Qumica Orgnica.

Preparador: Paco Martnez

Organic Chemistry Mechanisms

1. Free radical halogenation to alkanes

Free radical halogenation is a reaction that substitutes a chlorine or a bromine for a hydrogen on an alkane. This
reaction is a photochemical one. That is, it occurs only when performed in the presence of uv light (abbreviated h).
Typically, free radical reactions are described in three steps: initiation steps, propagation steps, and termination steps
(described below). Note the use of a single headed arrow when describing the movement of a single electron.
Initiation Step:
The reaction begins with an initiation step, which is the separation of the halogen (X2) into two radicals (atoms with a
single unpaired electron) by the addition of uv light. This is called the initiation step because it initiates the reaction.

Propogation Steps:
The initiation step, or the formation of the chlorine radicals, is immediately followed by the propogation steps--steps
directly involved in the formation of the product. As an example, isobutane (C 4H10) will be used in the chlorination
reaction. The first step is the abstraction of the hydrogen atom from the tertiary carbon (a tertiary carbon is a carbon
that is attached to three other carbon atoms) Note that these are not protons (H+ ions) that are being abstracted, but
actual hydrogen atoms since each hydrogen has one electron. This first propogation step forms the tertiary radical.

In the last step, the tertiary radical then reacts with another one of the chlorine molecules to form the product. Notice
that another chlorine radical is regenerated, so this reaction can, in theory, go on forever as long as there are
reagents. This is called a chain reaction.

A sidenote on free radical stabilities:

Hydrogens attached to more highly substituted carbons (ie. carbons with many carbons attached to them) are more
reactive in free-radical halogenation reactions because the radical they form is stabilized by neighboring alkyl groups.
These neighboring alkyl groups have the ability to donate some of their electron density to the electron-deficient
radical carbon (a radical is short one electron of filling the atom's valence octet). Thus the hydrogen on the tertiary
carbon here is abstracted in preference to the 9 other hydrogen atoms attached to a primary carbon (a carbon that is
attached to only one other carbon atom) because it forms a more stable radical.

Here, the tertiary radical is stabilized by electron donation from neighboring alkyl groups.
electivity of free-radical halogenation
A point of note about free radical processes is that the intermediates are so highly reactive and short lived that usually
you obtain a mixture of products, even though there is preference for forming more highly substituted free radical
intermediates. In this example with isobutane, for instance, there would certainly be some abstraction of hydrogens
attached to the primary carbons, leading to a different product than the above product (can you draw it out?).
Bromine reacts exactly the same way as chlorine; however, it is far more selective. If propane (CH 3CH2CH3), for
example, was the substrate, 2-bromopropane would be the dominant product, and there would be only a small
amount of 1-bromopropane. Free radical chlorination, though, would not be quite as selective, and there would be a
greater amount of the chlorination of the primary carbon than in the bromination reaction.
Termination Steps:
Side reactions that can stop the chain reaction are called termination steps. These termination steps involve the
destruction of the free-radical intermediates, typically by two of them coming together.

Qumica Orgnica.

Preparador: Paco Martnez

2. Electrophilic Addition to Alkenes Mechanism

Overview:
Electrophilic addition to alkenes takes the following general form:

nuc: = nucleophile
E+ = electrophile
Electrophilic addition to alkenes starts with the pi electrons attacking an electrophile, forming a
carbocation on the most stable carbon. A nucleophile then attacks the carbocation to form the product.
There are many different kinds of such addition, including:
Clearly, there are numerous kinds of products that can be formed as a result of this mechanism.
Orientation of Addition: Electrophilic Addition adds to give the Markovnikov Product, with the
nucleophile added to the more highly substituted carbon. This is because the carbocation intermediate is
significantly stabilized by alkyl substituents.

Example of electophilic addition to alkenes:

First, formation of the carbocation on the most highly substituted carbon

Followed by attack of chloride on the carbocation to give the addition product

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