14

HO CH2OH
HO
OH
O
O CH2OH Carbohydrates
HO O
OH O CH2OH
HO O
OH O CH2OH amylose
cellulose HO O
OH OH

CHAPTER SUMMARY

14.1 Chemical Nature of Carbohydrates -

Polyhydroxy Aldehydes and Ketones
Carbohydrates are a class of organic biopolymers which consist of
polyhydroxy aldehydes and ketones, their derivatives and polymers. Other
terms for carbohydrates include sugars and saccharides. A single monomer
unit is called a monosaccharide; several units are referred to as an
oligosaccharide; larger polymers are called polysaccharides. The
simplest carbohydrates are glyceraldehyde and dihydroxyacetone.

14.2 Nomenclature of Carbohydrates

The nomenclature of carbohydrates usually includes the suffix -ose.
Monosaccharides may also be identified according to the nature of the carbonyl
functional group (aldose or ketose), the number of carbons in the molecule
(tri-, tetr-, pent- ose) or a combination of these two. Monosaccharides also
have common names such as ribose, glucose, galactose, and fructose
(four of the most common monosaccharides found in nature).

14.3 Structures of Monosaccharides

A. D,L - Aldoses: Open Chain Structures

Monosaccharides have one or more chiral carbon centers and can
thereby form enantiomers and diastereomers. Most common
monosaccharides are in the D-family. This means that, using D-
glyceraldehyde as a starting point, other chiral carbons can be inserted
between the carbonyl group and the D- carbon, producing families of

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Chapter 14 Carbohydrates

diastereomers. If two monosaccharides differ in their structures by the

configuration at only one chiral center, then they are called epimers.

CONNECTIONS 14.1 Diabetes

B. Ketoses
Ketoses are the functional isomers of the aldoses. A family of ketose
structures can be generated in the same manner as aldoses.

C. Fischer Projections
The method of drawing saccharides in a vertical orientation with the most
highly oxidized carbon at the top is called a Fischer Projection. It
does not represent the real, three-dimensional structure of the molecule.

D. Cyclic Structures - Hemiacetal Formation

The carbonyl and alcohol groups within the same monosaccharide may
react together if the carbon chain is long enough. The result is a cyclic
hemiacetal. A new chiral center is formed at the carbon which was
previously the carbonyl. The two optical isomers that can result are
called anomers. Five- and six-membered cyclic structures predominate
with the alcohol oxygen as the last member of the ring. These are
referred to as furanoses and pyranoses, respectively. Cyclic
structures exist in equilibrium with the open-chain form.
Haworth Formulas show the cyclic nature of monosaccharides with
the -OH and -CH 2 OH groups oriented up and down around a planar ring,
that is, above and below the plane of the ring. Conformational
structures more accurately illustrate the three-dimensional nature of
cyclic monosaccharides, especially in the chair conformation of six-
membered rings. The -OH and -CH2 OH groups are oriented in axial and
equatorial positions around the ring and correspond to the up and down
placement in a Haworth Formula. Anomeric isomers are designated as
- if the -OH group is down or axial or as - if up or equatorial.

14.4 Some Reactions of Monosaccharides

A. Oxidation of Carbohydrates (Reducing Sugars)
The easy oxidation of the aldehyde group using a mild oxidizing agent
such as copper (II) and silver (I) can detect the presence of
carbohydrate. The carbohydrates are referred to as reducing sugars.
This type of test cannot distinguish between aldoses and ketoses,

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Carbohydrates Chapter 14

however, because the alkaline conditions of the reaction lead to

tautomerization of the ketone and immediate oxidation.

B. Reduction of Monosaccharides
The carbonyl group can be reduced to produce sugar alcohols such
as sorbitol and mannitol.

C. Esterification
Also the alcohol groups may be esterified with a variety of acids including
phosphoric acid. These esters are found extensively in metabolism.

