CHAPTER

10 ALKYL HALIDES

Animation 10.1: Alkyl Halides reaction

Source & Credit: chemwiki
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IN THIS CHAPTER YOU WILL LEARN:

1. How to name an alkyl halide and to classify it into primary, secondary and CH3 CI CH3 CH2 CI CH3 CH2 CH2 CI
tertiary alkyl halides. Chloromethane Chloroethane 1-Choropropane
2. Simple ways of generating alkyl halides.
Secondary alkyl halides are those in which halogen atom
3. The reason why C-X bond in chemistry is one of the most reactive type.
is attached with a carbon atom which is further attached to
4. The general mechanistic details of nucleophilic substitution and elimination
two other carbon atoms directly, e.g., secondary carbon atom.
reactions.
5. The preparation of Grignard’s reagent, the reactivity of C-Mg bond and its
synthetic applications in organic chemistry.

10.1 INTRODUCTION

In tertiary alkyl halides halogen atom is attached to a carbon

which is further attached to three carbon atoms directly.

Halogen derivatives of alkanes are called haloalkanes. They may be mono,

di, tn or poly haloalkanes depending upon the number of halogen atoms
present in the molecule.

10.2 NOMENCLATURE OF ALKYL HALIDES

Among these, monohaloalkanes are also called Alkyl Halides. Their

general formula is R -- X , where R may be methyl, ethyl, propyl, etc. and X
represents halogen atoms (F, Cl, Br, I). Mono haloalkanes or alkyl halides
are further classified into primary, secondary and tertiary alkyl halides
depending upon the type of carbon atom bearing the halogen atom. COMMON NAMES

In a primary alkyl halide halogen atom is attached with a Alkyl halides (monohaloalkanes) are named according to the nature
carbon which is further attached to one or no carbon atom e.g., of the alkyl group to which halogen atom is attached. For example,

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CH3 CI CH3 CH2 Br CH3 CH2 CH2 Br

Methyl chloride Ethyl bromide n-Propyl bromide

CH3 CH2 CH2 CH2 Cl

n-Butylchloride

IUPA C Nomenclature
The systematic names given to alkyl halides follow the underlying rules.
1. Select the longest continuous carbon chain and consider the compound to
have been derived from this structure.
2. Number the carbon atoms in the chain so that the carbon atom bearing the
functional group (F, Cl, Br, I) gets the lowest possible number, e.g.,

10.3 METHODS OF PREPARATION OF ALKYL HALIDES

3. If the same alkyl substituent occurs more than once on the chain, the prefix
di, tri and so on are used before the name of the alkyl group.
4. The positions of the substituents are indicated by the appropriate numbers
separated by commas. If the same substituent occurs twice or more on the
same carbon atom the number is repeated.
Alkyl halides can be prepared by the halogenation of alkanes
Examples which follow the above mentioned rules: and by the addition of halogen acids to alkenes. These methods
have already been discussed in the previous chapters. The best
method for the preparation of alkyl halides is from alcohols.

