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An Introduction to
2 Organic Compounds
Nomenclature, Physical Properties,
and Representation of Structure

CH3CH2Cl CH3CH2OH

CH3OCH3

T
his book organizes or-
ganic chemistry ac-
cording to how organic
compounds react. In studying CH3CH2NH2 CH3CH2Br
how compounds react, we must not
forget that whenever a compound undergoes a reaction, a new compound is synthe-
sized. In other words, while we are learning how organic compounds react, we will si-
multaneously be learning how to synthesize new organic compounds.
Y Z
Y is reacting Z is being synthesized

The main classes of compounds that are synthesized by the reactions you will study
in Chapters 3–11 are alkanes, alkyl halides, ethers, alcohols, and amines. As you learn
how to synthesize compounds, you will need to be able to refer to them by name, so
you will begin your study of organic chemistry by learning how to name these five
classes of compounds.
First you will learn how to name alkanes because they form the basis for the names
of almost all organic compounds. Alkanes are composed of only carbon atoms and
hydrogen atoms and contain only single bonds. Compounds that contain only carbon
and hydrogen are called hydrocarbons, so an alkane is a hydrocarbon that has only
single bonds. Alkanes in which the carbons form a continuous chain with no branches
are called straight-chain alkanes. The names of several straight-chain alkanes are
given in Table 2.1. It is important that you learn the names of at least the first 10.
The family of alkanes shown in the table is an example of a homologous series. A
homologous series (homos is Greek for “the same as”) is a family of compounds in
which each member differs from the next by one methylene (CH 2) group. The mem-
bers of a homologous series are called homologs. Propane (CH 3CH 2CH 3) and butane
(CH 3CH 2CH 2CH 3) are homologs.
If you look at the relative numbers of carbon and hydrogen atoms in the alkanes
listed in Table 2.1, you will see that the general molecular formula for an alkane is

60
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Introduction 61

CnH 2n + 2 , where n is any integer. So, if an alkane has one carbon atom, it must have
four hydrogen atoms; if it has two carbon atoms, it must have six hydrogens.
We have seen that carbon forms four covalent bonds and hydrogen forms only one
covalent bond (Section 1.4). This means that there is only one possible structure for an
alkane with molecular formula CH 4 (methane) and only one structure for an alkane
with molecular formula C2H 6 (ethane). We examined the structures of these com-
pounds in Section 1.7. There is also only one possible structure for an alkane with
molecular formula C3H 8 (propane).

name Kekulé structure condensed structure ball-and-stick model

H
methane H C H CH4
H

H H
ethane H C C H CH3CH3
H H

H H H
propane H C C C H CH3CH2CH3
H H H

H H H H
butane H C C C C H CH3CH2CH2CH3
H H H H

As the number of carbons in an alkane increases beyond three, the number of pos- 3-D Molecules:
sible structures increases. There are two possible structures for an alkane with molec- Methane; Ethane;
ular formula C4H 10 . In addition to butane—a straight-chain alkane—there is a Propane; Butane
branched butane called isobutane. Both of these structures fulfill the requirement that
each carbon forms four bonds and each hydrogen forms only one bond.
Compounds such as butane and isobutane that have the same molecular formula
but differ in the order in which the atoms are connected are called constitutional
isomers—their molecules have different constitutions. In fact, isobutane got its name
because it is an “iso”mer of butane. The structural unit—a carbon bonded to a hydro-
gen and two CH 3 groups—that occurs in isobutane has come to be called “iso.” Thus,
the name isobutane tells you that the compound is a four-carbon alkane with an iso
structural unit.

CH3CH2CH2CH3 CH3CHCH3 CH3CH

butane
CH3 CH3
isobutane an “iso”
structural unit
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62 CHAPTER 2 An Introduction to Organic Compounds

Table 2.1 Nomenclature and Physical Properties of Straight-Chain Alkanes

Number Boiling Melting
of Molecular Condensed point point Densitya
carbons formula Name structure (°C) (°C) (g> mL)

1 CH 4 methane CH 4 -167.7 -182.5

2 C 2H 6 ethane CH 3CH 3 -88.6 -183.3
3 C 3H 8 propane CH 3CH 2CH 3 -42.1 -187.7
4 C4H 10 butane CH 3CH 2CH 2CH 3 -0.5 -138.3
5 C5H 12 pentane CH 3(CH 2)3CH 3 36.1 -129.8 0.5572
6 C6H 14 hexane CH 3(CH 2)4CH 3 68.7 -95.3 0.6603
7 C7H 16 heptane CH 3(CH 2)5CH 3 98.4 -90.6 0.6837
8 C8H 18 octane CH 3(CH 2)6CH 3 127.7 -56.8 0.7026
9 C9H 20 nonane CH 3(CH 2)7CH 3 150.8 -53.5 0.7177
10 C10H 22 decane CH 3(CH 2)8CH 3 174.0 -29.7 0.7299
11 C11H 24 undecane CH 3(CH 2)9CH 3 195.8 -25.6 0.7402
12 C12H 26 dodecane CH 3(CH 2)10CH 3 216.3 -9.6 0.7487
13 C13H 28 tridecane CH 3(CH 2)11CH 3 235.4 -5.5 0.7546
o o o o o o o
20 C20H 42 eicosane CH 3(CH 2)18CH 3 343.0 36.8 0.7886
21 C21H 44 heneicosane CH 3(CH 2)19CH 3 356.5 40.5 0.7917
o o o o o o o
30 C30H 62 triacontane CH 3(CH 2)28CH 3 449.7 65.8 0.8097
a
Density is temperature dependent. The densities given are those determined at 20 °C 1d20°2.

There are three alkanes with molecular formula C5H 12 . Pentane is the straight-
chain alkane. Isopentane, as its name indicates, has an iso structural unit and five car-
bon atoms. The third isomer is called neopentane. The structural unit with a carbon
surrounded by four other carbons is called “neo.”

