Haloalkanes

Haloalkanes or Alkyl halides

Chloramphenicol
Haloalkanes or Alkyl halides

Chloroquine
Haloalkanes or Alkyl halides

Halothane
Haloalkanes or Alkyl halides

Chloroform
Haloalkanes or Alkyl halides

Phosgene
Haloalkanes or Alkyl halides

DDT
 Classification of Haloalkanes

Carbon is sp3 hybridized:

Primary Secondary Tertiary

 Classification of Haloalkanes

Carbon is sp3 hybridized:

10 Allylic 20 Allylic 30 Allylic

 Classification of Haloalkanes

Carbon is sp3 hybridized:

10 Benzylic 20 Benzylic 30 Benzylic

 Classification of Haloalkanes

Carbon is sp2 hybridized:

Vinylic halide Aryl halide

 Common Naming terms

Iso and Tert groups

 Common Naming terms

When two halogen atoms of the same type are present on the same carbon
atom, the compounds are named as alkylidene or geminal halides.

When two halogen atoms of the same type are present on adjacent carbon
atoms, the compounds are known as alkylene or vicinal dihalides.
Example
Example Draw the structures of all the eight structural isomers that have the molecular
formula C5H11Br. Name each isomer according to IUPAC system and classify
them as primary, secondary or tertiary bromide.
Nature of C – X bond
Nature of C – X bond
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Example Why is sulphuric acid not used during the reaction of alcohols with KI?
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
Preparation of Haloalkanes - From Alcohols
 Preparation of Haloalkanes - From Alkanes

Free Radical Halogenation

Reactivity of X2 :

Reactivity of H :
Preparation of Haloalkanes - From Alkanes
Reactivity - Selectivity Principle
Reactivity - Selectivity Principle
Example Among the isomeric alkanes of molecular formula C5H12, identify the one that
on photochemical chlorination yields
(i) A single monochloride.
(ii) Three isomeric monochlorides.
(iii) Four isomeric monochlorides.
Preparation of Haloalkanes - Allylic halogenation
Preparation of Haloalkanes - From Alkenes & Alkynes
Example The major product obtained in the reaction
Example 2,2-Dichloropentane can best be synthesised by
Preparation of Haloalkanes - SEAr
Preparation of Haloalkanes - SEAr
Preparation of Haloalkanes - Sandmeyer reaction
 Preparation of Haloalkanes - Finkelstein reaction

Alkyl iodides are often prepared by the reaction of alkyl chlorides/ bromides with
NaI in dry acetone. This reaction is known as Finkelstein reaction.
Example Which of the following can be used to prepare 3-bromopropene?
Example Draw the structures of major monohalo products in each of the following
reactions:
Example Draw the structures of major monohalo products in each of the following
reactions:
Example Which of the following sequence of reactions will give 1-bromo-
4-trichloromethylbenzene?
 Haloalkanes - Physical Properties

Alkyl halides are colourless when pure. However, bromides and iodides develop
colour when exposed to light.

Boiling points: RI > RBr > RCl > RF.

The boiling points of isomeric haloalkanes decrease with increase in branching.

 Haloalkanes - Physical Properties

Boiling points of isomeric dihalobenzenes are very nearly the same.

However, the para-isomers are high melting as compared to their ortho and meta-
isomers. It is due to symmetry of para-isomers that fits in crystal lattice better as
compared to ortho- and meta-isomers.
 Haloalkanes - Physical Properties

Density
Bromo, iodo and polychloro derivatives of hydrocarbons are heavier than
water. The density increases with increase in number of carbon atoms,
halogen atoms and atomic mass of the halogen atoms
 Haloalkanes - Physical Properties

Solubility
The haloalkanes are only very slightly soluble in water.

However, haloalkanes tend to dissolve in organic solvents because the new

intermolecular attractions between haloalkanes and solvent molecules have
much the same strength as the ones being broken in the separate haloalkane
and solvent molecules.
 Haloalkanes - Characteristic Reactions

Characteristic reactions of alkyl halide are substitution and elimination :

Haloalkanes - Substitution Reaction
Example
Haloalkanes - Substitution Reaction
Leaving Group
Leaving Group ability (Nucleofugality)
Leaving Group ability (Nucleofugality)
Leaving Group ability (Nucleofugality)
Example
Example
 Nucleophilicity Vs Basicity

Basicity is defined by the equilibrium constant for abstracting a

proton. Basicity is a thermodynamic phenomenon.
 Leaving Group

Nucleophilicity is defined by the rate of attack on an electrophilic

carbon atom. Nucleophilicity is a kinetic phenomenon.
 Trends in Nucleophilicity

A species with a negative charge is a stronger nucleophile than a similar

neutral species. In particular, a base is a stronger nucleophile than its
conjugate acid.