CONNECTIONS 14.2 Prevention of Disease and Detoxification

14.5 Disaccharides and Polysaccharides

A. Glycosidic Linkages or Bonds
A reaction between one of the many alcohol groups on a
monosaccharide with the hemiacetal group of an adjacent
monosaccharide molecule to form an acetal is the method by which
carbohydrates polymerize into disaccharides (sucrose and lactose),
oligosaccharides, and polysaccharides such as starch, cellulose and
glycogen. The α- or β- configuration of the anomeric carbon will be
locked into position by this polymerization process. Not only does the
diether linkage, called a glycosidic bond, resist oxidation by weak
oxidizing agents (becoming nonreducing sugars) but it also is
metabolically stable. Stereo-specific hydrolysis agents, known as
enzymes, are required to cleave the glycoside.

B. Disaccharides

The most common disaccharides are lactose and sucrose. Lactose is

found in milk and sucrose is table sugar from sugar cane and beets.
Lactose is a reducing sugar while sucrose is not. Bacteria in animal
mouths can use sucrose not only as food but also to form a cement which
bonds the bacteria to the teeth - plaque.

CONNECTIONS 14.3 Low-Calorie Sweeteners

C. Polysaccharides

Starch, glycogen and cellulose are all polyglucose but differ in the nature
of the glycosidic bonds, α- versus β-, and the positions of attachment.

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Chapter 14 Carbohydrates

Also the functions of these polysaccharides differ as do their commercial

uses.

Nature produces variations in the functional groups of polysaccharides

which gives rise to a diversity of overall structure and function. A good
example is the A, B, O -blood type variation found in humans.

CONNECTIONS 14.4 Nitrocellulose and Rayon

Connections 14.4 summarizes the history and manufacture of the semi-
synthetic materials rayon and nitrocellulose, both made from naturally
occurring cellulose.

SOLUTIONS TO PROBLEMS
14.1 Nomenclature of Carbohydrates: Section 14.2
Allose is an aldohexose while xylose is an aldopentose.

14.2 Structures of Monosaccharides: Section 14.3

Epimers have a different configuration at only one chiral carbon center.
Epimers of D-glucose would be D-allose, D-mannose, and D-galactose.
Diastereomers have different configurations at more than one chiral carbon
center. Therefore any of the non-epimers of D-glucose would be
diastereomers.

14.3 Structures of Monosaccharides: Section 14.3

CHO CHO
CHO CHOH H C OH HO C H

H C OH H C OH H C OH
HO C H HO C H HO C H
HO C H HO C H HO C H
H C OH H C OH H C OH
CH2OH CH2OH CH2OH
14.4 Structures of Monosaccharides: Section 14.1
CH2OH CH2OH
CH2OH C O C O There are only two
C O CHOH
H C OH HO C H ketopentoses derived
H C OH from D-erythrulose.
H C OH H C OH
CH2OH They are epimers.
CH2OH CH2OH

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Carbohydrates Chapter 14

14.5 Structures of Monosaccharides: Section 14.3

O
H OH H OH HO H
C C CH C

H- C-OH HO- C-H HO-C-H HO-C-H

CH2 CH2 CH2 CH2

H-C-O H-C-O HO-C-H H-C-O

CH2OH CH2OH CH2OH CH2OH

A B C D

The epimers are A & B; the anomers are B & D ; the diasteromers are A & B,
A & D , B & D . Compound C could be an enantiomer to the open-chain form of
A. In its current form, however, it doesn't have the same number of chiral
carbon centers as do the other compounds.

14.6 Structures of Monosaccharides: Section 14.3D

δ−
D-mannose δ+ O H OH HO H
H C α−D-mannose C β−D-mannose C

HO C H HO C H HO C H

HO C H HO C H HO C H

H C OH H C OH H C OH
δ−
H C O H H C O H C O
δ+
CH2OH CH2OH CH2OH

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Chapter 14 Carbohydrates

δ−
D-glucose δ+ O H OH HO H
H C α−D-glucose β−D-glucose C
C

H C OH H C OH H C OH

HO C H HO C H HO C H

H C OH H C OH H C OH
δ−
H C O H H C O H C O
δ+
CH2OH CH2OH CH2OH

14.7 Structures of Monosaccharides: Section 14.3D

δ− Five-membered rings
H δ+ O H OH HO H HO
C C C O OH
α−
HOCH HOCH HOCH OH
OH
HCOH HCOH HCOH
OH
δ+ HO
OH
HC O H HC O HC O O
β−
δ−
CH2OH CH2OH CH2OH
OH
D-arabinose α−D-arabinose β−D-arabinose

