General

Organic Chemistry
Two credits
Second Semester 2009

King Saud bin Abdulaziz University for Health Science

Reference Book: Organic Chemistry: A Brief Course,

by Robert C. Atkins and Francis A. Carey
Third Edition

Instructor: Rabih O. Al-Kaysi, PhD.

 Lecture 9

Chapter 3

Alcohols and Alkyl

Halides
Functional Groups
 Functional Group

a structural unit in a molecule responsible for its

characteristic behavior under a particular set of
reaction conditions
 Families of organic compounds
and their functional groups

Alcohol ROH
Alkyl halide RX (X = F, Cl, Br, I)
IUPAC Nomenclature
of Alkyl Halides
 IUPAC Nomenclature

There are several kinds of IUPAC nomenclature.

The two that are most widely used are:
functional class nomenclature
substitutive nomenclature

Both types can be applied to alcohols and

alkyl halides.
Functional Class Nomenclature of Alkyl Halides

Name the alkyl group and the halogen as

separate words (alkyl + halide)

CH3F CH3CH2CH2CH2CH2Cl

CH3CH2CHCH2CH2CH3 H
Br I
Functional Class Nomenclature of Alkyl Halides

Name the alkyl group and the halogen as

separate words (alkyl + halide)

CH3F CH3CH2CH2CH2CH2Cl
Methyl fluoride Pentyl chloride

CH3CH2CHCH2CH2CH3 H
Br I

1-Ethylbutyl bromide Cyclohexyl iodide

 Substitutive Nomenclature of Alkyl Halides

Name as halo-substituted alkanes.

Number the longest chain containing the

halogen in the direction that gives the lowest
number to the substituted carbon.

CH3CH2CH2CH2CH2F CH3CHCH2CH2CH3

Br

CH3CH2CHCH2CH3

I
 Substitutive Nomenclature of Alkyl Halides

Name as halo-substituted alkanes.

Number the longest chain containing the

halogen in the direction that gives the lowest
number to the substituted carbon.

CH3CH2CH2CH2CH2F CH3CHCH2CH2CH3
1-Fluoropentane Br

CH3CH2CHCH2CH3 2-Bromopentane

I 3-Iodopentane
Substitutive Nomenclature of Alkyl Halides

Cl Halogen and alkyl groups

are of equal rank when
it comes to numbering
the chain.
CH3
Number the chain in the
CH3 direction that gives the
lowest number to the
group (halogen or alkyl)
Cl that appears first.
Substitutive Nomenclature of Alkyl Halides

Cl

5-Chloro-2-methylheptane

CH3

CH3

2-Chloro-5-methylheptane
Cl
IUPAC Nomenclature
of Alcohols
 Functional Class Nomenclature of Alcohols

Name the alkyl group and add "alcohol" as a

separate word.

CH3CH2OH CH3

CH3CCH2CH2CH3

CH3CHCH2CH2CH2CH3 OH

OH
 Functional Class Nomenclature of Alcohols

Name the alkyl group and add "alcohol" as a

separate word.

CH3CH2OH CH3
Ethyl alcohol CH3CCH2CH2CH3

CH3CHCH2CH2CH2CH3 OH

OH 1,1-Dimethylbutyl
alcohol
1-Methylpentyl alcohol
 Substitutive Nomenclature of Alcohols

Name as "alkanols." Replace -e ending of alkane

name by -ol.
Number chain in direction that gives lowest number
to the carbon that bears the —OH group.

CH3CH2OH CH3

CH3CCH2CH2CH3

CH3CHCH2CH2CH2CH3 OH

OH
 Substitutive Nomenclature of Alcohols

Name as "alkanols." Replace -e ending of alkane

name by -ol.
Number chain in direction that gives lowest number
to the carbon that bears the —OH group.

CH3CH2OH CH3
Ethanol CH3CCH2CH2CH3

CH3CHCH2CH2CH2CH3 OH

OH 2-Methyl-2-pentanol
2-Hexanol
Substitutive Nomenclature of Alcohols

OH
Hydroxyl groups outrank
alkyl groups when
it comes to numbering
CH3 the chain.
Number the chain in the
CH3
direction that gives the
lowest number to the
carbon that bears the
OH OH group
Substitutive Nomenclature of Alcohols

OH

6-Methyl-3-heptanol

CH3

CH3

5-Methyl-2-heptanol
OH
Classes of Alcohols
and Alkyl Halides
 Classification

Alcohols and alkyl halides are classified as

primary
secondary
tertiary
according to their "degree of substitution."

