Reactions of Carbonyl

Compounds

Cinnamaldehyde is a carbonyl
compound found in the bark of
the cinnamon tree

CARBONYL COMPOUNDS - BONDING

Bonding the carbon is sp2 hybridised and three sigma (s) bonds are planar
the unhybridised 2p orbital of carbon is at 90 to these
it overlaps with a 2p orbital of oxygen to form a pi (p) bond
P ORBITAL

PLANAR
WITH
BOND
ANGLES
OF 120

ORBITAL
OVERLAP

as oxygen is more electronegative than carbon the bond is polar

NEW
ORBITAL

CARBONYL COMPOUNDS - STRUCTURE

Structure carbonyl groups consists of
a carbon-oxygen double bond
the bond is polar due to the
difference in electronegativity
ALDEHYDES - at least one H attached to the carbonyl group

KETONES - two carbons attached to the carbonyl group

NOMENCLATURE OF CARBONYL COMPOUNDS

Structure
the functional group of an aldehyde is a carbonyl group bonded to a H atom
and a carbon atom
the functional group of a ketone is a carbonyl group bonded to two carbon
atoms
O

HCH
Methanal
(Formaldehyde)

CH3 CH

CH3 CCH3

Ethanal
(Acetaldehyde)

Propanone
(Acetone)

CARBONYL COMPOUNDS - NOMENCLATURE

Aldehydes

Ketones

C2H5CHO

CH3COCH3
CH3CH2COCH3

propanal

propanone
butanone

CH3COCH2CH2CH3 pentan-2-one
CH3CH2COCH2CH3 pentan-3-one
C6H5COCH3

phenylethanone

CARBONYL COMPOUNDS - IDENTIFICATION

Method 1

strong peak around 1400-1600 cm-1 in the infra red spectrum

Method 2
formation of an orange crystalline precipitate with 2,4-dinitrophenylhydrazine
(DNP) also known as Bradys reagent.

Although these methods identify a carbonyl group, they cannot tell the difference
between an aldehyde or a ketone. To narrow it down you must do a second test.

IDENTIFICATION of CARBONYL COMPOUNDS

Tollens Reagent

Fehlings Solution

CARBONYL COMPOUNDS - NUCLEOPHILIC ADDITION

Mechanism
occurs with both aldehydes and ketones

involves addition to the C=O double bond

unlike alkenes, they are attacked by nucleophiles

attack is at the positive carbon centre due to the difference in electronegativities

alkenes are non-polar and are attacked by electrophiles undergoing electrophilic

addition

NUCLEOPHILIC ADDITION OF HYDROGEN CYANIDE TO CARBONYL COMPOUNDS

Reagent

hydrogen cyanide - HCN (in the presence of KCN or NaCN)

Conditions reflux in alkaline solution

Nucleophile

cyanide ion CN

Product(s) hydroxynitrile (cyanohydrin)

Equation

CH3CHO

Notes

HCN is a weak acid and has difficulty dissociating into ions

HCN

HCN > CH3CH(OH)CN

2-hydroxypropanenitrile

H+

CN

the reaction is catalysed by alkali (NaOH) which helps produce more of the nucleophilic CN

NUCLEOPHILIC ADDITION OF HYDROGEN CYANIDE

TO CARBONYL COMPOUNDS Mechanism Nucleophilic addition of hydrogen cyanide, HCN

STEP 1

STEP 2

2-hydroxypropanenitrile
Step 1: CN acts as a nucleophile and attacks the slightly positive C
One of the C=O bonds breaks; a pair of electrons goes onto the O
Step 2: A pair of electrons is used to form a bond with H +
Overall, there has been addition of HCN

REDUCTION of CARBONYL COMPOUNDS

with LITHIUM TETRAHYDRIDOALUMINATE(III) LiAlH4
Also known as (lithium aluminium hydride),

yields the HYDRIDE ion (H-) a nucleophile

a nucleophilic reducing agent which REDUCES:
o Aldehydes to primary (1) alcohols.
o Ketones to secondary (2) alcohols.
Example

1. CH3CHO + 2[H]
2. CH3COCH3 + 2[H]
Question

>
>

CH3CH2OH
CH3CHOHCH3

LiAlH4 doesnt reduce C=C bonds. WHY?

CH2 = CHCHO

2[H]

>

CH2 = CHCH2OH

used in the solvent

ethoxyethane
(diethyl
ether)/room
temperature
Note: Water must
be avoided as
LiAlH4 reacts
violently with
water!

REDUCTION OF ALDEHYDES
With LITHIUM TETRAHYDRIDOALUMINATE(III) LiAlH4

1.LiAlH4 /diethyl ether

Butanal
- an aldehyde

2. H2O (or acid)

- a primary alcohol

Mechanism:

ethan
al

ethan
ol

REDUCTION OF KETONES
With LITHIUM TETRAHYDRIDOALUMINATE(III) LiAlH4

1.LiAlH4 /diethyl ether

2. H2O (or acid)
Propanone
- a ketone

Propan-2-ol
- a secondary alcohol

REDUCTION of CARBONYL COMPOUNDS - WITH HYDROGEN

o Aldehydes are REDUCED to primary (1) alcohols.
o Ketones are REDUCED to secondary (2) alcohols.
1.
Butanal
- an aldehyde

Butanol - a primary alcohol

- a ketone

-a secondary alcohol

2.

Note: Hydrogen also reduces C=C bonds

CH2 = CHCHO

2H2

>

CH3CH2CH2OH

catalyst - nickel
or platinum

Catalytic
reductions are
generally carried
out at from 25 to
100C and 1 to 5
atm H2

CARBONYL COMPOUNDS - REDUCTION

Example What are the products when Compound X is reduced?

COMPOUND X

H2

LiAlH4

o C=O is polar so is attacked by the nucleophilic H

o C=C is non-polar so is not attacked by the nucleophilic H

2,4-DINITROPHENYLHYDRAZINE
Structure

C6H3(NO2)2NHNH2

Uses
o
o
o
o
o

reacts with carbonyl compounds (aldehydes and ketones)

used as a simple test for aldehydes and ketones
makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones
derivatives have sharp, well-defined melting points
also used to characterise (identify) carbonyl compounds.

Identification / characterisation
A simple way of characterising a compound (finding out what it is) is to
measure the melting point of a solid or the boiling point of a liquid.

2,4-DINITROPHENYLHYDRAZINE (DNP) C6H3(NO2)2NHNH2

The following structural isomers have similar boiling points because of similar van der
Waals forces and dipole-dipole interactions. They would be impossible to identify with any
precision using boiling point determination.
CHO

CHO

CHO

Cl

Cl
Cl

Boiling point

213C

214C

214C

Melting point of
2,4-dnph derivative

209C

248C

265C

By forming the 2,4-dinitrophenylhydrazone derivative and taking its melting

point, it will be easier to identify the unknown original carbonyl compound.