CH3 CH3
CH3CH2CH2CH2CH3 CH3CHCH2CH3 CH3CCH3 CH3CCH2
pentane
CH3 CH3 CH3
isopentane neopentane a “neo”
structural unit

There are five constitutional isomers with molecular formula C6H 14 . We are now
able to name three of them (hexane, isohexane, and neohexane), but we cannot name
the other two without defining names for new structural units. (For now, ignore the
names written in blue.)

CH3
CH3CH2CH2CH2CH2CH3 CH3CHCH2CH2CH3 CH3CCH2CH3
common name: hexane
systematic name: hexane CH3 CH3
isohexane neohexane
2-methylpentane 2,2-dimethylbutane

CH3CH2CHCH2CH3 CH3CH CHCH3

CH3 CH3 CH3
3-methylpentane 2,3-dimethylbutane
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Section 2.1 Nomenclature of Alkyl Substituents 63

There are nine alkanes with molecular formula C7H 16 . We can name only two of
them (heptane and isoheptane) without defining new structural units. Notice that neo- A compound can have more than one
heptane cannot be used as a name because three different heptanes have a carbon that name, but a name must specify only one
is bonded to four other carbons and a name must specify only one compound. compound.

CH3CH2CH2CH2CH2CH2CH3 CH3CHCH2CH2CH2CH3
common name: heptane
systematic name: heptane CH3
isoheptane
2-methylhexane

CH3CH2CHCH2CH2CH3 CH3CH CHCH2CH3 CH3CHCH2CHCH3

CH3 CH3 CH3 CH3 CH3
3-methylhexane 2,3-dimethylpentane 2,4-dimethylpentane

CH3 CH3
CH3CCH2CH2CH3 CH3CH2CCH2CH3 CH3CH2CHCH2CH3
CH3 CH3 CH2CH3
2,2-dimethylpentane 3,3-dimethylpentane 3-ethylpentane

CH3 CH3
CH3C CHCH3
CH3
2,2,3-trimethylbutane

The number of constitutional isomers increases rapidly as the number of carbons in

an alkane increases. For example, there are 75 alkanes with molecular formula C10H 22
and 4347 alkanes with molecular formula C15H 32 . To avoid having to memorize the
names of thousands of structural units, chemists have devised rules that name com-
pounds on the basis of their structures. That way, only the rules have to be learned. Be-
cause the name is based on the structure, these rules make it possible to deduce the
structure of a compound from its name.
This method of nomenclature is called systematic nomenclature. It is also called
IUPAC nomenclature because it was designed by a commission of the International
Union of Pure and Applied Chemistry (abbreviated IUPAC and pronounced “eye-you-
pack”) at a meeting in Geneva, Switzerland, in 1892. The IUPAC rules have been con-
tinually revised by the commission since then. Names such as isobutane and
neopentane—nonsystematic names—are called common names and are shown in red
in this text. The systematic or IUPAC names are shown in blue. Before we can under-
stand how a systematic name for an alkane is constructed, we must learn how to name
alkyl substituents.

2.1 Nomenclature of Alkyl Substituents

Removing a hydrogen from an alkane results in an alkyl substituent (or an alkyl
group). Alkyl substituents are named by replacing the “ane” ending of the alkane with
“yl.” The letter “R” is used to indicate any alkyl group.

CH3 CH3CH2 CH3CH2CH2 CH3CH2CH2CH2

a methyl group an ethyl group a propyl group a butyl group

R
any alkyl group
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64 CHAPTER 2 An Introduction to Organic Compounds

If a hydrogen of an alkane is replaced by an OH, the compound becomes an

alcohol; if it is replaced by an NH 2 , the compound becomes an amine; and if it is re-
placed by a halogen, the compound becomes an alkyl halide.
R OH R NH2 R X X = F, Cl, Br, or I
an alcohol an amine an alkyl halide

An alkyl group name followed by the name of the class of the compound (alcohol,
amine, etc.) yields the common name of the compound. The following examples show
how alkyl group names are used to build common names:
CH3OH CH3CH2NH2 CH3CH2CH2Br CH3CH2CH2CH2Cl
methyl alcohol ethylamine propyl bromide butyl chloride

CH3I CH3CH2OH CH3CH2CH2NH2 CH3CH2CH2CH2OH

methyl iodide ethyl alcohol propylamine butyl alcohol

Notice that there is a space between the name of the alkyl group and the name of the
class of compound, except in the case of amines.
Two alkyl groups—a propyl group and an isopropyl group—contain three carbon
atoms. A propyl group is obtained when a hydrogen is removed from a primary carbon
methyl alcohol
of propane. A primary carbon is a carbon that is bonded to only one other carbon. An
isopropyl group is obtained when a hydrogen is removed from the secondary carbon
of propane. A secondary carbon is a carbon that is bonded to two other carbons. No-
tice that an isopropyl group, as its name indicates, has its three carbon atoms arranged
as an iso structural unit.
methyl chloride a primary carbon a secondary carbon

CH3CH2CH2 CH3CHCH3

a propyl group an isopropyl group

methylamine CH3CH2CH2Cl CH3CHCH3

Cl
propyl chloride isopropyl chloride

Build models of the two representations
of isopropyl chloride, and convince
yourself that they represent the same
compound.
Molecular structures can be drawn in different ways. Isopropyl chloride, for exam-
ple, is drawn here in two ways. Both represent the same compound. At first glance, the
two-dimensional representations appear to be different: The methyl groups are across
from one another in one structure and at right angles in the other. The structures are
identical, however, because carbon is tetrahedral. The four groups bonded to the cen-
tral carbon—a hydrogen, a chlorine, and two methyl groups—point to the corners of a
tetrahedron. If you rotate the three-dimensional model on the right 90° in a clockwise
direction, you should be able to see that the two models are the same. (You can simu-
late this rotation on the Web site www.prenhall.com/bruice by visiting the Molecule
Gallery in Chapter 2.)
two different ways to draw isopropyl chloride

