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Chemistry
10th Edition
ISBN: 9781305957404
Author: Steven S. Zumdahl, Susan A. Zumdahl, Donald J. DeCoste
Publisher: Cengage Learning
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What is the peroxide effect? What does it mean when there is a reversal of orientation? Detailed answers are appreciated. Thanks in advance!
![Free Radical Addition w/ Peroxides/Alkoxyl Radicals
These additions synthesize anti-Markovnikov products. This is because the
formation of a more substituted radical is preferred, meaning the halogen will add
on the less substituted side.
A small amount of peroxide will yield a
minimal amount of the Markovnikov
product. An appreciable amount of
peroxide will lead to only the
anti-Markovnikov product being
created.
Peroxide effect = reversal of
orientation (specifically with bromine).
This does not occur with chlorine.
Chlorine will still add on the more
substituted side/Markovnikov.
Initiation: Radicals are formed.
R
R-O: +
Propagation: A radical reacts to generate another radical.
Step 1: A bromine radical adds to the double bond to generate an alkyl radical on the secondary carbon atom.
Br
H
H₂C
Br
H
A
C-C
H
H
H3C
H
-R
-Br
+ Br
-H +
heat
R-O + ·O-R
R-0-H + Br.
H-Br
H
Step 2: The alkyl radical abstracts a hydrogen atom from HBr to generate the product and a bromine radical.
H3C
C-H
H Br
T
H-C-C-H + Br.
CH3 H
The bromine radical generated in Step 2 goes on to react with another molecule of the alkene in another Step 1, continuing the chain.
H
on the 2° carbon](https://content.bartleby.com/qna-images/question/c061ccfc-c5c1-460b-8498-b5bc9ae72844/41fadd5a-f48c-479e-9e85-ea71431dc07c/61medh2_thumbnail.png)
Transcribed Image Text:Free Radical Addition w/ Peroxides/Alkoxyl Radicals
These additions synthesize anti-Markovnikov products. This is because the
formation of a more substituted radical is preferred, meaning the halogen will add
on the less substituted side.
A small amount of peroxide will yield a
minimal amount of the Markovnikov
product. An appreciable amount of
peroxide will lead to only the
anti-Markovnikov product being
created.
Peroxide effect = reversal of
orientation (specifically with bromine).
This does not occur with chlorine.
Chlorine will still add on the more
substituted side/Markovnikov.
Initiation: Radicals are formed.
R
R-O: +
Propagation: A radical reacts to generate another radical.
Step 1: A bromine radical adds to the double bond to generate an alkyl radical on the secondary carbon atom.
Br
H
H₂C
Br
H
A
C-C
H
H
H3C
H
-R
-Br
+ Br
-H +
heat
R-O + ·O-R
R-0-H + Br.
H-Br
H
Step 2: The alkyl radical abstracts a hydrogen atom from HBr to generate the product and a bromine radical.
H3C
C-H
H Br
T
H-C-C-H + Br.
CH3 H
The bromine radical generated in Step 2 goes on to react with another molecule of the alkene in another Step 1, continuing the chain.
H
on the 2° carbon
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