CHM143L / GROUP 2

Cruz, Patricia Anne D.

De Guzman, Anne K.

Dela Cruz, Maria Victoria

Duron, Marc John

Professor Oliver Villaflores

Introduction to Carbonyl
compounds
A compound containing the carbonyl
group is known as a carbonyl compound
Carbonyl
group - a
functional group
composed of a
carbon atom
double-bonded to
an oxygen atom

The carbon and oxygen atoms of the carbonyl group are sp2 hybridized
and planar in geometry
This generally undergoes nucleophilic substitution, triggering an attack at
107

 The carbonyl group is treated as an electrophile

due to resonance and inductive effects:

The resonance structure show a positive charge

on the carbonyl carbon (lack of electron density)
Due to the electronegativity of the oxygen atom,
induction renders the carbon atom partially
positive

ALDEHYDE
A simple type of
carbonyl compound
with at least one
hydrogen atom as a
substituent

KETONE
A simple type
of carbonyl
compound with
two substituent
other than the
hydrogen atom

The difference between

aldehydes and ketones
Aldehydes are more reactive than ketones
toward nucleophilic attack:
Steric effects: ketone is more sterically
hindered than aldehyde
Electronic effects: The partial positive charge
of an aldehyde is less stabilized than that of a
ketone:

Classifying carbonyl compounds:

CHEMICAL TESTS
The ease of oxidation helps chemists distinguish aldehydes from
ketones.

Aldehydes are easily oxidized by all sorts of different oxidizing

agents, ketones aren't.

1. Benedicts test
Benedict's solution contains copper(II) ions complexed with
citrate ions in sodium carbonate solution. Benedicts reagent
has Cu2+ ions which gives it a deep blue color.
During the oxidation, Cu2+ is reduced to Cu2O (a precipitate).
If the blue color does not change no oxidation occurs. If the
blue color stays and you have a precipitate, oxidation occurs.

Benedicts test continued

POSITIVE RESULT:
ketone
No change in the blue solution.
aldehyde
The blue solution produces a dark red
precipitate

Classifying carbonyl compounds:

CHEMICAL TESTS
2. Tollens test

Tollens reagent, is an alkaline solution of silver (Ag+) ion

complexed with ammonia (NH3), which keeps the Ag+ ion
in solution.
When Tollens reagent oxidizes an aldehyde, the Ag+ ion is
reduced to free silver (Ag). Deposited on a clean glass
surface, the silver produces a mirror.

Tollens test continued

RESULTS:

ketone
No change in the colorless solution.
aldehyde
The colorless solution produces a silver
mirror on the test tube. Less spectacular, but
just as valid is the formation of a grey or
black precipitate.

CHEMICAL TESTS
3. Carbonyl group reactions
Condensation Reaction
REAGENT/S and USES: 2,4-dinitrophenylhydrazine
- utilized as a test for the carbon-oxygen double bond in
ketones and aldehydes
MECHANISM: Nucleophilic addition-elimination rxn.
The 2,4-dinitrophenylhydrazine first adds
across the carbon-oxygen double bond (the
addition stage) to give an intermediate
compound which then loses a molecule of
water (the elimination stage).

POSITIVE RESULT:
A bright orange or
yellow precipitate
shows the presence of
the carbon-oxygen
double bond in an
aldehyde or ketone.

CHEMICAL TESTS
- Addition Reaction
REAGENT/S and USES: Sodium bisulfite (NaHSO3)
- utilized as a test for the carbon-oxygen double bond in
conjunction with the condensation rxn.
MECHANISM: Addition reaction
POSITIVE RESULT:
Formation of white
crystals (precipitate)
indicating presence of
C=O group

This reaction only works well for aldehydes. In

the case of ketones, one of the hydrocarbon
groups attached to the carbonyl group needs to
be a methyl group. Bulky groups attached to the
carbonyl group get in the way of the reaction
happening. The reason that cyclohexanone react
with sodium bisulfite and not in 3-pentanone is
that cyclohexanone is an unhindered ketone
while 3-pentanone only has ethyl groups and
this is already bulky enough to interfere with the
reaction.

3. Carbonyl group reactions

2,4-dinitrophenylhydrazine test

Sodium bisulfite test

CHEMICAL TESTS
5. Alkyl group reactions Haloform reaction
The haloform reaction is the reaction of
a methyl ketone with chlorine, bromine, or
iodine in the presence of hydroxide ions to
give a carboxylate ion and a haloform. There
is one aldehyde that undergoes the haloform
reaction, which is acetaldehyde.

Iodoform Test
When the halogen used is iodine.

TEST COMPOUNDS

Acetaldehyde

Acetone

1.

OBSERVATIONS

Acetaldehyde+H2O+8M NaOH-Pale
Yellow
+ I2 in KI- Golden Yellow
+heat- pale yellow precipitate
Acetone+H2O+8M NaOH-Clear
+ I2 in KI- Pale Yellow
+heat- pale yellow precipitate

References
Klein, David M. Organic Chemistry 2nd
Ed. 2012 John Wiley and Sons, Inc.