Functional Groups

Functional Groups Oxidation-Reduction Reactions

Functional Groups

Bromine reacts with 2-butene to form 2,3-dibromobutane.

It also reacts with 3-methyl-2-pentene to form 2,3-dibromopentane.

Instead of trying to memorize both equations, we can build a general rule that bromine reacts with
compounds that contain a C=C double bond to give the product expected from addition across the
double bond. This approach to understanding the chemistry of organic compounds presumes that
certain atoms or groups of atoms known as functional groups give these compounds their
characteristic properties.

Functional groups focus attention on the important aspects of the structure of a molecule. We don't
have to worry about the differences between the structures of 1-butene and 2-methyl-2-hexene, for
example, when these compounds react with hydrogen bromide. We can focus on the fact that both
compounds are alkenes that add HBr across the C=C double bond in the direction predicted
by Markovnikov's rule.

Some common functional groups are given in the table below.

Common Functional Groups

Functional Group Name Example

 Alkane CH3CH2CH3 (propane)

Alkene CH3CH=CH2 (propene)

Alkyne CH3C CH (propyne)
F, Cl, Br, or I Alkyl halide CH3Br (methyl bromide)
Alcohol CH3CH2OH (ethanol)
Ether CH3OCH3 (dimethyl ether)
Amine CH3NH2 (methyl amine)

The C=O group plays a particularly important role in organic chemistry. This group is called
a carbonyl and some of the functional groups based on a carbonyl are shown in the table below.

Functional Groups That Contain a Carbonyl

Functional Group Name Example

Aldehyde CH3CHO (acetaldehyde)

Ketone CH3COCH3 (acetone)

Acyl chloride CH3COCl (acetyl chloride)

Carboxylic acid CH3CO2H (acetic acid)

Ester CH3CO2CH3 (methyl acetate)

Amide CH3NH2 (acetamide)

Practice Problem 1:

Root beer hasn't tasted the same since the use of sassafras oil as a food additive was outlawed because
sassafras oil is 80% safrole, which has been shown to cause cancer in rats and mice. Identify the functional
groups in the structure of safrole.
Click here to check your answer to practice problem 1

Practice Problem 2:

The following compounds are the active ingredients in over-the-counter drugs used as analgesics (to relieve
pain without decreasing sensibility or consciousness), antipyretics (to reduce the body temperature when it
is elevated), and/or anti-inflammatory agents (to counteract swelling or inflammation of the joints, skin, and
eyes). Identify the functional groups in each molecule.

Click here to check your answer to practice problem 2

Practice Problem 3:

The discovery of penicillin in 1928 marked the beginning of what has been called the "golden age of
chemotherapy," in which previously life-threatening bacterial infections were transformed into little more
than a source of discomfort. For those who are allergic to penicillin, a variety of antibiotics, including
tetracycline, are available. Identify the numerous functional groups in the tetracycline molecule.
 Click here to check your answer to practice problem 3

Oxidation-Reduction Reactions

Focusing on the functional groups in a molecule allows us to recognize patterns in the behavior of
related compounds. Consider what we know about the reaction between sodium metal and water,
for example.

2 Na(s) + 2 H2O(l) H2(g) + 2 Na+(aq) + 2 OH-(aq)

We can divide this reaction into two half-reactions. One involves the oxidation of sodium metal to
form sodium ions.

Oxidation: Na Na+ + e-

The other involves the reduction of an H+ ion in water to form a neutral hydrogen atom that
combines with another hydrogen atom to form an H2 molecule.

Reduction:

Once we recognize that water contains an OH functional group, we can predict what might
happen when sodium metal reacts with an alcohol that contains the same functional group. Sodium
metal should react with methanol (CH 3OH), for example, to give H2 gas and a solution of the
Na+ and CH3O- ions dissolved in this alcohol.

2 Na(s) + 2 CH3OH(l) H2(g) + 2 Na+(alc) + 2 CH3O-(alc)

Because they involve the transfer of electrons, the reaction between sodium metal and either water
or an alcohol are examples of oxidation-reduction reactions. But what about the following reaction,
in which hydrogen gas reacts with an alkene in the presence of a transition metal catalyst to form an
alkane?

There is no change in the number of valence electrons on any of the atoms in this reaction. Both
before and after the reaction, each carbon atom shares a total of eight valence electrons and each
hydrogen atom shares two electrons. Instead of electrons, this reaction involves the transfer of
atoms in this case, hydrogen atoms. There are so many atom-transfer reactions that chemists
developed the concept of oxidation number to extend the idea of oxidation and reduction to
reactions in which electrons aren't necessarily gained or lost.