CH3CHCH3 CH3CHCl
Cl CH3
3-D Molecules:
Isopropyl chloride

isopropyl chloride isopropyl chloride

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Section 2.1 Nomenclature of Alkyl Substituents 65

There are four alkyl groups that contain four carbon atoms. The butyl and isobutyl
groups have a hydrogen removed from a primary carbon. A sec-butyl group has a hy-
drogen removed from a secondary carbon (sec-, often abbreviated s-, stands for sec-
ondary), and a tert-butyl group has a hydrogen removed from a tertiary carbon (tert-,
A primary carbon is bonded to one
sometimes abbreviated t-, stands for tertiary). A tertiary carbon is a carbon that is carbon, a secondary carbon is bonded to
bonded to three other carbons. Notice that the isobutyl group is the only group with an two carbons, and a tertiary carbon is
iso structural unit. bonded to three carbons.

a primary carbon a primary carbon a secondary carbon a tertiary carbon CH3

CH3CH2CH2CH2 CH3CHCH2 CH3CH2CH CH3C

CH3 CH3 CH3
a butyl group an isobutyl group a sec-butyl group a tert-butyl group

A name of a straight-chain alkyl group often has the prefix “n” (for “normal”), to Tutorial:
emphasize that its carbon atoms are in an unbranched chain. If the name does not have Alkyl group nomenclature
a prefix such as “n” or “iso,” it is assumed that the carbons are in an unbranched chain.

CH 3CH 2CH 2CH 2Br CH 3CH 2CH 2CH 2F

butyl bromide pentyl fluoride
or or
n-butyl bromide n-pentyl fluoride

Like the carbons, the hydrogens in a molecule are also referred to as primary, sec-
ondary, and tertiary. Primary hydrogens are attached to primary carbons, secondary
hydrogens to secondary carbons, and tertiary hydrogens to tertiary carbons.

primary hydrogens tertiary hydrogen secondary hydrogens CH3

CH3CH2CH2CH2OH CH3CHCH2OH CH3CH2CHOH CH3COH
CH3 CH3 CH3

butyl alcohol isobutyl alcohol sec-butyl alcohol tert-butyl alcohol

or or or
n-butyl alcohol s-butyl alcohol t-butyl alcohol

Because a chemical name must specify only one compound, the only time you 3-D Molecules:
will see the prefix “sec” is in sec-butyl. The name “sec-pentyl” cannot be used be- n-Butyl alcohol; sec-Butyl
cause pentane has two different secondary carbon atoms. Therefore, there are two alcohol; tert-Butyl alcohol
different alkyl groups that result from removing a hydrogen from a secondary car-
bon of pentane. Because the name would specify two different compounds, it is not
a correct name.

Both alkyl halides have five carbon atoms with a chloride attached to a Tutorial:
secondary carbon, so both compounds would be named sec-pentyl chloride. Degree of alkyl substitution

CH3CHCH2CH2CH3 CH3CH2CHCH2CH3
Cl Cl
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66 CHAPTER 2 An Introduction to Organic Compounds

The prefix “tert” is found in tert-butyl and tert-pentyl because each of these sub-
stituent names describes only one alkyl group. The name “tert-hexyl” cannot be used
because it describes two different alkyl groups. (In older literature, you might find
“amyl” used instead of “pentyl” to designate a five-carbon alkyl group.)
CH3 CH3 CH2CH3 CH3
CH3C Br CH3C Br CH3CH2C Br CH3CH2CH2C Br
CH3 CH2CH3 CH3 CH3
tert-butyl bromide tert-pentyl bromide Both alkyl bromides have six carbon atoms with a
bromine attached to a tertiary carbon, so both
compounds would be named tert-hexyl bromide.

If you examine the following structures, you will see that whenever the prefix “iso”
is used, the iso structural unit will be at one end of the molecule and any group replac-
ing a hydrogen will be at the other end:
CH3CHCH2CH2OH CH3CHCH2CH2CH2Cl CH3CHCH2NH2
CH3 CH3 CH3
isopentyl alcohol isohexyl chloride isobutylamine
or
isoamyl alcohol

CH3CHCH2Br CH3CHCH2CH2OH CH3CHBr

CH3 CH3 CH3
isobutyl bromide isopentyl alcohol isopropyl bromide

Notice that an iso group has a methyl group on the next-to-the-last carbon in the chain.
Notice also that all isoalkyl compounds have the substituent (OH, Cl, NH 2 , etc.) on a
primary carbon, except for isopropyl, which has the substituent on a secondary carbon.
The isopropyl group could have been called a sec-propyl group. Either name would
have been appropriate because the group has an iso structural unit and a hydrogen has
been removed from a secondary carbon. Chemists decided to call it isopropyl, howev-
er, which means that “sec” is used only for sec-butyl.
Alkyl group names are used so frequently that you should learn them. Some of the
most common alkyl group names are compiled in Table 2.2 for your convenience.

PROBLEM 1 ◆
Draw the structures and name the four constitutional isomers with molecular formula
C4H 9 Br.

Table 2.2 Names of Some Alkyl Groups

CH3
methyl CH3 sec-butyl CH3CH2CH neopentyl CH3CCH2
ethyl CH3CH2 CH3 CH3
propyl CH3CH2CH2 CH3 hexyl CH3CH2CH2CH2CH2CH2
isopropyl CH3CH tert-butyl CH3C isohexyl CH3CHCH2CH2CH2
CH3 CH3 CH3
butyl CH3CH2CH2CH2 pentyl CH3CH2CH2CH2CH2
isobutyl CH3CHCH2 isopentyl CH3CHCH2CH2
CH3 CH3
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Section 2.2 Nomenclature of Alkanes 67

PROBLEM 2 ◆
Which of the following can be used to verify that carbon is tetrahedral?
a. Methyl bromide does not have constitutional isomers.
b. Tetrachloromethane does not have a dipole moment.
c. Dibromomethane does not have constitutional isomers.