δ−
H OH HO H HO
H δ+ O O
C C C OH α
OH
HCOH HCOH HCOH
OH
HOCH HOCH HOCH
HC O H OH
HO
δ− δ+ HC O HC O O
β
CH2OH OH
CH2OH CH2OH

D-xylose α−D-xylose β−D-xylose

318 OH
Carbohydrates Chapter 14

Six-membered rings

H O H OH HO H
O
C C C α
HCOH
HCOH HCOH OH OH
HCOH OH OH
HCOH HCOH OH
O
HCOH
HCOH HCOH β
H2C O H
OH
CH2 O CH2 O
OH OH
D-arabinose α− D-arabinose β−D-arabinose

HC=O H OH H
OH O
C C OH
HCOH
HCOH HCOH OH OH
HOCH
OH
HOCH HOCH
HCOH OH
O
HCOH OH
CH2OH HCOH

CH2 O OH
D-xylose CH2 O
OH

14.8 Structures of Monosaccharides (Cyclic and Open-chain

Structures): Section 14.3
HO H
CH2OH OH
HC=O
H OH
OH O CH2OH
OH HO
HCOH C O
HOCH HCOH OH
OH HO
HOCH
HOCH CH2OH OH OH
HOCH OH OH
O CH2OH
HCOH OH
HC O HO
O
CH2OH CH2OH
OH
D-galactose Fischer Haworth OH
projection Formulas ConformationalHO
Structures
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Chapter 14 Carbohydrates

14.9 Structures of Monosaccharides (Cyclic and Open-chain

Structures): Section 14.3
top HC O
a) b) HC O
CH2OH CH2OH
OH HCOH
HO O O HCOH
HCOH OH
bottom HOCH
OH
HOCH
HCOH
HO OH HCOH OH
CH2OH CH2OH
unwind

c) CH2OH d) CH2OH
O OH CH2OH CH2OH
C O O C O
HO HO OH
HOCH HCOH
HO CH2OH OH
HOCH OH HOCH

HCOH HCOH

CH2OH CH2OH

14.10 Some Reactions of Monosaccharides: Section 14.4

HC O
H C OH
D-glucose
CH2OH CHOH HO C H
H C O C OH H C OH
HO C H HC O
HO C H H C OH
HO C H
H C OH H C OH CH2OH
H C OH HO C H
H C OH
H C OH
CH2OH CH2OH
H C OH
D-fructose enol D-mannose
CH2OH

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Carbohydrates Chapter 14

14.11 Some Reactions of Monosaccharides (Oxidation): Section 14.4

CHO CHO
CO2H
HO C H HO C H
H C OH
HO C H H C OH
HO C H
H C OH HO C H
H C OH
H C OH H C OH
CH2OH
CO2H CO2H

mannuronic acid xylonic acid iduronic acid

oxidized on C-6 oxidized on C-1 oxidized on C-6

14.12 Some Reactions of Monosaccharides (Reduction): Section

14.4B

CH2OH CH2OH Neither of these sugar

H C OH HO C H alcohols is a reducing
agent to Cu (II) or Ag (I)
HO C H HO C H because they are not
H C OH H C OH aldehydes nor are they
2-ketoses.
CH2OH CH2OH
D-xylitol D-arabitol

14.13 Disaccharides and Polysaccharides: Section 14.5

CH2OH CH2OH CH2OH CH2OH

O O O O
OH 1 4 OH OH
OH
OH OH OH OH OH O OH
OH OH OH α−1,4 OH
- H2O
maltose

CH2OH
CH2OH CH2OH CH2OH O
O OH O O
4 OH
OH OH OH
1 O OH
OH OH OH OH OH
OH OH OH
- H 2O β−1,4
Cellobiose

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Chapter 14 Carbohydrates

OH OH OH
O O O
HO OH HO
O
HO O HO HO
OH OH OH
O OH
HO
maltose OH cellobiose
OH

14.14 Disaccharides and Polysaccharides (Glycosidic Linkages or

Bonds): Section 14.5A

OH
(a) (b) OH
O OOH 4 OH
1 5 HO O 1
HO HO O HO O
O OH
HO OH
HO
OH OH 1' OH OH 1'
1,5 1,4
OH
O HO O OH
(c) (d)
3 HO 2
OH OH
O O HO O 2,6

