Halogen Compounds

Introduction

Haloalkanes are the halogen derivatives of hydrocarbons with general formula C nH2n+1X and
are represented as R–X where R is an alkyl group and X represents halogen. In haloalkanes
the carbon–halogen bond is formed by sp3-p overlap. Being more electronegative compared
to carbon, halogens impart a polar character to C–X bond where halogens acquire a negative
charge and carbon acquires a positive charge.

Depending upon the number of carbons attached to the carbon to which halogen is attached,
haloalkanes may be classified as primary (1°), secondary (2°), or tertiary (3°).

The aromatic halogen compounds can be classified into two categories, namely (i) the
compounds where halogen is directly attached to benzene ring called haloarenes or aryl
halides and (ii) the compounds where halogen is attached to the side chain of benzene ring
are called benzyl/aralkyl halides.

Vinyl Halides have a X-atom bonded to a C=C and Allyl Halides

have a X-atom bonded to a carbon that is attached to C=C.
IUPAC Nomenclature

However, common names are often used for simple alkyl halides.

Physical properties

1. Bond polarity: Since halogen atoms are more electronegative than carbon, the carbon-
halogen bond of alkyl halide is polarized; the carbon atom bears a partial positive charge
whereas the halogen atom bears a partial negative charge.

As we go down the periodic table, the size of the halogen increases (F<Cl<Br<I).
Therefore the C-X bond becomes longer and hence weaker. The polar C-X bond makes
the C-atom electron deficient which facilitates the attack of nucleophile (Nucleophilic
substitution reaction).
2. Boiling points: Due to greater polarity as well as higher molecular mass as compared to
the parent hydrocarbon, the intermolecular forces of attraction (dipole-dipole and van der
Waals) are stronger in the halogen derivatives. That is why the boiling points of chlorides,
bromides and iodides are considerably higher than those of the hydrocarbons of
comparable molecular mass.
3. Solubility: The haloalkanes are only very slightly soluble in water, but readily soluble in
organic solvents. They do not form intermolecular hydrogen bonding.

Chemical Reactions
Alkyl halides are very reactive and can undergo:
1. Substitution reactions
2. Elimination reactions
3. Reduction reactions
4. Reaction with metals

1. Reduction Reaction

Alkyl halides are reduced to alkanes by:

(i) H2 in presence of Ni or Pd
(ii) Zn + HCl
(iii) LiAlH4

Aryl halides gives arenes on reduction with Ni-Al alloy in presence of NaOH.

Benzyl chloride on reduction with Zn-Cu couple gives toluene.

2. Formation of Grignard Reagent (RMgX)

3. Nucleophilic Substitution Reactions

In haloalkanes, the C–X bond is polarized due to high electronegativity of halogen, and thus
carbon is electrophilic in nature (electron deficient). The substitution reactions in haloalkanes
involve the replacement of halogen (leaving group) by a nucleophile (entering group) and are
called nucleophilic substitution reactions. Halide ions being weak bases are easily displaced
by nucleophiles and thus behave as good leaving groups. The general reaction is expressed as

Depending upon the nature of substrate and to some extent on the nature of reagent and
reaction conditions, the course of the nucleophilic substitution reactions may follow the
following mechanisms (or pathways):

(a) Substitution Nucleophilic Unimolecular mechanism (SN1 mechanism)

(b) Substitution Nucleophilic Bimolecular mechanism (SN2mechanism)

Substitution nucleophilic unimolecular (SN1) mechanism

When the rate of a nucleophilic substitution reaction depends only upon the concentration of
the reactant e.g. alkyl halide and is independent of the concentration of the nucleophile i.e.,
OH etc. The reaction is said to be of first order and designated as SN1.

The reaction consists of two steps:

Step-1: Slow ionization of the alkyl halide to produce the planar carbocation and is
considered as the rate determining step.
Step-2: Fast attack of the nucleophile onto the carbocation, which can occur from either side
giving racemic mixture or mixture of inversion and retention product.

Potential energy diagram

Step1: formation of carbocation – Slow step

Step2: attack of nucleophile – Fast step

E1 act > E2 act

Stereochemistry in SN1 mechanism

 frontside R1
(a)
Nu
C

R2 R3
R1 R1
step-1 Retention
X
C C Racemic Mixture
-X- (Racemization)
R2 R3 R2 R3
R1
backside frontside
(b) (a) Nu
C
- backside
Nu can attack from either side R2 R3
(b)
Inversion

Inverted configuration is more preferred than retention because of hindrance during

frontside attack due to the presence of halide ion in close proximity (intimate ion pair).

