Haloalkanes and Haloarenes
Functional +R -R +I -I
Group
-NH2 ✔ ✔
-OH ✔ ✔
-NO2 ✔ ✔
-CHO ✔ ✔
-CH3 ✔
-NH3⊕ ✔
-O⊖ ✔ ✔
Why SOCl2 is preferred?
By product (SO2 and HCl) are gases which are escapable, leaving only the alkyl halide
Physical properties:
● Boiling points of alkyl halides decreases in the order RI>RBr>RCl>RF because of the
increase in size and the mass of hydrogen atom and the magnitude of the van der
Waal forces increases
● Para isomers are high melting as compared to their ortho and meta isomers. It is due
to symmetry of para isomers that fit in crystal lattice better as compared to ortho and
meta isomers.
● Solubility: haloalkanes are slightly soluble in water. Less energy is released when
new attractions are set up between the haloalkane and the water molecule as they
are not as strong as the original hydrogen bonds in water. As a result solubility of
haloalkanes in water is low.
SN1: 3>2>1
SN2: 1>2>3
Aryl halides are less reactive towards nucleophilic substitution reactions:
● Resonance effect : C—Cl bond acquires a partial double bond character due to
resonance. As a result, the bond cleavage in haloarene is difficult than haloalkane
and therefore, they are less reactive towards nucleophilic substitution reactions.
● Difference in hybridisation of carbon atom in C—X bond: Since it is difficult to break a
shorter bond than a longer bond, therefore, haloarenes are less reactive than
haloalkanes towards nucleophilic substitution reaction.
● Instability of phenyl cation
● Because of the possible repulsion, it is less likely for the electron rich nucleophile to
approach electron rich arenes.
Alcohols, Phenols and Ethers
Physical Properties (alcohols and phenols):
● The boiling points of alcohols and phenols increase with increase in the number of
carbon atoms (increase in van der Waals forces).
● Solubility of alcohols and phenols in water is due to their ability to form hydrogen
bonds with water molecules.
Physical Properties (ethers):
● The large difference in boiling points of alcohols and ethers is due to the presence of
hydrogen bonding in alcohols.
● The miscibility of ethers with water resembles those of alcohols of the same
molecular mass
Aldehyde, ketones and C-acids
Physical Properties:
● The boiling points of aldehydes and ketones are higher than hydrocarbons and
ethers of comparable molecular masses. It is due to weak molecular association in
aldehydes and ketones arising out of the dipole-dipole interactions. Also, their boiling
points are lower than those of alcohols of similar molecular masses due to absence
of intermolecular hydrogen bonding.
● The lower members of aldehydes and ketones such as methanal, ethanal and
propanone are miscible with water in all proportions, because they form hydrogen
bond with water.
● Aldehydes are generally more reactive than ketones in nucleophilic addition reactions
due to steric and electronic reasons
Amines
Physical Properties:
● Lower aliphatic amines are soluble in water because they can form hydrogen bonds
with water molecules. However, solubility decreases with increase in molar mass of
amines due to increase in size of the hydrophobic alkyl part.
● Moreover, amines behave as nucleophiles due to the presence of unshared electron
pair.
● Arylamine vs ammonia:
pKb value of aniline is quite high. It is because in aniline or other arylamines,
the -NH2 group is attached directly to the benzene ring. It results in the unshared
electron pair on nitrogen atom to be in conjugation with the benzene ring and thus
making it less available for protonation.
Why no Friedel Crafts with aniline?
Aniline does not undergo Friedel-Crafts reaction (alkylation and acetylation) due to salt
formation with aluminium chloride, the Lewis acid, which is used as a catalyst. Due to this,
nitrogen of aniline acquires positive charge and hence acts as a strong deactivating group
for further reaction.
