Chapter 6: Electrophilic addition

Learning Objectives
By the end of this section, you should be able to apply concepts related to basic organic techniques
such as:

• Predict the addition products of alkene reactions based on their chemical reactivity
• Illustrate the electrophilic addition mechanisms
• Distinguish the difference in the intermediates (Halonium and carbocations) formed in the reactions
between alkenes with halogen or hydrogen halides
• Apply the electrophilic addition mechanism to the reaction of alkenes with halogen under
aqueous/non-aqueous solvents
• Explain Markonikov’s rule in electrophilic addition of water/hydrogen halide with unsymmetrical
alkenes.
• Sketch energy profile diagrams for addition mechanisms
• Apply the rearrangement mechanisms to the electrophilic addition of alkenes with hydrogen halides
or acid/water.
• Predict the addition products of alkenes reactions based on their chemical reactivity.
• Illustrate the electrophilic addition mechanisms.
• Distinguish the difference in the intermediates (halonium and carbocations) formed in the reactions
between alkenes with halogen or hydrogen halides.

Chemical reactivity of alkynes, alkenes and alkanes (NOT carbonyl)

Alkanes
- The bonding electrons are inaccessible to approaching reactants because:
- The electrons are sheltered in bonds between nuclei
- All valence electrons are used to form strong non-polar C-C or C-H bonds
- Alkanes are thus relatively inert and non-reactive

Alkenes or Alkynes
- Alkenes and alkynes have C=C or C≡C bonds which are electron rich and thus nucleophilic in
nature.
- They bear electrons in π bonds which are accessible to approaching reactants because:
- The electrons are located above and below the plane of multiple bonds and are not
sheltered between the nuclei
- Akenes and alkynes are thus relatively reactive, and typically react in electrophilic addition
reactions, whilst their preparation are primarily elimination reactions

Catalytic Hydrogenation
- Metal-catalysed addition of hydrogen
- Exothermic, rapid at room temperature and the
alkane is produced in high yield
- Pt, Ni, Pd or Rh are used as catalysts
Step 1
Addition of alkenes
Electrophilic addition of halogen to alkenes
- Only bromine and chlorine are used in the formation of 1,2-dihaloalkanes
- Fluorine is too reactive and iodine does not react
In non-aqueous solutions (e.g.CCl4) In aqueous solutions
Step 1 (RDS)
- Alkene and halogen react to form halonium ion intermediate
- The halonium ion intermediate allows X and both C of the ring to have octet of e -, such that it is very stable
Note: Dipole moment is
induced in the halogen
Nuc (temporary)
Elec
Step 2 Step 2
- Backside nucleophilic attack of halide anion on halonium - Water solvates the elec and prevents halogen attack
ion to form 1,2-dihaloalkane - Backside nucleophilic attack of water on halonium ion to
- Attack the C which is more accessible and less steric form halohydrin: Contains a halogen and hydroxyl on
hinderance adjacent C
- 2 halogens add to opposite faces of the double bond  - Attacks the C with most bonds (most substituted)!!
anti-addition (the halogen atoms are opposite each - For unsymmetrical alkenes, the preferred product has X+
other) bonded to the less substituted C, and H2O bonded to
- In cycloalkanes, the trans stereoisomer is majorly more substituted C.
formed
Step 3
- Deprotonation
- The Halogen and -OH add to opposite faces of the double
bond  anti-addition
 Electrophilic addition of hydrogen halides to alkenes Acid catalysed Electrophilic addition of water to alkenes (HYDRATION)
Marvonikov’s rule
- Both Electrophilic addition of hydrogen halides and of water to alkenes are regiospecific: follows Markovnikov’s rule where the Hydrogen attaches to the C with more
substituents (H), and the halogen attaches to the C with less substituents (H)
- By adding a H to a C with more H, it helps create a more stable carbocation intermediate

Step 1 (RDS) Step 1 (RDS)

- Alkene and hydrogen halide reacts to form a carbocation ion intermediate and
the H binds to the C with the most H)  there will be major and minor
- NOTE: Rearrangement may occur, to get a more substituted carbocation for
stability
- The more stable the carbocation intermediate, the faster the rate of reaction
- Catalysed by acid
- Protonation of carbon-carbon double bond to form stable carbocation (H binds to the C
with the most H)  There will be major and minor
- NOTE: Rearrangement may occur, to get a more substituted carbocation for stability
- The more stable the carbocation intermediate, the faster the rate of reaction

Step 2 Step 2
- Halide attacks the carbocation ion intermediate form alkyl halides - Water attacks the carbocation intermediate to form the oxonium intermediate

Step 3
- Deprotonation of oxonium to form alcohol
Energy Diagram

 The energy diagram for the overall electrophilic addition reaction shows:
o 2 peaks (2 transition states)
o 1 valley (1 carbocation intermediate).
 The energy level of the intermediate is higher than that of the starting alkene, but the reaction as a whole is
exothermic.
 The first step, the protonation of the alkene to yield the intermediate carbocation, is relatively slow.
 Once formed, the carbocation intermediate rapidly reacts further to yield the final bromoalkane product in the
second step.