Brock

University
FIRST YEAR CHEMISTRY

STUDY.GUIDB FOR ORGANIC CHEMISTRY

TABLE OF CONTENTS

STUDY GUIDE FOR ORGANIC CHEMISTRY I

Alkanes I
Alkenes and Alkynes.. 4
Aromatic Hydrocarbons.

Alkyl Halides. 8
Alcohols. 9
Aldehydes and Ketones. I2
Carboxylic Acids. I4
Esters. t6
Amines 18
Amides 20
Summary Problems 2I
ORGANIC FUNCTIONAL GROUPS. 22
REACTIONS OF ORGANIC COMPOUNDS........ 26
DEFINITIONS 29
Summary Table of Classesof Organic Compounds........... 32
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STUDY GUIDE FOR ORGANIC CHEMISTRY

This study guide is intended to supplement standard
first-year texts, whose coverage of organic chemistry
varies depending on the authors. Structures, nomenclature
rules, physical properties, and a few important reactions
are covered for major classes of organic compounds that
contain a single functional group. Isomerism in organic
compounds is treated in Experiment 21 in the First Year
Lab Manual.
The key to organic chemistry is the functional
group—the part of the molecule which is responsible for
the characteristic chemical and physical properties of the
compound. For example, the general formula of alkenes is
R2C = CR2, where the R's represent hydrogens or alkyl
groups. All alkenes undergo certain reactions that depend
primarily on the presence of the C=C bond, and not on
the R groups. Functional groups and examples of each
class of compound are given in the table located on the
inside back cover of this Study Guide.

ALKANES

Structure and Nomenclature Table 1. Names of Alkanes

Alkanes are molecules that contain carbon bonded by Condensed Structure Name Formula
four single bonds to other carbons or to hydrogens. The
simplest alkane is methane, CH4. Higher alkanes contain CH4 Methane CH4
additional carbons. The general formula for noncyclic CH3CH3 Ethane C2H6
alkanes is CnH2n+2 where n is an integer. Normal or
“straight-chain” alkanes contain all of the carbons CH3CH2CH3 Propane C3H8
connected together in a single continuous sequence. CH3(CH2)2CH3 n-Butane C4H10
Condensed structural formulas and names of the first ten
CH3(CH2)3CH3 n-Pentane C5H12
straight-chain alkanes are given in Table 1.
CH3(CH2)4CH3 n-Hexane C6H14
In the early days of organic chemistry, a new name
was created for every new compound. For instance, when CH3(CH2)5CH3 n-Heptane C7H16
it was found that there were two compounds with the
CH3(CH2)6CH3 n-Octane C8H18
formula C4H10, one was called n-butane and the other
isobutane (for “isomeric butane”). CH3(CH2)7CH3 n-Nonane C9H20

CH 3CH 2CH 2CH 3 CH 3 CH CH 3 CH3(CH2)8CH3 n-Decane C10H22

CH 3
n-butane
isobutane The number of isomers with a given formula
increases dramatically with the number of carbons—e.g.,
When a second isomer of n-pentane was discovered,
there are 75 isomers with the formula C10H22! Clearly, a
it was called isopentane, and a third necessitated the name
systematic method of naming compounds is desirable.
neopentane (“neo” means “new”—thus neopentane is the
This system is called the IUPAC system of nomenclature;
new pentane).
IUPAC is the International Union of Pure and Applied
CH 3CH 2CH 2CH 2CH 3 CH 3 CH CH 2CH 3 Chemistry.
CH 3 In order to name compounds, you must also know the
n-pentane isopentane names of the common alkyl groups. Alkyl groups,
symbolized R, are obtained from alkanes by removing a
CH 3
hydrogen from the corresponding alkane. Thus, CH3– is
CH 3 C CH 3 the methyl group, derived by removing a hydrogen from
CH 3
methane so as to leave an empty valence. Names of alkyl
groups are derived from the names of the parent
neopentane
hydrocarbons, by dropping the terminal -ane and adding -
 2

Table 2. Alkyl Groups 5 4 3 2 1

CH 3CHCH3 CH 3CH 2CH 2CHCH3
Structure Name
CH 3
I II CH 3
CH 3 methyl
Methylpropane 2-Methylpentane
CH 3CH 2 ethyl
1 2 3 4 5
CH 3
4 3 2 1
CH 3CH 2CH 2 n-propyl CH 3CH 2CHCH2 CH3 H3 C CH CH 2 C CH 3
(or 1-propyl)
CH 3 H3 C CH 2 CH 3
H III 6 5 IV
CH 3 C isopropyl 3-Methylpentane 2,2,4-Trimethylhexane
(or 2-propyl)
CH 3 CH 3 CH 2CH 3
1 2 3 4 5
H3 C CH C CH CH 3
CH 3CH 2CH 2CH 2 n-butyl
(or 1-butyl) V CH 3CH 2 CH 3
H
3,3-Diethyl-2,4-dimethylpentane
CH 3CH 2 C sec-butyl
(or 2-butyl) 2. Where necessary, as in the isomeric methylpentanes
CH 3 (II and III above), use a number to indicate the
carbon to which the alkyl group is attached.
CH 3
3. In numbering the parent carbon chain, start at
CH 3 C CH 2
isobutyl whichever end results in the lowest numbers. Thus
H compound II is 2-methylpentane, not 4-methyl-
pentane.
CH 3
4. If the same alkyl group occurs more than once as a
CH 3 C
tert-butyl or t-butyl substituent, indicate this by the prefixes di, tri, tetra,
CH 3 etc., to show the number of these alkyl groups. Also,
there must be a number for the position of each
H H group, as in 2,2,4-trimethylhexane (compound IV).
phenyl
C C
5. If there are different alkyl groups attached to the
H C C parent chain, name them in alphabetical order. For
C C example, compound V is 3,3-diethyl-2,4-dimethyl-
H H pentane.
6. Note the correct use of commas and dashes, and the
yl. IUPAC names for some common alkyl groups are fact that there is no space between the substituent
given in Table 2. name(s) and the chain name.

Dashes between numbers and letters

IUPAC Rules for Naming Alkanes
1. Select as the parent structure the longest continuous 3,3-Diethyl-2,4-dimethylpentane
chain (longest “straight chain”). Consider the
compound to have been derived from this structure Commas between numbers
by replacement of hydrogen by various alkyl groups.
No space between "dimethyl"
Compound I can be derived from propane by
and "pentane"
replacing one hydrogen by a methyl group. It is thus
named methylpropane (or 2-methylpropane, but the 7. Sometimes the carbon chain is arranged to form a
2- is unnecessary since there is only one ring. These cyclic alkanes are named as shown
methylpropane). below:
 3

CH2 into smaller ones. Alkenes and hydrogen are also

H2 C CH2 produced. The general reaction for cracking is
CH2 H2 C CH2

CH2 CH2
H2 C CH2 
H2 C CH2 long-chain alkanes
CH2
cyclopropane cyclobutane cyclohexane shorter-chain alkanes, alkenes, and H2

H2 C CH 2

H3 C C C CH 3 Problems on Alkanes
H3 C CH 3 1. Give structural formulas of the following compounds:

1,1,2,2-tetramethylcyclobutane (a) 2,2,3,3-tetramethylpentane

Note that cyclic alkanes have a molecular formula of (b) 2,3-dimethylbutane
CnH2n rather than CnH2n+2. (c) 2,5-dimethylhexane
(d) 4-ethyl-3,4-dimethylheptane
Physical Properties
(e) 3-ethyl-2-methylpentane
Alkanes are nonpolar molecules and have (f) 3,4,4,5-tetramethylheptane
comparatively low melting and boiling points. Methane,
ethane, propane, and butane are gaseous at room
2. Give the IUPAC name of the following compounds:
temperature, attesting to the low forces of attraction
between the molecules. Higher alkanes such as octane (a) (CH3)2CHCH2CH2CH3
(part of the gasoline fraction) are liquids, and alkanes (b) CH3CH2C(CH3)2CH2CH3
with even greater chain lengths are solids at room
(c) (CH3CH2)2C(CH3)CH2CH3
temperature. Alkanes are not soluble in water because the
alkane molecules cannot undergo hydrogen bonding with (d) (CH3)3CCH(CH3)CH2C(C2H5)2CH3
water molecules. However, alkanes dissolve readily in (e) CCl3CCl2CCl3
nonpolar solvents such as toluene, chloroform, and other
(f) (CH3)2CHCCl2CH3
alkanes.

Reactions 3. Below are given the the structural formula and an

incorrect IUPAC name for the compound. What is wrong
Alkanes do not react with most chemical reagents at with the name? Give a correct name for each structure.
ordinary temperatures and pressures. Their most
important reactions, combustion and cracking, take place CH 2CH 3 CH 2CH 3
at high temperatures. (a) H3 C C CH 2CH 2 C CH 3
Combustion. Combustion of natural gas or gasoline CH 2CH 3 CH 2CH 3
provides energy for heating homes and running
automobiles. In combustion, the alkanes react with 2,2,4,4-tetraethylhexane
oxygen from the air to produce carbon dioxide and water
(b) (CH3)3 CCH2 CH3 1,1,1-trimethylpropane
vapour. An example is:
2 C 6H 14 + 19 O2 12 CO2 + 14 H2 O
(c) CH3 CBr2CH 2CH 3 2-dibromobutane
(d) CH3 CH2 CH2 CHClCH3 4-chloropentane
Cracking. Crude petroleum consists of high-
molecular-weight alkanes that are not useful for fuel or
for organic synthesis. However, they can be converted to
smaller molecules by heating in the absence of air. The
heat causes the large molecules to decompose or “crack”
 4

ALKENES AND ALKYNES

Structure Table 3. Common and IUPAC Names of Alkenes

Alkenes contain a carbon–carbon double bond. One
Common
of the bonds is a bond, and the other is a bond. The Structure
Name
IUPAC Name
carbons in the double bond are both sp2 hybridized. The
geometry in the simplest alkene, ethylene, is shown H2 C CH 2 ethylene ethene
below. Ethylene is a planar molecule with angles of 120°
about the sp2 hybridized carbon atoms. H2 C CHCH3 propylene propene
H2 C CHCH2 CH3 butylene 1-butene
H 120°H
H H
C C 120°
C C cis-2-butene
H H
120° H3 C CH 3
Alkynes contain a carbon–carbon triple bond. One of
H3 C H
the bonds is a bondand the other two are bonds. The
carbons that make up the triple bond are both sp C C trans-2-butene
hybridized. The simplest alkyne, acetylene, is a linear H CH 3
molecule: H CH 3
180° C C isobutylene methylpropene
H C C H H CH 3

H H
180°
C C 4-methyl-cis-2-
H3 C CH CH 3 pentene
Nomenclature
CH 3
The IUPAC name of an alkene is derived from the 1,3-butadiene
H2 C CH CH CH 2
longest continuous sequence of carbon atoms containing
the double bond. The name of the alkene is then obtained
by dropping the -ane ending from the alkane name and CH 3
3 4 5 4 5 6
adding -ene. The position of the double bond is indicated H CH 2CH 2CH 3 H CH 2 C CH 3
1 2 2 3
by numbering the parent chain from the end that gives the C C C C CH 3
lowest possible number of the double bond. Geometric
H CH 2CH 3 H3 C H
isomers are indicated by the prefixes cis and trans. For 1
example,
2-ethyl-1-pentene trans-5,5-dimethyl-2-hexene
Common and IUPAC names are given in Table 3 for
some alkenes.
Similarly, the longest continuous sequence of carbon
atoms containing the triple bond is the basis for the parent
 5

name of an alkyne. The position of the triple bond is CH2 = CHCH3 + HBr
indicated by numbering the parent chain from the end that
H2 C CHCH3 + H2 C CHCH3
gives the lowest possible number of the triple bond.
Alkyne names end in -yne: drop the -ane from the alkane H Br Br H
name and add -yne to obtain the alkyne name, as shown
2-bromopropane 1-bromopropane
in the examples (Table 4). (major product) (minor product)

Physical Properties H+
CH2 = CHCH3 + H2 O
Alkenes and alkynes are nonpolar, and their physical +
H2 C CHCH3 H2 C CHCH3
properties are similar to those of alkanes. They have low
melting and boiling points. They do not dissolve in water H OH OH H
or other polar solvents, but are soluble in nonpolar 2-propanol 1-propanol
solvents such as hexane. (major product) (minor product)

Reactions In order to produce 1-bromopropane the HBr has

Many of the reactions of alkenes involve converting
the double bond to a single bond. Important classes of this
type include addition reactions, oxidation, and
polymerization. These are discussed below.
Addition reactions. These are said to occur in
alkenes when a molecule X—Y combines with the alkene
so that the X and Y groups become bonded to the carbons
that were in the double bond. The double bond is thereby
converted to a single bond. The X and Y can be the same,
as in H—H or Br—Br, or they may be different, as in
H—Cl or H—OH (H2O). The general reaction is shown
below:
added across the double bond so that the Br goes to the
first carbon, whereas in the production of 2-
bromopropane the HBr has added in the reverse way—Br
has gone to the second carbon. Markovnikov studied
many reactions of this type and summarized his findings
as Markovnikov's rule: when an unsymmetrical reagent
HX adds to an unsymmetrical alkene, the major product
produced is the one in which the hydrogen in HX goes to
the alkene carbon with the most hydrogens already on it.
The X goes to the other carbon.

One bond breaks

C C
X Y + C C
X Y

Bond breaks New bonds

Table 4. Common and IUPAC Names of Alkynes
Some specific examples of the addition reactions of
Common
ethylene are given in the following equations. Structure IUPAC Name
Name
Pd acetylene ethyne
Hydrogenation: CH2 = CH2 + H2 CH 3CH 3 HC CH

Halogenation: CH2 = CH2 + X 2 CH2 XCH2X HC CCH 3 propyne

(X2 = Cl2 , Br2 , I2 ) HC CCH 2CH 3 1-butyne
Addition of HX: CH 2 = CH2 + HX CH3 CH2 X 2-butyne
CH 3C CCH 3
(X = Cl, Br, I)
CH 3C C CH CH 3 4-methyl-2-
Addition of H2 O: pentyne
H+ CH 3
CH2 = CH2 + H2O CH3CH 2OH
If the alkene is unsymmetrical (i.e., its two ends are
not the same), addition of HX or H2O will give two
products instead of one. This can be seen by considering
the addition of HBr or H2O to propene:
 6

1 H on this C H H H H H H Cat.
2 H on this C C C + C C + C C +...
H3 C H H H H H H H H H H
C C + HCl H C C C H H H H H H H
H H H Cl H ... C C C C C C ...
hydrogen goes to this C major product H H H H H H
part of a polyethylene chain
(CH 3CH 2CH 2Cl is produced as a minor product.)
H Ph H Ph H Ph
C C + C C + C C +...
Figure 1. Markovnikov's rule shows how to predict
H H H H H H
the major product of adding an unsymmetrical
reagent to an unsymmetrical alkene. H Ph H Ph H Ph
Cat.
... C C C C C C ...
Oxidation by aqueous KMnO4. Alkenes react with
H H H H H H
strong oxidizing agents such as aqueous KMnO4. The
part of a polystyrene chain
purple permanganate ion is reduced to brown MnO2 in
Ph is the symbol for a phenyl group, C6H5
this reaction, and the alkene is oxidized to a glycol. (A
glycol is a compound that has –OH groups on two
Polyethylene and polystyrene are sometimes written
adjacent carbons.) Note that the following equations are
(–CH2CH2–)n and (–CH2CHPh–)n, respectively. The
not balanced.
group in parentheses is the repeating unit of the polymer.
CH2 = CH2 + KMnO4 H2 C CH2 + MnO 2 Addition reactions of alkynes. Although many
HO OH reactions are possible for alkynes, we will focus on
addition reactions only. Addition reactions of alkynes are
ethylene glycol
(1,2-ethanediol) similar to those of alkenes. Two moles of H2, X2, or HX
can be added across the triple bond so that the products of
CH 3CH = CHCH3 + KMnO4
reaction contain only single bonds.
CH 3CH CHCH3 + MnO 2 H3 C C CH + 2 H2 CH3 CH2 CH3
HO OH
H3 C C CH + 2 X2 CH3 CX2 CHX2
2,3-butanediol
Polymerization. The final important reaction of H3 C C CH + 2 HX CH3CX 2CH 3
alkenes is polymerization. Polymerization is a special major product
kind of addition reaction that involves the linking of When HX is added to an unsymmetrical alkyne, as in
hundreds or thousands of small alkene molecules the example above, three products can be produced. The
(monomers) to each other to form long-chain compounds. one expected in greatest amount is predictable from
That is, the addition that occurs is not between two Markovnikov's rule.
different chemical compounds, but between molecules
that are the same. Note that polymerization of an alkene Problems on Alkenes and Alkynes
converts double bonds to single ones. A catalyst is
1. Give acceptable names (IUPAC or common) for the
required for the reaction.
following compounds.
Polymers are the foundation of the modern plastics
industry. Examples of common polymers include
polyethylene and polystyrene. The production of these
two polymers from their monomers is shown below:
 7

H3 C CH 3 H3 C CH 3

(a) C C (b) C C
H H H3 C CH 3

H3 C H H3 C CH 2CH 3

(c) C C (d) C C
H CH 2CH 3 H3 C H

(e) CH 3CH 2CH 2C CH (f) (CH3 )3CC C CH 3

2. Write structural formulas for the following compounds:

(a) ethylene (b) 1-propyne
(c) cis-2-hexene (d) 4,4-dimethyl-1-pentene
(e) trans-2-pentene (f) 2-methylpropene
3. Which of the alkenes and alkynes in Questions 1 and 2
are unsymmetrical?
4. Write equations to show how the following alkenes
react with (i) Cl2, (ii) HCl; (iii) H2O; (iv) KMnO4. Only
the organic reaction products need to be shown.
H CH3 H CH3
(a) C C (b) C C
H3 C H H CH3
5. Write equations to show how the following alkynes
react with (i) H2, (ii) HBr; (iii) Br2. Only the organic
reaction products need to be shown.

(a) H C C H (b) H3 C C C CH 3

(c) CH 3CH 2 C C H
6. Three products can be produced when HX adds to
propyne. What are they? Give the sequence of reactions
that show how they are formed.
 8

AROMATIC HYDROCARBONS

Structure Table 5. Some Benzene Derivatives

Aromatic compounds contain the benzene ring. Structure and Name Structure and Name
Benzene itself is C6H6, and two equivalent resonance
forms may be written for its structure: O
Cl C
H H
OH
H C H H C H chlorobenzene (a benzoic acid
C C C C (a
phenyl halide) carboxylic acid)
C C C C
H C H H C H O
H H CH 3 C
The double-headed arrow means that the electron pairs in OCH2 CH3
benzene are delocalized about the ring, i.e., they do not toluene ethyl benzoate (an
remain fixed between the pairs of atoms. ester)
Usually chemists do not write the full structure of H Cl
benzene, but rather abbreviate it by means of line-bond C
drawings as shown below. CH 2 Cl
styrene (an 1,2-dichlorobenzene
alkene) (o-dichlorobenzene)

OH
line representation of alternative representation
benzene: each vertex of C6 H6: the circle in the Cl Cl
phenol (an
represents a C-H bond centre represents 3 pairs 1,3-dichlorobenzene
alcohol)
(m-dichlorobenzene)
of delocalized electrons
O
C Cl Cl
The benzene ring is planar, with C-C-C and H-C-C
angles all equal to 120°. The carbon atoms are sp2 H
hybridized. benzaldehyde 1,4-dichlorobenzene
(an aldehyde) (p-dichlorobenzene)
Nomenclature
In disubstituted benzenes, it is still common to use
Systematic nomenclature of aromatic compounds can
the prefixes ortho (o) for 1,2-substitution, meta (m) for
be quite complex, so only a brief guide to nomenclature is
1,3-substitution, and para (p) for 1,4-substitution. See the
included here. Names of a few monosubstituted benzene
dichlorobenzene examples in Table 5.
derivatives are given in Table 5. If there is more than one
substituent, the ring carbons are numbered in sequence so Reactions
that the lowest numbers are obtained for substituents, and
the compound is named as a benzene derivative. For If you know the reactions of the functional groups,
example, you will be able to predict many reactions of compounds
that contain a phenyl group. For example, you would
6
H3 C 5 1 CH 3 expect styrene to add bromine, to be oxidized by
potassium permanganate, and to undergo polymerization
1,2,4,5-tetramethylbenzene
just as do other alkenes—and it does.
H3 C 4 2 CH 3
3
 9

ALKYL HALIDES

Structure and Nomenclature Table 6. Names of Some Chloroalkanes

Alkyl halides can be regarded as alkanes in which Common
Structure IUPAC Name
one or more hydrogen atoms has been replaced by a Name
halogen atom (F, Cl, Br, or I). Thus, structures of alkyl
halides are similar to those of the parent alkanes. CH 3Cl methyl chloromethane
chloride
In the IUPAC system, alkyl halides are named as
derivatives of the parent alkanes. Choose the longest CH 3CH 2Cl ethyl chloroethane
continuous chain containing the halogen as the parent chloride
hydrocarbon. Number the chain so that the halogen CH 3CH 2CH 2Cl n-propyl 1-chloropropane
substituents get the lowest numbers. Give halogen chloride
locations and numbers just as you give alkyl locations and
H
numbers.
isopropyl 2-chloropropane
CH 3 C CH 3
Substituents are named in alphabetical order. Note chloride
Compound I—“bromo” comes before “chloro” in the Cl
alphabet, and hence the name is 2,2-dibromo-1-
CH 3CH 2CH 2CH 2Cl n-butyl 1-chlorobutane
chloropropane. The numerical prefixes (di-, tri-, etc.) are
chloride
not considered in deciding the order.
H
1 2 3
CH 2ClCBr 2CH 3 I sec-butyl 2-chlorobutane
CH 3CH 2 C CH 3
chloride
2,2-Dibromo-1-chloropropane Cl
1 2 3 4
CH 3
CF3 CH2CHCH3 II isobutyl 1-chloro-2-
CH 3 C CH 2Cl
CH 3 chloride methylpropane
H
1,1,1-Trifluoro-3-methylbutane
The common names of alkyl halides are obtained by CH 3
naming the alkyl group, then the halide: e.g., CH3I is tert-butyl 2-chloro-2-
CH 3 C CH 3
methyl iodide and CH3CH2CH2CH2CH2CH2CH2CH2Br chloride methylpropane
Cl
is n-octyl bromide. Common and IUPAC names of some
chloroalkanes are given in Table 6 Freon dichlorodifluoro-
CF2Cl2
methane
.
CHCl3 chloroform trichloromethane
Physical Properties
The C-X bond in alkyl halides is not very polar Reactions
because the electronegativities of C and X are not very
The very extensive chemistry of alkyl halides will not
different when X is Cl, Br, or I. Thus alkyl halides do not
be covered in first-year chemistry.
dissolve well in water and other polar solvents.
 10

ALCOHOLS

Structure and Nomenclature Table 7. Structures and Names of Some Alcohols

In alcohols, the functional group is an –OH group Common
Structure IUPAC Name
covalently bonded to a carbon atom: Name

CH 3OH methyl methanol

C OH alcohol
CH 3CH 2OH ethyl ethanol
Alcohols are subclassified into primary, secondary, and alcohol
tertiary alcohols as shown in Figure 2. The rates and CH 3CH 2CH 2OH n-propyl 1-propanol
products of some reactions depend on whether the alcohol alcohol
is classified as 1°, 2°, or 3°.
H
isopropyl 2-propanol
H CH 3 C CH 3
alcohol
R C OH 1° alcohol: the C in the C-OH group
OH
is bonded to one carbon
H
CH 3CH 2CH 2CH 2OH n-butyl 1-butanol
R' alcohol
R C OH 2° alcohol: the C in the C-OH group
H
is bonded to two carbons sec-butyl 2-butanol
H CH 3CH 2 C CH 3
alcohol
R' OH
R C OH 3° alcohol: the C in the C-OH group
is bonded to three carbons CH 3
R" isobutyl 2-methyl-1-
CH 3 C CH 2OH
Figure 2. Alcohols can be subclassified as primary alcohol propanol
(1°), secondary (2°), or tertiary (3°). H

CH3
The following rules apply to IUPAC nomenclature of tert-butyl 2-methyl-2-
CH3 C OH
alcohols; examples of nomenclature are given in Table 8. alcohol propanol
The longest continuous sequence of carbon atoms to CH3
which the OH group is connected is the basis for the
CH 2 CH 2 ethylene 1,2-ethanediol
parent name of an alcohol. Alcohol names are obtained
glycol
from the alkane name by dropping the final -e and adding OH OH
-ol. The position of the alcohol functional group is
CH 2 CH CH 2
indicated by numbering the parent chain from the end that
glycerine 1,2,3-propanetriol
gives the lowest possible number to the OH group. For OH OH OH
example, the following compound is named as shown
rather than as 2,2-dimethyl-5-heptanol.
Physical Properties
CH 3
The presence of the –OH group in the alcohol makes
H3 C C CH 2 CH 2 CH CH 2 CH 3 the molecule quite polar, since the electronegativities of
CH 3 OH carbon, oxygen, and hydrogen are 2.5, 3.5, and 2.1,
respectively. Alcohol molecles interact with each other as
6,6-dimethyl-3-heptanol
shown in Figure 3. The dashed lines represent the
 11

attraction between a partially positively charged hydrogen carboxylic acid combines with the –OH from the alcohol
on one molecule with a partially negatively charged to give water. The R group from the alcohol bonds to the
oxygen atom on a different molecule. This interaction oxygen in the carboxylic acid. This reaction
between two molecules is called a hydrogen bond. It has a is called a condensation reaction because two organic
bond energy of 20 kJ/mol, approximately 5–10% of the molecules “condense” to form the product.
strength of a normal covalent bond. O H+
R – OH + C R'
– R H O
(a) R O
O – O
H 
H C R' + H2 O
 R joins here
R O
R O Hydrogen bonds ester
–
Two specific examples of esterification are the
– 
H
 H production of ethyl hexanoate from ethanol and hexanoic
O
acid, and of methyl anthranilate from methanol and
R anthranilic acid. Ethyl hexanoate is one of the dominant
R constituents of a “green apple” flavour, and methyl
O
– anthranilate is the ester that gives native North American
(b)
H  grapes their characteristic taste.
– H
O  O O
H H+
H H CH3 (CH2 )4 C + CH3 CH2 OH
OH
Hydrogen bonds
O
Figure 3. Alcohol molecules hydrogen bond with each
CH3 (CH2 )4 C + H2O
other (a) and with water (b).
OCH2CH 3

Hydrogen bonding interactions are weaker than ethyl hexanoate (apples)

covalent bonds, but stronger than the London dispersion
interactions in alkanes, and thus alcohols melt and boil NH2
significantly higher than do alkanes and other nonpolar H+
+ HOCH3
compounds. The lower alcohols are soluble in water OH
because their –OH groups can hydrogen-bond to water C
molecules (Figure 3b). Alcohols with chain lengths of 5 O NH2
carbon atoms or more are not very water-soluble because
their long nonpolar “tail” does not interact with water. + H2 O
OCH3
C
Reactions
O
Reaction with Na. Alcohols react with sodium metal methyl anthranilate (Concord grapes)
so as to displace the hydrogen in the –OH group.
Hydrogen gas is liberated in the reaction. An example is
the reaction of ethanol with sodium to produce sodium Polyesters. When a difunctional alcohol reacts with a
ethoxide and hydrogen. dicarboxylic acid, polyesters are formed. They are known
as condensation polymers to distinguish them from
2 CH3CH2OH + 2 Na Na+CH3CH2O– + H2
addition polymers formed by alkenes. For example, pop
All alcohols undergo this reaction, but the rate varies with bottles are made of poly(ethyleneterephthalate) or PET.
structure type. In general, primary alcohols react faster This plastic is made by reacting terephthalic acid with
than secondary alcohols, and tertiary alcohols react the ethylene glycol. Each of these compounds has two
slowest. reactive “ends” so that esterification is possible in two
Esterification. Esterification occurs when an alcohol directions at once. Terephthalic acid residues alternate
reacts with a carboxylic acid. An acid catalyst is required with ethylene glycol residues to give very long chains.
to make the reaction proceed rapidly. The –H from the
 12

O O
H OH H
C C conc.
CH3 CH2 C C C H
HO O—H HO—CH 2CH 2OH 3 2 1 H2 SO4
H H H
terephthalic acid ethylene glycol
CH3 CH2 CH2 CH = CH2 + CH3 CH2 CH = CHCH3 + H2 O
ester 1-pentene 2-pentene
linkage
O O Oxidation by aqueous KMnO4. The structure type
C C is very important in this reaction. Primary and secondary
O O—CH2 CH2 — alcohols give different products when they react, and
n tertiary alcohols do not react at all with aqueous KMnO4.
The oxidation product of primary alcohols is a carboxylic
acid, whereas secondary alcohols give ketones. Tertiary
repeating unit of the polymer, alcohols do not react because there is no hydrogen
poly(ethyleneterephthalate)
attached to the functional group carbon.

Elimination of H2O. When alcohols are heated with H

aqueous O
concentrated sulfuric acid, an alkene and water are R C OH R C
produced. This is called an elimination reaction because a KMnO4 OH
H
new compound appears to have been generated by
eliminating a molecule of some simpler compound. 1° alcohol carboxylic acid
H
aqueous O
The OH from one carbon and R C OH R C
the H from an adjacent carbon KMnO4
are split out of the molecule. R' R'

2° alcohol ketone
OH H R"
conc. aqueous
R C C R R2 C = CR2 + H2 O R C OH No reaction
H2 SO 4 KMnO4
R R R'
Double bond between the No H on this C
3° alcohol
carbons that were originally
bonded to the OH and H
Specific examples of KMnO4 oxidations include the
Figure 4. Alcohols split out water to give alkenes when
oxidation of the primary alcohol 1-propanol to propanoic
treated with hot, concentrated sulfuric acid.
acid, and of the secondary alcohol 2-propanol to acetone.
For example, propanol gives propene when it is
aqueous O
heated with sulfuric acid:
CH3 CH2 CH2 OH CH3 CH2 C
H OH H KMnO4
conc. OH
H C C C H CH3 CH = CH2 + H2 O 1-propanol propanoic acid
H2 SO4 H
H H H aqueous O
Some alcohols can give two products when heated H3 C C OH H3 C C
with sulfuric acid, depending on which hydrogen is KMnO4
CH3 CH3
removed. For example, 2-pentanol can give either
1-pentene or 2-pentene, depending on whether a 2-propanol acetone (propanone)
hydrogen is taken from carbon #1 or carbon #3:
 13

Problems on Alcohols (c) HCO2H (with acid catalyst)

1. Give structures of the following alcohols: (d) Na
(a) 3-methyl-2-pentanol 4. Repeat question 3 for 2-propanol.
(b) 2-methyl-2-butanol 5. Repeat question 3 for 2-methyl-2-propanol.
(c) 4,4-dimethyl-1-hexanol 6. How many alkenes can be obtained when the following
alcohol is heated with sulfuric acid? Draw their
(d) 2,2-dimethyl-1-propanol
structures.
2. Which of the monofunctional alcohols in Table 2 are
CH2 CH3
primary alcohols? Which are secondary alcohols? Which
are tertiary alcohols? CH3 CH2 CH2 C OH

3. Give the structure(s) of the organic products when CH3

ethanol reacts with the following reagents. Write NR if 7. Draw a diagram to show how methanol undergoes
there is no reaction. hydrogen-bonding with water.

ALDEHYDES AND KETONES

(a) KMnO4
(b) H2SO4 (with heat applied)

Structure and Nomenclature CH 3 O

6 5 4 3 2 1
Aldehydes and ketones contain the carbonyl group, H3 C C CH 2 CH 2 CH C H
C = O. This group is moderately polar, with the negative CH 3 CH 2CH 3
end of the dipole residing on the oxygen atom.
2-ethyl-5,5-dimethylhexanal

C O For ketones, the IUPAC name is, as usual, derived

  from the longest chain containing the carbonyl group. The
position of the carbonyl group is indicated by numbering
The polarity of this group accounts for much of the
chemistry of aldehydes and ketones. The carbon and
oxygen atoms are sp2 hybridized, and the angles about the parent chain from the end that gives the lowest
the carbon are approximately 120°. possible number to the carbonyl carbon. Ketone names
are obtained from the alkane name by dropping the final -
For aldehydes, the IUPAC name is derived from the
e and adding -one. An example of a IUPAC name for a
longest continuous sequence of carbon atoms containing
ketone follows:
the carbonyl group. The numbering proceeds from the
carbonyl carbon. It is not necessary to designate the CH 3 O
5 4 3 2 1
aldehyde position as -1- since it must occur at the end of H3 C C CH 2 C CH 3
the chain. Aldehyde names are obtained from the alkane
CH 3
name by dropping the final -e and adding -al. For
example,
4,4-dimethyl-2-pentanone
The formulas and names of the low-molecular weight
aldehydes and ketones are given in Table 8.
 14

Table 8. Structures and Names of Some Aldehydes concerned with in first year chemistry is the oxidation
and Ketones of aldehydes to carboxylic acids. Ketones are not
oxidized by the normal oxidizing agents.
Structure Common Name IUPAC Name
Aqueous potassium permanganate oxidizes
O
aldehydes quite readily to the corresponding carboxylic
H C formaldehyde methanal
acids. It is easy to tell that a reaction has occurred,
H because the purple
O colour of permanganate ion disappears and a brown
CH 3 C acetaldehyde ethanal precipitate of MnO2 is formed. The general equations
are shown below:
H
O O O
aqueous
CH 3 C propion- propanal R C R C
aldehyde H KMnO4 OH
H
O aldehyde carboxylic acid
CH 3CH 2CH 2 C butyraldehyde butanal
O
H aqueous
R C No reaction
O KMnO4
R
CH 3 CH C iso- 2-methyl-
ketone
H butyraldehyde propanal
CH 3
A specific example is the oxidation of
O benzaldehyde to benzoic acid:
acetone 2-propanone
CH 3 C CH 3 O
O
O aqueous C + MnO2
C
methyl ethyl 2-butanone
CH 3 C CH 2CH 3 H KMnO4 OH
ketone
benzaldehyde benzoic acid
O CH 3 methyl 3-methyl-2-
isopropyl butanone Unfortunately, the test with KMnO4 is not very
CH 3 C CHCH3 specific. KMnO4 is a strong oxidizing agent and reacts
ketone
with alcohols and alkenes as well as with the easily
oxidized aldehydes. However, there is a very mild
oxidizing agent that is used as a specific test for
Physical Properties aldehydes. It is Fehling's solution, and consists of an
Aldehydes and ketones are polar, and hence have aqueous solution of a copper(II) salt. In the reaction,
higher boiling and melting points than nonpolar aldehydes are oxidized to carboxylic acids but alkenes
compounds with similar molecular weights. They cannot and alcohols do not react. Reaction is easy to detect,
undergo hydrogen bonding with each other because there because the blue colour of the copper(II) solution
are no hydrogen atoms with significant partial positive disappears and a red precipitate of Cu2O is produced.
charge; thus they have lower melting and boiling points The following equations show the oxidation of
than the alcohols. propanal to propanoic acid by Fehling's solution, and the
Aldehydes and ketones with five or fewer carbons failure of other classes of organic compounds to react.
are quite soluble in water. The carbonyl group undergoes
O O
hydrogen bonding interactions with the water molecules.
Aldehydes and ketones are also soluble in the usual CH3 CH2 C + Cu2+ CH3 CH2 C + Cu2O
nonpolar organic solvents. H Fehling OH red
solution ppt.
Reactions
Although aldehydes and ketones undergo many
different kinds of reactions, the only one that we are
 15

ketones O
alkenes + Cu2+ No reaction (e) CH3 CH2 CH2 C
alcohols CH2 CH2 C(CH3 )3
Fehling
solution 2. Write the organic products of the reactions of the
compounds in Question 1 with potassium permanganate.
The test with Fehling's solution is used in the laboratory If there is no reaction, state NR.
to distinguish between aldehydes and other oxidizable
3. You have an unknown that could be one of the
compounds.
following compounds: 2-methyl-2-propanol, 2-propanol,
propanone, or propanal. Your unknown reacts with
potassium permanganate but not with Fehling's solution.
Problems on Aldehydes and Ketones What is the compound? Explain your reasoning.
1. Name the following compounds. 4. You have an unknown that could be one of the
following compounds: 2-methyl-2-propanol, 2-propanol,
propanone, or propanal. Your unknown reacts with

CARBOXYLIC ACIDS

O O sodium but not with potassium permanganate. What is the

(a) H3 C C (b) CH3 C compound? Explain your reasoning.
H CH(CH3)2 5. You have an unknown that could be one of the
following compounds: 2-methyl-2-propanol, 2-propanol,
O O
propanone, or propanal. Your unknown reacts with
(c) H C (d) H3 C C potassium permanganate and also with Fehling's solution.
CH2 CH2 CH3 CH2 CH2 CH3 What is the compound? Explain your reasoning.
6. Make a drawing that shows how acetone can undergo
hydrogen bonding with water.

it by -oic acid. The carboxylic acid group must be at the

Structure and Nomenclature
end of the chain, so it is not necessary to specify the
The functional group of carboxylic acids is the — number -1- for its location. Names of common carboxylic
CO2H group, acids are shown in Table 9.
Names of the carboxylate anions are derived from the
O sp2
acid name. Drop the final “–ic acid” ending and replace it
C with –ate. Thus the HCO2– ion is methanoate (IUPAC
sp3
sp2 name) or formate (common name), since the parent acid
O H HCO2H is methanoic (formic) acid. Additional examples
of carboxylate anion nomenclature are given in Table 10.
You will note that a carboxylic acid contains both a
carbonyl group and a hydroxyl group on the same carbon.
Table 9. Structures and Names of Carboxylic Acids
The carbon and oxygen atoms of the carbonyl group are
sp2 hybridized, whereas the oxygen atom of the OH Common
Structure IUPAC Name
group is sp3 hybridized. The angles about the carbon Name
atom are 120°, and the H–O–C angle is about 109.5°.
The IUPAC name of the carboxylic acid is obtained
by dropping the final -e in the alkane name and replacing
 16

O formed by reaction with the base, and they are water-

H C
formic methanoic acid soluble.
acid
O H
Reactions
O
acetic ethanoic acid Acidity. Carboxylic acids derive their name because
CH 3 C
acid they are weak acids. They dissociate to form hydrogen
O H ions and carboxylate anions as is shown by the following
O equation for dissociation of acetic acid.
CH 3CH 2 C
propionic propanoic acid
O O
acid
O H CH3 C CH3 C + H+
O O H O
CH 3CH 2CH 2 C
butyric butanoic acid
acid
O H acidic hydrogen
O in a carboxylic acid
CH 3 CH C
isobutyric 2-methyl- The acetate ion produced has two equivalent
acid propanoic acid resonance forms.
CH 3 O H

O O O O
C C
oxalic ethanedioic
CH3 C CH3 C
acid acid
HO OH O O
CH3(CH2)16CO2H stearic octadecanoic
acid acid Salt formation. Carboxylic acids react with bases to
form salts. Examples include the reaction of formic acid
with copper hydroxide to form copper formate, and the
Table 10. Names and Formulas of Carboxylate Anions reaction of acetic acid with ammonia to form ammonium
acetate.
Formula Common Name IUPAC Name
O
HCO2– formate methanoate 2 H C + Cu(OH)2 Cu(HCO2 )2 + 2 H2 O
CH3CO2– acetate ethanoate O H

CH3CH2CO2– propionate propanoate O

CH 3 C + NH3 NH4+CH 3CO 2–
C6H5CO2– benzoate
O H
C2O42– oxalate ethanedioate
proton transfer

Physical Properties
Carboxylic acids are very polar because of the
presence of both a carbonyl oxygen atom and a hydroxyl
group on the same carbon. As a consequence, they form
strong hydrogen bonds to each other as well as to water
molecules. Their melting and boiling points are relatively
high, even when compared to other polar organic
compounds such as alcohols that also undergo hydrogen
bonding.
Carboxylic acids containing up to approximately five
carbon atoms are water-soluble. Carboxylic acids with
longer carbon chains do not readily dissolve in water, but
dissolve in aqueous NaOH because carboxylate salts are
Amide formation. Carboxylic acids react with
ammonia or amines in a two-step reaction to produce
amides. In the first step, a carboxylic acid reacts with
ammonia or an amine to produce a salt. In the second
step, the salt is heated until it splits out water to form the
amide. The following reaction shows the steps in the
production of acetamide, CH3CONH2, from acetic acid
and ammonia. Note that a covalent C–N bond is formed
in the second step.
 17

Step 1 (a) formic acid (b) acetic acid

O O
(c) oxalic acid (d) potassium formate
CH3 C + NH3 CH3 C
O– NH4+
(e) sodium acetate (f) magnesium oxalate
O H
salt 3. Give structures for the products of the following room-
Step 2 temperature reactions:
O O
 O
CH3 C CH3 C + H2 O
(a) NaOH + C
O– NH4+ N H
OH
H

ESTERS

Additional examples of amide formation are given in (b) KOH + CH3(CH 2)16CO 2H
the section on amines.
(c) CH3 CO2 H + CH3NH2
Esterification. The reaction of alcohols with
carboxylic acids to produce esters has been covered
(d) HCO2H + (CH3 )2NH
previously in the section on alcohols.
(e) CH3CH 2CO 2H + NH 3
Problems on Carboxylic Acids
1. Give names of the following carboxylic acids and salts: 4. Suppose that the products of 3(c), 3(d), and 3(e) are
heated. Write structures of the new compounds that will
(a) CH3(CH2)4CO2H (b) CH2FCH2CO2H
be formed.
(c) (CH3)3CCO2H (d) CCl3CO2H
5. Draw the structure of the polyamide that results when
(e) Cu(CH3CO2)2 (f) CaC2O4 H2N(CH2)5CO2H polymerizes.

(g) NaHCO2 (h) Ca[CH3(CH2)16CO2]2

2. Give formulas for the following acids and salts:

Structure and Nomenclature Acid part of the ester:

alkyl group attached to
Esters are named as derivatives of carboxylic acids.
O carbonyl C
The alkyl group derived from the alcohol is named first,
R C
as an initial separate word. The second word is the parent Alcohol part of the ester:
OR'
name of the carboxylic acid in which the suffix -oate alkyl group attached to O
replaces -oic acid. Examples of ester names follow in
Table 11. It is thus important to be able to recognize the O
alcohol and acid parts of an ester: the alcohol part has the R'O C
Acid part of the ester
R group attached to an oxygen, the acid part has the R R
group attached to the carbonyl carbon as shown below.
Alcohol part of the ester

Don't get confused if the ester is written in different

ways!
 18

O
Physical Properties H C
ethyl ethyl
formate methanoate
Esters are polar molecules because of the presence of O CH 2CH 3
two oxygens in the ester functional group, but they
O
H C
n-propyl 1-propyl
formate methanoate
O CH 2CH 2CH 3
cannot undergo hydrogen bonding with each other
because there are no –OH groups. Their physical O
properties are similar to those of aldehydes and ketones.
H C isopropyl 2-propyl
Esters containing up to about five carbons are fairly water
soluble because the oxygens in the ester linkage can O CH CH 3 formate methanoate
participate in hydrogen bonding with water. CH 3
Esters generally have pleasant aromas if they are
O
volatile, and are major constituents of natural fruit
CH 3 C
methyl methyl
flavours.
acetate ethanoate
O CH 3
Reactions
O
Hydrolysis. Hydrolysis literally means “the breaking methyl methyl
apart of water.” In the hydrolysis of an ester, e.g., water is CH 3CH 2 C
propionate propanoate
split apart when the ester reacts to produce a carboxylic O CH 3
acid and an alcohol. The reaction is catalyzed by acids.
The reaction is reversible; at equilibrium there are O
significant amounts of both products and reactants present CH 3CH 2CH 2 C
methyl methyl
in the mixture. The reaction can be forced to the right by butyrate butanoate
O CH 3
using large amounts of water, or by adding base to react
with the acid. CH 3 O methyl methyl 2-
Note that the isopropyl formate ester produces CH 3 CH C isobutyrate methyl-
2-propanol when it is hydrolyzed: O CH 3 propanoate
O
H+
H C CH 3 + H2 O
O CH CH 3 Saponification. Saponification means “soap
making.” Soaps are the sodium or potassium salts of long-
O chain carboxylic acids (12 or more carbons). Soaps are
+ H3 C CH CH 3 made by hydrolyzing a fat (an ester of glycerine) in the
H C
presence of NaOH or KOH; the products are an alcohol
OH OH
and a sodium carboxylate salt (soap).

Table 11. Structures and Names of Some Esters

Common IUPAC
Structure
Name Name

O
H C
methyl methyl
formate methanoate
O CH 3
 19

H2 C O C(O)(CH2)16CH 3
HC O C(O)(CH2)16CH 3 + 3 NaOH
H2 C O C(O)(CH2)16CH 3
This is a typical fat –
glyceryl tristearate

H2 C OH
O
HC OH + 3 C (CH2 )16CH3
H2 C OH Na+ - O

Glycerine—a triol This is a soap—

(3 OH groups) sodium stearate

Problems on Esters
1. Write structures of the following esters:
(a) isopropyl formate (b) methyl propanoate
(c) n-octyl acetate (d) n-propyl octanoate

2. Give the names of the following esters:

O
(a) CH 3 C
OCH2 CH2 CH3

O
(b) CH 3CH 2O C
CH 2CH 2CH 3

O
(c) CH 3(CH 2)4 C
OCH3

O
(d) H C
OCH2 CH2 CH2 CH3

3. Show the structures of the products obtained when

each of the esters in Question 1 undergoes the following
reactions: (a) hydrolysis in the presence of an acid
catalyst; (b) reaction with aqueous sodium hydroxide.
 20

AMINES

Structure and Nomenclature Table 13. Structures and Names of Cations Derived by
Alkyl amines are related to ammonia; one or more of Protonating Amines
the hydrogen atoms of ammonia are replaced by alkyl Structure Name
groups. The mono-, di-, and trisubstituted amines are
pyramidal at the nitrogen because of the lone pair of CH3NH3+ methylammonium
electrons. The C-N-C angles are close to the tetrahedral (CH3)2NH2+ dimethylammonium
angle of 109.5°.
(CH3)3NH+ trimethylammonium
N
R"
R
R' N H pyridinium
Amines in which the nitrogen replaces a CH group
in a benzene ring, as in pyridine (Table 12) are planar at
the nitrogen rather than pyramidal. The nitrogen in NH3 anilinium
pyridine is sp2 hybridized, and the C-N-C angle in
pyridine is 120°.
Alkyl amines are named by listing the alkyl groups acid solution because they react to form soluble salts.
and adding -amine. Hence CH3CH2NH2 is ethylamine.
Amines are not pleasant compounds to work with
When amines are protonated, they are named as
because of their intense, unpleasant aromas. Low
derivatives of the ammonium cation (NH4+). Thus
molecular weight alkyl amines such as the methylamines
CH3CH2NH3+ is the ethylammonium cation. Further
have a strong “rotten fish” odor. Other amines smell like
examples of nomenclature are found in Tables 12 and 13.
corpses or worse.

Physical Properties Reactions

Amines are less polar than alcohols. Their hydrogen
bonds to each other are weaker than in alcohols, and
amines have lower boiling points than alcohols with the
same number of carbons in the chain. Amines whose
molecular weight is low are relatively soluble in water.
Amines that do not dissolve readily in water are soluble in
Table 12. Structures and Names of Some Amines
Structure Name
Basicity. Amines dissolve in water to give basic
solutions. The basicity results because a proton from the
water molecule is transferred to the lone pair of the
amine, resulting in a solution that contains hydroxide.
Amines are weak bases because this reaction does not
proceed very far to the right. The reactions of
methylamine and pyridine with water are shown below.
proton transfer
H +

CH3NH2 methylamine H3 C N H + H2 O H3 C N H + OH –

(CH3)2NH dimethylamine H H
+
(CH3)3N trimethylamine

N + H2 O N H + OH –
pyridine
N
Salt formation. Amines react with inorganic and
organic acids to give salts. Again, a proton is transferred
NH2 aniline (phenylamine, from the acid to the lone pair of electrons on the nitrogen.
aminobenzene) Shown following is the reaction of dimethylamine with
 21

hydrogen chloride to produce dimethylammonium R O R O

chloride. enzyme
H2 N C C H N C C
proton transfer H OH H H OH
H +
H3 C N H + HCl H3 C N H Cl– R O
CH3 CH3 H2 N C C R O + H2O
dimethylammonium H N C C
chloride H H OH
Amide formation. Amide formation was discussed
above in the section on carboxylic acids. An additional
example is shown below, where the salt of dimethylamine Problems on Amines
and formic acid is heated to give N,N- 1. Give the structures of the following amines:
dimethylformamide.
(a) ethylamine (b) diethylamine
O O
 (c) triethylamine (d) isopropylamine
H C H C + H2 O
(e) n-butylamine
O– (CH3 )2NH2 + N CH3
2. Write structures of the room-temperature reaction
CH3 products of the following amines with these reagents: (i)
dimethylammonium
formate N,N-dimethylformamide HCl; (ii) CH3CO2H.
Polyamides. Polyamides result when difunctional (a) CH3CH2CH2NH2 (b) (CH3)3N
amines react with difunctional acids. Nylon is a (c) (CH3CH2)2NH (d) pyridine
polyamide, and is synthesized from hexanedioic acid and
1,6-diaminohexane according to the following equation: 3. Write structures for the monomers needed to produce
the following polymers:
O O
 O O
n C (CH2 )4 C + n H2N(CH2 )6NH2
C (CH2 )2 C
HO OH
(a) N N (CH2 )8
O O
H H
C (CH2 )4 C n
N N (CH2 )6 + 2n H2 O (2 monomers)

H H
n O H CH 3
(b)
Nylon - a polyamide C N CH
n
Polyamides also result when amino acids condense (1 monomer)
in biochemical syntheses, in which an enzyme catalyzes
the reaction. The reaction of two amino acids to form a 4. Write equations to show how the following monomers
dipeptide is shown below. Continued reaction of the react to produce polyamides:
dipeptide with more amino acids results in long-chain
(a) HO2CCO2H + H2N(CH2)6NH2 
molecules called proteins.
(b) H2NCH2CO2H (this is the amino acid glycine)
 22

AMIDES

Structure and Nomenclature

Hydrogen bond
Amides have two resonance structures as shown
'R
below. (R and R' may be hydrogen or alkyl groups.) The
amide group is planar because of the resonance, which N H O R'
(a)
requires that the amide carbon, oxygen, and nitrogen C
+ – C N
O
atoms all be sp2 hybridized. The bond angles about the R R H 
carbon and nitrogen atoms are approximately 120°.
 –
O H O R'

O R' O R' C N
H

C N C N R H
(b)
R H R H –
Hydrogen bonds O H
Amide nomenclature is based on the name of the
parent acid. The rule is to drop the “-oic acid” ending H
from the IUPAC name, or the “-ic acid” ending from the Figure 4. Amides hydrogen bond with each other (a)
common name, and add "amide.” Thus HCONH2 is and with water molecules (b).
methanamide or formamide. If the amide is derived from
an organic amine, the amine substituents are named and Reactions
their locations are indicated by the prefix N- (to show that
they are bonded to the nitrogen). An example is Hydrolysis. Amides react with water to generate the
parent carboxylic acid and amine (which then combine to
O form the salt). For example, N-methylacetamide
CH 3CH 2 C hydrolyzes to give N-methylammonium acetate:
N CH 3
O
CH 3 CH3 C + H2 O (CH3 NH3+)(CH 3CO 2– )
N,N-dimethylpropanamide NH CH3

First year students will not be required to name amides. Similarly, protein digestion in your stomach involves
hydrolysis to the constituent amino acids:
Physical Properties
R O R O
Amides, especially those containing an N-H group,
are high-melting and high-boiling because of strong H2 N C C N C C + n H2O
hydrogen bonding between adjacent molecules. Note that H H H OH
the hydrogen bond is from the amide hydrogen atom to n
the carbonyl oxygen atom. Many amides are quite soluble R O
in water because of their ability to undergo hydrogen enzyme
n H2 N C C
bonding with water molecules.
H OH
 23

SUMMARY PROBLEMS

1. To which class of organic compounds does each of the (a) Suppose that your unknown is water-soluble and tests
following molecules belong? basic with pH paper. Which of the above compounds is
it?
Compound B.p., °C
(b) Suppose that your unknown is not soluble in water but
(a) CH3CO2H 118
does dissolve in carbon tetrachloride. It decolourizes Br2.
(b) CH3CH2CH2NH2 48 What is it?
(c) CH3CH2CH = CH2 -6 (c) Suppose that your unknown dissolves in water but is
(d) CH3CH2CH2OH 97 neither acidic nor basic. It reacts with Fehling's solution.
What is it?
(e) CH3CH2CHO 49
8. You have an unknown that could be one of the
(f) CH3C  CCH3 8 following compounds:
(g) CH3C(O)NH2 221 O O
(h) HCO2CH3 32 CH 3CH 2CH 2 C CH 3CH 2CH 2 C

(i) CH3CH2CH2CH3 -1 OH H
O
(j) (CH3)2CO 56
CH 3CH 2 C CH 3
OCH3 CH 3CH 2 CH OH
2. Name each compound in Question 1.
CH 3
3. The compounds in Question 1 all have approximately
the same formula weight. However, their boiling points CH 3CH 2 C OH
are not the same. List the compounds in order of CH 2CH 3
increasing boiling point. Explain the variations in boiling
(a) Suppose that your unknown tests neutral with pH
point in terms of molecular polarity and hydrogen
paper. It reacts with sodium metal but not with aqueous
bonding.
potassium permanganate. Which of the compounds listed
4. Which of the compounds in Question 1 will be soluble above is it?
in water?
(b) Suppose that your unknown tests neutral with pH
5. Which of the molecules in Question 1 can hydrogen- paper. It does not react with sodium metal or with
bond to other molecules of the same compound? aqueous potassium permanganate. What is it?
6. Which of the molecules in Question 1 can undergo (c) Suppose that your unknown tests neutral with pH
hydrogen bonding to water molecules? paper. It does not react with sodium metal, but does react
7. You have an unknown that could be one of the with potassium permanganate and with Fehling's solution.
following compounds: What is it?

(CH3CH2)3N CH3CH2CO2H
CH3(CH2)4CH3 CH3CH2CH2CH2OH
CH3CH2CHO CH3CH2CH2CH2CH = CH2
 CLASSES OF ORGANIC COMPOUNDS

Class and description Example Class and description Example

Alkanes—contain only C- H H H Ketones—contain the H O H

H and C-C single bonds. O
Abbreviation: RH, where H C C C H H C C C H
R C group.
R is an alkyl group. H H H H H
R
propane Abbreviation: R2CO, where acetone; propanone
R is an alkyl group.

Alkenes—contain at least H H tain H

O
one C-C double bond. C C Carboxylic Acids—con- H C C
Abbreviation: R2C=CR2, H H O OH
where R is H or alkyl. ethylene; ethene H
the C group.
OH
acetic acid; ethanoic acid
Abbreviation: RCO2H, where
R is an alkyl group.

Alkynes—contain at least H H Esters—contain the H

O
one C-C triple bond. O H
H C C C C H H C C
Abbreviation: RC  CR, C group.
where R is H or alkyl. O C H
H H O R H
2-butyne Abbreviation: RCO2R', H
where R is H or alkyl and R' methyl acetate;
is alkyl. methyl ethanoate

Alkyl Halides—contain H H H Amines—Derivatives of H H H

C-X bonds, where X is a ammonia in which one or
H C C C H H C N C H
halogen (F, Cl, Br, I). more of the hydrogens are
Abbreviation: RX, where H Cl H replaced by alkyl groups. H H
R is an alkyl group. 2-chloropropane; Abbreviations: RNH2, dimethyl amine
isopropyl chloride R2NH, R3N, where R is
alkyl.
H
Alcohols—contain H H H H Amides—contain the O
O H C C
the C O H group. H C C C C H
C group. N H
H
H H OH H N
Abbreviation: ROH, H
where R is an alkyl group. 2-butanol
Abbreviation: RCONR2, acetamide
where R is H or alkyl.
Aromatic Compounds—
Aldehydes—contain the H H OH
O contain the benzene ring,
O
H C C H H C C
C group. H C C O
H H C H
H C C C C
acetaldehyde; ethanal H C H
Abbreviation: RCHO,
C C
where R is an alkyl group. H C H H

H benzoic acid