AN INTRODUCTION TO

SYNTHETIC ORGANIC
CHEMISTRY

KNOCKHARDY PUBLISHING
 KNOCKHARDY PUBLISHING

ORGANIC REACTION SEQUENCES

INTRODUCTION
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CONVERSIONS
 REACTIONS OF ORGANIC COMPOUNDS

POLYMERS DIBROMOALKANES KETONES

ALKANES ALKENES ALCOHOLS

ALDEHYDES

HALOGENOALKANES ESTERS

AMINES NITRILES CARBOXYLIC ACIDS

CONVERSIONS
 REACTIONS OF ORGANIC COMPOUNDS

POLYMERS DIBROMOALKANES KETONES

P
F C S

D
ALKANES E ALKENES ALCOHOLS
M
N

A B L G T U R
V
ALDEHYDES

HALOGENOALKANES ESTERS

U O Q
H I
T

AMINES J NITRILES K CARBOXYLIC ACIDS

 A
CHLORINATION OF METHANE

Initiation Cl2 ——> 2Cl• radicals created

Propagation Cl• + CH4 ——> CH3• + HCl radicals used and

Cl2 + CH3• ——> CH3Cl + Cl• then re-generated

Termination Cl• + Cl• ——> Cl2 radicals removed

Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Summary
Due to the lack of reactivity of alkanes you need a very reactive species to persuade them to
react
Free radicals need to be formed by homolytic fission of covalent bonds
This is done by shining UV light on the mixture (heat could be used)
Chlorine radicals are produced because the Cl-Cl bond is the weakest
You only need one chlorine radical to start things off
With excess chlorine you will get further substitution and a mixture of chlorinated products

CONVERSIONS
B
ELECTROPHILIC ADDITION OF HBr

Reagent Hydrogen bromide... it is electrophilic as the H is slightly positive

Condition Room temperature.
Equation C2H4(g) + HBr(g) ———> C2H5Br(l) bromoethane

Mechanism

Step 1 As the HBr nears the alkene, one of the carbon-carbon bonds breaks
The pair of electrons attaches to the slightly positive H end of H-Br.
The HBr bond breaks to form a bromide ion.
A carbocation (positively charged carbon species) is formed.

Step 2 The bromide ion behaves as a nucleophile and attacks the carbocation.
Overall there has been addition of HBr across the double bond.

CONVERSIONS
C
ELECTROPHILIC ADDITION OF BROMINE

Reagent Bromine. (Neat liquid or dissolved in tetrachloromethane, CCl4 )

Conditions Room temperature. No catalyst or UV light required!

Equation C2H4(g) + Br2(l) ——> CH2BrCH2Br(l) 1,2 - dibromoethane

Mechanism

It is surprising that bromine

should act as an electrophile
as it is non-polar.

CONVERSIONS
D DIRECT HYDRATION OF ALKENES

Reagent steam
Conditions high pressure
Catalyst phosphoric acid
Product alcohol

Equation C2H4(g) + H2O(g) C2H5OH(g) ethanol

Use ethanol manufacture

Comments It may be surprising that water needs such vigorous conditions to

react with ethene. It is a highly polar molecule and you would expect
it to be a good electrophile.

However, the O-H bonds are very strong so require a great deal of
energy to be broken. This necessitates the need for a catalyst.

CONVERSIONS
E HYDROGENATION

Reagent hydrogen
Conditions nickel catalyst - finely divided
Product alkanes
Equation C2H4(g) + H2(g) ———> C2H6(g) ethane
Use margarine manufacture

CONVERSIONS
F POLYMERISATION OF ALKENES
EXAMPLES OF ADDITION POLYMERISATION

ETHENE POLY(ETHENE)

PROPENE POLY(PROPENE)

CHLOROETHENE POLY(CHLOROETHENE)
POLYVINYLCHLORIDE PVC

TETRAFLUOROETHENE POLY(TETRAFLUOROETHENE)
PTFE “Teflon”

CONVERSIONS
G
NUCLEOPHILIC SUBSTITUTION
AQUEOUS SODIUM HYDROXIDE

Reagent Aqueous* sodium (or potassium) hydroxide

Conditions Reflux in aqueous solution (SOLVENT IS IMPORTANT)
Product Alcohol
Nucleophile hydroxide ion (OH¯)

Equation e.g. C2H5Br(l) + NaOH(aq) ———> C2H5OH(l) + NaBr(aq)

Mechanism

* WARNING It is important to quote the solvent when answering questions.