Degree of substitution is determined by counting

the number of carbon atoms directly attached to
the carbon that bears the halogen or hydroxyl group.
 Classificatio
n
H
CH3CH2CH2CH2CH2F OH
primary alkyl halide
secondary alcohol

CH3
CH3CHCH2CH2CH3 CH3CCH2CH2CH3

Br OH
secondary alkyl halide tertiary alcohol
Bonding in Alcohols
and Alkyl Halides
 Dipole Moments

alcohols and alkyl halides are polar

H δ + H
H
H H
δ + δ + δ –
C Oδ – C Cl

H H
µ = 1.7 D µ = 1.9 D
 Dipole-Dipole Attractive Forces

δ + δ – δ + δ – δ + δ – δ + δ –

δ – δ +
 Dipole-Dipole Attractive Forces

δ + δ – δ + δ – δ + δ – δ + δ –

δ – δ +
 Physical Properties of
Alcohols and Alkyl Halides:
Intermolecular Forces

Boiling point
Solubility in water
Density
 Effect of Structure on Boiling Point

CH3CH2CH3 CH3CH2F CH3CH2OH

Molecular 44 48 46
weight

Boiling -42 -32 +78

point, °C
0 1.9 1.7
Dipole
moment, D
Just for general knowledge, will not be tested on
 Effect of Structure on Boiling Point

CH3CH2CH3
Molecular 44 Intermolecular forces
weight are weak.

Boiling -42
Only intermolecular
point, °C forces are induced
0 dipole-induced dipole
Dipole attractions.
moment, D
Just for general knowledge, will not be tested on
 Effect of Structure on Boiling Point

CH3CH2F
Molecular 48 A polar molecule;
weight therefore dipole-dipole
and dipole-induced
Boiling dipole forces contribute
-32
point, °C to intermolecular
attractions.
Dipole
1.9
moment, D
Just for general knowledge, will not be tested on
 Effect of Structure on Boiling Point

CH3CH2OH
Molecular 46 Highest boiling point;
weight strongest intermolecular
attractive forces.
Boiling +78
point, °C Hydrogen bonding is
stronger than other
Dipole dipole-dipole attractions.
1.7
moment, D
Just for general knowledge, will not be tested on
 Hydrogen bonding in ethanol

δ –
δ +

δ +
δ –

Just for general knowledge, will not be tested on

 Boiling point increases with increasing
number of halogens

Compound Boiling Point

CH3Cl -24°C
CH2Cl2 40°C
CHCl3 61°C
CCl4 77°C
Even though CCl4 is the only compound in this list without a
dipole moment, it has the highest boiling point.
Induced dipole-induced dipole forces are greatest in
CCl4 because it has the greatest number of Cl atoms.
Cl is more polarizable than H.
But trend is not followed when halogen
is fluorine

Compound Boiling Point

CH3CH2F -32°C
CH3CHF2 -25°C
CH3CF3 -47°C
CF3CF3 -78°C

Just for general knowledge, will not be tested on

 But trend is not followed when halogen
is fluorine

Compound Boiling Point

CH3CH2F -32°C
CH3CHF2 -25°C
CH3CF3 -47°C
CF3CF3 -78°C
Fluorine is not very polarizable and induced dipole-
induced dipole forces decrease with increasing
fluorine substitution.
Just for general knowledge, will not be tested on
 Solubility in water

Alkyl halides are insoluble in water.

Methanol, ethanol, isopropyl alcohol are

completely miscible with water.

The solubility of an alcohol in water

decreases with increasing number of
carbons (compound becomes
more hydrocarbon-like).
 Hydrogen Bonding Between Ethanol
and Water

δ +

δ –
δ +
δ – δ +

δ –

Just for general knowledge, will not be tested on

 Density

Alkyl fluorides and alkyl chlorides are

less dense than water.

Alkyl bromides and alkyl iodides are

more dense than water.

All liquid alcohols have densities of

about 0.8 g/mL.
Preparation of Alkyl Halides from
Alcohols and Hydrogen Halides

ROH + HX → RX + H2O
 Reaction of Alcohols with Hydrogen Halides

ROH + HX → RX + HOH

Hydrogen halide reactivity

HF HCl HBr HI

least reactive most reactive

 Reaction of Alcohols with Hydrogen Halides

ROH + HX → RX + HOH

Alcohol reactivity

CH3OH RCH2OH R2CHOH R3COH

Methanol Primary Secondary Tertiary

least reactive most reactive

 Preparation of Alkyl Halides
25°C
(CH3)3COH + HCl (CH3)3CCl + H2O
78-88%

80-100°C
OH + HBr Br + H2O

73%