Chapter 45 Inter-conversions of Carbon Compounds

(A) Inter-conversions between the Functional Groups

In organic synthesis, chemists change the functional group(s) of organic compounds so that we
can synthesize compounds with desired properties.

The following table is a summary of typical reactions of different functional groups.

Reactions of Alkanes
Conversion

Example

Reagents and conditions Type of reaction

Alkane
(excess)
CH3CH2CH3
X2 (X: Cl or Br) in Substitution
haloalkane
CH3CH2CH2X (major product) organic solvent, light
Reactions of Alkenes
Conversion

Example

Reagents and conditions Type of reaction

Alkene
alkane

CH3CH=CH2 CH3CH2CH3

H2, Ni or Pt, 150 Addition

200oC

Alkene
dihaloalkane

CH3CH=CH2
CH3CHXCH2X

X2 (X: Cl, Br or I) in Addition

organic solvent

Alkene
haloalkane

CH3CH=CH2 CH3CHXCH3 HX (X: F, Cl, Br or I)

(major product)

Addition

Reactions of Haloalkanes
Conversion

Example

Reagents and conditions Type of reaction

Haloalkane
alcohol

CH3CHXCH3
CH3CH(OH)CH3

NaOH(aq), heat

Substitution

Reactions of Alcohols
Conversion

Example

Reagents and conditions

Type of reaction

Alcohol
haloalkane

CH3CH(OH)CH3
CH3CHXCH3

HX or PX3 (X: F, Cl, Br or

I), heat if X = Br or I

Substitution

Alcohol alkene

CH3CH2CH2OH
CH3CH=CH2

Concentrated H2SO4, 180oC

OR Al2O3, 350oC

Elimination
(Dehydration)

1o alcohol
aldehyde

CH3CH2CH2OH
CH3CH2CHO

Acidified K2Cr2O7,
distillation

Oxidation

1o alcohol
carboxylic acid

CH3CH2CH2OH
CH3CH2COOH

Acidified K2Cr2O7, heating

under reflux

Oxidation

2o alcohol ketone

CH3CH(OH)CH3
CH3COCH3

Acidified K2Cr2O7, heating

under reflux

Oxidation

Inter-conversions of Carbon Compounds

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Reactions of Aldehydes and Ketones

Conversion

Example

Reagents and conditions

Type of reaction

Aldehyde

Acidified K2Cr2O7, heating

under reflux

Oxidation

carboxylic acid

CH3CH2CHO
CH3CH2COOH

Aldehyde
1o alcohol

CH3CH2CHO
CH3CH2CH2OH

LiAlH4 in dry ether then H+(aq)

OR NaBH4, H2O

Reduction

Ketone
2o alcohol

CH3COCH3
CH3CH(OH)CH3

LiAlH4 in dry ether then H+(aq)

OR NaBH4, H2O

Reduction

Reactions of Carboxylic Acids

Conversion

Example

Reagents and conditions Type of reaction

Carboxylic acid
ester

CH3CH2COOH
CH3CH2COOCH3

CH3OH, concentrated
H2SO4, heat

Esterification

Carboxylic acid 1o
alcohol

CH3CH2COOH
CH3CH2CH2OH

(1) LiAlH4 in dry ether,

(2) dilute acid

Reduction

Carboxylic acid
amide

CH3CH2COOH
CH3CH2CONH2

(1) PCl3 or SOCl2,

(2) NH3

Amide formation

Reactions of Esters
Conversion

Example

Reagents and conditions

Type of reaction

Ester alcohol +
carboxylic acid

CH3COOCH3 ===
CH3COOH + CH3OH

H (aq), heating under

reflux

Acid hydrolysis

Ester alcohol + salt

of carboxylic acid

CH3COOCH3
CH3COONa +
CH3OH

(1) OH-(aq), heating

under reflux
(2) H+(aq)

Alkaline
hydrolysis

Reactions of Amides
Conversion

Example

Reagents and conditions Type of reaction

Amide carboxylic
acid

CH3CONH2
CH3COOH + NH4+

H+(aq), heating under

reflux

Acid hydrolysis

Amide salt of
carboxylic acid

CH3CONH2
CH3COONa + NH3

(1) OH-(aq), heating

under reflux
(2) H+(aq)

Alkaline hydrolysis

The flowchart below summarizes the inter-conversions of functional groups and the reagents
and conditions required.

