Title: Redox Reactions
1Redox Reactions
33.1 Organic Synthesis 33.2 Redox
Reactions 33.3 Oxidation of Alkylbenzenes 33.4 Oxi
dation of Alcohols 33.5 Redox Reactions of
Aldehydes and Ketones 33.6 Redox Reactions of
Carboxylic Acids 33.7 Redox Reactions of
Alkenes 33.8 Autooxidation of Fats and Oils
2Organic Synthesis
333.1 Organic Synthesis (SB p.51)
Organic Synthesis
- In planning syntheses,
- ? we need to think backwards
- ? think backwards from the desired product to
simpler molecules (precursors)
Target molecule
433.1 Organic Synthesis (SB p.51)
Organic Synthesis
- A synthesis usually involves more than one step
Target molecule
533.1 Organic Synthesis (SB p.51)
Organic Synthesis
- Usually more than one way to carry out a synthesis
Target molecule
633.1 Organic Synthesis (SB p.52)
Number of Steps Involved in the Synthesis
- Most organic reactions are
- ? reversible reactions
- ? seldom proceed to completion
- ? impossible to have a 100 yield of the
product from each step of the synthetic route
733.1 Organic Synthesis (SB p.52)
Number of Steps Involved in the Synthesis
- Consider the following synthetic route
- ? each step has a yield of 60
What is the yield of the desired product?
833.1 Organic Synthesis (SB p.52)
Number of Steps Involved in the Synthesis
Yield of the desired product 60 ? 60 ? 60
? 60 12.96
933.1 Organic Synthesis (SB p.52)
Number of Steps Involved in the Synthesis
- An efficient route of synthesis should consist of
a minimal number of steps - Limit the total number of reaction steps in a
synthesis to not more than four
1033.1 Organic Synthesis (SB p.52)
Availability of Starting Materials and Reagents
- Only a restricted number of simple, relatively
cheap starting materials is available - Include
- ? simple haloalkanes and alcohols of not more
than four carbon atoms - ? simple aromatic compounds (e.g. benzene and
methylbenzene)
1133.1 Organic Synthesis (SB p.52)
Duration of the Synthetic Process
- Many organic reactions proceed at a relatively
low rate - e.g. the acid-catalyzed esterification requires
refluxing the reaction mixture of alcohols and
carboxylic acids for a whole day - Inclusion of these slow reactions in a synthetic
route is impractical
12Redox Reactions
1333.2 Redox Reactions (SB p.53)
Redox Reactions
- Redox reactions are reactions that involve a
change of oxygen or hydrogen content in organic
compounds
1433.2 Redox Reactions (SB p.53)
Oxidation
- Oxidation of an organic compound usually
corresponds to - ? an increase in oxygen content
- ? a decrease in hydrogen content
1533.2 Redox Reactions (SB p.53)
Oxidation
- e.g.
- The change of ethanol to ethanoic acid is an
oxidation - ? the oxygen content of ethanoic acid is higher
than that of ethanol
1633.2 Redox Reactions (SB p.53)
Oxidation
- e.g.
- Converting ethanol to ethanal is also an
oxidation process - ? the hydrogen content of ethanal is lower than
that of ethanol
1733.2 Redox Reactions (SB p.53)
Oxidation
- Common oxidizing agents used in organic reactions
include - Acidified potassium manganate(VII) (KMnO4/H)
- Alkaline potassium manganate(VII) (KMnO4/OH)
- Acidified potassium dichromate(VI) (K2Cr2O7/H)
- Ozone (O3/CH3CCl3, Zn/H2O)
1833.2 Redox Reactions (SB p.54)
Reduction
- Reduction of an organic compound usually
corresponds to - ? an increase in hydrogen content
- ? a decrease in oxygen content
1933.2 Redox Reactions (SB p.54)
Reduction
- e.g.
- Converting ethanoic acid to ethanal is a
reduction - ? the oxygen content of ethanal is lower than
that of ethanoic acid
2033.2 Redox Reactions (SB p.54)
Reduction
- e.g.