Oxidation involves an increase in the oxidation number of an atom.

Reduction occurs when the oxidation number of an atom decreases.

During the transformation of ethene into ethane, there is a decrease in the oxidation number of the
carbon atom. This reaction therefore involves the reduction of ethene to ethane.

Reactions in which none of the atoms undergo a change in oxidation number are called metathesis
reactions. Consider the reaction between a carboxylic acid and an amine, for example.

Or the reaction between an alcohol and hydrogen bromide.

These are metathesis reactions because there is no change in the oxidation number of any atom in
either reaction.

The oxidation numbers of the carbon atoms in a variety of compounds are given in the table below.

Typical Oxidation Numbers of Carbon

 Oxidation Number of
Functional Group Example
Carbon in the Example
Alkane CH4 -4
Alkyllithium CH3Li -4
Alkene H2C=CH2 -2
Alcohol CH3OH -2
Ether CH3OCH3 -2
Alkyl halide CH3Cl -2
Amine CH3NH2 -2
Alkyne HC CH -1
Aldehyde H2CO 0
Carboxylic acid HCO2H 2
CO2 4

These oxidation numbers can be used to classify organic reactions as either oxidation-reduction
reactions or metathesis reactions.

Practice Problem 4:

Classify the following as either oxidation-reduction or metathesis reactions.

Click here to check your answer to practice problem 4

Because electrons are neither created nor destroyed, oxidation can't occur in the absence of
reduction, or vice versa. It is often useful, however, to focus attention on one component of the
reaction and ask: Is that substance oxidized or reduced?

Practice Problem 5:

Determine whether the following transformations involve the oxidation or the reduction of the carbon atom.
 Click here to check your answer to practice problem 5

Assigning oxidation numbers to the individual carbon atoms in a complex molecule can be
difficult. Fortunately, there is another way to recognize oxidation-reduction reactions in organic
chemistry:

Oxidation occurs when hydrogen atoms are removed from a carbon atom or when an oxygen
atom is added to a carbon atom.

Reduction occurs when hydrogen atoms are added to a carbon atom or when an oxygen atom
is removed from a carbon atom.

The first reaction in practice problem 5 involves oxidation of the carbon atom because a pair of
hydrogen atoms are removed from that atom when the alcohol is oxidized to an aldehyde.

The second reaction in practice problem 5 is an example of oxidation because an oxygen atom is
added to the carbon atom when an aldehyde is oxidized to a carboxylic acid.

Reduction, on the other hand, occurs when hydrogen atoms are added to a carbon atom or when an
oxygen atom is removed from a carbon atom. An alkene is reduced, for example, when it reacts
with H2 to form the corresponding alkane.

The figure below provides a useful guide to the oxidation-reduction reactions of organic
compounds. Each of the arrows in this figure involves a two-electron oxidation of a carbon atom
along the path toward carbon dioxide. A line is drawn through the first arrow because it is
impossible to achieve this transformation in a single step.

Organic Chemistry: Functional Groups

Functional Groups | Alkyl Halides | Alcohols and Ethers | Aldehydes and Ketones | The Carbonyl Group | Amines,
Alkaloids, and Amides | Grignard Reagents
Research in the 1990's: The Chemistry of Garlic

Periodic Table | Glossary | Cool Applets

Gen Chem Topic Review | General Chemistry Help Homepage | Search: The general chemistry web site.

5 Functional Groups; Alcohols and Ethers

The reactivity of organic compounds can be attributed to particular atoms or groups of atoms within
the molecules. A site of reactivity in an organic molecule is called a functional group because it
controls how the molecule behaves or functions. As we have seen, the presence of C C double
bonds or C C triple bonds in a hydrocarbon markedly increases its reactivity. Furthermore, these
functional groups each undergo characteristic reactions. Each distinct kind of functional group
often undergoes the same kinds of reactions in every molecule, regardless of the size and
complexity of the molecule. Thus, the chemistry of an organic molecule is largely determined by
the functional groups it contains.

