Carbonyl compounds 2814 1

CARBONYL COMPOUNDS - Aldehydes and Ketones

Q.1 Carbonyl compounds are formed by oxidation of alcohols;

a) Which type of alcohol is oxidised to an aldehyde?
b) Which type of alcohol is oxidised to a ketone?
c) What compounds are formed when aldehydes are oxidised?

Structure • carbonyl groups consists of a carbon-oxygen double bond

• the bond is polar due to the difference in electronegativity C O
• aldehydes and ketones differ in what is attached to the carbon.

ALDEHYDES - at H
least one H attached to C
the carbonyl group

C=O C=O
HCHO
H H
or CH3CHO
C6H5CHO

C
KETONES - two carbons attached to the carbonyl group
C=O
C CH3COCH3
C2H5COCH3
C6H5COCH3

Bonding • the carbonyl carbon is sp2 hybridised and three sigma (σ) 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 (π) bond
• as oxygen is more electronegative than carbon the bond is polar

C O C O

Formation Aldehydes • Oxidation of primary (1°) alcohols - beware of further oxidation to acids
• Reduction of carboxylic acids

Ketones • Oxidation of secondary (2°) alcohols.

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IDENTIFYING A CARBONYL COMPOUND

Methods • a characteristically strong peak around 1400-1600 cm-1 in the infra red spectrum or
• formation of an orange crystalline precipitate with 2,4-dinitrophenylhydrazine

However, to narrow it down to an aldehyde or ketone you must do a second test

Differentiating between Aldehydes and Ketones

Differentiation • to distinguish an aldehyde from a ketone you need a mild oxidising agent ...

Tollen’s Reagent • ammoniacal silver nitrate - contains the diammine silver(I) ion - [Ag(NH3)2 ]+
• acts as a mild oxidising agent and will oxidise aldehydes but not ketones
• the silver(I) ion is reduced to silver
Ag+(aq) + e¯ ——> Ag(s)
• the test is known as THE SILVER MIRROR TEST

Fehling’s Solution • contains copper(II) ions complexed with tartrate ions giving a blue solution
• on warming, it will oxidise aliphatic (but not aromatic) aldehydes
• copper(II) is reduced and a red precipitate of copper(I) oxide, Cu2O, is formed

The silver mirror test is the better alternative as it works with all aldehydes.

Ketones do not react with Tollen’s Reagent or Fehling’s Solution.

CHEMICAL PROPERTIES OF CARBONYL COMPOUNDS

OXIDATION • provides a way of differentiating between aldehydes and ketones

• mild oxidising agents are best
• aldehydes are easier to oxidise
• powerful oxidising agents can oxidise ketones to a mixture of carboxylic acids

ALDEHYDES easily oxidised to acids e.g. RCHO(l) + [O] ——> RCOOH(l)

CH3CHO(l) + [O] ——> CH3COOH(l)

KETONES only oxidised under vigorous conditions to acids with fewer carbon atoms.

e.g. C2H5COCH2CH3(l) + 3 [O] ——> C2H5COOH(l) + CH3COOH(l)

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NUCLEOPHILIC ADDITION REACTIONS

Mechanism • occurs with both aldehydes and ketones

• involves addition to the polar C=O double bond (oxygen has a greater electronegativity)
• attacked by nucleophiles at the positive carbon centre
• alkenes are non-polar and are attacked by electrophiles

Summary Bond Polarity Attacked by Result

Carbonyl C=O Polar Nucleophiles Addition

Alkene C=C Non-polar Electrophiles Addition

HCN Reagent hydrogen cyanide - HCN (in the presence of KCN)

Conditions reflux in alkaline solution
Nucleophile cyanide ion CN¯
Product(s) hydroxynitrile (cyanohydrin)

Equation CH3CHO + HCN ——> CH3CH(OH)CN 2-hydroxypropanenitrile

Mechanism Nucleophilic addition

H
+
H H H
C O CH3 C O CH 3 C OH
CH3 C C
_
N N
N—
—C
—

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

Notes • HCN is a weak acid ; HCN H+ + CN¯ few CN¯ ions produced
• the reaction is catalysed by alkali which helps produce more of the nucleophilic CN¯
• watch out for the possibility of optical isomerism in hydroxynitriles

_
N—
—C
— N N
CN¯ attacks from above C C
H
C O C C
H O H OH
CH3
H
+
CH3 CH3

+
CH3 H O H CH3 H OH
CN¯ attacks from below H C C
C O
CH3 C C
_
N—
—C
— N N

• hydrolysis of the CN group to COOH is possible

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Q.2 Write out equations for the reactions between HCN and...
• C2H5CHO + HCN ——>

• CH3COCH3 + HCN ——>

• hexanal + HCN ——>

Indicate which reactions give rise to optically active organic compounds?

Why is the addition of HCN such a useful reaction?

REDUCTION Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH4

Conditions aqueous or alcoholic solution
Mechanism Nucleophilic addition (also reduction as it is addition of H¯)
Nucleophile H¯ (hydride ion)
Product(s) Alcohols :- Aldehydes are REDUCED to primary (1°) alcohols.
Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + 2[H] ——> CH3CH2OH

CH3COCH3 + 2[H] ——> CH3CHOHCH3

H O H
H H H
C O CH3 C O CH 3 C OH + HO
CH3 H H

Notes The water provides a proton

NaBH4 doesn’t reduce C=C bonds. WHY?

e.g. CH2 = CHCHO + 2[H] ———> CH2 = CHCH2OH

Q.3 Draw a diagram to indicate

the bonding in NaBH4.
What shape is it ?
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Alternative
Method Reagent hydrogen
Conditions catalyst - nickel or platinum
Reaction type Hydrogenation, reduction
Product(s) Alcohols :- Aldehydes are REDUCED to primary (1°) alcohols.
Ketones are REDUCED to secondary (2°) alcohols.

Equation(s) CH3CHO + H2 ——> CH3CH2OH

CH3COCH3 + H2 ——> CH3CHOHCH3

Note Hydrogen also reduces C=C bonds

e.g. CH2 = CHCHO + 2H2 ——> CH3CH2CH2OH

Q.4 Draw structures of the organic products formed when the following are reduced using...
NaBH4 H2

CH2 = CHCH2 CHO

OH

O
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2,4-DINITROPHENYLHYDRAZINE NH
2
NH
C6H3(NO2)2NHNH2 NO2

Theory • reacts with carbonyl compounds (aldehydes and ketones)

• used as a simple test for aldehydes and ketones NO2
• makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones
• derivatives have sharp, well-defined melting points
• also used to characterise (identify) carbonyl compounds.

Identification A simple way of characterising a compound (finding out what it is) is to measure...

• the melting point of a solid • the boiling point of a liquid

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

isomeric Cl
chlorophenylmethanals

Cl
Cl

Boiling point of compound 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 derivatives and taking the melting point of the
crystalline product, it will be easy to identify the unknown original carbonyl compound.

CH 3
NH2 NH C N NH
Typical H
NO2 NO2
equation
+ CH CHO H2O +
3

NO2 NO2

Mechanism ADDITION-ELIMINATION