666 CHAPTER 31 TAOVHO

HO. 1CH2OH eotou eteseo lo noltareo

bommoiongS
B-Hemiketal B-Hemiketal
(0H
on Left) /(OH Up)
HO- H
OH
H -OH HO
HO CH2OH
1
OH
OH
6 CHe B-D-Fructopyranose
B-D-Fructose (Haworth)
(Fischer)

When fructose is component of a saccharide as in sucrose, it usually occurs in its furanose form
5-membered hemiketal). Thus B-D-fructose is assigned the name B-D-fructofuranose.

B-Hemiketal
(OH on Left)
sbove oaoioie
HO CH2OH
B-Hemiketal
6
(OH Up)
HO H
HOCH2 -0- OH
H -OH HO 2
3 CH2OH
H
OH H
6 CH2OH B-D-Fructopyranose
(Haworth)
B-D-Fructose
(Fischer)
The generic name of the Haworth structure for
5-membered sugars arose because of its similarity
with the heterocycle furan.

DISACCHARIDES
Disaccharides (C12H22011) are
carbohydrates that produce
acid-hydrolysis.
two monosaccharides on

owefi yd belongurs H2O/H

Sucrose Glucose + Fructose
Maltose HO/H 2 Glucose units
Lactose HgO/H
Glucose + Galactose
In disaccharide, the two monosaccharides are joined
a
The hemiacetal OH of one monosaccharide and an OH of together by acetal or glycoside formation.
the second
establish the bond (called glycosidic bond) between the two monosaccharide, dehydrate to
are composed of two units of monosaccharides
monosaccharides. That is, disaccharides
joined by a glycosidic linkage. This will be illustrated
by taking examples of individual disaccharides listed above.
Sucrose (Cane Sugar). Sucrose is ordinary table sugar. It is
obtained from cane sugar. Sucrose 15
composed of o-D-glucose unit and B-D-fructose unit. These units are joined by
between C-1 of the glucose unit and C-2 of the fructose unit. a,B-glycosidic linkage
 CARBOHYDRATES 667

CH20H CHOH
H
OH OH
HO 3 OH HO a,p-Linkage
H OH H OH
a-D-Glucose
H
HOCH2 0- OH HOCH2
KH HO H HO2
aCH2OH a CH2OH
OH H OH H
B-D-Fructose Sucrosee
Notice that in the above structure of sucrose, hemiacetal structure is missing. That is why
SucrOse: (a) does not form an osazone with phenylhydrazine; (b) does not reduce Tollens' reagent or
Fehling'ssolution (Sucrose is a non-reducing sugar); (c) does not exhibit mutarotation.

In everyday life, when we say the word

'sugar' we usually refer to sucrose, the
most widely occurring disaccharide in
nature. Sucrose is prepared commercially
in pure form in greater quantities than
any other chemical substance.

4Ose. It is obtained from starch. It is composed of two oa-D-glucose units joined by an

OSIdic linkage between C-1 of one unit and C-4 of the other unit.

a-Linkage
HOH CH2OH CH2OH CH2OH
H H H HH H
HOOH
OH HO OH OH HO
OH
Lo OH H OH
OH H OH H OH H OH
Two a-D-Glucose units Maltose

o hat C-1 of the second glucose unit in the maltose structure is a hemiacetal carbon.
qjuently,
ms. Since ititishas
in equ quilibrium with the open-chain aldehyde form. Thus maltose can exist in a and

educes Fehlin a potential aldehyde group, maltose shows mutarotation, forms osazone, and
j
S Solution (Maltose is a reducing sugar).

milkLact
6-7% K Sugar). It is found in the milk of all animals. Cow's milk contains 4-5% and human
lactose. Lactose is
Lactose is composed of B-D-galactose unit and a-D-glucose unit joined by
ycosidic linkage between C-1 of the galactose and C-4 of the glucose unit.
kage
668 CHAPTER 31 rcs

B-Linkage
CH2OH CH2OH CH2OH CHOH

HOHOH + OH
H
OH
H
OH
H H HO OH H OH
H OH H OH H OH H OH
B-D-Galactose a-D-Glucose Lactose

Like maltose, lactose can also exist in a. and B forms. Lactose is a reducing sugar and shows
mutarotation. It reacts with Tollens' reagent and Fehling's solution.
Of all the naturally occurring disaccharides, sucrose is by far the most important, and will be
discussed in greater detail.

