Written Report

in
Organic Chemistry

Topics:
Radical Addition to Alkenes: The Anti-Markovnikov Addition of Hydrogen Bromide
Radical Polymerization of Alkenes: Addition Polymers
Hydrogenation of Alkynes

Submitted by:
Jocelyn G. Corpuz

Submitted to:
Engr. Jeralyn G. Cabotaje

March 2017
Radical Additions to Alkenes: The Anti-Markovnikov Addition of Hydrogen
Bromide

In 1869, Vladimir Markovnikov, a Russian chemist, investigated the addition of

HBr across many different alkenes, and he noticed that the H is generally placed at
the vinylic position already bearing the larger number of hydrogen atoms.

Markovnikov described this regiochemical preference in terms of where the

hydrogen is ultimately positioned. However, Markovnikovs observation can
alternatively be described in terms of where the halogen (X) is ultimately positioned.
Specifically, the halogen is generally placed at the more substituted position:

The vinylic position bearing more alkyl groups is more substituted, and that is
where the Br is ultimately placed. This regiochemical preference, called Markovnikov
addition, is also observed for addition reactions involving HCl and HI. Reactions that
proceed with a regiochemical preference are said to be regioselective.

Interestingly, attempts to repeat Markovnikovs observations occasionally met

with failure. In many cases involving the addition of HBr, the observed
regioselectivity was, in fact, the opposite of what was expectedthat is, the bromine
atom would be installed at the less substituted carbon, which came to be known as
anti-Markovnikov addition. These curious observations fueled much speculation
over the underlying cause, with some researchers even suggesting that the phases
of the moon had an impact on the course of the reaction. Over time, it was realized
that purity of reagents was the critical feature. Specifically, Markovnikov addition was
observed whenever purified reagents were used, while the use of impure reagents
sometimes led to anti-Markovnikov addition. Further investigation revealed the
identity of the impurity that most greatly affected the regioselectivity of the reaction. It
was found that peroxides (ROOR), even in trace amounts, would cause HBr to add
across an alkene in an anti-Markovnikov fashion.
 In contrast, anti-Markovnikov addition of HBr is known to proceed via an
entirely different mechanism, one involving radical intermediates. This radical
pathway (anti-Markovnikov addition) is efficient for the addition of HBr but not
HCl or HI. (Klein, 2012)

Radical Polymerization of Alkenes: Addition Polymers

Low-molecular-weight alkanes (such as methane or ethane) are gases at
room temperature, alkanes of slightly higher molecular weight (such as hexane and
octane) are liquids at room temperature, and alkanes of very high molecular weight
(such as hectane, with 100 carbon atoms) are solids at room temperature. This trend
is explained by the increased London dispersion forces experienced by higher
molecular weight alkanes. With this in mind, consider an alkane composed of
approximately 100,000 carbon atoms. It should not be surprising that such an alkane
should be a hard solid at room temperature. This material, called polyethylene, is
used for a variety of purposes, including garbage containers, plastic bottles,
packaging material, bulletproof vests, and toys. As its name implies, polyethylene is
produced from polymerization of ethylene.

Polyethylene is an example of a polymer, because it is created by the joining

of small molecules called monomers. Over 100 billion pounds of polyethylene are
produced worldwide each year. In our everyday lives, we are surrounded by a variety
of polymers. From carpet fibers to plumbing pipes, our society has clearly become
dependent on polymers. (Klein, 2012)
A polymer is simply a largesometimes very largemolecule built up by
repetitive bonding together of many smaller molecules, called monomers.
Polyethylene and other simple alkene polymers are called chain-growth
polymers because they are formed in a chain reaction process in which an initiator
adds to a carboncarbon double bond to yield a reactive intermediate. The
intermediate then reacts with a second molecule of monomer to yield a new
intermediate, which reacts with a third monomer unit, and so on.
Historically, ethylene polymerization was carried out at high pressure (1000
3000 atm) and high temperature (100250 C) in the presence of a radical initiator
such as benzoyl peroxide, although other catalysts and reaction conditions are now
used. The key step is the addition of a radical to the ethylene double bond, a
reaction similar in many respects to what takes place in the addition of an
electrophile. In writing the mechanism, recall that a curved half-arrow, or fishhook,
is used to show the movement of a single electron, as opposed to the full curved
arrow used to show the movement of an electron pair in a polar reaction. (McMurry,
2012)

Mechanism of Polymerization:
 When ethylene is heated in the presence of peroxides, two initiation steps
produce a carbon radical. This carbon radical then attacks another molecule of
ethylene, generating a new carbon radical. These propagation steps continue,
adding one monomer at a time, until a termination step occurs. If the conditions are
carefully controlled to favor propagation over termination, the process can generate
very large molecules of polyethylene with over 10,000 repeating units. During the
polymerization process, chain branching inevitably occurs. The following scheme
shows a mechanism for the formation of chain branches, which begins with a
hydrogen abstraction that occurs on an existing chain:
 The extent of chain branching determines the physical properties of the
resulting polymer. For example, a flexible plastic squeeze bottle and its relatively
inflexible cap are both made from polyethylene, but the former has extensive
branching while the latter has relatively little. (Klein, 2012)

Radical Polymerization of a Substituted Ethylene

A substituted ethylene (ethylene that bears a substituent) will generally
undergo radical polymerization to produce a polymer with the following structure:

For example, vinyl chloride is polymerized to form polyvinyl chloride (PVC),

which is a very hard polymer used to make plumbing pipes. PVC can be softened if
polymerization takes place in the presence of compounds called plasticizers. PVC
made with plasticizers is a bit more flexible (although durable and strong) and is
used for a wide variety of purposes, such as garden hoses, plastic raincoats, and
shower curtains. Table 11.3 shows a number of common polymers produced via a
radical process. (Klein, 2012)
Hydrogenation of Alkynes
Catalytic Hydrogenation
Alkynes undergo many of the same addition reactions as alkenes. For
example, alkynes will undergo catalytic hydrogenation just as alkenes do:

In the process, the alkyne consumes two equivalents of molecular hydrogen:

Under these conditions, the cis alkene is difficult to isolate because it is even
more reactive toward further hydrogenation than the starting alkyne. The obvious
question then is whether it is possible to add just one equivalent of hydrogen to form
the alkene. With the catalysts we have seen thus far (Pt, Pd, or Ni), this is difficult to
achieve. However, with a partially deactivated catalyst, called a poisoned catalyst, it
is possible to convert an alkyne into a cis alkene (without further reduction):

There are many poisoned catalysts. One common example is called Lindlars
catalyst:

Another common example is a nickel-boron complex (Ni2B), which is often

called the P-2 catalyst. A poisoned catalyst will catalyze the conversion of an alkyne
into a cis alkene, but it will not catalyze the subsequent reduction to form the alkane.
Therefore, a poisoned catalyst can be used to convert an alkyne into a cis alkene.
This process does not produce any trans alkene. The stereochemical
outcome of alkyne hydrogenation can be rationalized in the same way that we
rationalized the outcome of alkene hydrogenation. Both hydrogen atoms are added
to the same face of the alkene (syn addition) to give the cis alkene as the major
product. (Klein, 2012)
References

Klein, D. (2012). Organic chemistry. Hoboken, NJ: John Wiley & Sons, Inc.

McMurry, J. (2012). Organic chemistry, eight edition. Belmont, CA: Brooks/Cole

Cengage Learning.