ELLA MAE B.

BOALOY
BS CHEMICAL ENGINEERING 3

ORGANIC CHEMISTRY 1 LEC

The Mechanism of Organic Reactions

Four broad classes of reactions based solely on the structural change occurring in the reactant
molecules:
Addition Reaction

In an addition reaction the number of σ-bonds in the substrate molecule increases, usually at the
expense of one or more π-bonds; a nucleophile or an electrophile is added.

Elimination Reaction

In elimination reactions, the number of σ-bonds in the substrate decreases, and new π-bonds are
often formed.

Substitution Reaction

Substitution reactions, as the name implies, are characterized by replacement of an atom or

group (Y) by another atom or group (Z). Aside from these groups, the number of bonds does not
change.

Rearrangement Reaction

A rearrangement reaction generates an isomer, and again the number of bonds normally does
not change.
*Electrophile: An electron deficient atom, ion or molecule that has an affinity for an electron
pair, and will bond to a base or nucleophile.
*Nucleophile: An atom, ion or molecule that has an electron pair that may be donated in bonding
to an electrophile (or Lewis acid).

 Example: Reaction of an Ester with Ammonia

The reaction of an ester with ammonia to give an amide, as shown, appears to be a substitution
reaction ( Y = CH3O & Z = NH2 ); however, it is actually two reactions, an addition followed
by an elimination.

The Three Phases of Radical Chain Reactions

A radical substitution reaction is a reaction that occurs by a free radical mechanism and results
in the substitution of one or more of the atoms or groups present in the substrate by different
atoms or groups.

The initiation step in a radical chain reaction is the step in which a free radical is first produced.
A termination step of a radical chain reaction is one in which two radicals react together in some
way so that the chain can no longer be propagated.

While radical halogenation of very simple alkanes can be an effective synthetic strategy, it
cannot be employed for larger more complex alkanes to yield specific alkyl halides, since the
reactive nature of radicals always leads to mixtures of single- and multiple-halogenated products.
Alkenes
Alkenes contains a carbon-carbon double bond. This carbon-carbon double bond changes
the physicals properties of alkenes. At room temperature, alkenes exist in all three phases, solid,
liquids, and gases. Melting and boiling points of alkenes are similar to that of alkanes, however,
isomers of cis alkenes have lower melting points than that of trans isomers. Alkenes display a
weak dipole-dipole interaction due to the electron-attracting sp2carbon.
Geometric (cis-trans) Isomerism

Cis-but-2-ene is also known as (Z)-but-2-ene; trans-but-2-ene is also known as (E)-but-2-ene.

Key Reactions of Alkenes

Alkynes
The physical properties of alkynes are very similar to those of the alkenes. Alkynes are
generally nonpolar molecules with little solubility in polar solvents, such as water. Solubility in
nonpolar solvents, such as ether and acetone, is extensive. Like the alkanes and alkenes, alkynes
of four or fewer carbon atoms tend to be gases.
Key Reactions of Alkynes
Like alkenes, the main pathway found in the reactions of alkynes is “addition” – that is,
breaking the C-C π bond and forming two new single bonds to carbon. The product of an
addition reaction to an alkyne is an alkene – alkene reactions undergo addition reactions too. The
result of this is that since alkynes possess two π bonds, one must always be alert to the possibility
of two addition reactions occurring. Furthermore, should only one addition occur, the
stereochemistry of the addition should be well noted, as it can lead to the formation of geometric
isomers (i.e. E/Z isomers). Finally, there is an additional complexity in certain alkyne reactions
that is not found in the reactions of alkenes. When water is added across an alkyne, the resulting
product is an “enol”.
Another reaction not present in the reactions of alkenes is deprotonation. Alkynes are
unusually acidic hydrocarbons. Lastly, alkynes also undergo oxidative cleavage reactions.
Treatment of alkynes with either ozone or KMnO4 leads to carboxylic acids [terminal alkynes
give carbonic acid, which decomposes to CO2 and water].