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1. From Alcohols
There are two main factors which govern the reactivity of R — X bond.
(a) Reaction of alcohols with halogen acids.
These are:
Alcohols may be converted to the corresponding alkyl halides by the
i) C— X Bond energy
action of halogen acid in the presence of ZnCl2 which acts as a catalyst.
ii) C— X Bond polarity
ZnCl2
CH3 CH2 OH + HX CH3 CH2 X + H2O Bond Energy
Ethyl halide The following table shows the bond energies of C— X bonds in alkyl halides.
(b) Alcohols also react with thionyl chloride in pyridine as a solvent to The strength of the bonds show that iodo compound (with the weakest
give alkyl chlorides. This method is especially useful since the by-products bonds) would be the most reactive one while fluoro compound will be
(HC1, SO2) are gases, which escape leaving behind the pure product. the least reactive i.e., the order of reactivity of alkyl halides should be
Pyridine R— I > R— Br > R— Cl > R— F
ROH + SOCl2 R Cl + SO2 + H2O
Bond Polarity
(c) Phosphorus trihalides or phosphorus pentahalides Electronegativities of halogen, carbon
Bond Energy
react with alcohols to replace -OH group by a halo group. and hydrogen atoms present in Bond
(kj/mole)
3CH3 CH2 OH + PBr3 3CH3 CH2 Br + H3PO3 alkyl halides are shown in the table. C—F 467
CH3 CH2 OH + PCl5 CH3 CH2 Cl + POCl3 + HCl The greatest electronegativity C—H 413
difference exists between carbon C — Cl 346
2. An excellent method for the preparation of simple alkyl iodide is the and fluorine atoms in alkyl fluorides. C — Br 290
treatment of alkyl chloride or alkyl bromide with sodium iodide. This C—I 228
method is particularly useful because alkyl iodides cannot be prepared by If an electrophile is the attacking reagent
then this difference suggests that alkyl Atom Electronegativity
the direct iodination of alkanes.
fluorides would be the most reactive
RCl Nal Rl + NaCl F 4.0
one. On the same lines, alkyl iodides Cl 3.0
RBr Nal Rl + NaBr should be the least reactive alkyl halides. Br 2.8
10.4 REACTIVITY OF ALKYL HALIDES In the light of the above discussion it I 2.5
is clear that the two factors mentioned H 2.1
above predict different types of behaviour C 2.5
about the reactivity of alkyl halides.
Experiments have shown that the strength of carbon halogen bond
is the main factor which decides the reactivity of alkyl halides.
An alkyl halide molecule (R — X) consists of two parts, an alkyl So the overall order of reactivity of alkyl halides for a particular alkyl group
group with a partial positive charge on the carbon atom attached to is:
halogen atom and the halide atom with a partial negative charge. Iodide > Bromide > Chloride > Fluoride
In fact the C-F bond is so strong that alkyl fluorides do not react under
ordinary conditions.
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10.5 REACTIONS OF ALKYL HALIDES Electrophile

It is a specie which attracts electrons (electron loving). The carbon
atom of an alkyl group attached with the halogen atom and bearing
a partial positive charge is called an electrophile or electrophilic
center. An electrophile may be neutral or positively charged.
The reactions of alkyl halides fall into two categories.
1. Those reactions in which the halogen is replaced by some other atom or
a group (nucleophilic substitution, or SN reactions).
2. Tnose which involve the removal of HX from the nanae (elimination, or
E reactions).
10.5.1 Nucleophilic Substitution Reactions
Before discussing specifically the nucleophilic substitution reactions
(SN) of alkyl halides, let us look at the nucleophilic reaction in general.
The overall process describing an SN reaction is shown as follows:
Animation 10.3: Electrophilic addition
Source & Credit: johnwiley

Leaving Group
In this equation the incoming group Nu is a nucleophile. Nucleophile means L is also a nucleopile. It is called leaving group because it departs with
nucleus loving. It has an unshared electron pair available for bonding and in an unshared pair of electrons. If we wish a SN reaction to proceed in the
most cases it is basic in character. It may be negatively charged or neutral. forward direction the incoming nucleophile must be stronger than the
departing one. Cl- , Br- , I- , HSO4- are good leaving groups. Poor leaving
Examples of Nucleophiles groups are OH- , OR and NH2-. Iodide ion is a good nucieophile as well as
a good leaving group.
:

HO- Hydroxide ion CI- Chloride ion Substrate Molecule

C2H5O- Ethoxide ion Br- Bromide ion The alkyl halide molecule on which a nucleophile attacks is called a
substrate molecule.
:

H S- Hydrogen sulphide ion NH3 Ammonia

10.5.2 Mechanism of Nucelophilic Substuitution Reactions
SCN- Thiocyanate ion CN- Cyanide ion
H2O: Water I- Iodide ion
Alkyl halides may undergo nucleophilic substitution reactions in two
NH2- Amino group different ways:
1. Nucleophilic Substitution Bimolecular (SN2)
2. Nucleophilic Substitution Unimolecular (SN1)

