1

Haloalkanes Haloarenes
halogen derivatives of hydrocarbons aromatic halogen compounds in which
containing alkanes with general formula halogen is directly attached to aromatic
CnH2n+1 are known as alkyl halides ring are known as aryl halides
denoted as R-X

X
Where X = F, Cl, Br, or I and R is an alkyl
group such as C2H5Cl haloarene
Classification of Haloalkanes/Haloarenes
(i) Monohaloalkane (one halogen
atom) {C2H5X}
on the basis of (ii) Dihaloalkane (two halogen atoms)
number of halogen
{XH2C-CH2X}
atoms
(iii) Trihaloalkane (three halogen atoms)
{XH2C-CHX-CH2X}
(haloalkane/
haloarene)

(i) Haloalkane/alkyl halide {R-X}

−

halogen attached with 1◦, 2◦ or 3◦C

compounds (ii) Allylic halides (halogen attached with C
containing sp3
→

C-X bond adjacent to C=C bond)

2

(iii)Benzylic halides (halogen attached with C

+

attached to aromatic ring

(aliphatic/
aromatic)
−

(i) Vinyl halides (halogen bounded to sp2-C of

compounds C=C)
containing sp2
C-X bond (ii) Aryl halides (halogen directly bonded to
sp2-C of aromatic ring 3
 H2C X
H2C X
CH X
H3C CH2 X CH2 X
H2C X
Monohaloalkane Dihaloalkane Trihaloalkane

X
X X
X

H CH CH3
H3C X3 X
HMonohaloarene H3C C
3C C Cl C
DihaloareneCl Trihaloarene
H H Cl CH3

Primary (10) Secondary (20) Tertiary (30)

alkyl halide alkyl halide alkyl halide
 CH2 Cl Cl
Cl

CH2 Cl
Allylic halide Benzylic halides
Vinyl halide Aryl halide

R R
R
C C CH2
R R
R
3
sp carbon sp2 carbon
*carbon atom bound to four atoms *carbon atom bound to three atoms
*have all four single bonds *have two single bonds & one
double bond
 Nomenclature Choose the longest carbon chain
of Haloalkanes (having maximum number of carbon
(These are the
atoms).
rules to be
followed)
Rule 2- Prioritize functional group (then
triple bond and double bond).
Rule 3- Give priority to halogen atoms (if
two halogen atoms are at both ends, then
priortize according to their alphabetical
order).

CH3
3 2 1 1 2 3 3 1
H3C CH2 CH2 Br H3C CH CH3 H3C HC CH2 Cl
2
Cl
IUPAC name 1-bromopropane 2-chloropropane 1-chloro-2-methyl-
propane
Common name n-propyl bromide isopropyl bromide isobutyl bromide

6
 Br Br
1 1
2 2
5
Br Br
3 Br 3 Br
4
IUPAC name bromobenzene 1,3-dibromobenzene 1,3,5-tribromobenzene

Common name bromobenzene m-dibromobenzene sym-tribromobenzene

CH3 Cl 1 2
3 1 2
H3C C CH2 Cl
1 H2C CH2
H3C CH
2 Cl Cl
CH3 Cl

1-chloro-2,2-dimethyl 1,1-Dichloroethane 1,2-Dichloroethane

IUPAC name
propane
ethylene chloride ethylene dichloride
Common name (gem-dihalide) (vic-dihalide)
 Preparation of Haloalkanes

1. From alcohols
H3C OH catalyst H3C Cl
CH2 + H Cl
(Conc.)
CH2
+ H2O
Ethanol Choloroethane

CH3 CH3
Room
H3C C OH + H Cl temp. H3C C Cl + H2O
(Conc.)
CH3 CH3
tert-butyl chloride
tert-butyl alcohol
H3C CH3
CH
H3C CH OH
+ SOCl 2 + SO 2 + H Cl

CH3 Thionyl Cl
Isopropyl chloride Isopropyl
alcohol chloride

8
 H3C CH3
H3C CH OH SOBr 2 CH
+ SO 2 +H Cl
CH3 Thionyl
Br
Isopropyl bromide
Isopropyl
alcohol bromide
H3C CH2 OH + PCl 5 H3C CH2 Cl + POCl 3 + H Cl

phosphorous Choloroethane phosphorous

Ethanol
pentachloride oxychloride

3R OH
+ PX3 3R Cl + H3PO 3 (X= Cl, Br)
R is an alkyl
phosphorous orthophosphoric
group
trihalide acid
Δ
H3C CH2 OH + KI + H3PO 3 H3C CH2 I + H2O

Ethanol hydrogen Iodoethane

iodide

H3C CH2 OH + NaBr H3C CH2 Br + NaHSO 4 + H2O

Ethanol sodium
bromide bromoethane sodium hydrogen
sulfate
9
2. From hydrocarbons

a) From alkanes: Cl Cl
Cl2/hν
H3C CH2 CH2 CH3 H3C CH2 CH2 CH2 + H3C CH2 CH CH3

Butane 1-chloro-butane 2-chlorobutane

b) From alkenes:
H2C CH2 H3C Br
+ H Br
CH2
Ethene bromoethane
H3C CH3 CH2 Cl
H3C CH
CH CH + H Cl
2-chlorobutane
but-2-ene CH3

H3C H3C H3C

CH CH2
+ H Br CH CH3
+ CH2 CH2 Br
propene Br 1-bromopropane
2-bromopropane 10
(major) (minor)
 Br Br
Br2/CCl4
H2C CH2 H2C CH2

Ethene 1,2-dibromoethane

Cl2/CCl4 Cl Cl
H3C CH CH2
H3C CH CH2
propene
1,2-dichloropropane

3. Halogen exchange
acetone
R X + Na I R I + Na X
(Finkelstein
(X= Cl, Br)
reaction)

H3C Br + Ag F H3C Br + Ag Br
(Swarts
reaction)
11
 Preparation of Haloarenes
1. From hydrocarbons by direct halogenation
CH3 Br2/hν CH2 Cl

Toluene (chloromethyl)benzene

CH3 CH3 CH3

Fe/dark
+ X2
X
+ X

Toluene p-halotoluene O-halotoluene

(X= Cl, Br)

FeCl3 Cl H Cl
+ Cl 2 +
Chlorobenzene
Benzene

HNO3 I
+ I2 + H I

Iodobenzene 12
Benzene
2. From amines by Sandmeyer’s reaction and Gattermann
reaction NH 2 N X 2
+ -

NaNO2 + HX
(X=Cl, Br)
273-278K
Benzene diazonium halide
Aniline
+
N2 X-
Cu2X2 X
+ N2 (Sandmeyer's reaction)
HCl
Aryl halide
+
N2 X-
KI I
+ N2

Iodobenzene

+
N2 Cl -
Cu/HCl Cl
+ N2
(Gattermann reaction)

Chlorobenzene 13
14