CSUS, CH06B Carbohydrates Instructor: J.T.

, P: 1
Carbohydrates

General Information
a. The name carbohydrate literally means water compounds of carbon.
b. The general formula for simple sugars is C
n
(H
2
O)
n
.

This class of compounds are better described as Polyhydroxy aldehydes and
ketones.

Methods of Classification:
Several methods are used to classify carbohydrates.

A) One is based on whether the carbohydrate can be broken
down into smaller units.

1) Monosaccharides - cannot be broken down into smaller units by
hydrolysis. Sometimes called simple sugars.
2) Disaccharides - can be broken down (hydrolyzed) into two
monosaccharide units.
3) Oligosaccharide - can be broken into three to six monosaccharide units.
4) Polysaccharides - composed of 7 or more monosaccharide units.

B) Another method is based on the number of carbons found in
a simple sugar.
1) If it has three carbons it is called a triose.
2) If it has four carbons it is called a tetrose.
3) If it has five carbons it is called a pentose.
4) If it has six carbons it is called a hexose.

C) Another method uses the kind of carbonyl group.

1) Aldose - a monosaccharide with an aldehyde group.
HC
O
C
C
CH
2
OH
OH
OH
H
H
erythrose


2) Ketose - a monosaccharide with a ketone group.
2
C
C
C
CH
2
OH
C
CH
2
OH
O
H
H
H
HO
OH
OH
fructose

Note: Usually combine the carbonyl classification and the number
classification together.
C
O
H
C OH H
C H HO
C OH H
C OH H
CH
2
OH
CH
2
OH
C O
C H HO
C OH H
C OH H
CH
2
OH
C
O
H
C OH H
CH
2
OH
glyceraldehyde
aldo
glucose fructose
aldo
keto
triose
hexose
hexose

Fischer Projection:

Horizontal lines represent bonds coming out of the plane of the paper.

Memory Aid? The horizontal bonds were coming out to hug you!

Vertical lines represent bonds going behind the plane of the paper.


3
Cyclic structures can also be represented using Fischer diagrams


Haworth Projection:
The ring structure representations are termed "Haworth Projections. In contrast to the ring
structures of the aromatic carbohydrates or the heterocyclic rings, the pyranose ring is not plane,
so that is should be written as Haworths projection formulas:



C
H
CH
2
OH
O
OH
HO
H OH
H
OH H
C H
O
CH
2
OH
HO
HO
OH
HO
1
2
5
3
4
1
6
4
3
2
6
5


4
I. Molisch's Test is a chemical test for the presence of carbohydrates

A. Molisch's reagent (-naphthol dissolved in ethanol)/ Sulfuric acid.
B. Reactions:
C
5
H
10
O
5
(pentose) + (conc.) H
2
SO
4
C
5
H
4
O
2
+ 3 H
2
O
C
5
H
4
O
2
(furfural) + 2 C
10
H
8
-OH (-naphthol) colored product

II. Seliwanoff's test is used to distinguish between aldehyde and ketone hexoses

A. Seiwanoff reagent: Resorcinol in diluted HCl )

Results:
Ketohexoses- cherry red solution (~ 1 min)
Ketopentoses- blue-green solution.
Aldose- no color change.
Disaccharides- no color change.

Note: sucrose will hydrolyze (by heating) to give Glucose (an aldohexose) and
Fructose (a ketohexose)


CHO
OH H
H HO
OH H
OH H
CH
2
OH
O
OH
OH
CH
2
OH
OH
H
2
COH
O
HOH
2
C
CHO
-3H
2
O
D-Glucose
D-Fructofuranose
5-hydroxy-methyl
furfural
H
3
O
+








5
This product (5-hydroxymethylfurfural) then reacts with resorcinol to form a deep red solution.

O
HOH
2
C
CHO
5-hydroxy
methyl furfural
+
HO OH
Resorcinol
(colorless)
H
+
R
OH
HO
OH O
R= 5-hydoxy furfuryl
(red)


III. Benedict's test for reducing sugars:
A. Benedicts Reagent: sodium carbonate, sodium citrate dihydrate, and copper
sulfate pentahydrate in water.
B. Reaction:
R-CHO + 2Cu
2+
+5OH
-
R-COO
-
+ Cu
2
O
(s, red)
+ 3H
2
O
CHO
OH H
H HO
OH H
OH H
CH
2
OH
+ 2 Cu
2+
+ 4 OH
-
COOH
OH H
H HO
OH H
OH H
CH
2
OH
D-Glucose
D-Gluconic acid
+
Cu
2
O
red
ppt
+ 2H
2
O

6
IV. Barfoed's test: a general test to distinguish between
monosaccharides and disaccharides.
A. Barfoed's Reagent: Copper acetate monohydrate, glacial acetic acid in water.