- Converting ethanal to ethanol is also a
reduction process - ? the hydrogen content of ethanol is higher
than that of ethanal
2133.2 Redox Reactions (SB p.54)
Reduction
- Common reducing agents used in organic reactions
include - Lithium tetrahydridoaluminate in dry ether
(LiAlH4/ether, H3O) - Sodium tetrahydridoborate (NaBH4/H2O)
- Hydrogen with palladium (H2/Pd)
22Oxidation of Alkylbenzenes
2333.3 Oxidation of Alkylbenzenes (SB p.55)
Alkylbenzenes
- A group of aromatic hydrocarbons in which an
alkyl group is bonded directly to a benzene ring - Sometimes called arenes
2433.3 Oxidation of Alkylbenzenes (SB p.55)
Alkylbenzenes
- Examples of alkylbenzenes
2533.3 Oxidation of Alkylbenzenes (SB p.55)
Oxidation of Alkylbenzenes
- Oxidation of alkylbenzenes
- ? carried out by the action of hot alkaline
potassium manganate(VII) solution - In the oxidation process, a benzoate is formed
2633.3 Oxidation of Alkylbenzenes (SB p.55)
Oxidation of Alkylbenzenes
- Benzoic acid can be recovered
- ? by adding a mineral acid such as dilute H2SO4
to the benzoate - This method gives benzoic acid in almost
quantitative yield
2733.3 Oxidation of Alkylbenzenes (SB p.55)
Oxidation of Alkylbenzenes
2833.3 Oxidation of Alkylbenzenes (SB p.55)
Oxidation of Alkylbenzenes
2933.3 Oxidation of Alkylbenzenes (SB p.56)
Oxidation of Alkylbenzenes
- All alkylbenzenes are oxidized to benzoic acid
- ? except the alkylbenzenes with a tertiary
alkyl group - ? they do not have a benzylic hydrogen atom
3033.3 Oxidation of Alkylbenzenes (SB p.56)
Oxidation of Alkylbenzenes
- In the above oxidation processes,
- ? the alkyl groups of alkylbenzenes are
oxidized, rather than the benzene ring - In the first step, the oxidizing agent abstracts
a benzylic hydrogen atom - The oxidizing agent oxidizes the side chain to a
carboxyl group
3133.3 Oxidation of Alkylbenzenes (SB p.56)
Oxidation of Alkylbenzenes
- Side-chain oxidation by KMnO4 is not restricted
to alkyl groups - C C bonds and C O groups in the side chain
are also oxidized by hot alkaline KMnO4
3233.3 Oxidation of Alkylbenzenes (SB p.56)
Oxidation of Alkylbenzenes
3333.3 Oxidation of Alkylbenzenes (SB p.56)
34Oxidation of Alcohols
3533.4 Oxidation of Alcohols (SB p.56)
Alcohols
- A group of compounds with one or more hydroxyl
groups (?OH) attached to an alkyl group - For alcohols having only one hydroxyl group,
- ? their general formula is CnH2n1OH
3633.4 Oxidation of Alcohols (SB p.56)
Alcohols
3733.4 Oxidation of Alcohols (SB p.57)
Alcohols
- Depending on the number of alkyl groups attached
to the carbon to which the hydroxyl group is
linked, - ? alcohols can be classified as primary,
secondary and tertiary alcohols
3833.4 Oxidation of Alcohols (SB p.57)
Alcohols
- Differentiating an alcohol as a 1o alcohol, a 2o
alcohol or a 3o alcohol is extremely important - ? when oxidized, these alcohols give different
products
3933.4 Oxidation of Alcohols (SB p.57)
Alcohols
Primary alcohols Secondary alcohols Tertiary alcohols
Can be oxidized to aldehydes Further oxidized to carboxylic acids Can be oxidized to ketones Cannot be further oxidized to carboxylic acids Generally resistant to oxidation
4033.4 Oxidation of Alcohols (SB p.57)
Oxidation of Primary Alcohols
- Primary alcohols are firstly oxidized to
aldehydes and subsequently to carboxylic acids - Using oxidizing agents like acidified KMnO4 and
acidified K2Cr2O7
4133.4 Oxidation of Alcohols (SB p.57)
1. Oxidation of Primary Alcohols to Aldehydes
- The oxidation of alcohols is difficult to stop at
the aldehyde stage - ? aldehydes are a reducing agent
- One way of solving this problem
- ? remove the aldehyde as soon as it is formed
- ? by distilling off the aldehydes from the
reaction mixture
4233.4 Oxidation of Alcohols (SB p.57)
1. Oxidation of Primary Alcohols to Aldehydes
- e.g.
