Take Home Practice Assignment: Electrophilic Addition of HX to an Alkene

1. What does it means when a chemical reaction occurs under “dry” conditions?
Having dry conditions means that there is no water present in the reaction mixture.
2. Give the chemical formula of the compound commonly referred to as ether.

3. For each of the following reactions give the structure of the major product(s). [Do not
consider stereochemistry.]
a.

b.

c.

d.

e.

f.

!
 g.

h.

! In this case we are assuming

the Br2 is in low
concentration. The reaction
would be better controlled
using NBS, rather than Br2.
4. Give the reaction mechanism for the reactions in 3a, b, g and h.

I will not ask this mechanism

on a test, but I could ask
questions about the
mechanism, so it is good to
practice!
5. The addition of HBr to an alkene will occur in an anti Markovnikov fashion even when trace
amounts of a peroxide is present. Explain.

Peroxides can homolytically break their O-O bond creating free radicals. If there
is HBr present, the oxygen radical of the cleaved peroxide will take H from HBr,
leaving a Br radical. Only a few Br radicals are required for the reaction to
continue because the propagation steps create Br radicals which sustains the
reaction.

Therefore, only trace amounts of peroxide is needed for this reaction because the
formation of only one Br radical will lead to the creation of many more during the
propagation steps.

6. Give the major constitutional product(s) produced by the following reactions. If stereoisomers
of the major constitutional product(s) are possible, show the stereochemistry of each possible
stereoisomer. Note that there are a variety of different ways to depict your answer (wedge and
dash, Fischer projection, etc). Be sure your stereochemistry is clearly indicated no matter
which depiction you choose to use.
a.

b.

!
c.

d.

e.

f. Think carefully about the mechanism to answer this one:

!
 g.

h.

7. For question 6, whenever stereoisomers are produced, state the relationship between the
products (i.e. enantiomer, diastereomers, etc). Then determine if the stereoisomers are
produced in equal amounts.
8. Provide a reaction mechanism (including all appropriate arrow pushing) to account for the
formation of the indicated product.

9. The following reaction yields a mixture of products. Propose a mechanism for the formation
of each of the products indicated. [Do not consider stereochemistry.]

!
10.R-3-methylcylcohexene undergoes the electrophilic addition of HCl under appropriate
conditions. The result is a mixture of products. One of the products is achiral. What is the
achiral product? Provide a complete reaction mechanism to show its formation.
 11.While working on your secret plans for world domination, your genetically altered laboratory
gremlin has proposed the following reagent for use in the preparation a sample of (1-
chloroethyl)cyclohexane. In light of you gremlin’s proposal, should you reward him a sneer
of approval or lock them in the “Broom Closet of Doom” until further notice? Why? [Do not
consider any stereochemistry.]

We see that carbocation rearrangement is very possible in

this reaction mechanism. And when rearrangements are
possible, they will likely occur, and we will get a mixture of
products. So unless you want to head to the lab and spend
hours trying to separate a mixture of very similar isomers,
you should have "the brooms" teach your gremlin a lesson
in looking for possible carbocation rearrangements.