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 Alkyl Halides
Alkyl halides
Classification
Nomenclature
Reactions
Mechanism of nucleophilic substitution reaction SN1,SN2,E1
andE2reaction Learning

Halogalk:anes
Halogalkenes:

Those organic compounds which contain –X(F,Cl,Br,I) as functional group are called alkyl halide or
halogalkanes.

Classification

Primary alkyl halide is alkyl halide

in which carbon to which halogen
is attached is linked to only one
carbon.

Secondary alkyl halide in which

carbon to which halogen is
attached is further linked to two
carbon atoms.

Tertiary alkyl halide is one in which

carbon to which halogen is
attached is further linked to three
carbon atoms
 Nomenclature of alkyl halide:

Common names: IUPAC Nomenclature:

 These are termed as haloalkanes  Selection of longest continuous chain
 Name as:  Assign lowest possible number to
Alkyl + halide carbon with which halogen is attached
 Use of prefix di, tri etc for presence of
more than one halogen

Ethyl bromide Methyl chloride

2-bromo-3-methyl butane

n-propyl bromide

iso-propyl bromide
Structure of alkyl halide:

 Alkyl halide molecule consists of two parts; an alkyl group and halide group
 Carbon of alkyl group bears the partial positive charge while negative charge appears on
halogen atom.

Reactivity of alkyl halide:

 Two factors govern the reactivity of alkyl halide; bond energy and bond length
Bond energy:

The order of reactivity of alkyl halide is:

R— I > R— Br > R— Cl > R— F
Bond Polarity

 If an electrophile is the attacking reagent then this difference suggests that alkyl
fluorides would be the most reactive one.
So the overall order of reactivity of alkyl halides for a particular alkyl group is:
Iodide > Bromide > Chloride > Fluoride
Overall order of reactivity:

 Experiments have shown that the strength of carbon halogen bond is the main factor
which decides the reactivity of alkyl halides.
 The overall order of reactivity of alkyl halides for a particular alkyl group is:
Iodide > Bromide > Chloride > Fluoride

Reactions of Alkyl halides:

Nucleophilic Substitution Reactions:

Important terms to remember:

 Nucleophile:
 Electron rich species
 Having unshared pair of electrons available for bonding
 Mostly basic in character
 Negatively charged or neutral
  Electrophile:
 Electron deficient specie
 Carbon attached to halogen bears partial positive charge and is Electrophilic in
character
 Electrophile may be neutral or positively charged.

 Leaving group:
 Leaving group is the group which departs with an unshared pair of electrons.
 It departs when comparatively stronger nucleophile approaches.
 Good leaving groups include: Cl-, Br-, I- and HSO4-
 Poor leaving groups include: OH-, OR- and NH2-
 Iodide ion is a good nucleophile as well as leaving group.
 Substrate:
 The alkyl halide molecule on which a nucleophile attacks is called a substrate
molecule.

Nucleophilic Substitution
Nucleophilic Bimolecular
Substitution (SN2)
Bimolecular (SN2) Nucleophilic Substitution Unimolecular (SN1)
Nucleophilic Substitution Unimolecular (SN1)
 Single
 Single
stepstep  Two step process; first step involves
 Two step process; first step involves reversible
 The
 Theextent of bond
extent formation
of bond is equal
formation to the
is equal to reversible ionization and second step
ionization and second step involves the attack of
extent of bond breakage.
the extent of bond breakage. involves the attack of nucleophile
nucleophile
 Transition
 Transition statestate
existsexists  Intermediate state exists
 Intermediate state exists
 Coming
 Coming nucleophile
nucleophilealways attack
always fromfrom
attack side  Coming nucleophile attacked from both sides
 Coming nucleophile attacked from both sides
opposite to leaving
side opposite togroup.
leaving group.  Ionization is carried out in aqueous acetone
 Ionization is carried out in aqueous acetone or
 The
 Thesubstrate
substratecarbon atom
carbon changes
atom changes its state
its or aqueous ethanol.
aqueous ethanol.
of hybridization from tetrahedral
state of hybridization 3
sp to
from tetrahedral  First step is the rate determining step.
 First step is the rate determining step.
planar 3
sp sp 2 2
in transition
to planar state.
sp in transition state.  Racemic mixture (50% retention of
 Racemic mixture (50% retention of configuration
 The
 Theattack of the
attack of nuclephile,
the nuclephile,the change
the change in in configuration and 50% inversion of
and 50% inversion of configuration) is formed
the state of hybridization
the state of hybridizationand and
the departure
the configuration) is formed (stereochemistry)
(stereochemistry)
of the leaving group,
departure everything
of the leaving occurs
group, at
everything  Rate = k [Alkyl halide]
the same
occurstime.at the same time.  1st order reaction (chemical kinetics)
 Inversion
 Inversion of configuration
of configuration (Stereochemistry)
 Rate(Stereochemistry)
= k [Alkyl halide] [Nucleophile]1
1

 2nd order
Rate =reaction halide]1 [Nucleophile]
k [Alkyl (Chemical kinetics). 1
 2nd order reaction (Chemical kinetics).
Wurtz synthesis:
Alkyl halides react with sodium in ether solvent to give alkanes. The reaction is particularly
useful for the preparation of symmetrical alkanes.