PROBLEM 3 ◆
Write a structure for each of the following compounds:
a. isopropyl alcohol d. neopentyl chloride
b. isopentyl fluoride e. tert-butylamine
c. sec-butyl iodide f. n-octyl bromide

2.2 Nomenclature of Alkanes

The systematic name of an alkane is obtained using the following rules:
1. Determine the number of carbons in the longest continuous carbon chain. This
chain is called the parent hydrocarbon. The name that indicates the number of
carbons in the parent hydrocarbon becomes the alkane’s “last name.” For exam-
ple, a parent hydrocarbon with eight carbons would be called octane. The
longest continuous chain is not always a straight chain; sometimes you have to First, determine the number of carbons
“turn a corner” to obtain the longest continuous chain. in the longest continuous chain.

8 7 6 5 4 3 2 1 8 7 6 5 4
CH3CH2CH2CH2CHCH2CH2CH3 CH3CH2CH2CH2CHCH2CH3
CH3 CH2CH2CH3
3 2 1
4-methyloctane
three different alkanes with an 4-ethyloctane
eight-carbon parent hydrocarbon

4 3 2 1
CH3CH2CH2CHCH2CH2CH3
CH2CH2CH2CH3
5 6 7 8
4-propyloctane

2. The name of any alkyl substituent that hangs off the parent hydrocarbon is cited
before the name of the parent hydrocarbon, together with a number to designate
the carbon to which the alkyl substituent is attached. The chain is numbered in
the direction that gives the substituent as low a number as possible. The sub- Number the chain so that the
stituent’s name and the name of the parent hydrocarbon are joined in one word, substituent gets the lowest possible
and there is a hyphen between the number and the substituent’s name. number.

1 2 3 4 5 6 5 4 3 2 1
CH3CHCH2CH2CH3 CH3CH2CH2CHCH2CH3
CH3 CH2CH3
2-methylpentane 3-ethylhexane

1 2 3 4 5 6 7 8
CH3CH2CH2CHCH2CH2CH2CH3
CHCH3
CH3
4-isopropyloctane
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68 CHAPTER 2 An Introduction to Organic Compounds

Numbers are used only for systematic Notice that only systematic names have numbers; common names never contain
names, never for common names. numbers.
CH3
CH3CHCH2CH2CH3
common name: isohexane
systematic name: 2-methylpentane

3. If more than one substituent is attached to the parent hydrocarbon, the chain is
numbered in the direction that will result in the lowest possible number in the name
of the compound. The substituents are listed in alphabetical (not numerical) order,
with each substituent getting the appropriate number. In the following example, the
Substituents are listed in alphabetical correct name (5-ethyl-3-methyloctane) contains a 3 as its lowest number, while the
order. incorrect name (4-ethyl-6-methyloctane) contains a 4 as its lowest number:
CH3CH2CHCH2CHCH2CH2CH3
CH3 CH2CH3
5-ethyl-3-methyloctane
not
4-ethyl-6-methyloctane
because 3 < 4

If two or more substituents are the same, the prefixes “di,” “tri,” and “tetra”
are used to indicate how many identical substituents the compound has. The
A number and a word are separated by numbers indicating the locations of the identical substituents are listed together,
a hyphen; numbers are separated by a separated by commas. Notice that there must be as many numbers in a name as
comma. there are substituents.
CH3 CH3
CH3CH2CHCH2CHCH3 CH3CH2CH2C CCH2CH3
CH3 CH3 CH3 CH3
2,4-dimethylhexane 3,3,4,4-tetramethylheptane

The prefixes di, tri, tetra, sec, and tert are ignored in alphabetizing substituent
groups, but the prefixes iso, neo, and cyclo are not ignored.
di, tri, tetra, sec, and tert are ignored in CH2CH3 CH3 CH3
alphabetizing.
iso, neo, and cyclo are not ignored in
CH3CH2CCH2CH2CHCHCH2CH2CH3 CH3CH2CH2CHCH2CH2CHCH3
alphabetizing. CH2CH3 CH2CH3 CHCH3
3,3,6-triethyl-7-methyldecane
CH3
5-isopropyl-2-methyloctane

4. When both directions lead to the same lowest number for one of the substituents,
the direction is chosen that gives the lowest possible number to one of the re-
maining substituents.
CH3 CH3 CH2CH3
CH3CCH2CHCH3 CH3CH2CHCHCH2CHCH2CH3
CH3 CH3 CH3
2,2,4-trimethylpentane 6-ethyl-3,4-dimethyloctane
not not
2,4,4-trimethylpentane 3-ethyl-5,6-dimethyloctane
because 2 < 4 because 4 < 5

5. If the same substituent numbers are obtained in both directions, the first group
cited receives the lower number.
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Section 2.2 Nomenclature of Alkanes 69

Cl CH2CH3
CH3CHCHCH3 CH3CH2CHCH2CHCH2CH3 Only if the same set of numbers is
obtained in both directions does the
Br CH3 first group cited get the lower number.
2-bromo-3-chlorobutane 3-ethyl-5-methylheptane
not not
3-bromo-2-chlorobutane 5-ethyl-3-methylheptane

6. If a compound has two or more chains of the same length, the parent hydrocar-
bon is the chain with the greatest number of substituents.
3 4 5 6 1 2 3 4 5 6
CH3CH2CHCH2CH2CH3 CH3CH2CHCH2CH2CH3 In the case of two hydrocarbon chains
2 CHCH3 CHCH3 with the same number of carbons,
choose the one with the most
1 CH3 CH3 substituents.
3-ethyl-2-methylhexane (two substituents) not
3-isopropylhexane (one substituent)

7. Names such as “isopropyl,” “sec-butyl,” and “tert-butyl” are acceptable sub-

stituent names in the IUPAC system of nomenclature, but systematic substituent
names are preferable. Systematic substituent names are obtained by numbering
the alkyl substituent starting at the carbon that is attached to the parent hydrocar-
bon. This means that the carbon that is attached to the parent hydrocarbon is
always the number 1 carbon of the substituent. In a compound such as
4-(1-methylethyl)octane, the substituent name is in parentheses; the number in-
side the parentheses indicates a position on the substituent, whereas the number
outside the parentheses indicates a position on the parent hydrocarbon.

