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PEROXIDE EFFECT
BY
SHIYANI NIJO FATHIMA S
BPHARM 2ND
SEMESTER
2025 BATCH
DEFINITION
“When an unsymmetrical reagents adds to an
unsymmetrical alkene , the positive part of the reagents
becomes attached to the double bonded carbon which
bears the lesser number of hydrogen atoms in the presence
of Organic peroxide.”
Other names- 1. ANTIMARKOVNIKOV’S ADDITION
2. KHARASH EFFECT
3. ADDITION OF HYDROGEN BROMIDE
Antimarkovnikov addition or peroxide effect follows Free radical
mechanism.
Example : Propylene when reacts with HBr
RULE CONDITION PRODUCT
Markovnikov addition In absence of peroxide Isopropyl bromide
Antimarkovnikov
addition
In presence of
peroxide
n-propylbromide
REACTION
MECHANISM [FREE RADICAL ADDITION]
Step 1: Peroxide dissociate to give alkoxy free radicals
 Step 2 : Alkoxy free radical attacks HBr to form a Bromine free radical
 Step 3 : Bromine atom can attack propylene to give a primary and
secondary free radicals
 Step 4: HBr attacks the most stable free radical to form a required product
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