OH
ribose OH
galactose

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 Oxidation of Monosaccharides
• Aldehydes and ketones that have an OH group on
the carbon next to the carbonyl group react with a
basic solution of Cu2+ (Benedict’s reagent) to form
a red-orange precipitate of copper(I) oxide (Cu2O).
• Sugars that undergo this reaction are called
reducing sugars. (All of the monosaccharides are
reducing sugars.)
oxidation
Reducing sugar + Cu2+ product
+ Cu2O
deep blue red-orange
solution ppt

Benedict’s Reagent Copper(I) oxide

(blue) (red-orange ppt)
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 Formation of Phosphate Esters
O
O
–
O P O CH2 –
O P O CH2 OH
O– O O
OH O– HO

CH2OH
OH OH
OH
OH fructose 6-phosphate
glucose 6-phosphate
• Phosphate esters can form at the 6-carbon of
aldohexoses and aldoketoses.
• Phosphate esters of monosaccharides are found in
the sugar-phosphate backbone of DNA and RNA, in
ATP, and as intermediates in the metabolism of
carbohydrates in the body.
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 Glycoside Formation
• The hemiacetal and hemiketal forms
of monosaccharides can react with CH2OH
alcohols to form acetal and ketal
structures called glycosides. The O
new carbon-oxygen bond is called OH
the glycosidic linkage.
OH OCH3
CH2OH
OH
O methyl -D-glycopyranoside
OH + CH3OH H+ +
CH2OH
OH OH OCH3
O
OH OH
-D-glucose
OH
OH 42
methyl -D-glycopyranoside
 Glycoside Formation
• Once the glycoside is formed, the ring can no longer
open up to the open-chain form. Glycosides,
therefore, are not reducing sugars.

Glycoside + Cu2+ NR

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 Examples: Glycoside Formation
• Identify the glycosidic linkage in each of the
following molecules:

CH2OH
CH2OH OCH 3
OH
O O
OH
CH2OH
OCH2CH3
OH OH
OH

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 Important Monosaccharides
CH2OH OH CH2OH OH
O O

OH OH OH
-D-ribose CH2OH -D-deoxyribose
Forms the sugar backbone of Forms the sugar backbone of
ribonucleic acid (RNA) OH O
OH deoxyribonucleic acid (DNA)
OH

OH
-D-galactose
Incorporated with glucose
into lactose (milk sugar) 45
 Important Monosaccharides
CH2OH CH2OH OH
O
OH
O HO
OH
CH2OH
OH OH
-D-fructose
OH Also known as levulose and fruit
-D-glucose sugar. Fructose is the sweetest of
Also known as dextrose and blood the monosaccharides. It is present
sugar; present in honey and fruits. in honey (1:1 ratio with glucose),
Glucose is metabolized in the body fruits, and corn syrup. It is often
for energy. Other sugars absorbed used to sweeten foods, since less
into the body must be converted to fructose is needed to achieve the
glucose by the liver. same degree of sweetness.

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