Nucleophilicity decreases from left to right in the periodic table, following

the increase in electronegativity from left to right.
 Trends in Nucleophilicity

Nucleophilicity increases down the periodic table, following the increase in

size and polarizability, and the decrease in electronegativity.
Trends in Nucleophilicity
Steric Effects on Nucleophilicity
Example For each pair, predict the stronger nucleophile
Example For each pair, predict the stronger nucleophile
 Solvent Effects on Nucleophilicity

A protic solvent is one that has acidic protons and can solvate both cations
and anions.

Small anions are solvated more strongly than large anions in a protic solvent
and this reduces their nucleophilicity.
Solvent Effects on Nucleophilicity
 Solvent Effects on Nucleophilicity

Polar aprotic solvents have strong dipole moments to enhance solubility, yet
they have no H capable of forming hydrogen bonds with anions. These can only
solvate cations.
Example
Example
Example
Example
Example
 Nucleophilic Substitution

Nucleophilic substitution reactions are among the most fundamental types of

organic reactions. In a nucleophilic substitution reaction a nucleophile (NuC)
displaces a leaving group (LG) in the molecule that undergoes the substitution
(the substrate).

When does the bond between the leaving group and the carbon break?
 Bimolecular Nucleophilic Substitution - SN2

General Reaction:

Order of Reaction:
Bimolecular Nucleophilic Substitution - SN2
 Bimolecular Nucleophilic Substitution - SN2

Single step reaction. No intermediates, no

rearrangements.

Complete Inversion - Walden Inversion

Bimolecular Nucleophilic Substitution - SN2
Bimolecular Nucleophilic Substitution - SN2
 Factors affecting Rate of SN2 reaction

Effect of substrate

Sn2 reactions are faster in less hindered environment

Example Rank the following alkyl bromides in order of decreasing reactivity (from
fastest to slowest) as a substrate in an SN2 reaction.
 Factors affecting Rate of SN2 reaction

Concentration and Reactivity of Nucleophile

Strong Nucleophile required

 Factors affecting Rate of SN2 reaction

Nature of Solvent

Favored in Polar Aprotic Solvent

 Factors affecting Rate of SN2 reaction

Leaving Group

Good leaving group helps the reaction go faster.

Example Which alkyl halide would you expect to react more rapidly by an SN2
mechanism? Explain your answer.
Example Which SN2 reaction of each pair would you expect to take place more
rapidly in a protic solvent?
Example Which SN2 reaction of each pair would you expect to take place more
rapidly in a protic solvent?
Example
Example
Nucleophilic Substitution
Example The synthesis of alkyl fluorides is best accomplished by
(a) Sandmeyer’s reaction.
(b) Finkelstein reaction.
(c) Swarts reaction.
(d) Free radical fluorination.
(JEE Main 2015)
Example Which of the following is the correct order of decreasing SN2 reactivity?
(a) RCH2X>R3CX>R2CHX (b) RCH2X>R2CHX>R3CX
(c) R3CX>R2CHX>RCH2X (d) R2CHX>R3CX>RCH2X
(where X = halogen)
(AIEEE 2007)
Example The organic chloro compound, which shows complete stereochemical
inversion during a SN2 reaction, is
(a) (C2H5)2CHCl (b) (CH3)3CCl
(c) (CH3)2CHCl (d) CH3Cl
(AIEEE 2008)
Example Which SN2 reaction of each pair would you expect to take place more rapidly
in a protic solvent?
Example
Example
 Unimolecular Nucleophilic Substitution - SN1

General Reaction:

Order of Reaction:
 Unimolecular Nucleophilic Substitution - SN1

Mechanism & Stereochemistry

Unimolecular Nucleophilic Substitution - SN1
Unimolecular Nucleophilic Substitution - SN1
Unimolecular Nucleophilic Substitution - SN1
Example What product(s) would you expect from the following solvolysis?
Example Rank the following carbocations in order of increasing stability:
 Factors affecting Rate of SN1 reaction

Effect of substrate

Concentration and Reactivity of Nucleophile

 Factors affecting Rate of SN1 reaction

Nature of Solvent

Favored in Polar protic Solvent

 Factors affecting Rate of SN1 reaction

Leaving Group

Good leaving group helps the reaction go faster.

