Carbonyl

Chemistry
Oxidation/ Reduction
Reactions – Redox
chemistry

1
 Introduction
 Several functional groups contain the carbonyl group
 Carbonyl groups can be converted into alcohols by various reactions

 Structure of the Carbonyl Group

 The carbonyl carbon is sp2 hybridized and is trigonal planar
 All three atoms attached to the carbonyl group lie in one plane

Chapter 12 2
 Reactions of Carbonyl Compounds with
Nucleophiles
 Carbonyl groups can undergo nucleophilic addition
 The nucleophile adds to the d+ carbon
 The p electrons shift to the oxygen
 The carbon becomes sp3 hybridized and therefore tetrahedral
 Hydride ions and carbanions are two examples of nucleophiles that react
with the carbonyl carbon

 Carbonyl groups and alcohols can be interconverted by

oxidation and reduction reactions
 Alcohols can be oxidized to aldehydes; aldehydes can be reduced to alcohols

Chapter 12 3
 Introduction Cont’d
• A defined centre is said to be
oxidized if the electron density
decreases, and reduced if electron
density increases, during a
reaction. The rule is:
• Loss of electrons equates w ith
Oxidation
• Gain of electrons equates w ith
Reduction
4
Introduction Cont’d

5
 Oxidation-Reduction Reactions in Organic
Chemistry
 Reduction: increasing the hydrogen content or decreasing
the oxygen content of an organic molecule
 A general symbol for reduction is [H]

 Oxidation: increasing the oxygen content or decreasing

the hydrogen content of an organic molecule
 A general symbol for oxidation is [O]
 Oxidation can also be defined as a reaction that increases the content
of any element more electronegative than carbon

Chapter 12 6
 Alcohols by Reduction of Carbonyl
Compounds
 A variety of carbonyl compounds can be reduced to
alcohols

 Carboxylic acids can be reduced to primary alcohols

 These are difficult reductions and require the use of powerful reducing
agents such as lithium aluminum hydride (LiAlH4 also abbreviated LAH)

Chapter 12 7
 The key step in the reduction is reaction of hydride with the
carbonyl carbon

 Carboxylic acids and esters are considerably less reactive to

reduction than aldehydes and ketones and require the use of
LAH

 Lithium aluminium hydride is very reactive with water and

must be used in an anhydrous solvent such as ether
 Sodium borohydride is considerably less reactive and can be used in solvents
such as water or an alcohol
Chapter 12 8
 Reduction by addition of H- and H+
The reducing agents are NaBH4 or LiAlH4.
Hydride ion adds to the carbonyl carbon and the alkoxide ion that
is formed is protonated by water.
O O- OH
H2O
H- C C + HO-
C

Aldehydes and ketones are reduced by NaBH4

O
1. NaBH4
CH3CH2CH2CH 2. H+, H2O
CH3CH2CH2CH2OH
an aldehyde a primary alcohol

O OH
1. NaBH4
CH3CH2CH2CCH3 2. H+, H2O CH3CH2CH2CHCH3
a ketone 20
a
secondary alcohol
 Esters are also reduced to primary alcohols
 LAH or high pressure hydrogenation can accomplish this transformation

 Aldehydes and ketones are reduced to 1o and 2o alcohols

respectively
 Aldehydes and ketones are reduced relatively easily; the mild reducing agent
sodium borohydride (NaBH4) is typically used
 LAH and hydrogenation with a metal catalyst can also be used

Chapter 12 10
The metal-hydrogen bonds in LiAlH4 are more polar than those in
NaBH4 and as a result, LiAlH4 is a stronger reducing agent.
Both will reduce aldehydes and ketones, but only LiAlH4
will reduce carboxylic acids, esters and amides.

O
1. LiAlH4
CH3CH2CH2CH2OH + H2
CH3CH2CH2COH 2. H+, H2
O
a primary alcohol O
O
1. LiAlH4
CH3CH2CH2OH
CH3CH2COCH3 2. H+, H2 + H2O
O a primary alcohol

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 O
1. LiAlH4
CH3CH2CH2CH2NH2
CH3CH2CH2CNH2 2. H2O
a primary amine
O 1. LiAlH4
2. H2O
CH3CH2CH2CH2NHCH3
CH3CH2CH2CNHCH3 a secondary amine
O CH3 CH3
1. LiAlH4
CH3CH2CH2C NCH3 2. H2O
CH3
a tertiary
CH2CH amine
2CH2NCH3

In order to obtain a neutral (non-protonated) amine,

acid is not used in the second step of the reaction.

