Topic 16 : Haloalkanes SMK Sacred Heart, Sibu

ROH + PX5 → RX + HX + POX3

1. Alkylhalides, RX
ROH + SOCl2 → HCl + RCl + SO2
RX → ROH + NaX
Hydrolysis
RXRX → R(OH)R(OH)
𝑁𝑢− substitution, reflux

+ NaOH(aq) RX2 → → R=O + H2O +NaX

RX3 → → HO R=O + H2O +NaX

Formation of
+ ethanolic KCN → RCN + KX
Nitrite compound + 2H2O + H+ → RCOOH + NH4+
RCN
LiAlH4/ether
RCH2NH2
H3O+/∆
Formation of amines
RX + NH3 → R-NH2 + HX 1o
+ conc alcoholic NH3(aq) excess 4o
+excess R-X
3o
+excess R-X +excess R-X
2o R2NH R 3N

Elimination Ethanolic NaOH + HX

C C
Reflux
+2Li → RLi + LiX
4 C2H5Br + 4Pb(Na) → (C2H5)4Pb + 4NaBr + 3Pb
+Mg in dry ether
Alkanes
RMgX + HOH→ RH + MgX(OH)
RCOOH H3O+
RMgX RMgX + CO2 → RCO2MgX ∆
RCOOH + MgX(OH)
𝐻2 𝑂
RMgX + H2C=O → H2C=O H2C-OH + MgX(OH)
Alcohol
R MgX R
𝐻2 𝑂
RMgX + RCH=O → RCH=O RCH-OH + MgX(OH)

R MgX R
𝐻2 𝑂
RMgX + R’RC=O → R’RC=O R’RC-OH + MgX(OH)

R MgX R

Chemical Tests of Haloalkanes

A) NaOH(aq), ∆, dilute HNO3 , AgNO3(aq) B) Ethanolic AgNO3 solution, warm

R-X + NaOH + AgNO3 → R-OH + NaNO3 + AgX R-X + Ag+ + H2O→ R-OH + AgX + H+
R-Cl white ppt; R-Br cream ppt; R-I yellow ppt 1o RX – cloudiness after several
minutes
-Used to differentiate R-X from X 2 RX – cloudiness after 1 minute
o

and X 3o RX – cloudiness after a few minutes

Topic 16 : Haloalkanes SMK Sacred Heart, Sibu

2. Chlorobenzene (aryl halide) C–Cl bond in Cl is strong

+NaOH, 300oC, 200atm ONa +NaCl + H2O

+Mg in ether MgCl

Cl

+Cl2, dry AlCl3 Cl + Cl Cl

Conc HNO3, conc H2SO4, 55oC NO2

Conc H2SO4, ∆ SO3H
+RX, dry AlCl3 R
+RCOCl, dry AlCl3 COR

3. Chloromethylbenzene (aryl halide)

+NaOH(aq)
CH2OH
𝑁𝑢− substitution
+alcoholic KCN CH2CN
𝑟𝑒𝑓𝑙𝑢𝑥
+alcoholic NH3 CH2NH2

CH2Cl 𝑅 ⦁ substitution
+Cl2, UV light
CHCl2
KMnO4/H+
COOH

Cl

+Cl2, dry AlCl3 CH2Cl + Cl CH2Cl

Conc HNO3, conc H2SO4, 55oC NO2

Conc H2SO4, ∆ SO3H
+RX, dry AlCl3 R
+RCOCl, dry AlCl3 COR

4. Uses of haloalkanes
Fluoro alkane Non sticking coating for cookwares
Chloroalkane DDT (Insectiside)
Chlorofluoroalkane Aerosol propellants, solvents, coolants, fire extinguishers
𝑈𝑉
CHF2Cl ⦁
𝐶𝐻𝐹2 + 𝐶𝑙⦁
𝐶𝑙 ⦁ + O3 → 𝐶𝑙𝑂⦁ + O2 NO + O3 → NO2 + O2
𝐶𝑙𝑂⦁ + O → 𝐶𝑙 ⦁ + O2 NO2 + O → NO + O2
O3 + O → 2O2 O3 + O → 2O2

EDG (Ortho and para activator)

Attached to benzene ring Halogen (Ortho and para activator)
EWG (meta activator)