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)
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)
2
RMgX + H2C=O H2C=O H2C-OH + MgX(OH)
Alcohol
R MgX R
2
RMgX + RCH=O RCH=O RCH-OH + MgX(OH)

R MgX R
2
RMgX + RRC=O RRC=O RRC-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) CCl 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
substitution
+alcoholic KCN CH2CN

+alcoholic NH3 CH2NH2

CH2Cl 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

CHF2Cl
2 +
+ O3 + O2 NO + O3 NO2 + O2
+ O + 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)