- Ethanal can be synthesized from ethanol using
acidified K2Cr2O7 - ? ethanal is removed by distillation
4333.4 Oxidation of Alcohols (SB p.58)
1. Oxidation of Primary Alcohols to Aldehydes
A typical laboratory set-up for the oxidation of
ethanol to ethanal
4433.4 Oxidation of Alcohols (SB p.58)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
- Primary alcohols can be oxidized to carboxylic
acids by acidified KMnO4 - Acidified KMnO4 is a powerful oxidizing agent
- ? the oxidation of the alcohols does not stop
at the aldehydes - ? but directly to the carboxylic acids
4533.4 Oxidation of Alcohols (SB p.58)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
- e.g.
- Ethanol can be oxidized to ethanoic acid by
acidified KMnO4
4633.4 Oxidation of Alcohols (SB p.59)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
A reflux apparatus used for the oxidation of
ethanol to ethanoic acid
4733.4 Oxidation of Alcohols (SB p.59)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
A distillation apparatus used for the separation
of ethanoic acid from the reaction mixture
4833.4 Oxidation of Alcohols (SB p.59)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
- The oxidation of ethanol by acidified K2Cr2O7
- ? the basis of the breathalyser used by the
police - ? to rapidly estimate the ethanol content of
the breath of suspected drunken drivers
4933.4 Oxidation of Alcohols (SB p.59)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
- When the drunken driver blows into the bag
- ? the ethanol molecules reduce the orange
Cr2O72- ions to green Cr3 ions - If more than a certain amount of the orange
crystal changes colour, - ? the driver is likely to be over the limit
5033.4 Oxidation of Alcohols (SB p.59)
2. Oxidation of Primary Alcohols to Carboxylic
Acids
Demonstration of the use of the breathalyser
5133.4 Oxidation of Alcohols (SB p.59)
Oxidation of Secondary Alcohols
- Secondary alcohols can be oxidized to ketones by
either acidified K2Cr2O7 or acidified KMnO4
5233.4 Oxidation of Alcohols (SB p.59)
Oxidation of Secondary Alcohols
- The reaction usually stops at the ketone stage
- ? further oxidation requires the breaking of a
carbon-carbon bond - ? difficult to proceed
5333.4 Oxidation of Alcohols (SB p.60)
Oxidation of Secondary Alcohols
- e.g.
- Propan-2-ol can be oxidized to form propanone
5433.4 Oxidation of Alcohols (SB p.60)
Oxidation of Tertiary Alcohols
- Tertiary alcohols are generally resistant to
oxidation unless they are subjected to severe
oxidation conditions - ? any oxidation would immediately involve the
cleavage of the strong C ? C bonds in the
alcohol molecule
5533.4 Oxidation of Alcohols (SB p.60)
Oxidation of Tertiary Alcohols
- Tertiary alcohols can be oxidized by acidified
KMnO4 - ? give a mixture of ketones and carboxylic
acids - ? both with fewer carbon atoms than the
original alcohol
5633.4 Oxidation of Alcohols (SB p.60)
Oxidation of Tertiary Alcohols
57Redox Reactions of Aldehydes and Ketones
5833.5 Redox Reactions of Aldehydes and Ketones
(SB p.62)
Aldehydes and Ketones
- Carbonyl compounds that contain the carbonyl group
5933.5 Redox Reactions of Aldehydes and Ketones
(SB p.62)
Oxidation of Carbonyl Compounds
- Aldehydes are readily oxidized by acidified KMnO4
or K2Cr2O7 to form carboxylic acids
6033.5 Redox Reactions of Aldehydes and Ketones
(SB p.62)
Oxidation of Carbonyl Compounds
- Ketones do not undergo oxidations readily
- ? their oxidation involves the cleavage of the
strong C?C bond - ? more severe conditions are required to bring
about the oxidation
6133.5 Redox Reactions of Aldehydes and Ketones
(SB p.62)
Oxidation of Carbonyl Compounds
