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ALKYL HALIDES
INTRODUCTION
● Halogen derivatives of alkanes obtained by replacement
of one or more hydrogen atoms with halogen atoms
● General formula: CnH2n+1X
-H
● R-H R-X
+X
alkane haloalkane
Classification
On the basis of number of halogen atoms :
1. Mono Haloalkanes : With only one halogen atom. Simply
called haloalkanes.
For example, CH3 - Cl (Chloromethane), CH3- CH(Br)-CH3
(2-bromopropane) etc.
2. Dihaloalkanes : With two halogen atoms. They are of
different types as,
a. Vicinal(Vic-) dihalides : They contain two halogen
atoms on adjacent carbon atoms. Eg.
CH2Cl - CH2Cl (1,2-dichloroethane)
b. Geminal (gem-) dihalides : They contain two halogen
atoms on same carbon atoms. Eg.
CH3 - CHCl2 (1,1-Dichloroethane)
3. Polyhaloalkanes : With three or more halogen atoms. Eg.
CHCl3(Trichloromethane, Chloroform), CCl4
(Tetrachloromethane or Carbon tetrachloride) etc.
Classification of monohaloalkanes
● Primary haloalkane: Halogen atom is bonded to primary(10)
carbon atom.
Quaternary
carbon
NOMENCLATURE
● IUPAC SYSTEM: halo+alkane
Cl
CH3
CH3-C-Cl (2-chloro-2-methylpropane)
CH3
NOMENCLATURE
● COMMON SYSTEM: alkyl+halide
CH3
UV light
CH4 + Cl2 CH3Cl + HCl
Methane Chloromethane
● The reaction continues in excess of halogen until
all hydrogen atoms are replaced with halogen.
HNO3 or HIO3
CH3-CH3 + I2 CH3-CH2-I + HI
But,
HNO3 + HI H2O + NO2 + I2
CH3-CH=CH-CH3(But-2-ene) CH3-CH2-CH=CH2(But-1-ene)
Propene 1-Chloropropane
(Unsymmetrical alkene) ✔ (Minor)
CH3 - CH - CH3
Cl
2-Chloropropane
(Major)
● Explanation: The addition reaction of alkene is
electrophilic addition i.e. the positive part adds first to
give carbocation which then adds negative part to give
final product.During addition of positive part, the more
stable carbocation is formed(Stability order 30 >20 >10
carbocation) which then adds -ve part to give Markovnikov’s
product.
● 1st step:
+
CH3-CH2-CH2
+ 10 Carbocation
CH3-CH=CH2 + H
+
Propene
CH3-CH-CH3
20 Carbocation(More stable)
2nd step:
Br
+
CH3-CH-CH3 + Br - CH3-CH-CH3
More stable 2-bromopropane
carbocation (Markovnikov’s product)
PEROXIDE EFFECT
● It is applicable for addition of HBr to unsymmetrical
alkenes in presence of organic peroxides like benzoyl
peroxide.
ii. H-I bond easily breaks but iodine free radical too
reactive and combines to form iodine molecule.
For example,
Peroxide
CH3 - CH = CH2 + H-Br CH3 - CH2 - CH2 - Br
Propene
(Unsymmetrical alkene) 1-bromopropane
(Major)
No Peroxide Anti-Markovnikov’s
product
CH3 - CH - CH3
Br
2-bromopropane
(Minor)
Markovnikov’s product
(Without peroxide)
2. From alcohols:
a) Using phosphorus tri and pentahalides(PCl3 or PCl5)
Haloalkanes can be prepared by reacting alcohols with
phosphorus trihalides and pentahalides.(PBr5 or PI5 does
not exist.
Similarly,
P4 + 6I2 PI3
3CH3-CH2-OH + PI3 3CH3-CH2-I + H3PO3
b) Using thionyl chloride( SOCl2):
pyridine
R-OH + SOCl2 R-Cl + HCl + SO2
pyridine
CH3-CH2-OH + SOCl2 CH3-CH2-Cl + HCl + SO2
Ethanol Chloroethane
anhydrous ZnCl2
R-OH + HX R-X + H2O
alcohol haloalkane
CH3 CH3
CH3-C-OH + HCl CH3-C-Cl + H2O
CH3 CH3
2-methyl-propan-2-ol 2-chloro-2-methylpropane
Reactivity decreases
Cl OH
2-chloropropane Propan-2-ol
(isopropyl alcohol)
● Haloalkanes also produce alcohols by reacting with moist
silver oxide.
Ag2O + H2O 2AgOH
chloroethane ethanol
For example,
Conc. HCl
CH3-CH2-CN CH3-CH2-CO-NH2
propanenitrile Propanamide
(ethyl cyanide)
CONTD…
● Complete hydrolysis: On complete hydrolysis cyanides in
presence of dil.HCl, carboxylic acids are obtained.