If AgNO3 is added to an alkyl halide in a good ionizing solvent

Example Give mechanisms for the following silver-promoted rearrangements.
Example Which SN1 reaction of each pair would you expect to take place more
rapidly? Explain your answer.
Example Which SN1 reaction of each pair would you expect to take place more
rapidly? Explain your answer.
Example Propose a mechanism involving a hydride shift or an alkyl shift for each
solvolysis reaction. Explain how each rearrangement forms a more stable
intermediate.
Example Propose a mechanism involving a hydride shift or an alkyl shift for each
solvolysis reaction. Explain how each rearrangement forms a more stable
intermediate.
Example Show the products expected from SN1 solvolysis of these halides in ethanol.
Example A solution of (–)-1-chloro-1-phenylethane in toluene racemizes slowly in the
presence of a small amount of SbCl5, due to the formation of
(a) carbene. (b) carbocation.
(c) free radical. (d) carbanion.
(JEE Main 2013)
Example In a nucleophilic substitution reaction:

Which one of the following undergoes complete inversion of configuration?

(a) C6H5CHC6H5Br (b) C6H5CH2Br
(c) C6H5CH2CH3Br (d) C6H5CCH3C6H5Br
(JEE Main Online 2014)
Example The order of reactivity of the following halides towards a SN1 reaction is

(a) II > III > I (b) III > II > I

(c) III > I > II (d) I > III > II
Example Predict the compound in each pair that will undergo solvolysis (in aqueous
ethanol) more rapidly.
Example Vinyl and aryl halides generally don't undergo SN1 or SN2 reactions.
Explain why ?
Nucleophilic Substitution
Ion pair effect in SN1 reaction
Example KI in acetone, undergoes SN2 reactions with each P, Q, R and S. The rates of
the reactions vary as

(a) P > Q > R > S

(b) S > P > R > Q
(c) P > R > Q > S
(d) R > P > S > Q (JEE
Advanced, 2013)
Example Draw perspective structures or Fischer projections products of the substitution
products of the following reactions.
Example Predict the products of the following SN2 reactions.

(1)

(2)

(3)

(4)
Example Predict the products of the following SN2 reactions.

(5)

(6)

(7)

(8)
Example The order of reactivities of the following alkyl halides for a S N2 reaction is
(a) RF > RCl > RBr > RI
(b) RF > RBr > RCl > RI
(c) RCl > RBr > RF > RI
(d) RI > RBr > RCl > RF (IIT 2007)
Example An SN2 reaction at an asymmetric carbon of a compound always gives
(a) An enantiomer of the substrate
(b) A product with opposite optical rotation
(c) A mixture of diastereomers
(d) A single stereoisomer (IIT 2007)
Example (a) Mixture of (i) and (ii)
(b) Mixture of (i) and (iii)
(c) Only (iii)
(d) Only (i)
Example
 Internal Nucleophilic Substitution - SNi

Case 1: Retention Of Configuration

 Internal Nucleophilic Substitution - SNi

Case 2: Inversion Of Configuration

 Elimination Reactions of Alkyl Halides

General Reaction
Dehydrohalogenation
 Elimination Bimolecular E2 Reaction

General Reaction

Mechanism
Elimination Bimolecular E2 Reaction
 Orientation of Elimination

In most eliminations with two or more possible products, the product with the
most substituted double bond predominates. This principle is called Zaitsev’s
rule, and the most highly substituted product is called the Zaitsev product.
 Elimination Bimolecular E2 Reaction

Stereochemistry
 Elimination Bimolecular E2 Reaction

Stereochemistry
 Elimination Bimolecular E2 Reaction

Energy Profile
 Factors affecting Rate of E2 reaction

Effect of substrate

Concentration and Strength of Base

 Factors affecting Rate of E2 reaction

Nature of Solvent

Solvent polarity is not so important

 Elimination Unimolecular E1 Reaction

General Reaction

Mechanism
Competition with SN1 Reaction
Energy Profile for E1 Reaction
Example When the following compound is heated in methanol, several different products
are formed. Propose mechanisms to account for the four products shown.
Example Predict the mechanisms and products of the following reactions.
Example Solvolysis of bromomethylcyclopentane in methanol gives a complex product
mixture of the following five compounds. Propose mechanisms to account for
these products.
Example The major product of the following reaction is IIT
2008
 Factors affecting Rate of E1 reaction

Effect of substrate

Concentration and Strength of Base

 Factors affecting Rate of E1 reaction

Nature of Solvent
 Comparison of E1 and E2

E1 E2

Weak base required Strong Base required

Good ionizing solvent req. Solvent polarity not important

Substrate: 3°> 2° >> 1° 3°> 2° > 1°

Rate= k[RX] Rate= k[RX][Base]

