Chapter 6: Organohalogens

-Organohalogens are a class of compounds which has

halogens as the functional group.
-General formula: CnH2n+1X
There are 5 major classes:
1. Alkyl halide: compound which has an X atom bonded
to one of the sp3 hybrid C atoms of an alkyl grp.
2. Vinyl halide: compound which has an X atom bonded
to one of the sp2 hybrid C atoms of an alkene.
3. Aryl halide: compound which has a X atom bonded to
one of the sp2 hybrid C atoms of an aromatic ring
Examples:

H H I
H H
H C C Br C C
H H H Cl
alkyl halide vinyl halide aryl halide

Chloroethane chloroethene p-dichlorobenzene

Iodomethane benzyl chloride 1-chloro-2-butene

More Examples:

Alkyl Halide
H
CH3I CH3CH2Cl
R-C-X iodomethane chloromethane

Vinyl Halide Br
H H
CH2=CHCl CH3CH=CCH3
C=C
H H chloroethene 2-bromo-2-butene

Aryl Halide

Br Cl Cl
x bromobenzene
p-dichlorobenzene

Nomenclature

A. Common Name and Trivial Names

 constructed by naming the alkyl grp followed by the
halide, i.e isopropyl bromide. (origin of term alkyl
halide).
 suitable for simple alkyl halides.
 trivial names are also similar to common names. Trivial
names are names which are not clearly related to their
structures. Examples:

 CH2Cl2 is methylene chloride (IUPAC: dichloromethane)

 CHCl3 is chloroform (IUPAC: trichloromethane)
 CCl4 is carbon tetrachloride (IUPAC:
tetrachloromethane)

B. IUPAC
 Named as haloalkane
 Choose the longest carbon chain, even if the halogen is
not bonded to any of those C’s
 Use lowest possible C atom numbers for the position of
halide.
 Examples:
CH3 CH CH2CH3 CH3
Cl CH3 CH CH2F
Common: sec-butyl chloride isobutyl fluoride
IUPAC : 2-chlorobutane 1-fluoro-2-methylpropane

Common: cyclohexyl iodide Common: n-butyl chloride

IUPAC: iodocylohexane IUPAC: 1-chlorobutane
 Classes of Alkyl Halides

There are 4 classes according to the nature of the C atom

bonded to the halogen:
1. Methyl halides: only one C, CH3X
2. Primary: C to which X is bonded has only one C-C
bond [R-CH2-X]
3. Secondary: C to which X is bonded has two C-C
bonds [R2CH-X]
4. Tertiary: C to which X is bonded has three C-C
bonds [R3C-X]

Examples:

CH3I (1oC) CH3CH2CH2F (2oC)

IUPAC: Iodomethane 1-fluoropropane
Common: methyl bromide n-propyl fluoride

I
CH3CHCH2CH3 (CH3)3CCl

IUPAC: 2-iodobutane 2-chloro-2-methylpropane

Common: sec-butyl iodide t-butyl chloride

-There is another class of halides whereby 2 halogen

atoms attached to the molecule.

Br
Br Br
R-C-R H C C H
Br H H
geminal dibromide vicinal dibromide
 PHYSICAL PROPERTIES

a. Boiling Point
-There are 2 intermolecular forces which influence b/pt,
VdW forces and dipole-dipole attractions.
-VdW are surface attractions in which molecules with
large surface area have larger VdW forces, hence higher
b/pt.
-Dipole-dipole attraction arise from polar C-X bond also
affect b/pt but only very little.

-B/pt. is proportional to the increase of MW. ( MW, B/pt)

-B/pt increase by the order of F < Cl < Br < I.
-B/pt of alkyl halides with one halogen atom increase with
increasing length of parent C chain. Examples:
CH3Cl < CH3CH2Cl < CH3CH2CH2Cl
B/pt -24oC 12oC 47oC

- Increase in branching is inversely proportional to b/pt.

