Functional groups

One of the organizing principles of organic chemistry is the functional group. While it might
seem that there are infinite possibilities o f how atoms might be connected to each other, it
turns out that there are a small number of typical patterns. Why is this the case? First, we
primarily work with only four elements: hydrogen, carbon, nitrogen, and oxygen. Second,
remember the bonding rules we have for typical, stable atoms in a moleculecarbon forms
four bonds, nitrogen forms three bonds and has a lone pair, and oxygen forms two bonds and
has two lone pairs. With these limitations, there are only a few patterns that we need to
recognize, and we call each pattern of bonding a functional group and give it its own name.

Below are the major functional groups that we will study. It is essential that you have the
following skills:
Be able to recognize what distinguishes each functional group from the others.
Be able to recognize the functional group within the context of a larger molecule.
Be able to name the functional group
Know and be able to use a few other terms that are related to each functional group

1. Alkane

The alkane is the most basic unit in organic chemistry, made up of carbon/carbon single
bonds and carbon/hydrogen single bonds. In fact, we often dont consider the alkane to be a
functional group at all, but rather the molecular scaffold on which functional groups are placed.
Think of the alkane as the canvas on which a picture is painted. We can use the term alkane
to refer to a whole molecule that contains nothing but carbon and hydrogen single bonds, or
we can refer to a portion of a molecule as the alkane portion of the molecule. Alkanes are a
type of hydrocarbon, a molecule that contains only carbon and hydrogen.

Some other important common terms associated with alkanes include straight-chain alkane,
branched alkane, and cyclic alkane.

Examples of alkanes:

cyclic

straight-chain branched

The molecule below is cholesterol. We might say that the molecule has an alkane portion
which is circled. An older term that is still common is to say that cholesterol contains an
aliphatic portion because it is all carbon and hydrogen single bonds.
HO

2. Alkenes

The alkene is also a hydrocarbon because it contains only carbon and hydrogen, but it also
contains a carbon-carbon double bond. We say that the alkene is unsaturated because it is not
saturated with hydrogen atomsit does not contain as many C-H bonds as possible. The base
unit of the alkene is the C=C, with hydrogen atoms or R groups attached. The R group is the
generic variable of any alkane group. We refer to this as an alkyl group.

R or H R or H

C C base unit of an alkene

R or H R or H

We might use the term alkene in two ways: we might refer to the C=C bond itself as an alkene,
or we might refer to a whole molecule containing the carbon-carbon double bond as an alkene.
For example, we might say that there are three alkenes shown below, or we might say that the
three molecules below all contain the alkene functional group. Because of their structural
similarities, all alkenes have some similarities in their properties and reactivity.

a cyclic alkene
3. Alkyne

The alkyne is similar to the alkene except that alkynes contain carbon-carbon triple bonds.
They are also unsaturated hydrocarbons. A terminal alkene has at least one hydrogen directly
attached to the triple bonded carbon. An internal alkene has two R groups. The prime symbol
in R designates that this R group may be different than the other R group.

R C C H R C C R'

terminal alkyne internal alkyne

4. Aromatic
In this course, we will learn quite a bit about aromatic compounds. For now, we will discuss the
most common aromatic structure: benzene. Benzene is a six member carbon ring with three
double bonds.

benzene aromatic compounds

5. Alcohol

An alcohol is a molecule that contains the hydroxyl group, -OH. Therefore, the generic
representation of an alcohol is ROH. The base unit is carbon single bonded to oxygen, which is
single bonded to hydrogen.

R or H

R' or H C O H

OH OH
R' or H

base unit of moleucle A molecule B

alcohol

The two example molecules above both contain the base unit C-O-H. All of the following
statements would be proper to make:
Molecules A and B are alcohols.
Molecule A contains a hydroxyl group.
Molecule B is an alkene.
Molecule B is a cyclic molecule containing a hydroxyl group.

6. Phenol

Alcohols that are directly connected to benzene have a special name: phenol. It is important to
recognize that the phenol involves the hydroxyl directly connected to the benzene, not simply
in the same molecule.

OH

OH

a phenol
not a phenol--an alcohol

5. Ether
The ether is a functional group similar to the alcohol, but there is one crucial distinction: the
oxygen atom is bonded to two carbon atoms. Therefore the base unit of the ether is C-O-C.

O O

a symmetrical ether

a cyclic ether O

an unsaturated ether

6. Amine

The distinctive of the amine group is that it contains a nitrogen atom bonded to hydrogen
and/or alkyl groups. Amines can look quite different, as in the examples below.

H
N
H2N

N
H

7. Nitrile

A nitrile contains the cyano functional group, which is a carbon-nitrogen triple bond. Due to
the nature of nitrogen bonding, the cyano group is always a terminal group in a compound. It is
often written in its condensed formula, CN. Therefore, the general representation of a nitrile
is RCN.

CN
N

an aromatic nitrile an aliphatic nitrile

7. Thiol

Thiols are the equivalent of alcohols that have sulfur instead of oxygen. Therefore, the base
unit of a thiol is C-S-H and the general designation for a thiol is RSH.

8. Alkyl halide
The alkyl halide is a alkane skeleton with a halogen bonded. The halogens (fluorine, chlorine,
bromine, and iodine) can be represented generically as X, and therefore, the general alkyl
halide can be designated RX.

Cl
Br I

9. Ketone

The ketone is the first of many compounds that contains the carbonyl group, which is a carbon-
oxygen double bond. A compound is a ketone if the carbonyl carbon is directly attached to two
carbon atoms, typically alkanes or alkenes.

O O
O

C C C

base unit of
ketone cyclic keton an unsaturated ketone

10. Aldehyde

An aldehyde is very similar to a ketone, but in an aldehyde, the carbonyl is attached to carbon
on one side and hydrogen on the other. Therefore, the aldehyde is always at the end of a
molecule. In the condensed formula, the aldehyde is designated with CHO which does not
mean that hydrogen is single bonded to carbon and oxygen, but is meant to distinguish the
group from a hydroxyl group. The general designation of an aldehyde is RCHO.

O
H
C C H
CH3CH2CHO

base unit of a condensed formula

aldehyde of an aldehyde
an aromatic aldehyde

11. Carboxylic acid

A carboxylic acid contains a carbonyl attached to an R group on one side and a hydroxyl group
on the other side. NOTICE: The carboxylic acid is NOT a ketone and alcohol, but rather, a
whole new group. Therefore it is proper to say that all carboxylic acids contain a hydroxyl
group, but not all hydroxyl groups are carboxylic acids. Condensed formula for a carboxylic acid
is COOH, and these acids are generally written RCOOH.

Two carboxylic acids in the Citric Acid Cycle

O succinate fumarate
C C OH
COOH COOH
base unit of HOOC HOOC
aldehyde
an unsaturated carboxylic acid

12. Ester

The ester contains a carbonyl attached to an R group on one side and an OR group on the other
side.

O O O

C C OR
O O
base unit of
ester

13. Amide

An amide contains a carbonyl with an R group on one side and a nitrogen atom on the other.
The nitrogen may be attached to other R groups or hydrogens. NOTICE: The amide is NOT a
ketone attached to an amine, but a whole new group called an amide.

O
O O
H2N
C C N HN
N
base unit of H
O
ester