Stereochemistry of SN1 (Racemisation) 1-Bromo-1-phenylpropane

frontside C2 H5
SN1 (a)
OH
C

H Ph
C2 H5 C2H5
step-1 Retention
Br
C C Racemic Mixture
-Br- (Racemization)
H Ph H Ph
C2 H5
backside frontside
1-bromo-1-phenylpropane (b) (a) HO
C
- backside
OH can attack from either side H Ph
(b)
Inversion
Relative reactivity of alkyl halides in SN1 reactions

The ease of formation of carbocation is directly related to the stability of carbocation. This
means that a more stable carbocation is formed more readily. The order of stability of
carbocations is 3° > 2° > 1° > +CH3. Hence, the order of reactivity of haloalkanes is 3° > 2° >
1° > CH3X.
SN2 (bimolecular nucleophilic substitution)

When the rate of a nucleophilic substitution reaction is dependent both upon the
concentration of the substrate and the nucleophile, the reaction is said to be of second order
and is represented as SN2.

Rate α [substrate] [nucleophile]

The rate-determining step involves the participation of both the substrate and the nucleophile
molecules.

Br Br Br

• Breaking of C-X bond and making of C-Nu occurs at the same time.

• Mechanism involves formation of T.S. in which carbon is pentavalent.

• Frontside attack of nucleophile is hindered due to repulsion between negatively

charged X- and Nu-.

• It results in formation of inverted product.

Potential energy diagram

Strength of Nucleophile:
Rate of SN2 reaction depends on nucleophilicity. Stronger the Nu -, greater will be the rate of
reaction.

H2O < OH- < RO- < CN-

Stereochemistry of SN2 (Walden Inversion) 2-Bromobutane

SN 2

OH-
CH3 C2 H5 CH3

Br HO
C
Br-
C HO C Br
H C2 H5 H Ph H C2H5

2-bromobutane Transition State Walden Inversion

OH- can attack from backside

Relative reactivity of alkyl halides in SN2 reactions

The order of reactivity of haloalkanes is dependent on the stability of transition state. The
stability of the transition state is governed by the following factors:

(i) A primary haloalkane preferably undergoes SN2 mechanism because of least steric
hindrance in the transition state, which makes the transition state more stable.

(ii) A bulkier group attached to carbon, makes the transition state unstable because of steric
interactions. More the number of bulkier alkyl groups, more is the steric hinderance and
lesser will be the stability of transition state. This in turn causes a slow rate of reaction.
Hence, the order of reactivity of haloalkanes is CH3X > 1° > 2° > 3°.
Hydrolysis

Hydrolysis of alkyl halides involves the replacement of halogen atom by hydroxyl group
resulting in the formation of alcohols. It is an example of nucleophilic substitution reaction.
Alkyl halides react with aq. KOH/aq. NaOH or moist silver oxide (AgOH) to form alcohols.

Reactivity and ease of hydrolysis of alkyl, allyl, benzyl, vinyl and aryl halides towards
nucleophilic substitution

H2 H2
C X CH2 C C X C X CH2 C X X
H H

Alkyl halide allyl halide benzyl halide vinyl halide aryl halide

Alkyl halides can undergo nucleophilic substitution reaction either by SN1 or SN2 mechanism.
Similarly, allyl and benzyl halides are also reactive towards nucleophilic substitution. But,
vinyl and aryl halides are less reactive towards nucleophilic substitution.

Reactivity of Allyl and Benzyl Halides

In allyl and benzyl halides,

the halogen atom is attached to an sp3 carbon atom, which prevents the resonance between
the sp2 carbon and halogen. Hence, the C-X bonds remains purely single bond and can be
easily broken.
Once the allylic or benzylic carbocation is formed, it is stabilized by resonance. Therefore,
they are reactive towards Nu- substitution reactions.

SN1

Inertness of Vinyl and Aryl Halides

• C-Cl bond acquires some double bond character because of resonance due to which this
bond becomes stronger and hence more energy is required to break it.
• Cl is attached to sp2 hybridised carbon which is more electronegative than sp3 hybridised
carbon. Hence, the cleavage of C-Cl bond will be difficult with Cl- as a leaving group.
• Hence, vinyl and aryl halides are inactive towards nucleophilic substitution reaction.