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Nucleophilic substitution reactions on alkyl halides involve two Kinetic studies of the reactions involving SN2 mechanism have shown
main processes, the breakage of C — X bond and the formation that the rates of such reactions depend upon the concentrations of alkyl
of C — Nu bond. The mechanism of the nucleophilic substitution halide as well as the attacking nucleophile. Mathematically, the rate
reactions depends upon the timing of these two processes. can be expressed as:
If the two processes occur simultaneously the mechanism Rate = k [Alkyl halide]1 [Nucleophile]1
is called SN2 . If the bond breaks first followed by the Since the exponents of the concentration terms in the above expression
formation of a new bond, the mechanism is called SN1. are unity, so the order of a typical SN2 reaction will be 1 + 1 = 2.
Among the alkyl halides, the primary alkyl halides always follow
Nucleophilic Substitution Bimolecular (SN2)
SN2 mechanism whenever they are attacked by nucleophiles.

This is a single step mechanism. As soon as the nucleophile starts Nucleophilic Substitution Unimolecular (SN1)
attacking the electrophilic carbon of the substrate, the bond with
which the leaving group is attached, starts breaking. In other words
the extent of bond formation is equal to the extent of bond breakage. This type of mechanism involves two steps. The first step is
Another important feature of this mechanism is the direction of the the reversible ionization of the alkyl halide in the presence of
attack of the attacking nucleophile. It attacks from the side which is an aqueous acetone or an aqueous ethyl alcohol. This step
opposite to the leaving group. provides a carbocation as an intermediate. In the second step this
carbocation is attacked by the nucleophile to give the product.
In order to give to the nucleophile enough room to attack, the substrate
carbon atom changes its state of hybridization from tetrahedral sp3 First Step:
to planar sp2. The attack of the nuclephile, the change in the state
of hybridization and the departure of the leaving group, every thing
occurs at the same time.

Second Step:

During the reaction the configuration of the alkyl halide

molecule gets inverted. This is called inversion of configuration.
Molecularity of a reaction is defined as the number of molecules taking
Since the first step involves the breakage of a covalent bond so it
part in the rate determining step. Since in this mechanism, the reaction
is a slow step as compared to the second step which involves the
takes place in only one step which is also a rate determining step and two
energetically favourable combination of ions. The first step is, therefore,
molecules are participating in this step, so it is called a bimolecular reaction.
called the rate-determining step. The mechanism is called unimolecular
because only one molecule takes part in the rate determining step.

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In SN1 mechanism, the nucleophile attacks when the leaving group had already Like nucleophilic substitutions, the elimination reactions can also follow E2
gone, so the question of the direction of the attack does not arise. Moreover, or E1 mechanism.
the intermediate carbocation is a planar specie allowing the nucleophile In E2 mechanism, the nucleophile attacks and the leaving group leaves
to attack on it from both the directions with equal ease. We, therefore, at the same time with a formation of carbon carbon double bond.
observe 50% inversion of configuration and 50% retention of configuration.
The single step E2 elimination

Like SN2 reactions, the molecularity of E2 reactions is also two and these
Reactions involving SN1 mechanism show first order kinetics and the reactions show second order kinetics.
rates of such reactions depend only upon the concentration of the alkyl
halide. The rate equation of such reactions can be written as follows. In E1 mechanism, like SN1 mechanism, the first step is the slow
Rate = k [Alkyl halide] ionization of the substrate to give a carbocation. In the second step,
Tertiary alkyl halides when attacked by a nucleophile always follow SN1 the nucleophile attacks on hydrogen to give an alkene as a product
mechanism. Secondary alkyl halides, on the other hand, follow both SN1 and SN2
mechanisms.
10.5.3 b -Elimination Reactions