HO 1 1,3 6 OOH
OH
HO
OH OH OH

14.15 Disaccharides and Polysaccharides: Sections 14.5

CH2OH
a) CH2OH HO b) O CH2OH
O
HO O HO
HO O OH HO
OH O -1,2
OH
HO CH2OH
1,3 O
OH

HO

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14.16 Disaccharides and Polysaccharides: Sections 14.5

Besides the acetal and alcohol groups, chitin contains an amide. This
group is neither acidic nor basic.
Heparin contains alcohol and acetal groups as well as acidic sulfonic
acid and carboxyl groups.

14.17 Terms
a) A hexose is a six-carbon sugar while a pentose has five carbons.
b) An aldose has an aldehyde (RCH=O) functional group while a ketose
has a ketone (RCOR).
c) A reducing sugar has an alcohol and ether functional groups on the
same carbon. A nonreducing sugar is a diether.
d) Monosaccharides are small, single carbohydrate units, usually
containing five or six carbons. Polysaccharides are polymers of
monosaccharides linked by glycosidic bonds.
e) α- and β-D-glucose are anomers, that is, they are both the cyclic forms of
glucose with opposite configurations for the -OH group attached to the
new chiral center, the former carbonyl group.
f) Fischer projections are structures drawn vertically with the most oxidized
carbon appearing at the top. They are not related spatially to real
structures. Haworth formulas are cyclic carbohydrate structures in the
form of cyclopentane and cyclohexane-type rings.
g) Amylose is the “linear” form of starch in which all of the glucose units are
linked α-1,4 while amylopectin is branched, its main chain of glucose
units linked through an α-1,4 glycosidic bond with α-1,6 bonded-
branches about every 25 monomer units.
h) Glycogen is a polymer of glucose with a main chain having α-1,4
glycosidic bonds and α-1,6 branches every 8-10 units. Cellulose is
polyglucose linked β-1,4.
i) Type 1 diabetes involves the absence or near absence of insulin to
regulate body glucose concentrations. Type 2 diabetes is a more
complicated condition in which insulin is usually present but not
functioning properly.

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j) Viscose rayon is a form of cellulose which has been processed by

derivatization and reconstitution while acetate rayon is derivatized
cellulose.
k) Fehling’s test uses Cu (II) as a weak oxidizing agent while Tollen’s test
uses Ag (I).

14.18 Structure: Sections 14.3, 14.4 and 14.5

a) Cellobiose and maltose are both dimers of glucose and both are
reducing sugars. Cellobiose has a β-1,4 glycosidic bond while maltose
has an α-1,4 bond.
b) Galactose and glucose, linked β-1,4, are the units in the reducing sugar
lactose. Sucrose is nonreducing because of the β,α-2,1 glycosidic bond
between fructose and glucose.
c) α-D-glucose and α-D-galactose are epimers differing in the configuration
about C-4. Both are reducing sugars.
d) α-D-glucose and α-D-fructose are reducing sugars and functional
isomers of each other.
e) α-D-xylose and β-D-ribose are both aldopentoses and reducing sugars.
They differ in configuration at C-1 of the cyclic form as well as at C-3.
f) Maltose has two glucose units linked α-1,4 while lactose is composed of
galactose and glucose linked β-1,4; both are reducing.
g) Cellulose is a linear polyglucose linked β-1,4 while starch consists of
amylose (polyglucose α-1,4) and amylopectin (α-1,4 with α-1,6
branches). Both have reducing ends but not much would be seen with
Fehling’s or Tollen’s tests because of the large molecular weight of both
polymers.