CHO
OH H
H HO
OH H
OH H
CH
2
OH
CH
2
OH
C O
H HO
OH H
OH H
CH
2
OH
OH
-
+2 Cu
+2
+4 OH
-
COOH
OH H
H OH
OH H
OH H
CH
2
OH
+Cu
2
O +2 H
2
O
red
ppt.
D-fructose
(+ D-mannose)
D-glucose
(+ D-mannose)
D-gluconic acid
(+D-mannonic acid)


Glucose is oxidized to gluconic acid. The copper (II) is reduced to copper (I).
The rate of appearance of the red precipitate can distinguish reducing monosaccharides
from reducing disaccharides.

Note: It is more sensitive than the Benedicts test; it can be used to differentiate
between reducing monosaccharides and reducing disaccharides. The reduction
of Cu
2+
to copper (I) oxide occurs more rapidly for monosaccharides than for
disaccharides.
7
V. Bial's test distinguishes a pentose (5 carbons) from a hexose (6 carbons)
monosaccharide.
A. Bial'sReagent: orcinol, Concentrated HCl, ferric chloride hexahydrate
B. Reaction:

CHO
OH H
OH H
OH H
CH
2
OH
D-ribose
(an aldopentose)
C
OH H
OH H
CH
2
OH
O
CH
2
OH
D-ribulose
(a ketopentose)
O
CHO
furfural
-3H
2
O


The furfural then reacts with orcinol and ferric chloride to form a blue-green solution.
CH
3
OH HO
O CHO
CH
3
HO
R
H
CH
3
HO
OH
OH
H+
CH
3
CH
3
OH
OH
HO
+
FeCl
3
(oxidation)
orcinol
(colorless)
furfural
(colorless) R =furfuryl (colorless)
R =furfuryl (blue-green)
O
R


The rate of formation and the color of the solution can be used to distinguish pentoses
from hexoses. Pentose sugars form blue-green solutions; hexose sugars form reddish brown
complexes.

VI. The iodine test is used to differentiate between starch and glycogen.
I
2
+ KI I
3
-
+ K
+

The amylose in starch forms helices where iodine molecules assemble, forming a dark blue or black color.

Dehydration:
C
12
H
22
O
11
+ 11 H
2
SO
4
12 C + H
2
SO
4
. H2O




8

This is a list of some common monosaccharides:
Trioses:
o Aldotriose: glyceraldehyde
o Ketotriose: dihydroxyacetone
Tetroses:
o Aldotetrose: erythrose and threose
o Ketotetrose: erythrulose
Pentoses:
o Aldopentoses: arabinose, lyxose, ribose and xylose
o Ketopentoses: ribulose and xylulose
Hexoses:
o Aldohexoses: allose, altrose, galactose, glucose, gulose,
idose, mannose and talose
o Ketohexoses: fructose, psicose, sorbose and tagatose
Disaccharides - composed of two monosaccharide units.

2. Maltose - malt sugar.

a. Used in cereals, candies and the brewing of beverages.
b. Composed of two D-glucose sugars joined by an -1,4 linkage.
O O
H H
H
H H
H
O
H
OH OH H H
OH OH
OH
OH
CH
2
OH CH
2
OH
H

It contains a Hemiacetal functional group and has a reducing suger.

3. Lactose - milk sugar.

a. Found in milk and milk products.
b. Composed of one galactose and one glucose unit joined by a -1, 4 linkage.
9
O
H
H
H
OH
H
OH
OH
CH
2
OH
H
O
CH
2
OH
OH
H OH
H
H
OH
H
O

4. Sucrose - table sugar.

a. Product of sugar cane and sugar beets.
b. Composed of one glucose and one fructose unit.

O
O
OH
H
OH
H
H
O
H
H
H
OH H
H OH
CH
2
OH
OH
CH
2
OH
CH
2
OH

Polysaccharides - composed of many monosaccharide units.

5. Cellulose

a. Major structural material of plant cells.
b. Consists of many glucose units joined by -1, 4 linkages.
c. Disaccharide starting material is called Cellobiose.
O
H
H
H
OH
H
OH
OH
CH
2
OH
H
O
CH
2
OH
OH
H OH
H
H
OH
H
O

6. Starch

a. Storage form of glucose found in rice wheat, potatoes, grains and cereals.
b. Consists of many glucose units joined by -1, 4 linkages.
c. Maltose is the disaccharide starting material.

7. Glycogen
a. Animal starch. Storage form of glucose found in the liver and muscle of
animals.
b. Contains many highly branched glucose units.