HALO ALKANES &

HALOARENES
 STRUCTURE OF HALOGENOALKANES

Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)

Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group

Haloarenes - halogen is attached directly to a benzene (aromatic) ring

Structural
difference Halogenoalkanes are classified according to the environment of the halogen

PRIMARY 1° SECONDARY 2° TERTIARY 3°

 STRUCTURE OF HALOGENOALKANES

Format Contain the functional group C-X where X is a halogen (F,Cl,Br or I)

Halogenoalkanes - halogen is attached to an aliphatic skeleton - alkyl group

Haloarenes - halogen is attached directly to a benzene (aromatic) ring

Structural
difference Halogenoalkanes are classified according to the environment of the halogen

PRIMARY 1° SECONDARY 2° TERTIARY 3°

Names Based on original alkane with a prefix indicating halogens and position.
CH3CH2CH2Cl 1-chloropropane CH3CHClCH3 2-chloropropane

CH2ClCHClCH3 1,2-dichloropropane CH3CBr(CH3)CH3 2-bromo-2-methylpropane

 STRUCTURAL ISOMERISM IN HALOGENOALKANES

Different structures are possible due to...

Different positions for the halogen and branching of the carbon chain

1-chlorobutane 2-chlorobutane

2-chloro-2-methylpropane 1-chloro-2-methylpropane
 PHYSICAL PROPERTIES

Boiling point Increases with molecular size due to increased van der Waals’ forces

Mr bp / °C
chloroethane 64.5 13
1- chloropropane 78.5 47
1-bromopropane 124 71

Boiling point also increases for “straight” chain isomers.

Greater branching = lower inter-molecular forces

bp / °C
1-bromobutane CH3CH2CH2CH2Br 101
2-bromobutane CH3CH2CHBrCH3 91
2-bromo -2-methylpropane (CH3)3CBr 73

Solubility Halogenoalkanes are soluble in organic solvents but insoluble in water

 NUCLEOPHILIC SUBSTITUTION

Theory • halogens have a greater electronegativity than carbon

• electronegativity is the ability to attract the shared pair in a covalent bond
• a dipole is induced in the C-X bond and it becomes polar
• the carbon is thus open to attack by nucleophiles
• nucleophile means ‘liking positive’

the greater electronegativity of the halogen attracts the

shared pair of electrons so it becomes slightly negative;
the bond is now polar.
MIND MAP ON PREPARATION OF
HALOALKANES
 NUCLEOPHILIC SUBSTITUTION

Theory • halogens have a greater electronegativity than carbon

• electronegativity is the ability to attract the shared pair in a covalent bond
• a dipole is induced in the C-X bond and it becomes polar
• the carbon is thus open to attack by nucleophiles
• nucleophile means ‘liking positive’

the greater electro negativity of the halogen attracts the

shared pair of electrons so it becomes slightly negative;
the bond is now polar.

NUCLEOPHILES • ELECTRON PAIR DONORS

• possess at least one LONE PAIR of electrons
• don’t have to possess a negative charge
• are attracted to the slightly positive (electron deficient) carbon
• examples are OH¯, CN¯, NH3 and H2O (water is a poor nucleophile)

OH¯ CN¯ NH3 H2O

 NUCLEOPHILIC SUBSTITUTION - MECHANISM

the nucleophile uses its lone pair to provide the electrons for a new bond
the halogen is displaced - carbon can only have 8 electrons in its outer shell
the result is substitution following attack by a nucleophile
the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION
 NUCLEOPHILIC SUBSTITUTION - MECHANISM

the nucleophile uses its lone pair to provide the electrons for a new bond
the halogen is displaced - carbon can only have 8 electrons in its outer shell
the result is substitution following attack by a nucleophile
the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION

Points the nucleophile has a lone pair of electrons

the carbon-halogen bond is polar
a ‘curly arrow’ is drawn from the lone pair to the slightly positive carbon atom
a ‘curly arrow’ is used to show the movement of a pair of electrons
carbon is restricted to 8 electrons in its outer shell - a bond must be broken
the polar carbon-halogen bond breaks heterolytically (unevenly)
the second ‘curly arrow’ shows the shared pair moving onto the halogen
the halogen now has its own electron back plus that from the carbon atom
it now becomes a negatively charged halide ion
a halide ion (the leaving group) is displaced
 NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION

Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
The rate of reaction depends on the strength of the C-X bond

C-I 238 kJmol-1 weakest - easiest to break

C-Br 276 kJmol-1
C-Cl 338 kJmol-1
C-F 484 kJmol-1 strongest - hardest to break
 NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION

Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
The rate of reaction depends on the strength of the C-X bond

C-I 238 kJmol-1 weakest - easiest to break

C-Br 276 kJmol-1
C-Cl 338 kJmol-1
C-F 484 kJmol-1 strongest - hardest to break

Experiment Water is a poor nucleophile but it can slowly displace halide ions

C2H5Br(l) + H2O(l) ——> C2H5OH(l) + H+ (aq) + Br¯(aq)

If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible)

the displaced halide combines with a silver ion to form a precipitate of a silver
halide. The weaker the C-X bond the quicker the precipitate appears.
 NUCLEOPHILIC SUBSTITUTION - RATE OF REACTION

Basics An important reaction step is the breaking of the carbon-halogen (C-X) bond
The rate of reaction depends on the strength of the C-X bond

C-I 238 kJmol-1 weakest - easiest to break

C-Br 276 kJmol-1
C-Cl 338 kJmol-1
C-F 484 kJmol-1 strongest - hardest to break

Experiment Water is a poor nucleophile but it can slowly displace halide ions

C2H5Br(l) + H2O(l) ——> C2H5OH(l) + H+ (aq) + Br¯(aq)

If aqueous silver nitrate is shaken with a halogenoalkane (they are immiscible)

the displaced halide combines with a silver ion to form a precipitate of a silver
halide. The weaker the C-X bond the quicker the precipitate appears.

