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 2
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 3
 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
 D and L Sugars
• D 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

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Chapter 23 6
 Erythro and Threo
• Terms used for diastereomers with two
adjacent chiral C’s, without symmetric ends.
• For symmetric molecules, use meso or d,l.

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Chapter 23 7
 Epimers
Sugars that differ only in their
stereochemistry at a single carbon.

=>
Chapter 23 8
 Cyclic Structure for Glucose
Glucose cyclic hemiacetal formed by
reaction of -CHO with -OH on C5.

=>
Chapter 23 D-glucopyranose 9
 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

=>
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.

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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.

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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
=>
 Fischer’s 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 -OH’s, then hydrolysis.
H excess CH3I H
H +
CH2OHO CH2OCH3 H3O CH2OCH3
HO Ag2O O O
CH3O CH3O
H H H H
HO OH H H OH
CH3O OCH3 CH3O
OH CH3O
CH3O
H H H H
H H

=>
Chapter 23 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
Two glucose units linked 1-4’.

=>
Chapter 23 31
 Lactose
• Galactose + glucose linked 1-4’.
• “Milk sugar.”

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Chapter 23 32
 Gentiobiose
• Two glucose units linked 1-6’.
• Rare for disaccharides, but commonly
seen as branch point in carbohydrates.

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Chapter 23 33
 Sucrose
• Glucose + fructose, linked 1-1’
• Nonreducing sugar

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Chapter 23 34
 Cellulose
• Polymer of D-glucose, found in plants.
• Mammals lack the -glycosidase enzyme.

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Chapter 23 35
 Amylose
• Soluble starch, polymer of D-glucose.
• Starch-iodide complex, deep blue.

=>

Chapter 23 36
 Amylopectin
Branched, insoluble fraction of starch.

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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.

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Chapter 23 38
 Chitin
• Polymer of N-acetylglucosamine.
• Exoskeleton of insects.

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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