No particular geometry required Anti-coplanar geometry preferred

Rearrangements are common No rearrangements

Multi-step reaction mechanism Single step mechanism

Not stereospecific Stereospecific

Stereoselective Stereoselective
Predicting Substitution Vs Elimination
Example The final product is
Example Which will give white ppt. with AgNO3 + NH4OH?
Example Rate of SN1 is maximum when X is

A. X = –OCH3
B. X = –CH3
C. X = –NO2
D. X = –Br
Example Which of the following is the most reactive towards SN1?

(A) (B) (C) (D)

Example The final product is
Example Which will give white ppt. with AgNO3 + NH4OH?
Example The decreasing order of SN2 reaction for the given compounds is

AIIMS 2018
Example Under identical conditions, solvolysis of which of the following substrates would
lead to maximum racemization?
 Predicting Substitution Vs Elimination

SN2 Vs E2
Predicting Substitution Vs Elimination
 Predicting Substitution Vs Elimination

Tertiary Halides: SN1 Vs E1

1. It is usually difficult to influence the relative position between S N1 and E1

products.
2. Increasing the temperature of the reaction favors reaction by the E1
mechanism at the expense of the SN1 mechanism.
3. If elimination product is desired, it is more convenient to add a strong base
and force an E2 reaction to take place.
Predicting Substitution Vs Elimination
Example Which product (or products) would you expect to obtain from each of the
following reactions?
Example Which product (or products) would you expect to obtain from each of the
following reactions?
Example The correct order of reactivity in SN1 reaction for the following compounds is

AIIMS 2018
Example
 Elimination Unimolecular E1CB

It occurs In basic medium, where a poor L. G. (eg. F, -OH, -OR and an acidic H
eliminate to form an additional bond.

Substrate must have acidic H

Presence of a poor L.G.

Elimination Unimolecular E1CB
Example
Example
Example
Example
Example
Example
Example
Example
Example
 Reactions of Haloarenes

Aryl halides are extremely less reactive towards nucleophilic substitution

reactions due to the following reasons:

1. Resonance effect
 Reactions of Haloarenes

2. Difference in hybridisation of carbon atom in C—X bond

Thus, C—Cl bond length in haloalkane is 177pm while in haloarene is 169 pm.
 Reactions of Haloarenes

3. Instability of phenyl cation:

Replacement by hydroxyl group
Replacement by hydroxyl group
 Aromatic Nucleophilic Substitution SNAr

EWG groups activate the ring towards SNAr

Addition - Elimination Mechanism

Elimination - Addition Mechanism

 Addition - Elimination Mechanism

Nucleophilic substitution reactions of aryl halides do occur readily when an

electronic factor makes the aryl carbon bonded to the halogen susceptible to
nucleophilic attack.

Nucleophilic aromatic substitution can occur when strong electron-withdrawing

groups are ortho or para to the halogen atom
 Addition - Elimination Mechanism

Mechanism
 Addition - Elimination Mechanism

Order of reactivity for Halogens is:

Addition - Elimination Mechanism
Example What is the product of the following reaction?
 Elimination - Addition or Benzyne Mechanism

Although aryl halides such as chlorobenzene and bromobenzene do not react

with most nucleophiles under ordinary circumstances, they do react under highly
forcing conditions.
 Elimination - Addition or Benzyne Mechanism

Mechanism
Elimination - Addition or Benzyne Mechanism

Unactivated benzene derivatives react via this mechanism.

Favored in presence of a strong base e.g. NaNH 2 or high Temp and Pressure

Alpha Hydrogen must be present.

Example
Example
Example
Example Which of the following reagents can be used to distinguish
chlorobenzene from chlorocyclohexane?
Example The major product in the reaction
Example The final product obtained in the reaction
Example
Example
Example
Example
 Electrophilic Aromatic Substitution

These are characteristic reactions of benzene.

 Electrophilic Aromatic Substitution

Halogenation
 Electrophilic Aromatic Substitution

Nitration
 Electrophilic Aromatic Substitution

Sulphonation
 Electrophilic Aromatic Substitution

Friedel Craft Reactions

Example
Example Which of the following compounds are aromatic compounds?
Example How the following conversions can be carried out?

(i) Propene to propan-1-ol

(ii) Ethanol to but-1-yne
(iii) 1-Bromopropane to 2-bromopropane
Example How the following conversions can be carried out?

(iv) Toluene to benzyl alcohol

(v) Benzene to 4-bromonitrobenzene
(vi) Benzyl alcohol to 2-phenylethanoic acid
Example How the following conversions can be carried out?

(vii) Ethanol to propanenitrile

(viii) Aniline to chlorobenzene
(ix) 2-Chlorobutane to 3, 4-dimethylhexane
(x) 2-Methyl-1-propene to 2-chloro-2-methylpropane