CH3CH2CH2CH2CHCH2CH2CH3 CH3CH2CH2CH2CHCH2CH2CH2CH2CH3
2 2 3
1 CHCH3 CH2CHCH3
1
CH3 CH3
4-isopropyloctane 5-isobutyldecane
or or
4-(1-methylethyl)octane 5-(2-methylpropyl)decane

Some substituents have only a systematic name.

CH2CH2CH3 CH3 CH3

1
CH3CH2CH2CH2CHCH2CHCH2CH2CH3 CH3CHCHCH2CHCH2CHCH2CH3
2 3 4
2 3
CH3CHCHCH3 CH3 CH2CH2CH2CH2CH3
1
CH3
6-(1,2-dimethylpropyl)-4-propyldecane 2,3-dimethyl-5-(2-methylbutyl)decane

These rules will allow you to name thousands of alkanes, and eventually you will
learn the additional rules necessary to name many other kinds of compounds. The
rules are important if you want to look up a compound in the scientific literature, be-
cause it usually will be listed by its systematic name. Nevertheless, you must still learn
common names because they have been in existence for so long and are so entrenched
in chemists’ vocabulary that they are widely used in scientific conversation and are
often found in the literature.
Look at the systematic names (the ones written in blue) for the isomeric hexanes Tutorial:
and isomeric heptanes at the beginning of this chapter to make sure you understand Basic nomenclature of alkanes
how they are constructed.
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70 CHAPTER 2 An Introduction to Organic Compounds

PROBLEM 4 ◆
Draw the structure of each of the following compounds:

a. 2,3-dimethylhexane d. 2,2-dimethyl-4-propyloctane
b. 4-isopropyl-2,4,5-trimethylheptane e. 4-isobutyl-2,5-dimethyloctane
c. 4,4-diethyldecane f. 4-(1,1-dimethylethyl)octane

PROBLEM 5 SOLVED
a. Draw the 18 isomeric octanes.
b. Give each isomer its systematic name.
c. How many isomers have common names?
d. Which isomers contain an isopropyl group?
e. Which isomers contain a sec-butyl group?
f. Which isomers contain a tert-butyl group?

SOLUTION TO 5a Start with the isomer with an eight-carbon continuous chain. Then
draw isomers with a seven-carbon continuous chain plus one methyl group. Next, draw
isomers with a six-carbon continuous chain plus two methyl groups or one ethyl group.
Then draw isomers with a five-carbon continuous chain plus three methyl groups or one
methyl group and one ethyl group. Finally, draw a four-carbon continuous chain with four
methyl groups. (You will be able to tell whether you have drawn duplicate structures by
your answers to 3b because if two structures have the same systematic name, they are the
same compound.)

PROBLEM 6 ◆
Give the systematic name for each of the following compounds:

CH3 CH3
a. CH3CH2CHCH2CCH3 f. CH3CH2CH2CHCH2CH2CH3
CH3 CH3CHCH2CH3

CH3 CH2CH2CH3
b. CH 3CH 2C(CH 3)3 g. CH3C CHCH2CH3
CH2CH2CH3

c. CH 3CH 2C(CH 2CH 3)2CH 2CH 2CH 3 h. CH3CH2CH2CH2CHCH2CH2CH3

CH(CH3)2

CH3
d. CH3CHCH2CH2CHCH3
CH2CH3

e. CH 3CH 2C(CH 2CH 3)2CH(CH 3)CH(CH 2CH 2CH 3)2

PROBLEM 7
Draw the structure and give the systematic name of a compound with a molecular formula
C5H 12 that has
a. only primary and secondary hydrogens c. one tertiary hydrogen
b. only primary hydrogens d. two secondary hydrogens
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Section 2.3 Nomenclature of Cycloalkanes 71

2.3 Nomenclature of Cycloalkanes

Cycloalkanes are alkanes with their carbon atoms arranged in a ring. Because of the
ring, a cycloalkane has two fewer hydrogens than an acyclic (noncyclic) alkane with
the same number of carbons. This means that the general molecular formula for a
cycloalkane is CnH 2n . Cycloalkanes are named by adding the prefix “cyclo” to the
alkane name that signifies the number of carbon atoms in the ring.
CH2
CH2 H2C CH2
CH2 H2C CH2 H2C CH2
H2C CH2
H2C CH2 H2C CH2 H2C CH2 CH2
cyclopropane cyclobutane cyclopentane cyclohexane

Cycloalkanes are almost always written as skeletal structures. Skeletal structures

show the carbon–carbon bonds as lines, but do not show the carbons or the hydrogens
bonded to carbons. Atoms other than carbon and hydrogens bonded to atoms other
than carbon are shown. Each vertex in a skeletal structure represents a carbon. It is un-
derstood that each carbon is bonded to the appropriate number of hydrogens to give
the carbon four bonds.

cyclopropane cyclobutane cyclopentane cyclohexane

Acyclic molecules can also be represented by skeletal structures. In a skeletal struc-

ture of an acyclic molecule, the carbon chains are represented by zigzag lines. Again,
each vertex represents a carbon, and carbons are assumed to be present where a line
begins or ends.