Inter-conversions of Carbon Compounds

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Some functional groups can be converted to another by one step only. For example, an alkene
can be converted to a haloalkane directly by reacting with hydrogen halide.

However, for some conversions, more than one step is required. Therefore, one or more
intermediate compounds are formed.

(A1) Inter-conversions between alkanes, alkenes, haloalkanes and alcohols

Alkanes are obtained from the fractional distillation of crude oil.

Alkenes are important starting materials in organic syntheses. They are obtained from
cracking of alkanes.

Alkenes can be converted to haloalkanes by reacting with hydrogen halides.

Haloalkanes can be converted to alcohols by heating (under reflux) with sodium hydroxide
solution.

Alkanes can also be converted to haloalkanes by reacting with halogens in the presence of light
(Although it is not a good method to make haloalkanes as a mixture of haloalkanes is obtained).

Example 1: Suggest a synthetic route to convert chloroethane to ethene.

Answer:

CH3CH2Cl

OH-(aq)
CH3CH2OH

heat

conc. H2SO4
180oC

CH2=CH2

Example 2: For the following multi-step synthesis, identify A, B and C.

CH3CH2CH2OH

Answer:
A: CH3CH=CH2

conc. H2SO4

OH-(aq)

HCl
A

180oC

B: CH3CHCH3

Inter-conversions of Carbon Compounds

Cl

C: CH3CHCH3
OH

heat

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(A2) Inter-conversions between alcohols, aldehydes, ketones, carboxylic acids, esters and amides

The inter-conversions among primary alcohols, aldehydes and carboxylic acids are redox
reactions. On the other hand, the inter-conversions between secondary alcohols and ketones
are also redox reactions.

Carboxylic acids can be converted to esters and amides, and vice versa.

Remember that alcohols can be prepared from haloalkanes by heating them with sodium
hydroxide solution.

Example: Suggest a synthetic route to convert ethanol to ethanamide.

Answer:
CH3CH2OH

(1) SOCl2 or PCl3

(2) NH3

K2Cr2O7 / H+

CH3CONH2

CH3COOH

heat

(A3) Inter-conversions between functional groups of common homologous series

We can divide organic compounds into two main groups compounds with oxygen and
compounds without oxygen.

If we want to convert an organic compound with oxygen to a compound without oxygen,

alcohol should be one of the intermediate.

Example: Suggest a synthetic route to convert cis-but-2-ene to butanone.

Answer:

H H

NaOH(aq)

H3C C C CH3

C C
H3C

HCl

CH3

H Cl

Inter-conversions of Carbon Compounds

heat

H H
H3C C C CH3
H OH

K2Cr2O7 / H+
heat

H
H3C C C CH3
H O

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Example: Compound A, C3H7Br, reacts with sodium hydroxide solution to give B, C 3H8O. On
prolonged heating with acidified potassium dichromate solution, B gives C, C 3H6O2.
Identify A, B and C.
Answer: The conversion from compound A to compound B is a substitution reaction, while the
conversion from compound B to compound C is an oxidation reaction. As there are 2
oxygen atoms in compound C, C is likely to be a carboxylic acid. Therefore, compound B
is a primary alcohol and compound A is a primary bromoalkane.
H the
H structures
H
H H
So,
ofHcompounds
A, B H
andHC are:
H C C C H
H H Br
A

H C C C H
H H OH
B

H C C C OH
H H O
C

Exercise: Compound A, C4H8, reacts with hydrogen chloride to give B, C 4H9Cl (without isomeric
product, ignore stereoisomer). B reacts with sodium hydroxide solution to give C,
C4H10O. When C is mixed with acidified potassium dichromate solution, compound D,
C4H8O, is obtained. Draw the structural formulae of A, B, C and D.

(B) Considerations in Planning a Synthetic Route

Several factors should be considered in planning a synthetic route. They are:

1.

Availability of starting materials and reagents

- the starting materials and reagents should be readily available and cheap
- usually haloalkanes and alcohols are common starting materials

2.

Rate of reactions
- many organic reactions require catalysts and heating to increase the reaction rate
- however, these lead to high production cost

3.

Percentage yield of the synthetic route

- organic syntheses seldom give a 100% yield as organic reactions seldom go to completion
- percentage yield of a product can be calculated as
Percentage yield of a product =

Actual mass of the product obtained

x 100%

Theoretical mass of the product obtained

4.

Number of steps in the synthetic route

- synthetic route should include as few steps as possible, as the overall yield will be reduced
after each step

5.