Reduction of Alkyl halide:

Alkyl halides can be reduced with zinc in the presence of an aqueous acid such as HCI or
CH3COOH.

Reaction with sodium lead alloy:

Methyl chloride and ethyl chloride react with sodium lead alloy giving tetramethyl lead and
tetraethyl lead,respectively. These compounds are important anti-knock agents and are used in
gasoline.
 Assessment 1
1. Which of the following alkyl halide is secondary alkyl halide?
a. Isopropyl chloride
b. Isobutyl chloride
c. n-propyl chloride
d. n-butyl chloride
2. The correct name given to alkyl halide containing 5 carbon and to 1 st carbon chlorine and at 2nd
carbon, methyl group is attached according to IUPAC is:
a. 2-methyl-1-chlorobutane
b. 1-chloro-2-methylhexane
c. 1-chloro-2-methylpentane
d. 2-methyl-1-chlorohexane
3. Which of the following carbon atom is tertiary carbon atom?

a. Carbon no 1
b. Carbon no 2
c. Carbon no 3
d. Carbon no 4
4. Depending upon the bond energy, which of the following is the least reactive alkyl halides?
a. Alkyl iodides
b. Alkyl chlorides
c. Alkyl bromides
d. Alkyl fluorides
5. Which of the following is/are correctly related to each other?
a. C-H bond, 413 KJ/mole
b. C-I bond, 413 KJ/mole
c. C-F bond, 228 KJ/mole
d. C-Cl bond, 290 KJ/mole
6. Alkyl fluorides do not react under ordinary conditions because of:
a. Stronger C-H bond
b. Weaker C-F bond
c. Stronger C-F bond
d. Stronger C-H bond
7. When the attacking specie is electrophile, which of the following alkyl halide is more reactive
depending upon the electronegativity difference between carbon and halogen is:
a. CH3-CH2-Br
b. CH3-CH2-Cl
c. CH3-CH2-I
d. CH3-CH2-F
8. Which of the following is not true about the nucleophile?
a. It has an unshared electron pair available for bonding.
b. In most cases it is basic in character.
c. It may be positively charged.
d. Nucleophile means nucleus loving.
9. Product formation in SN1 reaction given by tertiary alkyl halide proceeds by the intermediate:
a. Free radical
b. Carboanion
c. Carbocation
d. Molecular anion
10. The rate of SN1 reaction involving alkyl halide and nucleophile OH- depends only upon the
concentration of:
a. Nucleophile
b. OH-
c. Alkyl halide
d. Both a and b
 Assessment 2