During nucleophilic substitution reactions, the attacking nucleophile attacks

the electrophilic carbon atom of the alkyl halide. There is another site present
in the alkyl halide molecule where the nucleophile can attack at the same
time.Such a site is an electrophilic hydrogen atom attached to the b -carbon
of the alkyl halide.
E2 mechanism is a bimolecular mechanism and the rates of those
When the attack takes place on hydrogen, we get an alkene instead of a
reactions which follow this mechanism depend upon the concentrations
substitution product. Such a type of reactions are called elimination reactions.
of the alkyl halide as well as the attacking nucleophile or a base. E1
These reactions take place simultaneously with substitution reactions and often mechanism, on the other hand, is a unimolecular mechanism and the rates
compete with them. of those reactions which follow this mechanism depend only upon the
concentration of the alkyl halide molecule. Primary alkyl halides generally
follow E2 mechanism whereas tertiary alkyl halides follow E l mechanism.
Examples of SN reactions are given below.These reactions show the
usefulness of alkyl halides as synthetic reagents.
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Substrate Attacking Nucleophile Product

1. Wurtz Synthesis
δ+ δ−
CH3 CH2 Br + OH C2H5OH + Br Alkyl halides react with sodium in ether solvent to give alkanes. The
−

Ethyl alcohol reaction is particularly useful for the preparation of symmetrical alkanes.
δ+ δ− Ether
CH3 CH2 Cl + 2Na + Cl CH2 CH3 CH3 CH2 CH2 CH2 CH3+ 2NaCl
CH3 CH2 Br + I C2H5I + Br
− −

n-Butane
Ethy liodide
2. Reduction of Alkyl Halides
δ+ δ −

CH3 CH2 Br + CN C2H5CN + Br

−
−

Propane nitrile Alkyl halides can be reduced with zinc in the presence of an aqueous
acid such as HCI or CH3COOH.
δ+ δ−
CH3 CH2 CH2 Cl + Zn + H+ + Cl CH3 CH2 CH3 + ZnCl2
−

CH3 CH2 Br + NO2 C2H5NO2 + Br

−

Nitroethane Propane
3. Reaction with Sodium Lead Alloy (Na4Pb)
δ+ δ−
CH3 CH2 Br + CH3O CH3 CH2 O CH3 + Br
− −

Ethyl methyl ether Methyl chloride and ethyl chloride react with sodium lead alloy
giving tetramethyl lead and tetraethyl lead,respectively. These
δ+ δ− .. compounds are important anti-knock agents and are used in gasoline.
CH3 CH2 Br + NH3 C2H5 NH2 + HBr
Ethylamine
4CH3Cl + Na4Pb (CH3)4Pb + 4NaCl
δ+ .. Tetramethyl lead
δ−
CH3 CH2 Br + CH3 CH2 NH2 (CH3 CH2)2NH + HBr
4CH3CH2 Cl + Na4Pb (CH3CH2)4Pb + 4NaCl
Diethylamine
Tetramethyl lead
δ+ δ− .. 10.6 GRIGNARD REAGENT
CH3 CH2 Br + (CH3 CH2)2 NH (CH3 CH2)3N + HBr
Triethylamine

δ+ δ− ..
CH3 CH2 Br + (CH3 CH2)3 N (CH3 CH2)4N + Br
−

Quaternary ethylammonium ion

Grignard reagents RMgX are derivatives of alkyl halides belonging
δ +
δ− to class of organo-metallic compounds. Grignard reagent was
CH3 CH2 Br + SH C2H5SH + Br
−

first prepared by Victor Grignard in 1900. These reagents are so

Ethyl thioalcohol
important in organic synthesis that almost all the classes of organic
δ+ δ− −
compounds can be prepared from them. Due to their importance and
CH3 CH2 Br + CH3COO Na+ CH3COOC2H5 + NaBr applications Victor Grignard was awarded Nobel prize in chemistry.
Ethyl acetate
Other reactions shown by alkyl halides are as follows:
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Preparation: (ii) With ammonia

Grignard reagents are prepared by the reaction of magnesium metal with

alkyl halides in the presence of dry ether (alcohol free, moisture free).