By-products formed in the synthetic route

- the best synthetic route should produce little or no by-products
- for example, it is better to use ethene to prepare chloroethane instead of using ethane, as

Inter-conversions of Carbon Compounds

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many by-products are formed when ethane and chlorine react together.
(C) Laboratory preparation of simple carbon compounds

In the followings, the ways to prepare ethanoic acid and ethyl ethanoate will be discussed.

(C1) Preparation of ethanoic acid

In the laboratory, ethanoic acid is prepared by the oxidation of ethanol.

The oxidizing agent used is acidified potassium dichromate solution.

Ethanal is the intermediate of the preparation of ethanoic acid. In order to ensure complete
oxidation of ethanol to ethanoic acid,

excess oxidizing agent is used, and

the reaction mixture is heated under reflux for 20 to 30 minutes.

The equation for the oxidation of ethanol is:

H H
H C C H

H
[O]

H OH

H C C H

H2O

H O

(oxygen atom from

an oxidizing agent)

[O]

H
H C C OH
H O

Step 1 Heating the reaction mixture under reflux

The set-up for the preparation of ethanoic acid from ethanol is shown below.

The function of the reflux condenser is to condense the vapour formed during the reaction, so
that the loss of volatile substances on heating is prevented.

Inter-conversions of Carbon Compounds

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As a result, the reaction is ensured to go to completion and ethanol can be oxidized to ethanoic
acid.
Step 2 Distilling the product mixture

The ethanoic acid formed can be obtained from the reaction mixture by distillation, and the setup is shown below.

On heating, an aqueous solution of ethanoic acid is obtained.

The purity of ethanoic acid can be increased by redistilling the aqueous ethanoic acid solution
and the fraction that boils between 116oC and 118oC is collected.

(C2) Preparation of ethyl ethanoate

In the laboratory, ethyl ethanoate is prepared by the esterification between ethanol and
ethanoic acid. Concentrated sulphuric acid is used as catalyst.

The equation for the esterification is:

O

H3C C OH

H+
H O CH2CH3

H3C C O CH2CH3

H2 O

heat

Remember that esterification is a reversible reaction. In order to produce more ester, water is
removed as it is formed.

Step 1 Heating the reaction mixture under reflux

Equal volumes of ethanoic acid and ethanol are

mixed with concentrated sulphuric acid*. The
mixture is heated under reflux. The experimental
set-up is shown on the right.

Inter-conversions of Carbon Compounds

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*(the functions of concentrated sulphuric acid are:

1. It acts as a catalyst.
2. It removes water so that more esters are produced.)
Step 2 Distilling the product mixture

To separate the organic compounds from the

aqueous solution, about two-thirds of the
reaction mixture is distilled off. The
distillation set-up is shown on the right.

The distillate obtained should have a much

lower percentage of water and relatively
higher percentages of ethanol, ethanoic acid
and ethyl ethanoate.
Step 3 Removing unreacted ethanoic acid and sulphuric acid

First, the distillate is poured into a separating funnel.

Then, excess sodium carbonate solution is added to the separating funnel. Sodium carbonate
reacts with the acids so that all the acidic substances are removed from the distillate.
2CH3COOH(aq) + CO32-(aq) 2CH3COO-(aq) + H2O(l) + CO2(g)
2H+(aq) + CO32-(aq) H2O(l) + CO2(g)

The lower aqueous layer is then discarded, and the upper organic layer is retained.
Step 4 Removing unreacted ethanol

Then, excess calcium chloride solution is added to the separating funnel. Calcium chloride
reacts and removes excess ethanol from the distillate.
CaCl2(aq) + 4CH3CH2OH(aq) CaCl2(aq) 4CH3CH2OH(aq)

Again, the lower aqueous layer is then discarded, and the upper organic layer is retained.
Step 5 Removing trace amounts of water

Pour out the organic layer to a small conical flask. Then, a few lumps of anhydrous calcium
chloride are added to the conical flask. Anhydrous calcium chloride is a drying agent so that
trace amount of water in the organic layer can be removed.

After that, filter the organic layer to obtain the filtrate.

Step 6 Re-distillation of the filtrate

The filtrate is re-distilled and the fraction that boils between 74 oC and 79oC is collected. It is

Inter-conversions of Carbon Compounds

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ethyl ethanoate.
Answer (P.5):
A.

but-2-ene (cis- or trans-)

B.

Inter-conversions of Carbon Compounds

2-chlorobutane

C.

butan-2-ol

D.

butanone

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