CHAPTER

6 Haloalkanes and Haloarenes

PCl5 NaBr+H2SO4
H3C–CH2—OH H3C–CH2—OH

PCl3 HI
3H3C–CH2—OH H3C–CH2—OH
KI/H3PO4
Red P + Br2
3H3C–CH2—OH Cl2/hv
CH3–CH3
PREPARATION

SOCl2
H3C–CH2—OH
CH 3–CH 2–X HBr
CH2=CH2
H3C–CH2—OH SOCl2 (X=F,Cl,Br,I) CCl4
(SN2)

N
H3C–CH2–COAg Br2 NaI H3C–CH2—Cl
O
(Hunsdiecker Reaction)
CCl4 Acetone (Finkelstein Reaction)

HCl/ZnCl2 AgF or Hg2F2 H3C–CH2—Cl

H3C–CH2—OH (Swart reaction)
Lucas Reagent

NBS
H3C–CH=CH2 BrH2C–CH=CH2
(allylic substitution) CCl4

CH3–CH2–CH2–Br
 or

PHYSCIAL PROPERTIES
(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
Br Br

(4) Density: n–C3H7Cl < n–C3H7Br < n–C3H7I

(5) Solubility → slightly soluble in water

+
CHO
, KOH

14 JEE (XII) Module-2 PW

 Wurtz-Fitting Reaction

(A) Reactivity toward Nucleophile (B) Boiling point

F Cl Br I
F Cl Br I
(i) > > >
(i) > > >
Cl Cl Cl
NO2 NO2 NO2 NO2 Cl
(ii) > >
Cl
Cl Cl Cl Cl
NO2 NO2 O2N NO2 (C) Melting point
(ii) > > Cl Cl Cl
Cl
NO2 NO2 (i) > >
Cl
Cl

P
W Haloalkanes and Haloarenes 15