Wade 23

Organic Chemistry, 5th Edition
L. G. Wade, Jr.
Chapter 23
Carbohydrates and Nucleic
Acids
Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003,Prentice Hall
Carbohydrates
Synthesized by plants using sunlight to
convert CO2 and H2O to glucose and O2.
Polymers include starch and cellulose.
Starch is storage unit for solar energy.
Most sugars have formula Cn(H2O)n,
hydrate of carbon.
=>
Chapter 23
Classification of Carbohydrates
Monosaccharides or simple sugars
polyhydroxyaldehydes or aldoses
polyhydroxyketones or ketoses
Disaccharides can be hydrolyzed to two

monosaccharides.
Polysaccharides hydrolyze to many
monosaccharide units. E.g., starch and
cellulose have > 1000 glucose units.
=>
Chapter 23
Monosaccharides
Classified by:
aldose or ketose
number of carbons in chain
configuration of chiral carbon farthest from
the carbonyl group
glucose, a
D-aldohexose
fructose, a
D-ketohexose
Chapter 23
=>
4
and L Sugars
sugars can be degraded to the

dextrorotatory (+) form of glyceraldehyde.
L sugars can be degraded to the
levorotatory (-) form of glyceraldehyde.
Chapter 23
5 =>
The D Aldose Family
=>
Chapter 23
Erythro and Threo

Terms used for diastereomers with two
adjacent chiral Cs, without symmetric ends.
For symmetric molecules, use meso or d,l.
Chapter 23
=>
7
Epimers
Sugars that differ only in their
stereochemistry at a single carbon.
=>
Chapter 23
Cyclic Structure for Glucose

Glucose cyclic hemiacetal formed by
reaction of -CHO with -OH on C5.
=>
ChapterD-glucopyranose
23
Cyclic Structure for Fructose

Cyclic hemiacetal formed by reaction of
C=O at C2 with -OH at C5.
D-fructofuranose
Chapter 23
10
=>
Anomers
Chapter 23
11 =>
Mutarotation
Glucose also called

dextrose; dextrorotatory.
Chapter 23
=>
12
Epimerization
In base, H on C2 may be removed to form
enolate ion. Reprotonation may change
the stereochemistry of C2.
=>
Chapter 23
13
Enediol Rearrangement
In base, the position of the C=O can shift.
Chemists use acidic or neutral solutions
of sugars to preserve their identity.
=>
Chapter 23
14
Reduction of Simple Sugars

C=O of aldoses or ketoses can be
reduced to C-OH by NaBH4 or H2/Ni.
Name the sugar alcohol by adding -itol
to the root name of the sugar.
Reduction of D-glucose produces
D-glucitol, commonly called D-sorbitol.
Reduction of D-fructose produces a
mixture of D-glucitol and D-mannitol.
=>
Chapter 23
15
Oxidation by Bromine
Bromine water oxidizes aldehyde, but not
ketone or alcohol; forms aldonic acid.
=>
Chapter 23
16
Oxidation by Nitric Acid

Nitric acid oxidizes the aldehyde and the
terminal alcohol; forms aldaric acid.
Chapter 23
17 =>
Oxidation by Tollens Reagent

Tollens reagent reacts with aldehyde,
but the base promotes enediol
rearrangements, so ketoses react too.
Sugars that give a silver mirror with
Tollens are called reducing sugars.
=>
Chapter 23
18
Nonreducing Sugars
Glycosides are acetals, stable in base, so
they do not react with Tollens reagent.
Disaccharides and polysaccharides are
also acetals, nonreducing sugars.
=>
Chapter 23
19
Formation of Glycosides
React the sugar with alcohol in acid.
Since the open chain sugar is in
equilibrium with its - and -hemiacetal,
both anomers of the acetal are formed.
Aglycone is the term used for the group
bonded to the anomeric carbon.
=>
Chapter 23
20
Ether Formation
Sugars are difficult to recrystallize from
water because of their high solubility.
Convert all -OH groups to -OR, using a
modified Williamson synthesis, after
converting sugar to acetal, stable in base.
Chapter 23
21
=>
Ester Formation
Acetic anhydride with pyridine catalyst
converts all the oxygens to acetate esters.
=>
Chapter 23
22
Osazone Formation
Both C1 and C2 react with phenylhydrazine.
=>
Chapter 23
23
Ruff Degradation
Aldose chain is shortened by oxidizing the
aldehyde to -COOH, then decarboxylation.
=>
Chapter 23
24
Kiliani-Fischer Synthesis
This process lengthens the aldose chain.
A mixture of C2 epimers is formed.
Chapter 23
25
=>
Fischers Proof
Emil Fischer determined the configuration
around each chiral carbon in D-glucose in
1891, using Ruff degradation and oxidation
reactions.
He assumed that the -OH is on the right in
the Fischer projection for D-glyceraldehyde.
This guess turned out to be correct!
=>
Chapter 23
26
Determination of Ring Size