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Because NaBH4 cannot reduce an ester, an amide, or a
carboxylic acid, it can be used to selectively reduce an
aldehyde or a ketone group.
O O OH O
1. NaBH4
CH3CCH2CH2COCH3 2. H2O
CH3CHCH2CH2COCH3

Sterically bulky donors can be used to deliver only one

equivalent of hydride ion. E.g esters and and acyl
chlorides are reduced to aldehydes.
O 1. [(CH3)2CHCH2]2AlH, -78 oC O
CH3CH2CH2COCH3 2. H2O CH3CH2CH2CH
an a
ester n aldehyde
1. LiAl[OC(CH3)3]3H, -78 o C
O CH3 CH2 CH2 CHO
2. H2O
CH CH2 an aldehyde
13
3CH2CH2CH2CCl

a
Multiply bonded carbon atoms of alkenes and alkynes do not react
with NaBH4 and LiAlH4.
It can therefore be used to selectively reduce a carbonyl group in
a compound that has multiply bonded carbon atoms.

CH3CH2CH CH2 NaBH4 No reaction

NaBH4 No reaction
CH3CH2C
CH O OH
1. NaBH4
CH3CH CH3 CHCH2CHCH3
CHCH2CCH3 2. H2O
CH

14
 Oxidation of Alcohols
 Oxidation of Primary Alcohols to Aldehydes
 A primary alcohol can be oxidized to an aldehyde or a
carboxylic acid
 The oxidation is difficult to stop at the aldehyde stage and usually proceeds
to the carboxylic acid

 A reagent which stops the oxidation at the aldehyde stage is

pyridinium chlorochromate (PCC)
 PCC is made from chromium trioxide under acidic conditions
 It is used in organic solvents such as methylene chloride (CH2Cl2)

Chapter 12 15
 Oxidation of Primary Alcohols to Carboxylic Acids
 Potassium permanganate (KMnO4) is a typical reagent used
for oxidation of a primary alcohol to a carboxylic acid
 The reaction is generally carried out in aqueous solution; a brown precipitate
of MnO2 indicates that oxidation has taken place

 Oxidation of Secondary Alcohols to Ketones

 Oxidation of a secondary alcohol stops at the ketone
 Many oxidizing agents can be used, including chromic acid (H2CrO4) and
Jones reagent (CrO3 in acetone)

Chapter 12 16
 A Chemical Test for Primary and Secondary Alcohols
 Chromium oxide in acid has a clear orange color which
changes to greenish opaque if an oxidizable alcohol is present

Chapter 12 17
 Oxidation of Alcohols
Most common reagent used is H2CrO4 (chromic acid) formed by
dissolving CrO3 or Na2Cr2O7 in aqueous acid.

OH CrO3 O
CH3CH2CHCH3 H2SO4 CH3CH2CCH3

OH O

Na2Cr2O7
H2SO4

OH O
H2CrO4
CHCH2CH3 CCH2CH3

2O alcohols are oxidised to 25

ketones
1o alcohols are first oxidised to aldehydes and then further oxidised to
carboxylic acids.

H2CrO4 O further
O
CH3CH2CH2CH2OH
CH3CH2CH2CH oxidation CH3CH2CH2COH
A primary alcohol
a a
Mechanism of oxidation
n aldehyde of alcohols carboxylic acid
O O H O
H+ HO Cr OH RCH2O Cr OH
HO Cr
OH -H+ O H O
O
RCH2OH
-H+
H+

O
O
RCH O
H2CrO3 + H2O + RCH
Cr

H2O OHester
A chromate H
19

O
Oxidation using pyridinium chlorochromate (PCC) as the oxidising agent
and an anhydrous solvent e.g. dichloromethane stops the reaction at the
aldehyde. O
PCC
CH3CH2CH2CH2OH CH3CH2CH2CH
CH2Cl2
a primary alcohol an aldehyde

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 Oxidation of aldehydes and ketones

O O
Na2Cr2O7
CH3CH2CH H2SO CH3CH2COH
4
O O
H2CrO4
CCH3 C
OH
aldehydes carboxylic acids

Ag2O in NH3(aq) (tollens’ reagent) will oxidise

and aldehyde but is too weak to oxidise an alcohol.
O O
1. Ag2O, NH3
CH3CH2CH 2. H+, H O CH3CH2COH + Ag
2 metallic silver

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