Elimination takes place when ethanol is the solvent
The reaction (and the one with water) is known as HYDROLYSIS

CONVERSIONS
H
NUCLEOPHILIC SUBSTITUTION
AMMONIA

Reagent Aqueous, alcoholic ammonia (in EXCESS)

Conditions Reflux in aqueous, alcoholic solution under pressure
Product Amine
Nucleophile Ammonia (NH3)

Equation e.g. C2H5Br + 2NH3 (aq / alc) ——> C2H5NH2 + NH4Br

(i) C2H5Br + NH3 (aq / alc) ——> C2H5NH2 + HBr

(ii) HBr + NH3 (aq / alc) ——> NH4Br

Mechanism

Notes The equation shows two ammonia molecules.

The second one ensures that a salt is not formed.
Excess ammonia is used to prevent further substitution (SEE NEXT SLIDE)
CONVERSIONS
H
NUCLEOPHILIC SUBSTITUTION
AMMONIA

Why excess ammonia?

The second ammonia molecule ensures the removal of HBr which would lead to the
formation of a salt. A large excess ammonia ensures that further substitution doesn’t
take place - see below

Problem
The amine produced is also a nucleophile (lone pair on N) and can attack another
molecule of halogenoalkane to produce a 2° amine. This in turn is a nucleophile and
reacts further producing a 3° amine and, eventually a quarternary ammonium salt.

C2H5NH2 + C2H5Br ——> HBr + (C2H5)2NH diethylamine, a 2° amine

(C2H5)2NH + C2H5Br ——> HBr + (C2H5)3N triethylamine, a 3° amine

(C2H5)3N + C2H5Br ——> (C2H5)4N+ Br¯ tetraethylammonium bromide, a 4° salt

CONVERSIONS
I
NUCLEOPHILIC SUBSTITUTION
POTASSIUM CYANIDE

Reagent Aqueous, alcoholic potassium (or sodium) cyanide

Conditions Reflux in aqueous , alcoholic solution
Product Nitrile (cyanide)
Nucleophile cyanide ion (CN¯)

Equation e.g. C2H5Br + KCN (aq/alc) ———> C2H5CN + KBr(aq)

Mechanism

Importance it extends the carbon chain by one carbon atom

the CN group can then be converted to carboxylic acids or amines.

J
Hydrolysis C2H5CN + 2H2O ———> C2H5COOH + NH3
K Reduction C2H5CN + 4[H] ———> C2H5CH2NH2

CONVERSIONS
L
ELIMINATION

Reagent Alcoholic sodium (or potassium) hydroxide

Conditions Reflux in alcoholic solution
Product Alkene
Mechanism Elimination
Equation C3H7Br + NaOH(alc) ———> C3H6 + H2O + NaBr

Mechanism

the OH¯ ion acts as a base and picks up a proton

the proton comes from a C atom next to the one bonded to the halogen
the electron pair moves to form a second bond between the carbon atoms
the halogen is displaced; overall there is ELIMINATION of HBr.

With unsymmetrical halogenoalkanes, a mixture of products may be formed.

CONVERSIONS
L
ELIMINATION OF WATER (DEHYDRATION)

Reagent/catalyst conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4)

Conditions reflux at 180°C
Product alkene
Equation e.g. C2H5OH(l) ————> CH2 = CH2(g) + H2O(l)
Mechanism

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation
Step 3 loss of a proton (H+) to give the alkene

Note Alcohols with the OH in the middle of a chain can have

two ways of losing water. In Step 3 of the mechanism,
a proton can be lost from either side of the carbocation.
This gives a mixture of alkenes from unsymmetrical alcohols...

