Chapter 5

Alcohols and Alkyl Halides:

Introduction to Reaction Mechanisms

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 Section 5.1

FUNCTIONAL GROUPS

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 Functional Groups-1
Alkanes are not generally considered to be
functional groups (although C–H bonds can be
reactive)
The multiple bonds in alkenes and alkynes are
considered functional groups
The six-membered rings consisting of sp2 hybridized
carbons in arenes are considered functional groups
In this chapter, we will focus on alcohols (ROH)
and alkyl halides (RX, X = F, Br, Cl, I)

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 Survey of Functional Groups

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 Survey of Functional Groups-1

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 Survey of Functional Groups-2

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 Section 5.2

IUPAC NOMENCLATURE OF
ALKYL HALIDES

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 Two Types of Nomenclature
There are two distinct types of nomenclature for
alkyl halides:
• Functional class nomenclature: the alkyl group is
treated as the “positive” portion of a halide salt

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 Two Types of Nomenclature-1
There are two distinct types of nomenclature for
alkyl halides:
• Functional class nomenclature: the alkyl group is
treated as the “positive” portion of a halide salt

• Substitutive nomenclature (preferred): the halogen is

treated as a “halo-” substituent on an alkyl chain

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 Two Types of Nomenclature-2
When the carbon chain bears both a halogen and
an alkyl substituent, the two are considered of
equal rank, and the chain is numbered so as to
give the lower number to the substituent nearer the
end of the chain.

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 Section 5.3

IUPAC NOMENCLATURE OF
ALCOHOLS

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 Two Types of Nomenclature-3
The two types of nomenclature we saw for alkyl
halides apply to alcohols as well:
• Functional class nomenclature: the alcohol is named as
an “alkyl alcohol”; the alkyl group is treated as a
substituent

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 Two Types of Nomenclature-4
The two types of nomenclature we saw for alkyl halides apply to
alcohols as well:
• Functional class nomenclature: the alcohol is named as an “alkyl
alcohol”; the alkyl group is treated as a substituent

• Substitutive nomenclature (preferred): the alcohol is named as an

“alkanol,” with a number before “alkan” or “ol” to denote the position
of the –OH group

Either the “n-alkanol” or “alkan-n-ol” names are acceptable.

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 Substitutive Nomenclature
When using the substitutive convention, it is
important that the parent chain includes the –OH or
–X substituent
For the purposes of numbering, the –OH group
takes precedence over halogen substituents and
alkyl groups

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 Alcohols that contain more than one
hydroxyl group

Alcohols containing two hydroxyl groups are

named –diols.
Alcohols containing three hydroxyl groups are
named –triols.
A number giving the position of each of the
hydroxyl groups is needed in these cases.

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 Section 5.4

CLASSES OF ALCOHOLS AND

ALKYL HALIDES

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 Substitution Pattern
Alcohols, alkyl halides, and other organic compounds are
often classified by substitution pattern
The key question is: how many alkyl groups are attached
directly to the carbon that bears the functional group?
• One alkyl group: primary (1 degree) Substitution pattern can
• Two alkyl groups: secondary (2 degree) profoundly affect the
• Three alkyl groups: tertiary (3 degree) reactivity of a carbon!

One attached alkyl group; Two attached alkyl groups;

Two implicit hydrogens Two implicit hydrogens

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 Substitution Pattern - 2
Alcohols, alkyl halides, and other organic compounds are
often classified by substitution pattern
The key question is: how many alkyl groups are attached
directly to the carbon that bears the functional group?
• One alkyl group: primary (1 degree) Substitution pattern can
• Two alkyl groups: secondary (2 degree) profoundly affect the
• Three alkyl groups: tertiary (3 degree) reactivity of a carbon!

Three attached alkyl Three attached alkyl

groups, no hydrogens. groups, no hydrogens.

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 Section 5.5

BONDING IN ALCOHOLS AND

ALKYL HALIDES

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 Hybridization, Geometry, and
Bonding
The carbon bonded to –OH or –X is sp3 hybridized and
tetrahedral
The C–O and C–X bonds are polarized toward the more
electronegative O or X atom
The carbon atom bonded to O or X is partially positive

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 Dipole Moments
Because the C–O and C–X bonds are polarized,
alcohols and alkyl halides are polar!
Dipole moments are comparable to that of water
Note the direction of the dipole vector and the
implied partial charges on C, O, and X

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 Electrostatic Potential Maps
In both compounds, the
heteroatom bears
significant negative charge
In methanol, the O–H
hydrogen bears most of
the positive charge

In chloromethane, the
nearby C–H hydrogens
bear most of the positive
charge
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 Section 5.6

PHYSICAL PROPERTIES OF
ALCOHOLS AND ALKYL HALIDES:
INTERMOLECULAR FORCES
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 Dipolar Forces
Alcohols and alkyl halides are polar. Hence, their
molecules engage in dipole-dipole and dipole-induced
dipole forces
These forces are much stronger than London forces,
and cause the boiling and melting points of alkyl halides
and alcohols to be higher than those of alkanes

Why is the boiling point of ethanol abnormally high?

