CH.

10 - RADICAL REACTIONS*

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 CH.10 - RADICAL REACTIONS*

PRACTICE: DRAW the structures of the transition states (geometry unnecessary) for the two
propagation steps (in either order) in the chlorination of chloromethane to dichloromethane, with
dotted lines to represent partial bonds. You may omit δ·.

PRACTICE: Use single-barbed curved arrows to show a homolytic bond cleavage of ethane to
produce two methyl radicals.

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 CH.10 - RADICAL REACTIONS*

SUMMARY: Radical Stability

PRACTICE: List the stability of different kinds of radicals: 1°, 2°, 3° and methyl radicals. Why?
(Use only one word/terminology to explain)

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Which is the most stable radical?

PRACTICE: Approximate the heat of reaction for the given halogenation reaction.

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 CH.10 - RADICAL REACTIONS*

SUMMARY: Free Radical Halogenation

PRACTICE: Use correct arrow formalism to show thepropagation steps in the chlorination of
propane to produce 2-chloropropane.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Determine the major product(s) formed from the radical reaction.

PRACTICE: Which of the following is the rate-determining step in the free-radical bromination
of methane?

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 CH.10 - RADICAL REACTIONS*

SUMMARY: Radical Selectivity

PRACTICE: Draw all possible monochlorination products of 3,3-dimethylpentane, including

stereoisomers.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Reaction of bromine radicals with the following polycyclic alkane would lead to the
formation of how many different alkyl halides (you may neglect stereoisomers)

PRACTICE: Which of the following statements is TRUE regarding the radical chain reaction of
diatomic iodine in excess alkane:

a. Would lead to a fully polyiodonized alkane products unless reacted in excess alkane.

b. Would yield mostly monoiodonized alkanes due to the high bond dissociation energy of diatomic
iodine and its very high selectivity.

c. Iodine is NOT used in radical halogenation due to its extremely high reactivity. It can lead to
lab explosions.

d. More than one of the above is true

e. None of the above are true

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 CH.10 - RADICAL REACTIONS*

PRACTICE: DRAW all different C5H 11Cl products from the monochlorination of 2,2-
dimethylpropane. Do not duplicate.

PRACTICE: Draw all of the monobromination products of the molecule below. Calculate the
percentage yields of each product. The relative rates for each position are given below.

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 CH.10 - RADICAL REACTIONS*

SUMMARY: Anti Markovnikov Addition of Br

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 CH.10 - RADICAL REACTIONS*

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Predict the product and show the mechanism for the following synthesis. (You are not
required to show any additional resonance structures in the problem)

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Propose a mechanism for the following reaction.

PRACTICE: The following alkyne can undergo multiple additions of a halogen. Correctly select
the reagents (A, B or C) which produce the 3 products by placing the letter in the circle.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Provide the mechanism of the propagation steps to explain the stereochemistry of the
products (why Br can be added from both sides). Be sure to include all arrows, formal charges,
radicals and intermediates if needed.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: The allylic bromination of the alkene below with NBS gives four different products.
Draw the two initially formed free radical intermediates together with any applicable resonance
structures and the four products.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Complete the following reaction with the correct structures of the products. Don’t forget
to specify the stereochemistry.

SUMMARY: Free Radical Polymerization

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Alkenes react with radical catalysts to undergo radical polymerization. Show how we
could synthesize the following alkene polymer, polyethylene.

PRACTICE: Provide a structural formula for polyacetylene. Note that any correct form of a structural
formula is acceptable. Be sure to identify stereoisomers properly.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Using arrows to show the flow of electrons, give a stepwise mechanism for the free-
radical chain reaction shown to the right. Give each intiation step and each propagation step. Give
four (4) termination steps; be sure that one of the four termination steps that you give is a
disproportionation reaction.Clearly show stereochemistry in each elementary step that you give in
the mechanism.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Using arrows to show the flow of electrons in elementary steps in the reaction
mechanism for the reaction shown below, give one initiation step, two propagation steps, three
radical-radical combination termination steps, and one disproportionation termination step. You do
not need to give more than one Lewis structure (resonance structure) for any reactive
intermediates. If a product is present as a mixture of enantiomers or diastereomers, show using
lines, wedges, or dashed wedges. Label each step as "initiation", “propagation”, or “termination”.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: In the boxes provided, predict the intermediate and product.

PRACTICE: Fill in the reagents required to effect the following transformations.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Propose a sequence of synthetic steps that would efficiently accomplish the
conversion shown below. Show all starting materials and necessary reagents, but do not give
mechanisms.

PRACTICE: Synthesis question. Show how the starting material can be converted to
the product. Show all the reagents you need and indicate the stereochemistry when appropriate.
You do not need to show arrow pushing like in a mechanism question, only the reactions. If a
racemic mixture is formed draw both enantiomers and write “racemic” next to the two structures. All
carbon atoms in the product should come from the starting material. Use as many molecules of the
starting material as you might need to get to the product.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Provide the reagent or starting material to perform the indicated transformation. All
reaction require 3 steps or less.

PRACTICE: For the reaction below, draw the structure of the missing starting materials, reagents,
or final major organic product(s) in the box(es) provided. Make sure to include all the pertinent
information about stereochemistry and charges.

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 CH.10 - RADICAL REACTIONS*

PRACTICE: Draw the starting material that, under the given reaction conditions, results in the
following products.

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