( branching, B/pt).

b. Density & Solubility

-All alkyl fluoride and alkyl chloride (R with only one
atom) are less dense than water.
-alkyl chloride with more than 2 atoms of Cl, alkyl
bromide and alkyl iodide are more dense than water.
-All alkyl halide are not miscible in aqueous but
dissolve/miscible in non-polar organic solvent i.e ether,
benzene, chloroform.
 Preparation Of Alkyl Halides

-There are 4 main methods to prepare alkyl halides;

1. Free-radical halogenation of alkanes
2. Halogenation of Alkenes & Alkynes
3. Alkyl Halide from Alcohol
4. From Other Halides

A. Free-radical Halogenation of Alkanes

-General eqn:
hv
RH X2 RX HX
alkyl halide
-It is a rarely effective method of alkyl halide synthesis
cause produces too many mixtures of products. Example:
hv
CH4 X2 CH3Cl CH2Cl2 CHCl3

CCl4 HCl
-In laboratory, this rxn can be performed to only
specialized compounds that give a single major product.
Examples:

H H
H Cl
hv
Cl2

chlorocyclohexane

CH3 CH3
hv
H 3C H Cl2 H3C Br
CH3 CH3
t-butyl bromide
-The above rxns are possible for both starting material
cause all the H in cyclohexane are equivalent and there is
only one 3o C atom in isobutane.

B. Halogenation of Alkenes
I. Addition of acids of halogens to alkenes
General Eqn.:

-This rxn follows the Markonikov rule.

Example:

II. Addition of halogens to Alkenes

General Eqn:

CCl4

Example:

CCl4
- This rxn produce vicinal alkyl halides.
III. Allylic Bromination (by using NBS)
-In 1942, Karl Ziegler found that alkenes react with N-
bromosuccinimide (NBS) to give allyl halide with the X
atom bonded to the C adjacent to C of C=C.

General Eqn:

-The result is that the rxn is highly selective, with only the
most stable radical being formed.
Example:
O

H H N Br Br
O
O
N H
hv, CCl4
H 3-bromocyclohexene O
(85%)
-Allylic halogenation can also occur under high
temperature. Example:
Cl

400oC HCl
Cl2

allylic
hydrogens
H H H Br
allylic
positions hv
Br2 HBr

H H

3-bromocyclohexene

Mechanism of Rxn:

H H H H
H Br
H
Br Br-Br
Br-H Br
H H H

-Abstraction of the allylic hydrogen by halogen radical will

give an allylic radical which is stabilized by resonance.
C. Alkyl Halide From Alcohol
-This is the most common and easiest method to prepare
alkyl halide.
-Involves rxn of tertiary alcohol with acid of halogens.
-Reactivity of rxn by different alcohols are as below:

3o > 2 o > 1o
General Eqn:
HX (X = Cl, Br or I)
ROH R-X H2O
H2SO4
Example:

HO CH3 Cl CH3
HCl (gas)
H2O
Ether, 0oC

1-methylcyclohexanol 1-chloro-1-methylcyclohexane
90%
-Alkyl halides synthesized from 2oC and 3oC alcohol via
reagents thionyl chloride (SOCl2) or phosphorus
tribromide (PBr3).
Examples:
a. O P(OH)3
PBR3
ether, 35oC CH2Br
O 2-(bromomethyl)-tetrahydrofuran

SOCl 2
CH2OH
O HCl SO2

CH2Cl
b.
OH 2-(chloromethyl)-tetrahydrofuran
OH
PBr3
CH3CH 2CHCH3 CH3CH2CHCH3 P(OH)3
ether, 35oC
2-bromobutane (86%)
Questions:
Give the reaction equation for the formation of each alkyl
halide below by free-radical halogenation.
1. 1-chloro-2,2-dimethylpropane
2. 2-bromo-2-methylbutane
3. 1-bromo-1-phenylbutane

Answers

1. CH3 CH3
hv
H3 C C CH3 Cl2 H3C C CH2Cl
CCl 4
CH3 CH3

2. CH3 CH3
hv
Br2 H3C C Br
H3C C H
CCl4
CH2CH3 CH2 CH3
O
3. N-Br
Br
O
CH2CH2CH2CH3 CHCH 2CH2CH3
hv, CCl4
D. From Other Alkyl Halides
General Eqn
acetone
R-X -
I R-I X-
Example:
acetone
H2C=CHCH2Cl NaI H2C=CHCH2Cl
allyl chloride allyl iodide