3 1 5 3 1
2
4 2 6 4

butane 2-methylhexane 3-methyl-4-propylheptane 6-ethyl-2,3-dimethylnonane

The rules for naming cycloalkanes resemble the rules for naming acyclic alkanes:
1. In the case of a cycloalkane with an attached alkyl substituent, the ring is the par-
ent hydrocarbon unless the substituent has more carbon atoms than the ring. In If there is only one substituent on a
that case, the substituent is the parent hydrocarbon and the ring is named as a sub- ring, do not give that substituent a
stituent. There is no need to number the position of a single substituent on a ring. number.

CH2CH3 CH2CH2CH2CH2CH3
CH3

methylcyclopentane ethylcyclohexane 1-cyclobutylpentane

2. If the ring has two different substituents, they are cited in alphabetical order and
the number 1 position is given to the substituent cited first.
CH3
CH3CH2
H3C
CH2CH2CH3 CH3 CH3
1-methyl-2-propylcyclopentane 1-ethyl-3-methylcyclopentane 1,3-dimethylcyclohexane

3. If there are more than two substituents on the ring, they are cited in alphabetical
order. The substituent given the number 1 position is the one that results in a second
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72 CHAPTER 2 An Introduction to Organic Compounds

substituent getting as low a number as possible. If two substituents have the same
low number, the ring is numbered—either clockwise or counterclockwise—in
the direction that gives the third substituent the lowest possible number. For
example, the correct name of the following compound is 4-ethyl-2-methyl-
1-propylcyclohexane, not 5-ethyl-1-methyl-2-propylcyclohexane:
CH3
CH3CH2CH2 CH3
CH3
CH3 CH2CH3
Tutorial: 4-ethyl-2-methyl-1-propylcyclohexane 1,1,2-trimethylcyclopentane
Advanced alkane not not
nomenclature 1-ethyl-3-methyl-4-propylcyclohexane 1,2,2-trimethylcyclopentane
because 2 < 3 because 1 < 2
not not
5-ethyl-1-methyl-2-propylcyclohexane 1,1,5-trimethylcyclopentane
because 4 < 5 because 2 < 5

PROBLEM 8 ◆
Convert the following condensed structures into skeletal structures (remember that con-
densed structures show atoms but few, if any, bonds, whereas skeletal structures show
bonds but few, if any, atoms):

CH3
a. CH 3CH 2CH 2CH 2CH 2CH 2OH c. CH3CHCH2CH2CHCH3
Br

CH3 CH3
b. CH3CH2CHCH2CHCH2CH3 d. CH 3CH 2CH 2CH 2OCH 3

PROBLEM 9 ◆
Give the systematic name for each of the following compounds:

a. CH2CH3 e. CH3CHCH2CH2CH3
CH3

b. CH2CH3 f. CH2CH3

CH2CHCH3
CH3

c. H3C g.

H3C CH2CH3

d. h. CH3CH2CHCH3

CH3CHCH3
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Section 2.4 Nomenclature of Alkyl Halides 73

2.4 Nomenclature of Alkyl Halides

Alkyl halides are compounds in which a hydrogen of an alkane has been replaced by a
halogen. Alkyl halides are classified as primary, secondary, or tertiary, depending on
the carbon to which the halogen is attached. Primary alkyl halides have a halogen
bonded to a primary carbon, secondary alkyl halides have a halogen bonded to a sec-
ondary carbon, and tertiary alkyl halides have a halogen bonded to a tertiary carbon
(Section 2.1). The lone-pair electrons on the halogens are generally not shown unless
they are needed to draw your attention to some chemical property of the atom.

a primary carbon a secondary carbon a tertiary carbon The number of alkyl groups attached to
R the carbon to which the halogen is
bonded determines whether an alkyl
R CH2 Br R CH R R C R halide is primary, secondary, or tertiary.
Br Br
a primary alkyl halide a secondary alkyl halide a tertiary alkyl halide

The common names of alkyl halides consist of the name of the alkyl group, fol-
lowed by the name of the halogen—with the “ine” ending of the halogen name re-
placed by “ide” (i.e., fluoride, chloride, bromide, iodide).

CH3Cl CH3CH2F CH3CHI CH3CH2CHBr

common name: methyl chloride ethyl fluoride CH3 CH3
systematic name: chloromethane fluoroethane
isopropyl iodide sec-butyl bromide
2-iodopropane 2-bromobutane

In the IUPAC system, alkyl halides are named as substituted alkanes. The substituent
prefix names for the halogens end with “o” (i.e., “fluoro,” “chloro,” “bromo,” “iodo”).
Therefore, alkyl halides are often called haloalkanes.

CH3 CH3
CH3CH2CHCH2CH2CHCH3 CH3CCH2CH2CH2CH2Cl
Br CH3
2-bromo-5-methylheptane 1-chloro-5,5-dimethylhexane CH3F
methyl fluoride

Br
I

CH2CH3 Cl
CH3Cl
CH3
methyl chloride
1-ethyl-2-iodocyclopentane 4-bromo-2-chloro-1-methylcyclohexane

PROBLEM 10 ◆
Give two names for each of the following compounds, and tell whether each alkyl halide is
primary, secondary, or tertiary: CH3Br
methyl bromide
a. CH3CH2CHCH3 c. Br
Cl

b. CH3CHCH2CH2CH2CH2Cl d. CH3CHCH3
CH3 F CH3I
methyl iodide
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74 CHAPTER 2 An Introduction to Organic Compounds

PROBLEM 11
Draw the structures and provide systematic names for a–c by substituting a chlorine for a
hydrogen of methylcyclohexane:
a. a primary alkyl halide b. a tertiary alkyl halide c. three secondary alkyl halides