Table 25.4 lists the most common functional groups and gives examples of each. Notice that in
addition to C C double bonds or C C triple bonds, there are also many functional groups that
contain elements other than just C and H. Many of the functional groups contain other nonmetals
such as O and N.
We can think of organic molecules as being composed of functional groups that are bonded to one
or more alkyl groups. The alkyl groups, which are made of C C and C H single bonds, are
the less reactive portions of the organic molecules. In describing general features of organic
compounds, chemists often use the designation R to represent any alkyl group: methyl, ethyl,
propyl, and so on. For example, alkanes, which contain no functional group, are represented as
R H. Alcohols, which contain the O H, or alcohol functional group, are represented as R
OH. If two or more different alkyl groups are present in a molecule, we will designate them as R,
R', R'', and so forth. In this section we examine the structure and chemical properties of two
functional groups, alcohols and ethers. In the next section we consider some additional functional
groups that contain C O bonds.

Alcohols (R OH)
Alcohols are hydrocarbon derivatives in which one or more hydrogens of a parent hydrocarbon
have been replaced by a hydroxyl or alcohol functional group, OH. Figure 25.12 shows the
structural formulas and names of several alcohols. Note that the name for an alcohol ends in
-ol. The simple alcohols are named by changing the last letter in the name of the corresponding
alkane to -ol for example, ethanebecomes ethanol. Where necessary, the location of the OH
group is designated by an appropriate numeral prefix that indicates the number of the carbon atom
bearing the OH group, as shown in the examples in Figure 25.12.

Figure 25.12 Structural formulas of several important alcohols. Their common names are given in
blue.

Recall that the O H bond is polar. This means that alcohols are much more soluble in polar
solvents such as water than are hydrocarbons. The OH functional group can also participate in
hydrogen bonding. As a result, the boiling points of alcohols are much higher than those of their
parent alkanes.

Figure 25.13 shows several familiar commercial products that consist entirely or in large part of an
organic alcohol. Let's consider how some of the more important alcohols are formed and used.

The simplest alcohol, methanol (methyl alcohol), has many important industrial uses and is
produced on a large scale. Carbon monoxide and hydrogen are heated together under pressure in
the presence of a metal oxide catalyst:
 [25.14]

Because methanol has a very high octane rating as an automobile fuel, it is used as a gasoline
additive and as a fuel in its own right.

Ethanol (ethyl alcohol), C2H5OH, is a product of the fermentation of carbohydrates such as sugar
and starch. In the absence of air, yeast cells convert carbohydrates into a mixture of ethanol and
CO2, as shown in Equation 25.15. In the process, yeast derives energy necessary for growth:

[25.15]

This reaction is carried out under carefully controlled conditions to produce beer, wine, and other
beverages in which ethanol is the active ingredient.

Many polyhydroxyl alcohols (those containing more than one OH group) are known. The simplest
of these is 1,2-ethanediol (ethylene glycol), HOCH 2CH2OH. This substance is the major ingredient
in automobile antifreeze. Another common polyhydroxyl alcohol is 1,2,3-propanetriol (glycerol),
HOCH2CH(OH)CH2OH. It is a viscous liquid that dissolves readily in water and is widely used as a
skin softener in cosmetic preparations. It is also used in foods and candies to keep them moist.

Phenol is the simplest example of a compound with an OH group attached to an aromatic ring. One
of the most striking effects of the aromatic group is the greatly increased acidity of the OH group.
Phenol is about 1 million times more acidic in water than a typical nonaromatic alcohol such as
ethanol. Even so, it is not a very strong acid (Ka = 1.3 1010). Phenol is used industrially in the
making of several kinds of plastics and in the preparation of dyes. It is also used as a topical
anesthetic in many sore throat sprays.

Cholesterol, shown in Figure 25.12, is a biochemically important alcohol. Notice that the OH group
forms only a small component of this rather large molecule. As a result, cholesterol is not very
soluble in water (0.26 g per 100 mL of H2O). Cholesterol is a normal component of our bodies;
however, when present in excessive amounts, it may precipitate from solution. It precipitates in the
gallbladder to form crystalline lumps called gallstones. It may also precipitate against the walls of
veins and arteries and thus contribute to high blood pressure and other cardiovascular problems.
The amount of cholesterol in our blood is determined not only by how much cholesterol we eat but
also by total dietary intake. There is evidence that excessive caloric intake leads the body to
synthesize excessive cholesterol.

Ethers (R O R')
Compounds in which two hydrocarbon groups are bonded to one oxygen are called ethers. Ethers
can be formed from two molecules of alcohol by splitting out a molecule of water. The reaction is
thus a dehydration process; it is catalyzed by sulfuric acid, which takes up water to remove it from
the system:
 [25.16]

A reaction in which water is split out from two substances is called a condensation reaction.

Ethers are used as solvents; both diethyl ether and the cyclic ether tetrahydrofuran are common
solvents for organic reactions