O
dil. HCl
CH3-CH2-C≡N + 2H2O CH3-CH2-C-OH + NH4Cl
propanenitrile propanoic acid
LiAlH4
CH3-CH2-C≡N + 4[H] CH3-CH2-CH2-NH2
Propanenitrile 1-aminopropane
Answer the following question
1. How would you convert ethane to propanoic acid?
LiAlH4
● CH3-CH2-N C + 4[H] CH3-CH2-NH-CH3
N-methylaminoethane
Identify A and B in the following reactions
CH3
N,N-dimethyl aminomethane
CH3-CH2-CH=CH2
but-1-ene,
minor product(19%)
dry ether
R-X + Mg RMgX
alkyl magnesium halide
dry ether
CH3-Br + Mg CH3MgBr
methyl methylmagnesium bromide
bromide
2. Wurtz reaction:
On heating haloalkanes (alkyl halides) with sodium metal
in presence of dry ether, higher symmetrical alkanes (even
number) having double the carbon atoms than haloalkanes
are produced.
dry ether
R-X + 2Na + X-R R-R + 2NaX
haloalkane alkane
dry ether
CH3-Cl + 2Na + Cl-CH3 CH3-CH3 + 2NaCl
chloromethane ethane
● Q. Show similar reactions using bromoethane and
1-chloropropane.
CH3 CH3 CH3 CH3
dry ether
CH3-CH-I + 2Na + I-CH-CH3 CH3-CH-CH-CH3 + NaI
2-iodopropane 2,3-dimethylbutane
dry ether
R-X + 2Li RLi + LiX
alkyl lithium
dry ether
CH3-Cl + 2Li CH3-Li + LiCl
chloromethane methyl lithium
2R-X + Zn dry ether R2Zn + ZnX2
dialkyl zinc
dry ether
CH3-Cl + Zn (CH3)2Zn + ZnCl2
dimethyl zinc
REDUCTION REACTION
● Haloalkanes are reduced into corresponding alkanes when
reacted with reducing agents like Zn/HCl or LiAlH4.
Zn/HCl
CH3-Cl + 2[H] CH4 + HCl
chloromethane methane
Zn/HCl
CH3-CH2-Br + 2[H] CH3-CH3 + HBr
bromoethane ethane
USES OF HALOALKANES
O
Ca(OH)2 + 2CCl3-C-H 2CHCl3 + Ca(HCOO)2
chloroform calcium formate
USING ACETONE
● Step 1: The three α-hydrogen atoms of acetone are
replaced by Cl atoms from Cl2 to form trichloroacetone.
O O
CH3-C-CH3 + 3Cl2 CCl3-C-CH3 + 3HCl
acetone trichloroacetone
sunlight
2CHCl3 + O2 COCl2 + HCl
phosgene
(carbonyl chloride)
NH2 N C
OH OH
+
CHO
+ CHCl3 + 3KOH H + 3KCl + 3H2O
aq. (60-70)℃
salicyldehyde
Phenol
CONTD…
8. Reduction:
In presence of Zn/HCl, chloroform is reduced into
methylene chloride whereas reduction in presence of Zn/H20
produces methane.
Zn/HCl
CHCl3 + 2[H] CH2Cl2 + HCl
ethanol
methylene
chloride
Zn/H2O
CHCl3 +6 [H] CH4 + 3HCl
methane
CONTD…
9. Action with silver nitrate solution:
Pure chloroform does not react with aqueous AgNO3
solution. This is because C-Cl bond in chloroform is
covalent in nature and does not ionize to release free Cl-
ions. Due to this, no white ppt. of AgCl is formed.
CHCl3 + AgNO3 No reaction
𝚫
CH3-CH2-OH + NaOH + I2 CHI3 + NaI + H2O + HCOONa
Yellow crystalline
ppt. (hospital smell)
Similarly,
O
𝚫
CH3-C-CH3 + NaOH + I2 CHI3 + NaI + H2O + CH3COONa
Yellow crystalline
Propanone ppt. (hospital smell)
Q. Follow the same set of reactions
using ethanal, propan-2-ol and
propanone.
USES:
● Used as solvent.
a. Chloroethane c. 2-chloro-2-methylpropane
b. 2-chlorobutane d. 2-bromo-2-methylpropane
a. Chloroethane c. 1-chloropropane
b. 2-bromopropane d. Chloromethane
MCQs
13. 2,2,2-trichloroethanal is commonly known as,
a. Carbylamine c. Phosgene
b. Chloral d. Freon-22
a. Chloretone c. Chlorofluorocarbon
b. Phosgene d. Chloropicrin
a. Hydroxy c. Alkoxy
b. Cyanide d. Halide
a. But-1-ene c. But-2-ene
b. Butan-2-ol d. Bromoethane
a. But-2-ene c. 2,3-dimethylbutane
b. 2-methylpropene d. But-1-ene