Aeoio
plenda1
N o C a l o r l eS w e e t e n e r
plenda Ob )98010e
reSweetener oituloe noinat
FRO
Sucralose is an artificial sweetener.
Sucralose is not broken down by the body,
Splenda, INo Calorie Sweetener so it is noncaloric. It is about 320 to 1,000
times as sweet as sucrose (table sugar). It is
MADE FROM SUGAR SO
TASTES LIRE SUGAR
stable under heat and over a broad range of
Aa pH conditions. Therefore, it can be used in
Ce baking. Common brand name of sucralose-
based sweetener is Splenda.

LOW LOW LESS LONG

Carb Sugar Pills Life

SUCROSE, Cane Sugar, C12Hz2O1

Sucrose is ordinary table sugar. It ocours chiefly in sugarcane and sugar beets. In smaller amounts
it is present in maple sap, honey, and several fruits.
Properties. (Physical). Sucrose is a colorless, odorless, crystalline substance, mp 185-186°C. Itis
very soluble in water, slightly soluble in alcohol, and insoluble in ether. An aqueous solution of
sucrose is dextrorotatory, its specific rotation
being 66.5°
(Chemical). Sucrose molecule is made of one D-glucose and one D-fructose unit joined Dy
glycosidic bond. It gives all the reactions of glucose and fructose, minus those due to free or poteni
carbonyl group. Thus it fails to reduce Fehling's solution, and does not react with hydrogen cyanide
or phenylhydrazine. At the glycosidic (or acetal) bond it reacts by hydrolysis to generate the component
units, the D-glucose and D-fructose.
Hydrolysis or Inversion of Sucrose. The hydrolysis ofsucrose by boiling with a mineral acid,or
or

by the enzyme invertase, produces a mixture of equal molecules of D-fructose and D-glucose.

C12Ha2011 H2O orInvertase CeH1206 + CeH20 s

D-Glucose D-Fructose
 CARBOHYDRATES 669
CucrOse solution is dextrorotatory but during hydrolysis it becomes levorotatory.e
The specific rotation of sucrose is +66.5°. D-Glucose has specific rotation +52° and D-fructose
neTherefore, the net specific rotation of an equimolar mixture of D-fructose and D-glucoseis
2
+52-92--20
2
te the process of hydrolysis, the specific rotation changes from +66.5° to -20°. The sign of specific
ation changes from (+) to (-), or is said to 'invert'. Hence the hydrolysis of sucrose to D-glucose
And D-fructose, is termed Inversion and the hydrolysis mixture is called Invert Sugar.

Sucrose Inversion D-Glucose + D-Fructose

specific rotation +66.5 4+SS SInvert Sugar 92
specific rotation -20°
The enzyme that brings about inversion is named as Invertase.
Uses. Sucrose is used: (1) as a food and as ingredient of jams. jellies, confections, syrups etc.,
2) in the manufacture of sucrose octaacetate required to denature alcohol, to render paper transparent,
and to make anhydrous adhesives.
WHAT ARE REDUCING AND NON-REDUCING SUGARS?
Those saccharides which reduce Fehling's reagent and Tollens' reagent are called Reducing
reduce or not to reduce
Sugars, and those which do not, Non-Reducing Sugars. The ability to
features.
Fehling's and Tollens' reagents depends on certain characteristic structural
Structural Features of Reducing Sugars (1) They contain a-hydroxyaldehyde
or

0-hydroxyketone functions.

H
-c=0
OH O
OH
o-Hydroxyaldehyde a-Hydroxyketone
hemiacetal hemiketal structures in equilibrium with the open-chain
(2) contain cyclic
Theya free CHO
1orm having
or
or C=O group as the case may be. Such sugars, therefore, reduce Fehling's
and Tollens' reagents. Reducing sugars also exhibit mutarotation.