14.19 Structure: Section 14.4

a) β-D-fructose b) α-D-idose c) β-D-talose d) α-D-lyxose

CH2OH CH2OH
O OH OH O OH O OH O
OH OH OH OH OH OH

OH CH2OH OH OH OH
OH OH

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Carbohydrates Chapter 14

14.20 Structure: Section 14.3

HC O
CH2 CH2OH OH 2-deoxyribose
2-deoxyribose O Haworth form
HC OH open-chain form
HC OH
OH
CH2OH

14.21 Reactions: Section 14.4

CH2OH OH CH2OH OH
O Ribose has 4 alcohol O
groups which can be
esterified, while 2-
OH OH deoxyribose has 3. OH

ribose 2-deoxyribose

14.22 Structure: Section 14.3

HC O CH2OH
(a) O (b) OHOH
HC OH O C O
OH HC OH HO CH
OH OH OH OH
HO
CH2 HC OH
CH2OH HC OH
CH2OH
(c) OH OH HC O (d) HO
O CH2 O HC O
OH
HO OH HC OH
HO CH
HO OH
HO CH HC OH

HC OH HC OH

CH2OH CH2OH

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Chapter 14 Carbohydrates

14.23 Optical Isomers: Section 14.3

There are two chiral carbons; four optical isomers are possible.
CHO CHO
CHO CHOH H C OH HO C H

H C OH H C OH H C OH
HO C H HO C H HO C H
HO C H HO C H HO C H
H C OH H C OH H C OH
CH2OH CH2OH CH2OH
a/b are identical because you can rotate b in the plane of the page and it
will superimpose on a . a is also obviously meso and is therefore not optically
active. c/d are enantiomers. a is a diastereomer of c and d.

14.24 Reactions: Section 14.4

In the presence of acid, which also assumes an aqueous solution, the α−
and β− forms of D-glucose will rapidly come into equilibrium with the open-
chain aldehyde. Both the α− and β− anomers can react with methanol to form
the methyl acetal.

14.25 Structure: Section 14.5

ketoheptose aldopentose
OH OH OH
(a) (b) O
O OH aldopentose
OH O
OH OH
HO HO HO OH
HO O O
OH
O
aldohexose - 1,4 - 1,5 OH
OH

OH OH OH
ketohexose
(c) O (d) ketopentose
OH O
HO aldopentose
HO OH
- 2,6
O HO O O
- 1,2
HO O HO
OH
aldohexose HO
OH

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14.26 Reactions: Section 14.4

In the previous question, the first three, a,b,c, are reducing sugars. The d
structure has both saccharides involved in an acetal-ketal linkage.

OH OH OH
(a) (b) O
O OH
OH O
OH OH
HO OHO HO HO OH
OH O
O
- 1,4 - 1,5 OH
OH
OH OH OH
(c) O (d)
OH O
HO
HO OH
- 2,6
O HO O O
- 1,2
HO O HO
OH
HO
OH

14.27 Structure: Section 14.5

a) OH OH OH OH
O O O O O O O OH
OH OH OH OH OH
OH OH OH OH

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Chapter 14 Carbohydrates

b) HO c)
O O O
OH OH OH
O O

O
HO d) OH OH
O
OH
O O OH
HO
O O 2,6
OH
HO O O
OH
O OH HO
OH O O OH
HO O
OH
O OH HO
O O
OH HO O
O
O O 2,4
OH
HO
O
OH
14.28 Reactions: Sections 14.4 and 14.5
OH OH
OH O OH OH O OCH3
(a) OH
+ CH3OH OH

OH OH
(b)
OH OH OH
OH O OH OH
O OH OH O
OH O OH
+ OH HO OH O OH HO
OH OH OH

CO2H
(c) OH H C OH
OH O OH -
OH
+ Cu2+ HO C H + Cu2O
OH
HO C H
OH
H C OH
CH2OH

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Carbohydrates Chapter 14

(d)
OH OH
OH O O OH O O OH
OH
OH + HO O HO
OH
OH OH OH OH
OH OH
OH OH

14.29 Reactions: Section 14.4

Fructose can tautomerize to glucose under the alkaline conditions of both the
Fehling and Tollens tests. Therefore both fructose and glucose will test positive.

14.30 Reactions: Section 14.4

Since Fehling’s test gives a positive result for any aldose or 2-ketose, it is
evidence that there could be a sugar in urine but would not be a definitive test
for glucose per se.

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