Chemical Reactions of Monosaccharides:

1. Oxidation to sugar acids

The redox chemistry of monosaccharides is closely linked to that of the alcohol and the aldehyde
functional groups.

Primary alcohol  Aldehyde  Carboxylic Acid

R - CH2OH R -CHO R – COOH

CH3CH2OH CH3CHO CH3COOH

Monosaccharide oxidation can yield 3 different types of sugar acids.

-Aldonic acids

-Aldaric aacids

- Uronic acids

a) Aldonic acids - Aldose  Aldonic Acid

Weak oxidizing agents such as Tollen’s, Fehling’s and Benedict’s solution oxidize the aldehyde group,
CHO, of an aldose to a carboxylic acid, COOH, to give the aldonic acid.

Benedict’s
+ solution (CuSO4,
Na2CO3, Na + Cu O2
citrate)
(reduced product)
(o.a)
(brick red
precipitate)
D-gluconic acid
D-glucose (r.a.)
(oxidized product)

“ + Fehling’s solution ->

(CuSO4, NaOH, Rochelle salt)

Na K tartrate

“ + Tollen’s reagent (AgNO3, NH4OH) ->

Reducing sugars-are carbohydrates that have reducing properties and give a positive result with the following
tests.

Solution Oxidizing agent Reduced product Positive result

Benedict`s copper(II) sulfate cuprous oxide brick red ppt.

CuSO4 Cu2O
Fehling`s copper(II) sulfate cuprous oxide brick red ppt.
Tollen`s silver nitrate silver silver mirror
AgNO3 Ag

Note: Tollen`s and Benedict`s solution can be used to test for glucose in urine, a symptom for diabetes.

The glucose content of urine can be determined by dipping a plastic strip treated with oxidizing agents
and comparing the color change of the strip to a color chart that indicates glucose concentration.

b) Aldaric acids
AldoseAldaric acid

Strong oxidizing agents like concentrated HNO3 can oxidize both ends of a monosaccharide
(the –CHO and –CH2OH groups)at the same time to produce a dicarboxylic acid.

Polyhydroxy dicarboxylic acids are known as aldaric acids.

D-glucose D-glucaric acid

D-galactose D-galactaric acid ( mucic acid)
D-mannose D-mannaric acid

conc.HNO3

D – glucaric acid
D-glucose
c) Uronic acids

AldoseAlduronic acid

In biological systems, enzymes can oxidize only the primary alcohol of an aldose to produce an
alduronic acid.

enzymes

D-glucose

D-glucoseD-glucuronic acid

D-galactoseD-galacturonic cid

D-mannoseD-mannuronic acid

Note: Uronic acids may also exist in closed ring structures.

enzymes

Alpha D-glucopyranose Alpha D-glucuronic acid

Uronic acids like alpha D-glucuronic acid is used by the body to detoxify foreign phenols and
alcohols.

-in the liver,these compounds are converted to glycosides of glucuronic acid and excreted in the
urine.

-it is widely distributed in the plant and animal world.

-in humans, it is an important component of an acidic polysaccharides of connective tissues.

2. Reduction to sugar alcohols

Aldose Alditol

Carboxylic Acid  Aldehyde  Primary Alcohol

R-COOH R-CHO R-CH2OH

The carbonyl group of a monosaccharide can be reduced to a hydroxyl group by a variety of

reducing agents, including NaBH4 and H2 in the presence of a transition metal like Pd or Pt.

D-glucose D-glucitol

D-galactose  D-galactitol

D-mannose  D-mannitol

NaBH4

Pd or Pt

D-glucose D-glucitol

Common Alditols and their Functions:

Xylitol – component of sugar free gum

D-glucitol or D-sorbitol - is found in the plant world in many berries, and in cherries, plums, pears,
apples, seaweed, and algae.

- also used as a sweetening agent.

Note: accumulation of D-sorbitol in the eye is a major factor in the formation of cataracts.

D-mannitol - is now used in the treatment of malignant brain tumors.

-it is injected directly into the brain`s main arteries to lower the blood- brain barrier and
allow chemotherapeutic agents to be administered intravenously.

Alditols -are used as moisturizing agents in food and in cosmetics.

3.) Amino sugars

If one of the hydroxyl groups of a monosaccharide is replaced with an amino (NH 2), an
amino sugar is produced.

Alpha D-glucopyranose Alpha D-glucosamine

Three naturally occurring amino sugars:

a) Alpha D- glucosamine
b) Alpha D-galactosaamine
c) AlphaD- mannosamine

Note: The –NH2 group replaces the carbon 2 hydroxyl group.

Amino sugars and their N-acetyl derivatives are important building blocks of chitin and
hyaluronic acid.

N-acetyl derivatives of glucosamine and galactosamine acts as biological markers of red blood
cells (RBC) which distinguishes various blood types.

The surface of red blood cells contain glycoproteins (sugar containing proteins) that
determines the blood type.

-Each blood type has specific antigens and antibodies against other blood types.
 4.) Phosphate Esters

The hydroxyl groups of a monosaccharide can react with phosphoric acid (H 3PO4) to
form phosphate esters.

Alpha D-glucopyranose Alpha D-glucopyranose-1-phosphate

CH2

+ 2

Alpha D-glucopyranose

Note: Most phosphate esters are intermediate products involved in metabolism.

5.) Glycosides

The cyclic form of monosaccharides are hemiacetals which may react with alcohols to
form an acetal.

A glycoside is an acetal formed from a cyclic monosaccharide by replacement of the –OH

group of the hemiacetal carbon with an –OR group.

+ CH3OH
+ H20

Alpha D-glucopyranose