δ+ δ−
R X+ Mg R Mg X (iii) With cyanogen chloride
Ether
CH3 CH2 Br + Mg CH3 CH2 Mg Br
Ether
Ethyl magnesium bromide

It is important that all the reactants must be absolutely

dry and pure because Grignard reagents are so reactive
that they may react with moisture or any impurity present.
(iv) With alcohols
Reactivity of alkyl halides with magnesium is in the following order:
Alkyl iodide > Alkyl bromide > Alkyl chloride
And for a given halogen the order of reactivity is as follows:
CH3X > C2H5X > C3H7X
Structure and Reactivity (v) With CO2

Grignard reagents are much reactive than most of the organic compounds.
The reactivity is due to the nature of C - Mg bond which is highly polar.

δ- δ+ δ-
CH3 CH2 -M g - X
Magnesium is more electropositive than carbon and the C-Mg
bond though covalent is highly polar, giving alkyl carbon the partial
negative charge. This negative charge is an unusual character (vi) With HCHO
which makes the alkyl groups highly reactive towards electrophile
centres. Mostly reactions shown by Grignard reagent are exothermic.
Reactions
(i) With Water

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(vii) With CH3CHO

Simulation 10.3: Interactive Periodic Table

Source & Credit: learnerstv

(viii) With CH3COCH3

(ix) With Epoxide

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KEY POINTS
iii) An alkyl group with a partial positive charge on the carbon atom is
1. Monohalo derivates of alkanes are called alkyl halides. called____________ centre.
2. The general formula of alky 1 halides is CnH2n +1X. iv) The mechanism is called __________if it involves one molecule in the
3. The best method for the preparation of alkyl halides is by the reactions of ratedetermining step.
alcohols with inorganic halides like SOCl2, PX3 and PX5. v) Molecularity of a reaction is defined as the number of molecules taking part
4. Alkyl halides are very reactive class of organic compounds. They undergo in the ______________.
nucleophilic substitution reactions and elimination reactions in the vi) The molecularity of E2 reactions is always two and the reactions show ________
presence of a nucleophile or a base. order kinetics.
5. Nucelophilic substitution reactions can take place in two distinct ways. A vii) Wurtz synthesis is useful for the preparation of____________ alkanes.
one step mechanism is called SN2 while a two step mechanism is called viii) Grignard reagents are prepared by the reaction of magnesium metal with
SN1. SN1 reactions show first order kinetics whereas SN2 reactions show alkyl halides in the presence of___________.
2nd order kinetic. Q.2. Indicate True or False.
6. Nucleophilic substitution reactions take place simultaneously with
elimination reactions and often compete with them. i) In secondary alkyl halides, the halogen atom is attached to a carbon which is
7. Elimination of two atoms or groups from adjacent carbon atoms in the further attached to two carbon atoms directly.
presence of a nucleophile or a base is called elimination reaction. Like ii) Alcohols react with thionyl chloride in ether as solvent to give alkyl halides.
nucleophilic substitution, (3-elimination reaction also take place in two iii) Order of reactivity of alkyl halides for a particular alkyl group is:
distinct ways E2 and E1. Iodide > Bromide > Chloride > Fluoride
8. Grignard reagent can be prepared by adding alkyl halide in a stirred iv) In SN2 reactions the attacking nucleophile always attacks from the side in
suspension of magnesium metal in diethyl ether. which the leaving group is attached.
9. Grignard reagent has a reactive nucleophilic carbon atom which can react v) Methyl magnesium iodide on hydrolysis yields ethyl alcohol.
with electrophilic centres to give the products in high yields. vi) Primary, secondary and tertiary amines react with Grignard reagents in the
10. Primary, secondary and tertiary alcohols can be best prepared by reacting sameway.
Grignard reagent with formaldehyde, any other aldehydes and ketones, vii) The reactions of secondary alkyl halides may follow both SN1 and SN2
respectively. mechanisms.
viii) SN1 mechanism is a one stage process involving a simultaneous bond
EXERCISE breakage and bond formation.
ix) In b -elimination reactions, the two atoms or groups attached to two adjacent
Q.1. Fill in the blanks.
carbon atoms are lost under the influence of an electrophile.
i) In tertiary alkyl halides the halogen atom is attached to a carbon which is x) The reactivity order of alkyl halides is determined by the strength of carbon-
further attached to __________ carbon atoms directly. halogen bond.

ii) The best method for the preparation of alkyl halides is the reaction of
_________ with inorganic reagents.