2.5 Nomenclature of Ethers

Ethers are compounds in which an oxygen is bonded to two alkyl substituents. If the
alkyl substituents are identical, the ether is a symmetrical ether. If the substituents
are different, the ether is an unsymmetrical ether.
R O R R O R´
a symmetrical ether an unsymmetrical ether

dimethyl ether
The common name of an ether consists of the names of the two alkyl substituents
(in alphabetical order), followed by the word “ether.” The smallest ethers are almost
always named by their common names.
CH3
CH3OCH2CH3 CH3CH2OCH2CH3 CH3CHCH2OCCH3
ethyl methyl ether diethyl ether
often called ethyl ether CH3 CH3
tert-butyl isobutyl ether
CH3
CH3CHOCHCH2CH3 CH3CHCH2CH2O
diethyl ether
CH3 CH3
Chemists sometimes neglect the prefix sec-butyl isopropyl ether cyclohexyl isopentyl ether
“di” when they name symmetrical
ethers. Try not to make this oversight a The IUPAC system names an ether as an alkane with an RO substituent. The sub-
habit. stituents are named by replacing the “yl” ending in the name of the alkyl substituent
with “oxy.”
CH3
CH3O CH3CH2O CH3CHO CH3CH2CHO CH3CO
methoxy ethoxy
CH3 CH3 CH3
isopropoxy sec-butoxy tert-butoxy

CH3CHCH2CH3 CH3CH2CHCH2CH2OCH2CH3
OCH3 CH3
2-methoxybutane 1-ethoxy-3-methylpentane

CH3CHOCH2CH2CH2CH2OCHCH3
CH3 CH3
1,4-diisopropoxybutane

PROBLEM 12 ◆
Tutorial: a. Give the systematic (IUPAC) name for each of the following ethers:
Nomenclature of ethers
1. CH 3OCH 2CH 3 3. CH3CH2CH2CH2CHCH2CH2CH3
OCH3

2. CH 3CH 2OCH 2CH 3 4. CH 3CH 2CH 2OCH 2CH 2CH 2CH 3

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Section 2.6 Nomenclature of Alcohols 75

CH3
5. CH3CHOCHCH2CH2CH3 6. CH3CHOCH2CH2CHCH3
CH3 CH3 CH3
b. Do all of these ethers have common names?
c. What are their common names?

2.6 Nomenclature of Alcohols

Alcohols are compounds in which a hydrogen of an alkane has been replaced by an The number of alkyl groups attached to
OH group. Alcohols are classified as primary, secondary, or tertiary, depending on the carbon to which the OH group is
attached determines whether an alcohol
whether the OH group is bonded to a primary, secondary, or tertiary carbon—the same
is primary, secondary, or tertiary.
way alkyl halides are classified.
R R
R CH2 OH R CH OH R C OH
R
a primary alcohol a secondary alcohol a tertiary alcohol methyl alcohol

The common name of an alcohol consists of the name of the alkyl group to which
the OH group is attached, followed by the word “alcohol.”
CH3
CH3CH2OH CH3CH2CH2OH CH3CHOH CH3CCH2OH
ethyl alcohol propyl alcohol
CH3 CH3
isopropyl alcohol neopentyl alcohol ethyl alcohol

The functional group is the center of reactivity in a molecule. In an alcohol, the

OH is the functional group. The IUPAC system uses a suffix to denote certain func-
tional groups. The systematic name of an alcohol, for example, is obtained by replac-
ing the “e” at the end of the name of the parent hydrocarbon with the suffix “ol.”
CH3OH CH3CH2OH
methanol ethanol

When necessary, the position of the functional group is indicated by a number im- propyl alcohol
mediately preceding the name of the alcohol or immediately preceding the suffix. The
most recently approved IUPAC names are those with the number immediately preced-
ing the suffix. However, names with the number preceding the name of the alcohol
have been in use for a long time, so those are the ones most likely to appear in the lit-
erature, on reagent bottles, and on standardized tests. They will also be the ones that
appear most often in this book.
CH3CH2CHCH2CH3
OH
3-pentanol
or
pentan-3-ol

The following rules are used to name a compound that has a functional group
suffix:
1. The parent hydrocarbon is the longest continuous chain containing the function-
al group.
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76 CHAPTER 2 An Introduction to Organic Compounds

2. The parent hydrocarbon is numbered in the direction that gives the functional
group suffix the lowest possible number.

1 2 3 4 5 4 3 2 1 3 2 1
CH3CHCH2CH3 CH3CH2CH2CHCH2OH CH3CH2CH2CH2OCH2CH2CH2OH
OH CH2CH3
2-butanol 2-ethyl-1-pentanol 3-butoxy-1-propanol
or or or
butan-2-ol 2-ethylpentan-1-ol 3-butoxypropan-1-ol

The longest continuous chain The longest continuous chain

has six carbons, but the longest
continuous chain containing the
OH functional group has five
carbons so the compound is
named as a pentanol.
has four carbons, but the longest
continuous chain containing the
OH functional group has three
carbons, so the compound is
named as a propanol.

When there is only a substituent, the 3. If there is a functional group suffix and a substituent, the functional group suffix
substituent gets the lowest possible gets the lowest possible number.
number.
When there is only a functional group CH3
suffix, the functional group suffix gets 1 2 3 4 3 2 1 5 4 3 2 1
the lowest possible number. HOCH2CH2CH2Br ClCH2CH2CHCH3 CH2CCH2CHCH3
When there is both a functional group
suffix and a substituent, the functional
OH CH3 OH
group suffix gets the lowest possible 3-bromo-1-propanol 4-chloro-2-butanol 4,4-dimethyl-2-pentanol
number.
4. If the same number for the functional group suffix is obtained in both directions,
the chain is numbered in the direction that gives a substituent the lowest possible
number. Notice that a number is not needed to designate the position of a func-
tional group suffix in a cyclic compound, because it is assumed to be at the
1-position.