1. Which of the following may undergo both SN1 and SN2 reaction?
a. CH3-CH2-Cl
b. CH3-CH2-CH2-Cl
c. CH3-CH(Cl)-CH3
d. CH3-C(CH3)(Cl) –CH3
2. When the nucleophile attacks on hydrogen instead of carbon to which halogen is attached,
the expected product is:
a. Alcohol
b. Aldehyde
c. Alkene
d. Esters
3. Which of the following is the prominent feature of Wurtz reaction carried out by alkyl halide?
a. This method is particularly useful for the preparation of unsymmetrical alkene
b. This method is particularly useful for the preparation of symmetrical alcohols
c. This method is particularly useful for the preparation of symmetrical alkene
d. This method is particularly useful for the preparation of symmetrical alkyne.
4. The reduction of alkyl halide is carried out by zinc in the presence of:
a. Water
b. Molten zinc
c. All of these
d. HCl(aq)
5. The formation of tetraethyl lead, an antiknocking agent involves the reaction of
a. Ethyl chloride and lead
b. Ethane, NaCl and lead
c. Ethyl chloride and sodium lead alloy
d. Methyl chloride and sodium lead alloy
6. The Reaction of ethyl chloride with sodium in presence of ether proceeds to form:
a. Ethane
b. Propane
c. n-butane
d. n-pentane
7. Which of the following is boiled with ethyl chloride to form ethyl alcohol:
a. Alcoholic KOH
b. Aqueous KOH
c. NaOH
d. H2O
8. . Which of the following alkyl halides cannot undergo both E1 mechanism:
a. Primary alkyl halide
b. Secondary alkyl halide
c. Tertiary alkyl halide
d. None of these
9. C2H5MgBr reacts with CNCl in presence of ether to produce intermediate product which on
hydrolysis in the presence of acid to give the final product:
a. 2-propanol
b. Propanoic acid
c. Ethyl nitrile
d. None
10. The removal of hydrogen halide experienced by adjacent carbon atoms of alkyl halide is
generally called:
a. Dehydrogenation
b. Hydrogenation
c. Dehydrohalogenation
d. Hydrohalogenation
 Assessment 3
1. For which mechanism shown by alkyl halide, the first step is carried out in same fashion:
a. E1 and E2
b. E2 and SN2
c. E1 and SN1
d. SN1 and SN2
2. Tertiary butyl chloride is practically non reactive to proceed under SN2 mechanism due to:
a. Its Insolubility
b. Its Instability
c. Its Inductive effect
d. Presence of Bulky alkyl group/steric hinderance
3. Which of the following is an example of good nucleophile as well as good leaving group?
a. F-
b. Br-
c. I-
d. Cl-
4. A carbon atom bearing positive charge and attached to three other carbon atoms or alkyl
groups is called:
a. Carbanion
b. Carbonium ion
c. Oxonium ion
d. hydroxo ion
5. 50% inversion of configuration and 50% retention of configuration is possible in SN1 reaction
given by alkyl halide due to:
a. Tetrahedral geometry of carbocation
b. Hexagonal geometry of carbocation
c. Trigonal planar geometry of carbocation
d. Linear geometry of carbocation
6. Which one of the following is not a nucleophile?
a. H2O
b. Br-
c. BF3
d. NH3
7. Which of the following haloalkane is a vicinal dihalide?
a. ClCH2CH2Cl
b. CH3CHCl2
c. BrCH2CH2CH2Br
d. BrCH2CH2CH2CH2Br
8. The increasing order of nucleophilicity would be?
a. Cl– < Br– < I–
b. I– < Cl– < Br–
c. Br– < Cl– < F–
d. I– < Br– < Cl–
9. The treatment of ethanol with phosphorous pentachloride produces:
a. C2H5Cl and POCl
b. C2H5Cl and HCl
c. C2H5Cl
d. C2H5Cl, POCl3 and HCl
10. Which of the following is formed by the reaction of Ethyl bromide with ethyl amine?
a. Ethylamine
b. Diethylamine
c. Triethylamine
d. nitroethane
 Assessment 4
1. The first step of SN1 reaction involves the ionization of alkyl halide. Which is more stable
carbocation:
a. Primary
b. Secondary
c. Tertiary
d. All have same stability
2. A mixture of1-chloropropane and 2-chloropropane on treatment with alcoholic KOH gives
a. 1-propene
b. 2-propene
c. Isopropylene
d. Hexane
3. The final product of reaction of ammonia with excess of ethyl chloride is:
a. Methyl amine
b. Dimethyl amine
c. Trimethyl amine
d. Tetraethyl ammonium chloride
4. The reagent used for dehalogenation of 1,2-dichloropropane is:
a. Zn-Cu
b. Zn-Hg
c. Zn dust
d. Na
5. Propyl bromide and isopropyl bromide are:
a. Metamers
b. Functiona group isomers
c. Position isomers
d. Chain isomers
6. Which of the following is not the characteristic of SN2 reaction?
a. 50% inversion of configuration.
b. It is favoured in non-polar solvents
c. It is bimolecular reaction.
d. It is single step reaction
7. The conversion of an alkyl halide into an alcohol involves:
a. Addition
b. Elimination
c. Substitution
d. Dehydrogenation
8. Which of the following factor favour the elimination reaction over substitution?
a. Crowding within substrate
b. Weak base
c. Increasing solvent polarity
d. Decrease in temperature
9. Reactivity of order of alkyl halides for dehydrohalogenation is:
a. 𝑅 − 𝐹 > 𝑅 − 𝐶𝑙 > 𝑅 − 𝐵𝑟 > 𝑅 − 𝐼
b. 𝑅 − 𝐼 > 𝑅 − 𝐵𝑟 > 𝑅 − 𝐶𝑙 > 𝑅 − 𝐹
c. 𝑅 − 𝐼 > 𝑅 − 𝐶𝑙 > 𝑅 − 𝐵𝑟 > 𝑅 − 𝐹
d. 𝑅 − 𝐹 > 𝑅 − 𝐼 > 𝑅 − 𝐵𝑟 > 𝑅 − 𝐶𝑙
10. In the following, which atom is acting as electrophile?

a. Br
b. C
c. H
d. None of these
 KEY
Assessment 1
1. A
2. C
3. C
4. D
5. A
6. C
7. D
8. C
9. C
10. C

Assessment 2

1. C
2. C
3. C
4. D
5. C
6. C
7. B
8. A
9. B
10. C
 Assessment 3

1. C
2. D
3. C
4. B
5. C
6. C
7. C
8. A
9. D
10. B

Assessment 4

1. C
2. A
3. D
4. C
5. C
6. A
7. C
8. A
9. B
10. B