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

ORBITAL
PLANAR OVERLAP
WITH NEW
BOND ORBITAL
ANGLES
OF 120°

as oxygen is more electronegative than carbon the bond is polar

 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 O O
HCH CH3 CH CH3 CCH3
Methanal Ethanal Propanone
(Formaldehyde) (Acetaldehyde) (Acetone)
 CARBONYL COMPOUNDS - NOMENCLATURE

Aldehydes C2H5CHO propanal

Ketones CH3COCH3 propanone

CH3CH2COCH3 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 Brady’s 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
Tollen’s Reagent

Fehling’s 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 + HCN ——> CH3CH(OH)CN

2-hydroxypropanenitrile

Notes HCN is a weak acid and has difficulty dissociating into ions

HCN 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 used in the solvent
Also known as (lithium aluminium hydride), ethoxyethane
(diethyl
 yields the HYDRIDE ion (H-) – a nucleophile ether)/room
temperature
 a nucleophilic reducing agent which REDUCES:
Note: Water must
o Aldehydes to primary (1°) alcohols. be avoided as
o Ketones to secondary (2°) alcohols. LiAlH4 reacts
Example violently with
1. CH3CHO + 2[H] ——> CH3CH2OH water!
2. CH3COCH3 + 2[H] ——> CH3CHOHCH3

Question LiAlH4 doesn’t reduce C=C bonds. WHY?

CH2 = CHCHO + 2[H] ———> CH2 = CHCH2OH
 REDUCTION OF ALDEHYDES
With LITHIUM TETRAHYDRIDOALUMINATE(III) LiAlH4

1.LiAlH4 /diethyl ether

2. H2O (or acid)

Butanal
- an aldehyde
- a primary alcohol
Mechanism:

ethanal
ethanol
 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.  catalyst - nickel
o Ketones are REDUCED to secondary (2°) alcohols. or platinum

1.  Catalytic
Butanal Butanol - a primary alcohol
reductions are
- an aldehyde generally carried
out at from 25° to
2. 100°C and 1 to 5
atm H2
- a ketone -a secondary alcohol

Note: Hydrogen also reduces C=C bonds

CH2 = CHCHO + 2H2 ——> CH3CH2CH2OH

 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 reacts with carbonyl compounds (aldehydes and ketones)
o used as a simple test for aldehydes and ketones
o makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones
o derivatives have sharp, well-defined melting points
o 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 213°C 214°C 214°C

Melting point of
2,4-dnph derivative 209°C 248°C 265°C

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

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