- With the action of hot acidified KMnO4,
- ? the C?C bonds in ketones would be broken
- ? a mixture of carboxylic acids would be formed
6233.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Reduction of Carbonyl Compounds
- Both aldehydes and ketones undergo reduction
reactions readily - ? forming 1o and 2o alcohols respectively
- Reducing agents
- ? lithium tetrahydridoaluminate (LiAlH4)
- ? sodium tetrahydridoborate (NaBH4)
6333.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Reduction of Carbonyl Compounds
- LiAlH4 is a powerful reducing agent
- ? it reacts violently with water
- Those reduction reactions using LiAlH4 must be
carried out in anhydrous solutions - ? usually in dry ether
6433.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Reduction of Carbonyl Compounds
6533.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Reduction of Carbonyl Compounds
- The reduction of aldehydes and ketones to
alcohols is most often carried out by NaBH4 - NaBH4 is a less powerful reducing agent
- ? it does not react with water
- ? the reduction reactions using NaBH4 can be
carried out in water or alcohols
6633.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Reduction of Carbonyl Compounds
67Redox Reactions of Carboxylic Acids
6833.6 Redox Reactions of Carboxylic Acids (SB
p.64)
Carboxylic Acids
- A group of organic compounds containing the
carboxyl group - Examples
6933.6 Redox Reactions of Carboxylic Acids (SB
p.64)
Reduction of Carboxylic Acids
- Reductions of carboxylic acids are difficult to
carry out - Can be achieved with the use of very powerful
reducing agents (e.g. LiAlH4) - LiAlH4 reduces carboxylic acids to 1o alcohols
in excellent yields
70Redox Reactions of Alkenes
7133.7 Redox Reactions of Alkenes (SB p.65)
Alkenes
- Alkenes are unsaturated hydrocarbons containing C
C bonds - The C C bonds are readily oxidized
- ? alkenes are able to undergo oxidation
reactions
7233.7 Redox Reactions of Alkenes (SB p.65)
Alkenes
- Alkenes can accept hydrogen to form alkanes
- ? alkenes are also able to undergo reduction
reactions
7333.7 Redox Reactions of Alkenes (SB p.65)
Oxidation of Alkenes by Potassium Manganate(VII)
- Alkenes react with alkaline KMnO4
- ? form 1,2-diols called glycols
7433.7 Redox Reactions of Alkenes (SB p.65)
Oxidation of Alkenes by Potassium Manganate(VII)
- Ethene is oxidized to ethane-1,2-diol
- The manganate(VII) ions are reduced to
manganese(IV) oxide
7533.7 Redox Reactions of Alkenes (SB p.65)
Oxidation of Alkenes by Potassium Manganate(VII)
- A change from the purple colour of manganate(VII)
ions to the brown precipitate of manganese(IV)
oxide - ? a chemical test to distinguish between
alkenes and alkanes
7633.7 Redox Reactions of Alkenes (SB p.66)
Oxidation of Alkenes by Ozone
- Alkenes react rapidly and quantitatively with
ozone - ? form an unstable compound, known as ozonide
- Ozonides are very unstable
- ? they are not usually isolated
- ? treated directly with a reducing agent
(Zn/H3O)
7733.7 Redox Reactions of Alkenes (SB p.66)
Oxidation of Alkenes by Ozone
- The reduction produces carbonyl compounds
- ? can be safely isolated and identified
7833.7 Redox Reactions of Alkenes (SB p.66)
Oxidation of Alkenes by Ozone
- The net result of this reaction is
- ? the breaking of the C C bond to form two
carbonyl groups - This process is called ozonolysis
- ? can be used to locate the position of the C
C bond in an alkene
7933.7 Redox Reactions of Alkenes (SB p.66)
Oxidation of Alkenes by Ozone
- e.g.
- Ozonolysis of but-1-ene gives two different
aldehydes
8033.7 Redox Reactions of Alkenes (SB p.66)
Oxidation of Alkenes by Ozone
- e.g.
