CHAPTER

10 Haloalkanes and Haloarenes

Preparation of Alkyl Halides

PCl5 NaBr + H2SO4

(3ºAlkene)
(3ºAlkene)
H3C—CH2—OH H3C—CH2—OH

PCl3 HI
3H3C—CH2—OH H3C—CH2—OH
KI/H3PO4
Red P + Br2 NBS H3C—CH=CH2
3H3C—CH2—OH
PREPARATION

CCl4 (allylic substitution)

SOCl2 CH3—X
H3C—CH2—OH Cl2/h
CH3—CH3
SOCl2 CH3—CH2—X
H3C—CH2—OH R—X HBr
CH2=CH2
(SN2) (X=F, Cl, Br, I) CCl4
N NaI H3C—CH2—Cl
H3C—COAg Br2
Acetone (Finkelstein Reaction)
O CCl4
(Hunsdiecker Reaction)
HCl/ZnCl2 AgF or Hg2F2 H3C—CH2—Cl
H3C—CH2—OH Lucas Reagent (Swarts reaction)

Br HBr HBr Br
—
—

H3C—CH2—CH2 Peroxide CCl4 H3C—CH—CH3

H
— —

H Br2/800K HCl Cl
—

Br—C—C=C — — H3C—CH=CH2

—

H H3C—CH—CH3
H H
Br NBS Br2/CCl4 H3C—CH—CH2—Br
—

CH2—CH=CH2 CCl4 Br
Chemical Reactions of Alkyl Halides

Nucleophilic substituion
CH3—X
(Reactivity order)
SN 1 : 3 > 2 > 1 CH3—CH2—X (R—I > R—Br > R—Cl > R—F)
RX – –
SN 2 : 1 > 2 > 3 Ambident Nucleophile:- CN, O—N=O
(X=F, Cl, Br, I)
NaI –
H3C—CH2—I OH
Acetone H3C—CH2—OH
Na Aq KOH
(C2H5)2CuLi Wurtz Moist Ag2O
H3C—CH2—CH2—CH3 reaction H3C—CH2—CH2—CH3

Reaction with metal

Et2O KCN
Corey house synthesis H3C—CH2—CN
NH3 EtOH
H3C—CH2—NH2 excess Br AgCN + –

– + Wurtz-Fitting H3C—CH2— N C
H—C CNa Reaction H3C—CH2 + –
H3C—CH2—CC—H Na/Et2O K O N=O
H3C—CH2—O—N=O
LiAlH4/Et2O Mg/Et2O O
H3C—CH2—H Ag—O—N=O
(l  2º not 3º R—X)
C2H5MgBr H3C—CH2—N
NaBH4/EtOH, 2º & 3º not 1ºR—X Alc. KOH AlCl3 O
H2C=CH2 CH2—CH3
O NaNO F.C. Alkylation
2 Alc. NaSH
H3C—CH2—N
DMF H3C—CH2—SH
O
CH3SNa RMgX
C2H5—O—C2H5 H3C—CH2—CH3 – R—R
– +
(R—Br  1º) H3C—CH2 ONa RCOO
RCOOCH3

Physical Properties of Alkyl Halides

(1) Dipole moment: CH3–Cl > CH3–F > CH3–Br > CH3–I
(2) Bond enthalpies: CH3–F > CH3–Cl > CH3–Br > CH3–I
(3) Boiling point: R–I > R–Br > R–Cl > R–F

> >
Br
BrBr
(4) Density: n–C3H7Cl < n–C3H7Br < n–C3H7I
(5) Solubility → slightly soluble in water

30 NEET (XII) Module-3 PW

Chemical Reactions of Haloarene (Chlorobenzene)
Cl Cl
Cl Cl Cl
Conc. HNO3 + Conc. H2SO4 Cl2/FeCl3
NO2 (ESR) (ESR)
+
+
Cl
NO2
Cl
Cl Cl
Ph—Br
H3 C CH3Cl Na/Et2O
+ AlCl3 Fittig Reaction
(ESR)

CH3
CH3
CH3Br
Cl O Cl
O Na/Et2O
C
CH3 + H3C—C—Cl Wurtz-Fittig Reaction
AlCl3 (ESR) NH2
Cl
C NaNH2
—

O CH3 liq. NH3

ArSN
H OH
—

Cl
CCl3—C=O
CCl3—C (1) NaOH.623K, 300 atm.
Conc. H2SO4 (ESR)
—

H Cl (2) H 
DDT
(Dichloro diphenyl trichloro ethane) Cl O-H

(NSR)
O2 N NO2 O2 N NO2
Ni-Al H2 O
NaOH warm

NO2 NO2
Cl Cl
SO3H Conc. H2SO4
+  (ESR)

SO3H
Reactivity of Haloarenes Towards Nucleophile Physical Properties of Haloarenes
F Cl Br I (A) Boiling Point
F Cl Br I
(i) > > >
(i) > > >
NO2 NO2 NO2 NO2
Cl Cl Cl Cl Cl Cl
NO2 NO2 O 2N NO2 Cl
(ii) > > (ii) > >
Cl
NO2 NO2 Cl

P
W Haloalkanes and Haloarences 31
(B) Melting Point
Cl Cl Cl
Cl
(i) > >
Cl
Cl

Preparation and Chemical Reactions of Trichloro-Methane

O OH
O2 Cl

—
Cl2 + NaOH
CH3—C—R or H3C—CH—H O=C —+ HCl
or NaOCl Light Cl
(Haloform test)
HNO3
O Cl3C—NO2
CaOCl2 (Chloropicrin) (tear gas)
Preparation

Reaction
H3C—C—CH3 Ag
Bleaching powder
HCC—H

OH O
O
NaOH CHCl3 C
Cl3C—C—H – NaOH H
H—C—O Na Chloroform
O OH
Reimer Tiemann
Fe/HCl reaction
CCl4
+ –
3Cl2/h CH3NH2/KOH CH3—NC
CH4
(Test of Primary amine)

32 NEET (XII) Module-3 PW