UNIT-III
Alkyl Halides
Ms. Shailaja S. Patil
Assistant Professor
Pharmaceutical Chemistry
ALKYL HALIDES
• Alkyl halides, also referred to as haloalkanes, are organic compounds
in which one or more hydrogen atoms of an alkane are substituted
with halogen atoms such as fluorine, chlorine, bromine or iodine.
• These compounds are generally denoted as R–X.
Where, R represents an alkyl group and X stands for a halogen (F, Cl, Br, or I).
TYPES OF ORGANIC HALIDES
✓Alkyl halides: Halogen bonded to a carbon in a single (C–C) bond.
✓Vinyl halides: Halogen bonded to a carbon in a double (C=C) bond.
✓Aryl halides: Halogen bonded to a carbon in an aromatic ring (Ar–C).
Classification of Alkyl Halides
Alkyl halides are classified as primary, secondary, or tertiary based on the number
of carbon atoms attached to the carbon that connected to the halogen.
✓Primary (1°): Halogen is attached to a carbon connected to one alkyl group.
✓Secondary (2°): Halogen is attached to a carbon connected to two alkyl groups.
✓Tertiary (3°): Halogen is attached to a carbon connected to three alkyl groups.
Nomenclature of Alkyl Halides
• Alkyl halides are named in two ways:
1. Common Name System:
• The name consists of two words: the alkyl group first, followed by the halogen.
• Example: ethyl chloride, (C₂H₅Cl)
2. IUPAC Names:
✓Choose the longest carbon chain that includes the halogen atom.
✓Number the chain starting from the end closest to the first substituent (alkyl or halogen).
✓If the same halogen appears more than once, use prefixes like di-, tri-, tetra- etc.
✓If there are different halogens, list them in alphabetical order with proper numbering.
Note: IUPAC names are written as a single word.
• Example-
1. CH₃–I
2. CH₃–CH₂–Br
3. CH₃–CH₂–CH₂–CH₂–Cl
4. (CH₃)₂CH–CH₂–Cl
5. (CH₃)₂CH–Cl
6. CH₃–CCl₂–CH₃
7. C₆H₅–Cl
8. C₆H₅–CH₂–Br
9. CH₃–CH(CH3)–C(CH3Br)–CH₂–CH3
Nucleophilic Substitution Reactions (SN1 and SN2)
✓A nucleophile is a species that has a lone pair of electrons (unshared
pair).
✓In a nucleophilic substitution reaction, the nucleophile reacts with
an alkyl halide by replacing the halogen atom (called the leaving
group).
✓ This process is called a Nucleophilic Substitution Reaction.
• In nucleophilic substitution reactions, the carbon–halogen (C–X) bond
breaks, and the nucleophile uses its lone pair of electrons to make a new
bond with the carbon.
• A nucleophile is a species that is nucleus-loving (positive charge)-it
donates a pair of electrons to form a covalent bond.
• There are two main types of nucleophilic substitution:
1. SN1 – Unimolecular Nucleophilic Substitution
2. SN2 – Bimolecular Nucleophilic Substitution
SN1 Reaction : Unimolecular Nucleophilic Substitution
• SN= Nucleophilic Substitution
• 1 = Rate-determining step involves only one molecule (the substrate)
Rate of Reaction:
• Follows first-order kinetics
• Rate ∝ [Substrate] only
• Rate = k[RX]
• Reactivity Order of Substrates:
Tertiary (3°) > Secondary (2°) > Primary (1°)
• Polar protic solvents like H2O and ROH favor SN1 reactions
• Example:
Hydrolysis of tert-butyl bromide → tert-butyl alcohol
Mechanism of SN1 Reaction
Reaction Order and kinetics of SN1 Mechanism
Stereochemistry
➢ Example
SN2: Bimolecular Nucleophilic Substitution Reaction
SN2: Bimolecular Nucleophilic Substitution
• SN - Nucleophilic Substitution
• 2- rate-determining step is bimolecular
(depends on both substrate and nucleophile).
• Rate of SN2 Reaction:
✓ Follows second-order kinetics – rate depends on both
substrate (RX) and nucleophile (Nu).
✓ Rate = k[RX][Nu]
✓ Reactivity order: 1º > 2º > 3º (due to less steric hindrance).
✓ Polar aprotic solvent (without OH) favors SN2.
Example: Hydrolysis of methyl bromide by aq. NaOH to form alcohol
Mechanism of SN2 Reaction
Reaction Order and kinetics of SN2 Mechanism
Evidence for Stereospecificity by SN2 Reaction Mechanism
Factors affecting SN1 and SN2 reactions
The rate of an SN1 & SN2 reaction depends upon 4 factors:
1. Effect of substrate structure (the alkyl halide)
2. Effect of nucleophile
3. Effect of leaving group
4. Effect of solvent
5. Stereochemistry
1. Effect of substrate structure
2. Effect of nucleophile
• The weak nucleophile favors an SN1 mechanism
• The strong nucleophile favors an SN2 mechanism
3. Effect of leaving group
1. On SN1 Reaction
Good leaving groups are essential for SN1 reactions. The leaving group should be highly polarisable
and least basic. The leaving group starts to take a partial negative charge as the cation starts to form.
Rate of leaving group reactivity is:
• H2O > ROH > AcO- > OH-
The more polarisable a group , the more will be its reactivity. Reactivity order of halogen is
• I>Br>Cl>F
2. On SN2 Reaction
Strong nucleophiles react faster. A charged nucleophile is a stronger nucleophile than corresponding
uncharged nucleophile.
RO- > OH- > RCOO- > ROH > H2O
4. Effect of solvent
• Polar protic solvents (like water and alcohol) support SN1 reactions because they stabilize the ions formed
during the reaction.
• Polar aprotic solvents support SN2 reactions because they don’t surround the nucleophile too much,
making it more reactive.
5. Stereochemistry
• Since SN2 proceeds through a backside attack, if a stereocenter is
present the SN2 reaction will give inversion of stereochemistry.
• By contrast, if the SN1 leads to the formation of a stereocenter, there
will be a mixture of retention and inversion since the nucleophile can
attack from either face of the flat carbocation.