- H

OH OH
Hemiacetal Hemiketal
do not contain free aldehyde or ketone
Structural Features of Non-Reducing sugars. (1) They
ErOups with OH on the carbon adjacent to the carbonyl group. structures cannot be opened
ketal structure that is stable. Their cyclic
)They contain acetal or
Thus they are unable to reduce Fehling's or
an open-chain form having a free carbonyl group. sugars do notexhibit
mutarotation (Table 31.1).
Cns
reagent. For the same reason, non-reducing

OR
Acetal
-- Ketal
670 CHAPTER 31

monosaccharides contain free or potential CHO or C=0 functions and

Examples. (1) All are
reducing sugars e.g., D-glucose and D-fructose.
(2) Of the disaccharides, sucrose is non-reducing because the anomeric carbons of hoth
monosaccharides are involved in glycoside or acetal formation. Maltose and lactose are reducin
ing
sugars, because in one of the monosaccharide units there is a hemiacetal group that can be opened to
give free CHO function.

Table 31.1 PROPERTIES OF REDUCING AND NONREDUCING SUGARS

Reducing Sugars Non-reducing Sugars

(1) Give positive (1) Give negative

Tollens' test Tollens' test
Agt (ammonia complex) Ag°
Clear solution Silver mirror
Benedict's test Benedict's test
Cutt (citrate complex) Cu04
Clear blue solution Yellow-red
precipitate
ehling's test Fehling's test A A
Cut* (tartrate complex) CuzO
Clear blue solution Yellow-red
precipitate
(2) Mutarotate (2) Do not mutarotate
(3) Functional units present (3) Functional units present
H

--C=o o-Hydroxyaldehyde
OH

Ca-Hydroxyketone
OH O

Hemiacetal Acetal
OH
OR

Hemiketal
Ketal
OH
OR ls99 esuto
STRUCTURE OF SUCROSE
The structure of sucrose has been established as
follows
(1) Elemental analysis and molecular weight la of
sucrose is C12H22011
determination show that the molecular formu
(2) Sucrose reacts with acetic
anhydride
in the presence of sodium Se
acetate to form su1
octaacetate. This reaction indicates the presence of
eight hydroxyl groups in a sucrose noho
Since sucrose is a stable compound, the eight
hydroxyl groups must be present on separa
atoms.
 CARBOHYDRATES 671
Hydrolysis of sucrose with dilute acids yields an equimolecular mixture of D-glucose and
foctose. This indicates that the sucrose molecule is made up one unit of these monosaccharides.
Sucrose does not reduce Tollens' reagent or Fehling's solution; does not form an osazone
ent on prolonged boiling), when glucosazone is formed (due to hydrolysis of sucrose); does not
methyl glucosides; and does not undergo mutarotation. All these observations indicate that the
tor.
lic forms of glucose and fructose are joined together through glycosidic linkage at points where
eyci
e carbonyl groups would otherwise become available, that is, C-1 in glucose and C-2 in fructose.
he

Sucrose reacts with dimethyl sulfate in an alkaline solution to form octamethylsucrose,

which on hydrolysis yields a mixture of 2,3,4,6-tetramethyl-D-glucopyranose and 1,3,4,6-tetramethyl-
D.Fructofuranose. The formation of these compounds indicates that the glucose unit in sucrose has
aDyranose form (6-menmbered ring), and the fructose unit in the furanose form (5-membered ring).
Ci2H1403(OH)8 + (CHg)2SO NaOH C12H1403(OCHa)sH
HO
Octamethylsucrose
CHOCH
H HaCOH&C
H,OH HO,
HgCO
OCH3 HCO
H CH2OCH3
OCH3 OCH H

2,3,4,6-Tetramethyl-D-glucopyranose 1,3,4,6-Tetramethyl-D-fructofuranose
(a- and B-forms) (o-and p-forms)
(6) Sucrose is hydrolysed by maltase, an enzyme that hydrolyses only o-glycosides. It is also
hydrolysed by invertase, an enzyme that hydrolyses B- but not o-fructofuranosides. These
oDservations indicate that sucrose is both an o-glucoside and a B-fructoside.
Theabove evidence clearly indicates that sucrose has the following structure:
6

CH2OH

HO
OH a,B-Linkage
H OH
a-D-Glucose unit O Structure of Sucrose

HOHC O-

H HO
H s CHOH
H H
B-D-Fructose unit

POLYSACCHARIDES
aSaccharides are made of many (10 or more) monosaccharide units joined together by glycosidic
inkages.y arthe most important naturally occurring polysaccharides are Starch and Cellulose.

STARCH,
Star
(CHhoOsn
the main contributor of carbohydrates in our diet. exclusively plants,
It exists in stored
the s of starch are cereals, potatoes, corn,
d riceroots, and fibres as food reserve. The chief sources