CH3
CH3CHCHCH2CH3 CH3CH2CH2CHCH2CHCH3
Cl OH OH CH3
OH
2-chloro-3-pentanol 2-methyl-4-heptanol 3-methylcyclohexanol
not not not
4-chloro-3-pentanol 6-methyl-4-heptanol 5-methylcyclohexanol

5. If there is more than one substituent, the substituents are cited in alphabetical
order.

CH2CH3 CH2CH3 HO CH3

Tutorial:
CH3CHCH2CHCH2CHCH3
Nomenclature of alcohols H3C OH CH3
Br OH 2-ethyl-5-methylcyclohexanol 3,4-dimethylcyclopentanol
6-bromo-4-ethyl-2-heptanol

Remember that the name of a substituent is stated before the name of the par-
ent hydrocarbon, and the functional group suffix is stated after the name of the
parent hydrocarbon.

[substituent] [parent hydrocarbon] [functional group suffix]

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Section 2.7 Nomenclature of Amines 77

PROBLEM 13
Draw the structures of a homologous series of alcohols that have from one to six carbons,
and then give each of them a common name and a systematic name.

PROBLEM 14 ◆
Give each of the following compounds a systematic name, and indicate whether each is a
primary, secondary, or tertiary alcohol:

a. CH 3CH 2CH 2CH 2CH 2OH d. CH3CHCH2CHCH2CH3

CH3 OH

b. CH3 e. CH3CHCH2CHCH2CHCH2CH3
CH3 OH CH3
HO

CH3
Cl
c. CH3CCH2CH2CH2Cl f.
OH CH3CH2 OH

PROBLEM 15 ◆
Write the structures of all the tertiary alcohols with molecular formula C6H 14O, and give
each a systematic name.

2.7 Nomenclature of Amines

Amines are compounds in which one or more of the hydrogens of ammonia have been
replaced by alkyl groups. Smaller amines are characterized by their fishy odors. Fer-
mented shark, for example, a traditional dish in Iceland, smells exactly like trieth-
ylamine. There are primary amines, secondary amines, and tertiary amines. The
classification depends on how many alkyl groups are bonded to the nitrogen. Primary
amines have one alkyl group bonded to the nitrogen, secondary amines have two, and
tertiary amines have three.

R R The number of alkyl groups attached to

NH3 R NH2 R NH R N R the nitrogen determines whether an
amine is primary, secondary, or tertiary.
ammonia a primary amine a secondary amine a tertiary amine

Notice that the number of alkyl groups attached to the nitrogen determines whether an
amine is primary, secondary, or tertiary. For an alkyl halide or an alcohol, on the other
hand, the number of alkyl groups attached to the carbon to which the halogen or the
OH is bonded determines the classification (Sections 2.4 and 2.6).

nitrogen is attached carbon is attached

to one alkyl group to three alkyl groups

R R R
R C NH2 R C Cl R C OH
R R R
a primary amine a tertiary alkyl chloride a tertiary alcohol

The common name of an amine consists of the names of the alkyl groups bonded to
the nitrogen, in alphabetical order, followed by “amine.” The entire name is written as
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78 CHAPTER 2 An Introduction to Organic Compounds

one word (unlike the common names of alcohols, ethers, and alkyl halides, in which
“alcohol,” “ether,” and “halide” are separate words).

CH3NH2 CH3NHCH2CH2CH3 CH3CH2NHCH2CH3

methylamine methylpropylamine diethylamine

CH3 CH3 CH3

CH3NCH3 CH3NCH2CH2CH2CH3 CH3CH2NCH2CH2CH3
trimethylamine butyldimethylamine ethylmethylpropylamine

The IUPAC system uses a suffix to denote the amine functional group. The “e” at
the end of the name of the parent hydrocarbon is replaced by “amine”—similar to the
way in which alcohols are named. A number identifies the carbon to which the nitro-
gen is attached. The number can appear before the name of the parent hydrocarbon or
before “amine.” The name of any alkyl group bonded to nitrogen is preceded by an
“N ” (in italics) to indicate that the group is bonded to a nitrogen rather than to a
carbon.

4 3 2 1 1 2 3 4 5 6 3 2 1
CH3CH2CH2CH2NH2 CH3CH2CHCH2CH2CH3 CH3CH2CH2NCH2CH3
1-butanamine
or NHCH2CH3 CH3
butan-1-amine N-ethyl-3-hexanamine N-ethyl-N-methyl-1-propanamine
or or
N-ethylhexan-3-amine N-ethyl-N-methylpropan-1-amine

The substituents—regardless of whether they are attached to the nitrogen or to the

parent hydrocarbon—are listed in alphabetical order, and then a number or an “N ” is
assigned to each one. The chain is numbered in the direction that gives the functional
group suffix the lowest possible number.

CH3
4 3 2 1 1 2 3
5 6 4
CH3CHCH2CH2NHCH3 CH3CH2CHCH2CHCH3
Cl NHCH2CH3
3-chloro-N-methyl-1-butanamine N-ethyl-5-methyl-3-hexanamine

Br CH2CH3
5 4 3 2 1
CH3CHCH2CHCH3
NHCH2CH2CH3
CH3NCH3
4-bromo-N,N-dimethyl-2-pentanamine 2-ethyl-N-propylcyclohexanamine

Nitrogen compounds with four alkyl groups bonded to the nitrogen—thereby giv-
ing the nitrogen a positive formal charge—are called quaternary ammonium salts.
Their names consist of the names of the alkyl groups in alphabetical order, followed
by “ammonium” (all in one word), and then the name of the counterion as a separate
word.

CH3 CH3
+
CH3 N CH3 HO− CH3CH2CH2 N + CH3 Cl−
CH3 CH2CH3
tetramethylammonium hydroxide ethyldimethylpropylammonium chloride

Table 2.3 summarizes the ways in which alkyl halides, ethers, alcohols, and amines
are named.