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Q. 3. Multiple choice questions. Encircle the correct answer.

i) In primary alkyl halides, the halogen atom is attached to a carbon which is ix) The rate of E1 reaction depends upon:
further attached to how many carbon atoms. (a) the concentration of substrate
(a) Two (b) Three (c) One (d) Four (b) the concentration of nucleophile
(c) the concentration of substrate as well as nucleophile
ii) The reactivity order of alkyl halides for a particular alkyl group is: (d) None of the above
(a) Fluoride > Chloride > Bromide > Iodide
(b) Chloride > Bromide > Fluoride > Iodide x) Which one of the following is not a nucleophile :
(c) Iodide > Bromide > Chloride > Fluoride (a) H2O (b) H2S (c) BF3 (d) NH3
(d) Bromide > Iodide > Chloride > Fluoride
Q.4. Define alkyl halide. Which is the best method of preparing alkyl halides?
iii) When CO2 is made to react with ethyl magnesium iodide, followed by acid
hydrolysis, the product formed is: Q.5. Write down a method for the preparation of ethyl magnesium bromide
(a) Propane (b) Propanoic acid (c) Propanal (d) in the laboratory?
Propanol
iv) Grignard reagent is reactive due to: Q.6. Give IUPAC names to the following compounds.
(a) the presence of halogen atom (b) the presence of Mg atom
i) ii)
(c) the polarity of C -Mg bond (d) none of the above

v) SN2 reactions can be best carried out with:

(a) Primary alkyl halides (b) Secondary alkyl halides iii)
(c) Tertiary alkyl halides (d) All the three iv) (CH3)3C CH2 Cl

vi) Elimination bimolecular reactions involve:

v) (CH3)2CHBr vi) (CH3)2CH CH2 CH(C2H5)CH2Cl
(a) first order kinetics (b) second order kinetics
(c) third order kinetics (d) zero order kinetics viii)
vii) CBr4
vii) For which mechanisms, the first step involved is the same.
(a) E1 and E2 (b)E2andSN2 (c)SN1andE2 (d) E1 and ix) CH2Cl2
SN1 x) (CH3)3C CH2 CH2 CH2 Br

viii) Alkyl halides are considered to be very reactive compounds towards xi) xii)
nucleophiles, because:
(a) they have an electrophilic carbon
(b) they have an electrophilic carbon and a good leaving group
xiii) (CH3CH2)3CBr
(c) they have an electrophilic carbon and a bad leaving group
(d) they have a nucleophilic carbon and a good leaving group
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Q.7. Draw all the possible structures that have the molecular formula C6H13CI.
Classify each as primary, secondary or tertiary chloride. Give their names
according to IUPAC system.

Q.8. Using ethyl bromide as a starting material how would you prepare the
following
compounds. Give also the inorganic reagents and conditions necessary
to carry
out these reactions:

(a) n-Butane (b) Ethyl alcohol

(c) Ethyl cyanide (d) Ethane
(e) Ethene (f) Propanoic acid
(g) Propane
Q.9. Write a detailed note on the mechanism of nucleophilic substitution reac-
tions.

Q.10. What do you understand by the term b-elimination reaction. Explain brief-
ly the two possible mechanisms of 3-elimination reactions.

Q.11. What products are formed when the following compounds are treated
with ethyl magnesium bromide, followed by hydrolysis in the presence of an
acid,
i) HCHO ii) CH3CHO iii) CO2
iv) (CH3)2CO v) CH3— CH2— CHO vi) CICN

Q. 12. How will you carry out the following conversions.

i) CH4 CH3CH2COOH

ii) CH3— CH3 (CH3— CH2)4N+ Br

iii) CH2 = CH2 CH3— CH2— CH2— CH2 — OH

iv) CH3CH2CH2CI CH3— CH = CH2

v) CH3COOH CH3CH2COOH
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