CONVERSIONS
 N
OXIDATION OF PRIMARY ALCOHOLS
Primary alcohols are easily oxidised to aldehydes

e.g. CH3CH2OH(l) + [O] ———> CH3CHO(l) + H2O(l)

it is essential to distil off the aldehyde before it gets oxidised to the acid

CH3CHO(l) + [O] ———> CH3COOH(l)

OXIDATION TO OXIDATION TO
ALDEHYDES CARBOXYLIC ACIDS
DISTILLATION REFLUX

Aldehyde has a lower boiling point so Aldehyde condenses back into the
distils off before being oxidised further mixture and gets oxidised to the acid

CONVERSIONS
O
OXIDATION OF ALDEHYDES
Aldehydes are easily oxidised to carboxylic acids

e.g. CH3CHO(l) + [O] ———> CH3COOH(l)

• one way to tell an aldehyde from a ketone is to see how it reacts to mild oxidation
• ALDEHYES are EASILY OXIDISED
• KETONES are RESISTANT TO MILD OXIDATION
• reagents include TOLLENS’ REAGENT and FEHLING’S SOLUTION

TOLLENS’ REAGENT
Reagent ammoniacal silver nitrate solution
Observation a silver mirror is formed on the inside of the test tube
Products silver + carboxylic acid
Equation Ag+ + e- ——> Ag

FEHLING’S SOLUTION
Reagent a solution of a copper(II) complex
Observation a red precipitate forms in the blue solution
Products copper(I) oxide + carboxylic acid
Equation Cu2+ + e- ——> Cu+

CONVERSIONS
P
OXIDATION OF SECONDARY ALCOHOLS
Secondary alcohols are easily oxidised to ketones

e.g. CH3CHOHCH3(l) + [O] ———> CH3COCH3(l) + H2O(l)

The alcohol is refluxed with acidified K2Cr2O7. However, on prolonged treatment

with a powerful oxidising agent they can be further oxidised to a mixture of acids
with fewer carbon atoms than the original alcohol.

CONVERSIONS
Q
REDUCTION OF CARBOXYLIC ACIDS

Reagent/catalyst lithium tetrahydridoaluminate(III) LiAlH4

Conditions reflux in ethoxyethane
Product aldehyde

Equation e.g. CH3COOH(l) + 2[H] ———> CH3CHO(l) + H2O(l)

CONVERSIONS
R
REDUCTION OF ALDEHYDES

Reagent sodium tetrahydridoborate(III) NaBH4

Conditions warm in water or ethanol
Product primary alcohol

Equation e.g. C2H5CHO(l) + 2[H] ———> C3H7OH(l)

CONVERSIONS
S
REDUCTION OF KETONES

Reagent sodium tetrahydridoborate(III) NaBH4

Conditions warm in water or ethanol
Product secondary alcohol

Equation e.g. CH3COCH3(l) + 2[H] ———> CH3CH(OH)CH3(l)

CONVERSIONS
T
ESTERIFICATION

Reagent(s) carboxylic acid + strong acid catalyst (e.g conc. H2SO4 )

Conditions reflux
Product ester

Equation e.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)

Notes Concentrated H2SO4 is also a dehydrating agent, it removes

water as it is formed causing the equilibrium to move to the right
and thus increasing the yield of ester.

Uses of esters Esters are fairly unreactive but that doesn’t make them useless
Used as flavourings

Naming esters Named from the alcohol and carboxylic acid which made them...
CH3OH + CH3COOH CH3COOCH3 + H2O

from ethanoic acid CH3COOCH3 from methanol

METHYL ETHANOATE

CONVERSIONS
U
HYDROLYSIS OF ESTERS

Reagent(s) dilute acid or dilute alkali

Conditions reflux
Product carboxylic acid and an alcohol

Equation e.g. CH3COOC2H5(l) + H2O(l) CH3CH2OH(l) + CH3COOH(l)

Notes If alkali is used for the hydrolysis the salt of the acid is formed

CH3COOC2H5(l) + NaOH(aq) ———> CH3CH2OH(l) + CH3COO-Na+(aq)

CONVERSIONS
V
BROMINATION OF ALCOHOLS

Reagent(s) conc. hydrobromic acid HBr(aq) or

sodium (or potassium) bromide and concentrated sulphuric acid
Conditions reflux
Product haloalkane

Equation C2H5OH(l) + conc. HBr(aq) ———> C2H5Br(l) + H2O(l)

Mechanism The mechanism starts off in a similar way to dehydration

(protonation of the alcohol and loss of water) but the carbocation
(carbonium ion) is attacked by a nucleophilic bromide ion in step
3.

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation (carbonium ion)
Step 3 a bromide ion behaves as a nucleophile and attacks the carbocation

CONVERSIONS
 AN INTRODUCTION TO

SYNTHETIC ORGANIC
CHEMISTRY

TH E
EN D

© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING