Substituted Hydrocarbons and

Their Reactions
Section 22.1 Alkyl Halides and
Aryl Halides
Section 22.2 Alcohols, Ethers,
and Amines
Section 22.3 Carbonyl Compounds
Section 22.4 Other Reactions of
Organic Compounds
Section 22.5 Polymers

Click a hyperlink or folder tab to view

the corresponding slides. Exit
Section 22.1 Alkyl Halides and Aryl Halides

• Define functional group, aliphatic compound: a

and give examples. nonaromatic
hydrocarbon, such as an
• Compare and contrast alkane, an alkene, or an
alkyl and aryl halide alkyne
structures.
• Evaluate the boiling
points of organic halides.
Section 22.1 Alkyl Halides and Aryl Halides
(cont.)

functional group plastic

halocarbon substitution reaction
alkyl halide halogenation
aryl halide

A halogen atom can replace a

hydrogen atom in some hydrocarbons.
Functional Groups

• In an organic molecule, a functional

group is an atom or group of atoms that
always reacts in a certain way.
• Addition of a functional group to a
hydrocarbon always produces a substance
with different chemical and physical
properties.
• Double and triple bonds between carbon
atoms are considered functional groups.
Functional Groups (cont.)
Organic Compounds Containing Halogens

• Any organic compound that contains a

halogen substituent is called a halocarbon.
• An alkyl halide is an organic compound
containing a halogen atom covalently bonded
to an aliphatic carbon atom.
• An aryl halide is an organic compound
containing a halogen bonded to an aromatic
group.
Organic Compounds Containing Halogens
(cont.)

• In naming halocarbons, a
prefix indicates which
halogen is present.
• If there is more than a
single halogen, they are
listed alphabetically.
Organic Compounds Containing Halogens
(cont.)

• Halocarbons have higher boiling points

because they have an increasing tendency
to form temporary dipoles.
• Dipoles attract each other, and require more
energy to separate.
• A plastic is a polymer that can be heated and
molded while relatively soft.
Organic Compounds Containing Halogens
(cont.)
Substitution Reactions

• Nearly all synthetic organic compounds

begin with petroleum.
• A substitution reaction is one in which one
atom or a group of atoms in a molecule is
replaced by another atom or group of atoms
• Hydrogen atoms in an alkane can be
replaced by atoms of halogens in a process
called halogenation.
Substitution Reactions (cont.)
Substitution Reactions (cont.)

• Once halogenated, alkanes can undergo

further reactions.
• Reacting an alkyl halide with a basic solution
results in replacement of the halogen atom
with an –OH group to form an alcohol.
Section 22.1 Assessment

Which of the following is NOT an alkyl

halide?
A. 2-fluorobutane
B. 1,3-dichlorobenzene
C. sodium chloride A. A
D. bromoethane B. B
C. C
D. D
Section 22.1 Assessment

An alkane with one or more halogen

substituents is called what?
A. aryl halide
B. metal halide
C. chlorofluorocarbon A. A
D. alkyl halide B. B
C. C
D. D
Section 22.2 Alcohols, Ethers, and Amines

• Identify the functional miscible: describes two

groups that characterize liquids that are soluble
alcohols, ethers, and in each other
amines.

• Draw the structures of

alcohols, ethers, and
amines.
• Discuss the properties
and uses of alcohols,
ethers, and amines.
Section 22.2 Alcohols, Ethers, and Amines
(cont.)

hydroxyl group
alcohol
denatured alcohol
ether
amine

Oxygen and nitrogen are two of the

most-common atoms found in organic
functional groups.
Functional Groups (cont.)
Alcohols

• Oxygen commonly forms two covalent

bonds to form a stable octet.
• An oxygen-hydrogen group covalently
bonded to a carbon atom is called a hydroxyl
group.
• An organic compound in which a hydroxyl
group replaces a hydrogen is called an
alcohol.
Alcohols (cont.)
• Alcohols contain an OH group connected to a saturated
C (sp3).
• They are important solvents and synthesis
intermediates.
• Phenols contain an OH group connected to a carbon in
a benzene ring.
• Methanol, CH3OH, called methyl alcohol, is a common
solvent, a fuel additive, produced in large quantities.
• Ethanol, CH3CH2OH, called ethyl alcohol, is a solvent,
fuel, beverage.
• Phenol, C6H5OH (“phenyl alcohol”) has diverse uses - it
gives its name to the general class of compounds.
• OH groups bonded to vinylic sp2-hybridized carbons are
called enols.
• To begin to study oxygen-containing functional groups:
• These groups lie at the heart of biological chemistry
 IUPAC Rules for Naming Alcohols
• Select the longest carbon chain containing the hydroxyl
group, and derive the parent name by replacing the -e
ending of the corresponding alkane with –ol.
• Number the chain from the end nearer the hydroxyl
group.
• Number substituents according to position on chain,
listing the substituents in alphabetical order.
• General classifications of alcohols based on substitution
on C to which OH is attached
• Methyl (C has 3 H’s),
• Primary (1°) (C has two H’s, one R)
• Secondary (2°) (C has one H, two R’s)
• Tertiary (3°) (C has no H, 3 R’s)
• General classifications of alcohols based on substitution
on C to which OH is attached
• Methyl (C has 3 H’s),
• Primary (1°) (C has two H’s, one R)
•
• General classifications of alcohols based on substitution
on C to which OH is attached
• Methyl (C has 3 H’s),
• Secondary (2°) (C has one H, two R’s)
•
• General classifications of alcohols based on substitution
on C to which OH is attached
• Methyl (C has 3 H’s),
• Tertiary (3°) (C has no H, 3 R’s)
3
5

Name these:
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3

2-methyl-1-propanol 2-butanol

CH3 OH
CH3 C OH
CH3 Br CH3

2-methyl-2-propanol 3-bromo-3-methylcyclohexanol
3
C
h
6
a
p
t
e
Unsaturated Alcohols
r
1
0
• Hydroxyl group takes precedence. Assign
that carbon the lowest number.
• Use alkene or alkyne name.

OH
CH2 CHCH2CHCH3 4-penten-2-ol (old)
 OH
CH2 CHCH2CHCH3
 Naming Phenols

• Use “phenol” (the French name for benzene) as the

parent hydrocarbon name, not benzene.
• Name substituents on aromatic ring by their position
from OH.
3
C
h
9
a
p
t
e
Naming Priority
r
1
0

• Acids • Alkenes
• Esters • Alkynes
• Aldehydes • Alkanes
• Ketones • Ethers
• Alcohols • Halides
• Amines

=>
 Alcohols (diols, triols)
•-diols or –triols mean two or three hydroxyl groups in the molecule

•Number the hydroxyl group carbons with the lowest possible numbers

•Prefix uses the full parent name, i.e butane

,
Ethane-1,2-diol (ethylene glycol)

Propane-1,2,3-triol (glycerol)

Pentane-1,3-diol
Alcohols (cont.)

• Alcohol is polar and mixes

completely with water.
• Denatured alcohol is ethanol
with small amounts of noxious
materials added to it.
• Alcohol names are based on
the alkane names, with the
ending –ol.
Ethers

• An ether is an organic compound

containing an oxygen bonded to two
carbon atoms.
Ethers (cont.)

• Ethers have no hydrogen atoms bonded to

their oxygen atoms, so they cannot form
hydrogen bonds with each other.
• Ethers are volatile and have low boiling
points.
• Ethers with identical chains are named by the
chain followed by the word ether.
• Ethers with different chains are named in
alphabetical order followed by ether.
Ethers R-O-R or R-O-R´

Nomenclature:
simple ethers are named: “alkyl alkyl ether”
“dialkyl ether” if symmetric

CH3 CH3
CH3CH2-O-CH2CH3 CH3CH-O-CHCH3

diethyl ether diisopropyl ether

Methoxymethane
Dimethyl ether
CH3-O-C(CH3)3 tert-butyl methyl ether

If complex, the ether part is named as an “alkoxy”

group:
CH3-O- = methoxy CH3CH2-O- = ethoxy, etc.

CH3-O-CH2CH2CH2-O-CH3 1,3-dimethoxypropane

HO-CH2CH2-O-CH2CH3 2-ethoxyethanol
CH3-O-C(CH3)3 tert-butyl methyl ether
HO-CH2CH2-O-CH2CH3 2-ethoxyethanol
Amines

• Amines contain nitrogen

atoms bonded to carbon
atoms in aliphatic chains
or aromatic rings.
Amines (cont.)

• Amines are primary, secondary, or tertiary

depending on if there are one, two, or three
hydrogen atoms replaced by organic
groups.
• Amines have the suffix –amine.
• Amines and carbonyl compounds are the
most abundant and have rich chemistry.

• In addition to proteins and nucleic acids, a

majority of pharmaceutical agents contain
amine functional groups.
Amines – Organic Nitrogen Compounds

• Organic derivatives of ammonia, NH3.

• Nitrogen atom with a lone pair of electrons, making
amines both basic and nucleophilic.
• Occur in plants and animals.
 Classes of Amines

• Primary (1): one C-N bond, 2 N-H

bonds.
• Secondary (2): two C-N bonds, 1 N-H
bond.
• Tertiary (3): three C-N bonds, no N-H
bond.
• Quaternary (4): four C-N bonds,
nitrogen has a + formal charge.
=>
 Classes of Amines

• Primary (1): one C-N bond, 2 N-H

bonds.
 Classes of Amines

• Secondary (2): two C-N bonds, 1 N-H

bond.
 Classes of Amines

• Tertiary (3): three C-N bonds, no N-H

bond.
Classify:

CH3
N
CH3
N
H

CH3 _
Br
CH3 C NH2 +
CH3CH2 N CH2CH3
CH3
CH3
 IUPAC Names – Multiple, Different Alkyl Groups

• Named as N-substituted primary amines

• Largest alkyl group is the parent name, and
other alkyl groups are considered N-
substituents
 IUPAC Names
• Name is based on longest carbon chain.
• -e of alkane is replaced with -amine.
• Substituents on nitrogen have N- prefix.

Br
NH2CH2CH2CHCH2CH3
N(CH3)2
CH3CH2CHCH2CH2CH3
3-bromo-1-
pentanamine
N,N-dimethyl-3-hexanamine
 Br
NH2CH2CH2CHCH2CH3 3-bromo-1-pentanamine
 N(CH3)2
CH3CH2CHCH2CH2CH3
N,N-dimethyl-3-hexanamine
 Aromatic Amines
Amino group is bonded to a benzene ring.
Parent compound is called aniline.

NH2
CH3
NH2 N
CH3 H3C

4-methylaniline
aniline N,N-dimethylaniline or p-toluidine
 Heterocyclic Amines
The nitrogen is assigned the number 1.

H
N N N N N CH3
H H
aziridine Pyrrole Pyrrolidine Pyridine 2-methylpyridine

=>
 Common Names

Name the alkyl or aryl groups bonded to

nitrogen, then add suffix -amine.

(CH3CH2)2NCH3

diethylmethylamine
NHCH3
NH

cyclopentylmethylamine

Diphenylamine
• Organic derivatives of ammonia
• Many are biologically active.

=>
Section 22.2 Assessment

Which of the following is an alcohol?

A. cyclohexamine
B. 1-chlorobutanol
C. bromobutene
A. A
D. butylpropyl ether
B. B
C. C
D. D
Section 22.2 Assessment

Which functional group is present in an

alcohol?
A. hydroxyl group
B. halogen
C. aromatic ring A. A
D. amino group B. B
C. C
D. D
Section 22.3 Carbonyl Compounds

• Identify the structures of electronegative:

carbonyl compounds, indicates the relative
including aldehydes, ability of an element’s
ketones, carboxylic atoms to attract
acids, esters, and electrons in a chemical
amides. bond
• Discuss the properties
of compounds containing
the carbonyl group.
Section 22.3 Carbonyl Compounds (cont.)

carbonyl group carboxyl group

aldehyde ester
ketone amide
carboxylic acid condensation reaction

Carbonyl compounds contain a double-

bonded oxygen in the functional group.
Organic Compounds Containing the
Carbonyl Group
• An oxygen atom double-bonded to a
carbon atom is a carbonyl group.
• Aldehydes are organic compounds in which
the carbonyl group is located at the end of the
carbon chain and is bonded to a carbon atom
on one side and a hydrogen on the other
side.
• Aldehydes are named with the suffix –al.
Organic Compounds Containing the
Carbonyl Group (cont.)
Organic Compounds Containing the
Carbonyl Group (cont.)
• A ketone is an organic compound in which
the carbon of the carbonyl group is bonded
to two other carbon atoms.
• Ketones are named by changing the –e at the
end of the alkane name to –one, and
including a number before the name to
indicate the position of the ketone group.
• Ketones and aldehydes share many chemical
and physical properties because their
structures are similar.
Organic Compounds Containing the
Carbonyl Group (cont.)
• Ketones are popular solvents for
moderately polar substances.
• Ketones are somewhat soluble in water.
Organic Compounds Containing the
Carbonyl Group (cont.)
ALDEHYDES AND KETONES

“carbonyl” functional group:

O
C
Aldehydes Ketones

O O O
C C C
H H R H R R'

R can be Ar
 Structure of Aldehydes and Ketones
• Both aldehydes and ketones have a carbonyl
group, a carbon atom doubly bonded to an
oxygen atom, C=O.
• Aldehydes have a carbonyl group bonded to
an H atom.
• Ketones have a carbonyl group bonded to two
carbon atoms.
• Common names
• For aldehydes, the common name is derived from the
common name of the corresponding carboxylic acid.
• Know formaldehyde and acetaldehyde.
• For ketones, name the alkyl or aryl groups bonded to
the carbonyl carbon and add the word ketone.
Nomenclature:
Aldehydes, common names:
Derived from the common names of carboxylic acids;
drop –ic acid suffix and add –aldehyde.

CH3
CH3CH2CH2CH=O CH3CHCH=O

butyraldehyde isobutyraldehyde
(α-methylpropionaldehyde)
 CH3
CH3CHCH=O

isobutyraldehyde
(α-methylpropionaldehyde)
 Nomenclature of Aldehydes and Ketones
• IUPAC nomenclature
• The parent chain is the longest chain that contains
the carbonyl group.
• For an aldehyde, change the suffix from –e to –al; for
a ketone change the suffix from –e to –one
• For an unsaturated aldehyde or ketone, show the
carbon-carbon double bond by changing the infix from
–an– to –en–; the location of the suffix determines the
numbering pattern.
• For a cyclic molecule in which –CHO is bonded to the
ring, add the suffix –carbaldehyde.
• Some aromatic aldehydes and ketones have reserved
names. (We need to know benzaldehyde,
acetophenone, benzophenone.)
9
C
h
0
a
p
t
e
Naming Priority
r
1
0

• Acids • Alkenes
• Esters • Alkynes
• Aldehydes • Alkanes
• Ketones • Ethers
• Alcohols • Halides
• Amines

=>
Aldehydes, IUPAC nomenclature:
Parent chain = longest continuous carbon chain
containing the carbonyl group; alkane, drop –e, add –al.
(note: no locant, -CH=O is carbon #1.)
CH3
CH3CH2CH2CH=O CH3CHCH=O

butanal 2-methylpropanal

H2C=O CH3CH=O

methanal ethanal
 CHO CHO
CH3

benzaldehyde o-tolualdehyde

O
C CH2CH=O
H H

formaldehyde phenylacetaldehyde
Some examples

Benzaldehyde
 Ketones, common names:

O
Special name: acetone
C
H3C CH3

“alkyl alkyl ketone” or “dialkyl ketone”

O O O
CH3CH2CCH3 CH3CH2CCH2CH3 CH3CCH2CH2CH3

ethyl methyl ketone diethyl ketone methyl n-propyl ketone

(o)phenones:
O
R C

Derived from common name of carboxylic acid, drop –ic

acid, add –(o)phenone.

O O
C C
H3C

benzophenone acetophenone
Ketones: IUPAC nomenclature:

Parent = longest continuous carbon chain containing the

carbonyl group. Alkane, drop –e, add –one. Prefix a
locant for the position of the carbonyl using the principle
of lower number.

O O O
CH3CH2CCH3 CH3CH2CCH2CH3 CH3CCH2CH2CH3

2-butanone 3-pentanone 2-pentanone

Carboxylic Acids

• Carboxylic acids are organic compounds

that have a carboxyl group.
• Carboxyl groups are carbonyls bonded to a
hydroxyl group
• Carboxylic acids are named by changing the
–ane to –anoic acid.
Carboxylic Acids (cont.)
 Carboxylic acids:
O
R-COOH, R-CO2H, R C
OH

Common names:
HCO2H formic acid L. formica ant
CH3CO2H acetic acid L. acetum vinegar
CH3CH2CO2H propionic acid G. “first salt”
CH3CH2CH2CO2H butyric acid L. butyrum butter
CH3CH2CH2CH2CO2H valeric acid L. valerans
Carboxylic acids, common names:
…
CH3(CH2)4CO2H caproic acid L. caper goat
CH3(CH2)5CO2H ---
CH3(CH2)6CO2H caprylic acid
CH3(CH2)7CO2H ---
CH3(CH2)8CO2H capric acid
CH3(CH2)9CO2H ---
CH3(CH2)10CO2H lauric acid oil of lauryl
 5 4 3 2 1
C—C—C—C—C=O
δ γ β α used in common names

Br CH3
CH3CH2CH2CHCOOH CH3CHCH2COOH

− bromovaleric acid  -methylbutyric acid

isovaleric acid
IUPAC nomenclature for carboxylic acids:
parent chain = longest, continuous carbon chain
that contains the carboxyl group → alkane, drop –e,
add –oic acid

HCOOH methanoic acid

CH3CO2H ethanoic acid
CH3CH2CO2H propanoic acid

CH3
CH3CHCOOH 2-methylpropanoic acid

Br
CH3CH2CHCO2H 2-bromobutanoic acid
Dicarboxylic acids:

HOOC-COOH oxalic acid

HO2C-CH2-CO2H malonic acid
HO2C-CH2CH2-CO2H succinic acid
HO2C-CH2CH2CH2-CO2H glutaric acid
HOOC-(CH2)4-COOH adipic acid
HOOC-(CH2)5-COOH pimelic acid

Oh, my! Such good apple pie!

Carboxylic Acids (cont.)

• Carboxylic groups are represented by

–COOH.
• Carboxylic acids are polar and reactive, and
ionize in water to form acids.
Organic Compounds Derived from
Carboxylic Acids
• An ester is any organic compound with a
carboxyl group in which the hydrogen in
the hydroxyl group is replaced by an alkyl
chain.
 Naming Names of esters
end in –oate.

Named after alcohol & carboxylic acid from which

they are derived.
O
C CH3
let’s name
CH3 CH2 O some esters!

ethyl ethanoate

this part comes from the this part from the acid
alcohol & is named after it and is named after it
 Structural formula
Although the previous structural formula are the clearest way
of showing esters, they can draw out in a shortened form.
In this version
ethyl ethanoate the acid part
has been
Or…
O written first
Either… O
CH3 C O CH2 CH3
CH3 CH2 O C CH3

✓ Identify the group attached to the C=O – this is

from the acid.
✓ The group attached to the –O- is from the alcohol.
 O
CH ethyl methanoate
CH3 CH2 O

O
C CH2 CH3 methyl propanoate
CH3 O

O
CH methyl methanoate

CH3 O
 What are they? How are they made?
✓Formed when an alcohol reacts with a
carboxylic acid.
✓Very slow reaction, unless! an acid catalyst
used (usually sulphuric acid)
✓A condensation reaction
✓The condensation reaction between the
hydroxyl group and the carboxylic acid
known as esterification.
✓Reverse reaction = ester hydrolysis
 Wait! What’s that smell?
ester fragrance
ethyl methanoate raspberries
3-methylbutyl ethanoate pears
ethyl 2-methylbutanoate apples
phenylmethyl ethanoate jasmine
• Esters have strong, sweet smells.
• Their bouquet is often floral or fruity.
• This means they are used in food flavourings &
perfumes.
• Also, very good at dissolving organic compounds so
often used as solvents.
1
2
1
Some Esters and Their Names

Flavor/Odor
Raspberries
HCOOCH2CH3 ethyl methanoate (IUPAC)
ethyl formate (common)

Pineapples
CH3CH2CH2 COOCH2CH3
ethyl butanoate (IUPAC)
ethyl butyrate (common)
Organic Compounds Derived from
Carboxylic Acids (cont.)
• To name an ester, write the alkyl group
followed by the name of the acid with the
–oic acid ending replaced with –oate.
• Esters are polar molecules and many are
volatile and sweet smelling.
• Many esters are found in fruits and flowers.
Organic Compounds Derived from
Carboxylic Acids (cont.)
• An amide group is an organic compound
in which the –OH group of a carboxylic acid
is replaced by a nitrogen atom bonded to
other atoms.
Amides
In an amide, the -OH group in the carboxyl group of a
carboxylic acid is replaced by an Amino group (-NH2).

O O
CH3 — C—OH CH3 — C — NH2
Formation of Amides
O
RCO H
A carboxylic acid

O O
Heat
RC- OH H-NHR' RCNHR' + H2O
A carboxylic acid An Amine An amide

O O
CH3 C- OH + HHNCH2 CH3 CH3 C- NHCH2 CH3 + H2 O
Acetic acid Ethanamine N-ethylethanamide
Organic Compounds Derived from
Carboxylic Acids (cont.)
• The amide functional group is found
repeated many times in natural proteins
and some synthetic materials.
Condensation Reactions

• In a condensation reaction, two smaller

organic molecules combine to form a more
complex molecule, accompanied by the
loss of a small molecule such as water.
• Condensation reactions are elimination
reactions that form bonds between two atoms
not previously bonded.
Section 22.3 Assessment

Which of the following is the carbonyl

group?
A. COOH
B. C=O
C. CONH2 A. A
D. R-O-R′ B. B
C. C
D. D
Section 22.3 Assessment

Which of the following does NOT contain

a carbonyl group?
A. ketones
B. esters
C. amines A. A
D. aldehydes B. B
C. C
D. D