This form of nucleophilic substitution is known as SN2; it is a bimolecular process.

An alternative method involves the initial breaking of the C-X bond to form a carbocation,
or carbonium ion, (a unimolecular process - SN1 mechanism), which is then attacked by
the nucleophile. SN1 is favoured for tertiary haloalkanes where there is steric hindrance
to the attack and a more stable tertiary, 3°, carbocation intermediate is formed.
 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

IMP.NOTE: When answering these questions, solvent must be quoted.

Elimination takes place when ethanol is the solvent
NUCLEOPHILIC SUBSTITUTION
AQUEOUS SODIUM HYDROXIDE

ANIMATED MECHANISM
 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
 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 extends the carbon chain by one carbon atom

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

Hydrolysis C2H5CN + 2H2O ———> C2H5COOH + NH3

Reduction C2H5CN + 4[H] ———> C2H5CH2NH2

NUCLEOPHILIC SUBSTITUTION
POTASSIUM CYANIDE

ANIMATED MECHANISM
 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.
 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
Amines are also nucleophiles (lone pair on N) and can attack another molecule of
halogenoalkane to produce a 2° amine. This too is a nucleophile and can react
further producing a 3° amine and, eventually an ionic 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 quaternary (4°) salt
 NUCLEOPHILIC SUBSTITUTION
WATER

Details A similar reaction to that with OH¯ takes place with water.
It is slower as water is a poor nucleophile.

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

 ELIMINATION v. SUBSTITUTION
The products of reactions between haloalkanes and OH¯ are influenced by the solvent

SOLVENT ROLE OF OH– MECHANISM PRODUCT

WATER NUCLEOPHILE SUBSTITUTION ALCOHOL

ALCOHOL BASE ELIMINATION ALKENE

Modes of attack
Aqueous soln OH¯ attacks the slightly positive carbon bonded to the halogen.
OH¯ acts as a nucleophile

Alcoholic soln OH¯ attacks one of the hydrogen atoms on a carbon atom adjacent
the carbon bonded to the halogen.

OH¯ acts as a base (A BASE IS A PROTON ACCEPTOR)

Both reactions take place at the same time but by varying

the solvent you can influence which mechanism dominates.
 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 carbon atom next to that bonded to the halogen
the electron pair left moves to form a second bond between the carbon atoms
the halogen is displaced
overall there is ELIMINATION of HBr.

Complication With unsymmetrical halogenoalkanes, you can get mixture of products

 ELIMINATION

ANIMATED MECHANISM
 ELIMINATION
Complication
The OH¯ removes a proton from a carbon atom adjacent the C bearing the halogen. If
there had been another carbon atom on the other side of the C-Halogen bond, its
hydrogen(s) would also be open to attack. If the haloalkane is unsymmetrical (e.g. 2-
bromobutane) a mixture of isomeric alkene products is obtained.

but-1-ene

but-2-ene
can exist as cis and trans isomers
IMPORTANT POINTS TO REMEMBER:
Preparation of Aryl halides from alcohol is not
possible because, the C-O bond has a partial
double bond character and is difficult to break,
being stronger than single bond.
Sandmeyer reaction Preparation of Haloarenes
from primary amines in the presence of NaNo2,
CuCl2.
The Boiling point of isomeric haloalkanes
decreases with increase in branching. Similarly, p-
isomer has high mp compared to their O- and m-
isomer due to symmetry of p-isomer that fits in a
crystal lattice better as compared to o- and pm-
isomer.
IMPORTANT POINTS TO REMEMBER:
SN2 reaction- Order of reactivity: Primary >
Secondary> Tertiary
Reason: The presence of bulky substituent on or
near the c atom have a dramatic inhibiting effect
SN1 reaction- Order of reactivity: Tertiary >
Secondary> Primary
Rate Determining step is the slow cleavage of
C-Br bond to produce Carbocation and a bromide
ion.
Rate of reaction is dependent only on the
concentration of R-X, greater the stability of
Carbocation, greater will be its ease of formation
from alkyl halides.
SN2 reaction shows Inversion, while SN1 reaction
shows racemisation.
IMPORTANT POINTS TO REMEMBER:
A mixture containing two enantiomers in
equal proportions will have Zero optical
rotation as the rotation due to one isomer will
be cancelled by the rotation due to other
isomer.
In case of β-elimination, Saytzeff rule is to be
remembered. In Dehyrohalogenation, the preferred
product is that alkene, which has greater number
of alkyl groups attached to the doubly bonded “C”
atoms.
Alkyl halides are extremely less reactive to
nucleiophyllic Substitution reactions due to
resonance effect, difference in hybridization of C-
atom in C-X bond, instability of phenyl Cation.
IMPORTANT POINTS TO REMEMBER:

Haloarenes undergo electrophillic substitution

reactions preferably at o- or p- positions, due

to resonance e- density increases at o- or p-

positions than at m-position.

Thank you