- Ozonolysis of but-2-ene gives one aldehyde
8133.7 Redox Reactions of Alkenes (SB p.68)
Reduction of Alkenes (Hydrogenation of Alkenes)
- Alkenes react with hydrogen in the presence of
metal catalysts (Ni, Pd and Pt) - ? form alkanes
8233.7 Redox Reactions of Alkenes (SB p.68)
Reduction of Alkenes (Hydrogenation of Alkenes)
- The atoms of the hydrogen molecule add to each
carbon atom of the C C bond of the alkene - ? the alkene is converted to an alkane
8333.7 Redox Reactions of Alkenes (SB p.68)
Reduction of Alkenes (Hydrogenation of Alkenes)
- Useful in analyzing unsaturated hydrocarbons
(alkenes or alkynes) - By measuring the number of moles of hydrogen
reacted with one mole of an unsaturated
hydrocarbon - ? the number of double or triple bonds present
in an unsaturated hydrocarbon molecule can be
deduced
84Autooxidation of Fats and Oils
8533.8 Autooxidation of Fats and Oils (SB p.69)
Oxidation of Fats and Oils
- Fats and oils are esters of propane-1,2,3-triol
and carboxylic acids of fairly long carbon chains - Some of these acids may contain one or more C C
bonds in them - ? known as unsaturated carboxylic acids
8633.8 Autooxidation of Fats and Oils (SB p.69)
Oxidation of Fats and Oils
- When fats and oils are exposed to air,
- ? the C C bonds will be oxidized
- ? the fats and oils will develop an off
odour and unpleasant flavour
8733.8 Autooxidation of Fats and Oils (SB p.70)
Oxidation of Fats and Oils
- Fats and oils having a high degree of
unsaturation are more susceptible to oxidation - The oxidation follows a free radical mechanism
- ? accelerated by trace metals, light and free
radical initiators
8833.8 Autooxidation of Fats and Oils (SB p.70)
Oxidation of Fats and Oils
- The hydroperoxides produced are flavourless and
odourless - ? decompose readily to form highly reactive
hydroperoxide free radicals
8933.8 Autooxidation of Fats and Oils (SB p.70)
Oxidation of Fats and Oils
- These radicals set up a chain reaction
- ? produce volatile, flavoured compounds of
aldehydes, ketones and carboxylic acids - ? responsible for their rancid flavour
- This process is called autooxidation
9033.8 Autooxidation of Fats and Oils (SB p.70)
Oxidation of Fats and Oils
- Autooxidation can be controlled but cannot be
stopped - The addition of antioxidants (e.g. BHA and BHT)
can slow down the oxidative spoilage of fats and
oils - Many vegetable oils contain natural antioxidants
(e.g. vitamin C) - ? can withstand autooxidation for a longer time
9133.8 Autooxidation of Fats and Oils (SB p.70)
Principle of BHA/BHT as Antioxidants
- BHA and BHT are common antioxidants used in food
- ? retard the development of oxidative rancidity
in unsaturated fats and oils
9233.8 Autooxidation of Fats and Oils (SB p.70)
Principle of BHA/BHT as Antioxidants
- BHA and BHT work by
- ? donating the hydrogen atom of the ?OH group
to the free hydroperoxide radical (ROO )
involved in the autooxidation of fats and oils - ? stopping the chain reactions in oxidative
spoilage - AH ROO ?? ROOH A
9333.8 Autooxidation of Fats and Oils (SB p.70)
Principle of BHA/BHT as Antioxidants
AH ROO ?? ROOH A
where AH represents the antioxidant, and A is a
radical derived from the antioxidant
9433.8 Autooxidation of Fats and Oils (SB p.71)
Principle of BHA/BHT as Antioxidants
Foods containing BHA and BHT
95The END
9633.1 Organic Synthesis (SB p.52)
Let's Think 1
Why are simple alcohols and simple aromatic
compounds relatively cheap starting materials for
organic syntheses?
Answer
They can be made from alkanes and benzene which
can be obtained directly from fractional
distillation of petroleum.
Back
9733.1 Organic Synthesis (SB p.53)
Check Point 33-1
(a) What are the main reasons for carrying out an
organic synthesis?
Answer
(a) To make new substances such as medicines,
dyes, plastics or pesticides To make new organic
compounds for studying reaction mechanisms or
metabolic pathways
9833.1 Organic Synthesis (SB p.53)
Check Point 33-1
(b) What are the factors that determine the
feasibility of an organic synthesis?
Answer
(b) Number of steps involved in the
synthesis Availability of starting materials and
reagents Duration of the synthetic process
Back
9933.2 Redox Reactions (SB p.54)
Check Point 33-2
(a) State two common oxidizing agents used in
organic reactions.
Answer
(a) Acidified potassium manganate(VII)
(KMnO4/H) Alkaline potassium manganate(VII)
(KMnO4/OH) Acidified potassium dichromate(VI)
(K2Cr2O7/H) Ozone (O3/CH3Cl3, Zn/H2O) (Any two)
10033.2 Redox Reactions (SB p.54)
Check Point 33-2
(b) State two common reducing agents used in
organic reactions.
Answer
(b) Lithium tetrahydridoaluminate in dry ether
(LiAlH4/ether, H3O) Sodium tetrahydridoborate
(NaBH4/H2O) Hydrogen with palladium
(H2/Pd) (Any two)
10133.2 Redox Reactions (SB p.54)
Back
Check Point 33-2
(c) State whether each of the following reactions
is an oxidation or a reduction. (i) Conversion
of ethanol to ethanal (ii) Conversion of ethene
to ethanol (iii) Conversion of nitrobenzene to
phenylamine (iv) Conversion of propene to
propane (v) Conversion of propan-2-ol to
propanone
Answer
(c) (i) Oxidation (ii) Oxidation (iii) Reduction
(iv) Reduction (v) Oxidation
10233.3 Oxidation of Alkylbenzenes (SB p.56)
Let's Think 2
Why is tert-butylbenzene resistant to
side-chain oxidation?
Answer
tert-Butylbenzene does not have a benzylic
hydrogen atom.
Back
10333.3 Oxidation of Alkylbenzenes (SB p.56)
Check Point 33-3
State the conditions under which ethylbenzene can
be converted to benzoic acid in the laboratory.
Answer
Reagents 1. potassium manganate(VII), sodium
hydroxide 2. dilute sulphuric
acid Condition heating under reflux
Back
10433.4 Oxidation of Alcohols (SB p.60)
Check Point 33-4
Back
Answer
10533.5 Redox Reactions of Aldehydes and Ketones
(SB p.63)
Let's Think 3
What is the species responsible for the
reducing property of LiAlH4 and NaBH4?
Answer
Hydride ion, H
Back
10633.5 Redox Reactions of Aldehydes and Ketones
(SB p.64)
Check Point 33-5
Answer
10733.5 Redox Reactions of Aldehydes and Ketones
(SB p.64)
Check Point 33-5
Back
10833.6 Redox Reactions of Carboxylic Acids (SB
p.65)
Check Point 33-6
Answer
10933.6 Redox Reactions of Carboxylic Acids (SB
p.65)
Back
Check Point 33-6
Answer
11033.7 Redox Reactions of Alkenes (SB p.67)
Example 33-7
Predict the structures of the following
hydrocarbons A, B and C using the information
given below
Hydrocarbon Molecular formula Products after ozonolysis
A C3H6
B C6H10
C C10H16
Answer
11133.7 Redox Reactions of Alkenes (SB p.67)
Example 33-7
11233.7 Redox Reactions of Alkenes (SB p.67)
Example 33-7
11333.7 Redox Reactions of Alkenes (SB p.67)
Example 33-7
Back
11433.7 Redox Reactions of Alkenes (SB p.68)
Check Point 33-7
Answer
11533.7 Redox Reactions of Alkenes (SB p.68)
Check Point 33-7
Back
11633.8 Autooxidation of Fats and Oils (SB p.71)
Check Point 33-8
(a) What causes fats and oils to go
rancid? (b) Explain how BHA and BHT can slow down
the oxidative spoilage of fats and oils.
Answer
(a) Carbon-carbon double bonds in fats and oils
as well as oxygen in air (b) BHA and BHT donate
the hydrogen atoms of their hydroxyl group to the
free hydroperoxide radical involved in the
autooxidation of fats and oils.
Back