Haworth determined the pyranose
structure of glucose in 1926.
The anomeric carbon can be found by
methylation of the -OHs, then hydrolysis.
H
HO
excess CH3I
Ag2O
CH2OHO
H H
HO
OH
OH
H
CH3O
H3O
CH2OCH3
O
CH3O
H H
CH3O
H
CH3O
OCH3
H
Chapter 23
CH2OCH3
O
H H
CH3O
H
CH3O
OH
H
=>
27
Periodic Acid Cleavage

Periodic acid cleaves vicinal diols to
give two carbonyl compounds.
Separation and identification of the
products determine the size of the ring.
Chapter 23
28
=>
Disaccharides
Three naturally occurring glycosidic
linkages:
1-4 link: The anomeric carbon is bonded
to oxygen on C4 of second sugar.
1-6 link: The anomeric carbon is bonded
to oxygen on C6 of second sugar.
1-1 link: The anomeric carbons of the two
sugars are bonded through an oxygen. =>
Chapter 23
29
Cellobiose
Two glucose units linked 1-4.
Disaccharide of cellulose.
A mutarotating, reducing sugar.
Chapter 23
30
=>
Maltose
=>
Chapter 23
31
Lactose
Galactose + glucose linked 1-4.
Milk sugar.
=>
Chapter 23
32
Gentiobiose
Rare for disaccharides, but commonly
seen as branch point in carbohydrates.
Chapter 23
=>
33
Sucrose
Glucose + fructose, linked 1-1
Nonreducing sugar
=>
Chapter 23
34
Cellulose
Polymer of D-glucose, found in plants.
Mammals lack the -glycosidase enzyme.
=>
Chapter 23
35
Amylose
Soluble starch, polymer of D-glucose.
Starch-iodide complex, deep blue.
=>
Chapter 23
36
Amylopectin
Branched, insoluble fraction of starch.
=>
Chapter 23
37
Glycogen
Glucose polymer, similar to amylopectin,
but even more highly branched.
Energy storage in muscle tissue and liver.
The many branched ends provide a quick
means of putting glucose into the blood.
=>
Chapter 23
38
Chitin
Polymer of N-acetylglucosamine.
Exoskeleton of insects.
=>
Chapter 23
39
Nucleic Acids
Polymer of ribofuranoside
rings linked by phosphate
ester groups.
Each ribose is bonded to
a base.
Ribonucleic acid (RNA)
Deoxyribonucleic acid
(DNA)
Chapter 23
=>
40
Ribonucleosides
A -D-ribofuranoside bonded to a
heterocyclic base at the anomeric
carbon.
=>
Chapter 23
41
Ribonucleotides
Add phosphate at 5 carbon.
Chapter 23
42
Structure of RNA
Chapter 23
=>
43
Structure of DNA
-D-2-deoxyribofuranose is the sugar.
Heterocyclic bases are cytosine,
thymine (instead of uracil), adenine,
and guanine.
Linked by phosphate ester groups to
form the primary structure.
=>
Chapter 23
44
Base Pairings
Chapter 23
45
=>
Double Helix of DNA

Two complementary
polynucleotide
chains are coiled
into a helix.
Described by
Watson and Crick,
1953.
Chapter 23
=>
46
DNA Replication
Chapter 23
=>
47
Additional Nucleotides
Adenosine monophosphate (AMP), a
regulatory hormone.
Nicotinamide adenine dinucleotide
(NAD), a coenzyme.
Adenosine triphosphate (ATP), an
energy source.
=>
Chapter 23
48
End of Chapter 23
Chapter 23
49

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Organic Chemistry, 5th Edition

Disaccharides can be hydrolyzed to two

sugars can be degraded to the

The D Aldose Family

Erythro and Threo

Cyclic Structure for Glucose

Cyclic Structure for Fructose

Glucose also called

Reduction of Simple Sugars

Oxidation by Nitric Acid

Oxidation by Tollens Reagent

Determination of Ring Size

Periodic Acid Cleavage

Double Helix of DNA

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