Carbohydrate

Reactions

Formation of Phosphate
Esters
Phosphate esters can form at the 6-carbon of

aldohexoses and aldoketoses.

Phosphate esters of monosaccharides are
found in the sugar-phosphate backbone of
DNA and RNA, in ATP, and as intermediates in
the metabolism of carbohydrates in the body.

Epimerization
In base, H on C2 may be removed to form
enolate ion.

Enediol Rearrangement
In base, the position of the C=O can
shift.
Chemists use acidic or neutral solutions
of sugars to preserve their identity

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
glucitol or called sorbitol
Reduction of D-fructofuranose
produces glucitol and mannitol.

Oxidation by Bromine

romine water oxidizes aldehyde, but not keton

r alcohol

Aldose Oxidation to Aldonic Acids

Oxidation of the -CHO group of an
aldose to a -CO2H group can be
carried out using Tollens,
Benedicts, or Fehlings solutions

Ketose Oxidation to Aldonic Acids

2-Ketoses are also oxidized by these reagents

because, under the conditions of the oxidation
2-ketoses equilibrate with isomeric aldoses

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.
All monosaccharides are reducing sugars

Nonreducing Sugars
Glycosides are acetals, which
stable in base, so they do not react
with Tollens reagent.
Some disaccharides are also
acetals.
All polysaccharides are also
acetals.

Oxidation by Nitric Acid

ic acid oxidizes both the aldehyde and the

minal alcohol

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

Ether Formation
Convert all -OH groups to -OR, using a
modified Williamson synthesis, after
converting sugar to acetal, stable in

base

Ester Formation

Acetic anhydride with pyridine catalyst

Converts all the oxygens to acetate esters

Osazone Formation

h C1 and C2 react with phenylhydrazine

Osazone

Ruff Degradation

ose chain is shortened by oxidizing the

ehyde to -COOH, then decarboxylation

Kiliani-Fischer Synthesis
This process lengthens the aldose
chain.
A mixture of C2 epimers is formed.

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

Periodic Acid Reactions

Periodic acid ( HIO4 or H5IO6 ) cleaves the C-C

bond between an alcohol and an adjacent

alcohol (vicinal) or carbonyl group.
Does not affect ethers or acetals.
Two carbonyl compounds are formed:
1 alcohols oxidize to formaldehyde
2 alcohols oxidize to aldehyde
aldehyde oxidize to formic acid ketones oxidize
to carboxylic acids carboxylic acids oxidize to
CO2

Use of Periodic Acid Cleavage

Separation and identification of the
Products determine the size of the ring

Reduction to Alditols
The carbonyl group of a monosaccharide
can be reduced to an hydroxyl group by
a variety of reducing agents, including
NaBH4 and H2/M

Amino Sugar
Glucosamine

Formation of Glycosides -Acetals

A monosaccharide hemiacetal can react

with a second molecule of an alcohol to
form an acetals

Glycosides
Glycoside bond: the bond from the anomeric

carbon of the glycoside to an -OR group.

Cyclic acetals are not in equilibrium with their
open chain carbonyl-containing forms.
Glycosides do NOT undergo mutarotation.
List the name of the alkyl or aryl group attached
to oxygen followed by the name of the
carbohydrate with the ending -e replaced by -ide
methyl -D-glucopyranoside
methyl -D-ribofuranoside

Formation of Glycosides

Acid catalyzed sugar reactions

Attack by a proton on the ring oxygen of a

reducing sugar results in ring opening.

Hydrolysis of the glycosidic linkage in reducing

and nonreducing sugars is catalyzed by

protonation of the exocyclic OR group.
A carbonium ion is formed that abstracts a
hydroxyl group from water to form free sugars

Acid catalyzed sugar reactions

Hydrolysis rates are predictable with furanose linkages

being hydrolyzed much faster than pyranose linkages.

-Glycosidic linkages are hydrolyzed faster than .
Hydrolysis rates of glycosidic linkages occur in the
following decreasing order: 1-2 > 1-3 > 1-4 > 1-6.
Sucrose (-furanose) will be hydrolyzed much easier
than maltose (-1-4), which undergoes hydrolysis at a
faster rate than lactose or cellobiose (both -1-4).
Gentiobiose ( -1-6) accumulates in corn syrup
manufacture due to delayed hydrolysis.

Acid catalyzed sugar reactions

Aldose

sugars will undergo acid-catalyzed

dehydration to form deoxy sugars and furfurals
Initial proton attack at C-3 results in hydroxyl
removal at C-3, and subsequent proton
removal at C-2 gives the 2-3-enol form; ketolenol
rearrangement
produces
3dexoyglucosone
Further dehydration occurs down the chain
with subsequent ring closure to produce
hydroxymethylfurfural from aldose sugars and
furfural from pentoses.

Significance of acid catalyzed rxn.

Furfurals have flavor significance, and they

are reactive in polymerization reactions.

A thin-layer chromatogram of separated
sugars can be sprayed with an acidic solution
and heated to produce furfurals that are
subsequently reacted with amines to give a
colored complex

Alkali catalyzed sugar reactions

Hydroxide ion initiates proton removal from the

anomeric hydroxyl, followed by ring opening.

In the case of nonreducing sugars, there is no

anomeric hydroxyl group. Therefore, under alkaline

conditions, hydrolysis will not take place.
Use of lime in sugar refining to render the extract
alkaline so that hydrolysis of the acid-labile furanose linkage (sucrose inversion) does not take
place.

Alkali catalyzed sugar reactions

Reducing sugars will undergo 1-2-enolization

to form different isomers

Alkali catalyzed sugar reactions

The reaction is favored in alkali.
This is one reason that Fehlings reagent is alkaline

The enediol is readily oxidized by metal ions, and, in

addition, acid hydrolysis of labile nonreducing sugars,

such as sucrose, is prevented.
One application of this reaction is to convert the glucose
moiety of lactose (4-O--D-galactopyranosyl-D-glucose)
to lactulose (4-O--D-galactopyranosyl-D-fructose).

Significance of alkaki catalyzed rxn.

Lactulose has higher water solubility than

lactose, and it is somewhat sweeter than

lactose, 0.5 sucrose.
Lactulose is not hydrolyzed by lactase, not
absorbed, and noncaloric.
It is used as a laxative but is not approved for
food use