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 Hydrogen Bonding
Alcohols contain a highly polarized O–H bond, which can
engage in a special type of dipole-dipole interaction called
a hydrogen bond
The partially negative O on one molecule is attracted to the
partially positive H on another

Hydrogen bonding occurs only in compounds containing

O–H or N–H bonds
Hydrogen bonds are directional—they involve a small
degree of electron sharing
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 Hydrogen Bonding - 2

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 Boiling Points
Boiling point increases with molecular weight.

TABLE 5.2 Boiling Point of Some Alkyl Halides and Alcohols

Substituent X and boiling point, °C (1 atm)
Name of alkyl group Formula X=F X = Cl X = Br X=I X = OH
Methyl CH3X −78 −24 3 42 65
Ethyl CH3CH2X −32 12 38 72 78
Propyl CH3CH2CH2X −3 47 71 103 97
Pentyl CH3(CH2)3CH2X 65 108 129 157 138
Hexyl CH3(CH2)4CH2X 92 134 155 180 157

Boiling points of alcohols are As polarizability of the halogen

quite high due to hydrogen increases, boiling point
bonding. increases.
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 Polarizability
The ability of the electron cloud around an atom to
distort its shape is called polarizability
Polarizability is greater for larger halogens; greater
polarizability means a larger boiling point

Alkyl fluorides show roughly the opposite trend—

fluorine is not very polarizable
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 Solubility
Alkyl halides are insoluble in water
Alcohols with low molecular weight (small
hydrocarbon portions) are soluble in water in all
proportions
Alcohols can hydrogen bond with water!

Alcohols with long alkyl

chains remain insoluble due
to the hydrophobic effect.

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 Section 5.7

PREPARATION OF ALKYL
HALIDES FROM ALCOHOLS
AND HYDROGEN HALIDES
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 Substitution Reactions
Alcohols and alkyl halides differ only in the group bound to
the alkyl group (–OH or –X)
A reaction that replaces –OH with –X or vice versa is called
a substitution reaction

Alkyl halides are valuable precursors to other organic

functional groups—they represent a synthetic “hub”
We will study this reaction to gain insight into reaction
mechanism and general principles of reactivity
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 Reactivity Trends
The reactivity of hydrogen halides parallels their acidity
HI > HBr > HCl > HF
too reactive too unreactive
The reactivity of alcohols depends on substitution pattern

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 Section 5.6

PHYSICAL PROPERTIES OF
ALCOHOLS AND ALKYL HALIDES:
INTERMOLECULAR FORCES
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 Reactivity Trends: Examples

Tertiary ROH react with HCl and HBr in minutes; secondary and
primary require HBr and elevated temperatures.

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 Structure and Properties
R-O-H portion of alcohol is similar to the structure
of water.
• The oxygen and two atoms bonded to it lie in the same
plane.
• The bond angle is 104°
Hydroxyl groups are very polar because of
significantly different electronegativities.
• Hydrogen bonding can form between alcohol
molecules.

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 Hydrogen Bonding

+
O
+ H
−
H
H O
−
R O
R
+ H

− O
H
H
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 Results of Hydrogen Bonding
Alcohols boil at much higher temperatures than
hydrocarbons of similar molecular weight.
Alcohols with fewer than five carbons are very
soluble in water.
Alcohols with five to eight carbons are moderately
soluble in water.
As the nonpolar (R) portion of the alcohol gets
larger, the water solubility decreases.

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 Solubility of Alcohols
Very large alcohols are not soluble in water.
Hydrophobic – “water fearing”; used to describe
nonpolar region of molecule
Hydrophilic – “water loving”; used to describe polar
region of molecule

CH3CH2CH2CH2CH2CH2CH2CH2CH2OH

Hydrophobic Hydrophilic
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 Solubility of Alcohols
An increase in the number of hydroxyl groups will
increase the influence of the polar hydroxyl group.
• Diols and triols are more water soluble
than alcohols with only a single hydroxyl
group.

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 Section 5.6

IMPORTANT ALKYL HALIDES AND

ALCOHOLS

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 Section 5.6

IMPORTANT ALKYL HALIDES AND

ALCOHOLS

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