Haloalkanes and Haloarenes

Short Notes

Classi cation of halogen derivative:-

1. Aliphatic halogen compounds - Haloalkanes

2. Aromatic halogen compounds - Haloarenes

A. By type of halogen atom

1. Fluroalkanes

2. Chloroalkanes

3. Bromoalkanes

4. Iodoalkanes

B. No. of halogen atoms

1. Monohalo compounds

2. Dihalo compounds

3. Trihalo compounds

4. Tetrahalo compounds

5. Polyhalo compounds

C. Nature of carbon atom

1. Primary halo compounds

2. Secondary halo compounds

3. Tertiary halo compounds

D. By type of compound
1. Alkyl halides(1-deg)

2. Allyl halides(1-deg)

3. Propargyl halide(1-deg)

4. Benzyl halide(2-deg)

5. Vinyl halide(2-deg)

6. Aryl halide(2-deg)

7. Gem-dihalides

Nomenclature of Haloalkanes and Haloarenes

IUPAC - Halo Alkane/Arene

Common Name - Alkyl Halide

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 # Fully halogenated hydrogen atoms are called as perhalohydrocarbons.

Methods of preparation of Haloalkanes

# Check organic chemistry database for reactions

1. From Alcohols
By nucleophilic substitution method
It is prepared in labaratories by replacing -OH with -X by reaction
with concentrated halogen acids, phosphorus halides or thionyl
chloride.

1. By Halogen Acid

# Anhyd. ZnCl2 is used to help in the cleavage of C—O bond. It

forms co-ordination with O atom and leaves with it forming a
carbocation.

# Preparation of uoroalkanes is impossible by this method

because uroalkanes are very low reactive.

HI > HBr > HCl & 3o >2o >1o alkanes.

2. By phosphorus halides

3. By thionyl chloride

2.By Alkanes
By electrophilic substitution method
# Reactivity of hydrogen in halo compounds

Benzylic = alylic>alkyl>vinyl=arylic

#Fluorination can’t take place since it leads to poly substitution of

uorine and is highly exothermic in nature.

#Iodination is reversible in nature but can be carried out in

presence of oxidising agents such as HIO3 driving the reaction in
forward direction.

3. By Alkenes
By addition reactions

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Markovnikov Rule
During reaction across unsymmetrical double bond , the negative
part of the attacking reagent attaches itself to the carbon atom
carrying lesser no. of hydrogen atoms while the positive part goes
to the carbon atom with more number of hydrogen atoms

Markovnikov rule is not followed in presence of R-OO-R. This

is known as peroxide e ect or kharash e ect. This is only
applicable to HBr.

# Allylic substitution of halogens can also be carried out with the

help of NBS, Sulphuryl Chloride.

4. By Alkynes
# This also follows markovnikov rule.

5.By Halogen exchange method

1.Finkelstein reaction

2. Swarts Reaction

6.From silver salts of acids

3.Hundsdieker reaction

#yield of halide here is 1deg > 2-deg > 3-deg

4. Birnbaum simonini reaction

Methods of preparation of Haloarenes

1. Halogenation of aromatic ring
# Electrophilic substitution takes place here.

#Fluroarene can’t be prepared directly since it is very violent and

exothermic.

2. From diazonium salts

A. Sandmeyer’s reaction

B. Balz-sciemann reaction

C. Gattermann reaction

D. Raschig process

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 Physical Properties of Haloalkanes
1. Physical state and smell.
haloalkanes are in general colourless in pure form, sweet
smelling liquids. Lower haloalkanes are are colourless gases at
room temperature. Higher members are liquids and solids.

2. Solubility
Haloalkanes are less soluble in water even tough they are
polar compounds. However chloro, bromo, iodo derivatives are
highly soluble in organic solvents like alcohol, ether, benzene.

3. Density
uoride<chloride<water<polychloro<bromo<iodo

4. M.pt & b.pt

Halogen derivatives usually have high m.pt & b.pt than those
of their parent hydrocarbon.

RI>RBr>RCl>RF (boiling point trend for same alkyl group)

Boiling point of chloro, broom and todo compounds increase

with increase in no.of halogen atoms.

For same halogen atom the boiling points of haloalkanes

increase with increase in the size of the chain of alkyl groups.

For isomeric alkyl halides boiling point decrease with

branching. Branching decreases surface area, so magnitude of van
der Waals forces decrease resulting in low boiling point.

5. In ammable Nature
Halogen compounds are less in ammable than hydrocarbons.
Carbon tetrachloride is used as a re extinguisher in the name of
pyrene.

6. Polarity & Dipole moment

F>Cl>Br>I. Exception : CH3Cl>CH3F due to smaller size of
uorine.

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Physical Properties of Haloarenes
They are generally colourless liquids or crystalline solids. They
are heavier than water hence insoluble in water but soluble in
organic solvents.

The melting points and boiling points of aryl halides are

almost same as those of alkyl halides containing same no. of C
atoms

Generally melting point of para isomer is higher than that of

others due to symmetry & its molecules are easily packed in crystal
lattices. As a result, intermolecular forces of attraction are stronger.

Fluro, chloro, Iodo benzenes have more dipole moment than

that of their methyl halides. Lowest dipole moment is uoro
benzene due to its small size.

p-isomer of same dihalo arenes have 0 dipole moment.

Chemical Properties of Haloalkanes

1. Nucleophilic substitution reaction
a. By hydroxyl group (-OH)

with boiling aqueous alkali or moist silver oxide.

b. By alkoxy group (-OR)

with sodium/potassium alkoxide


(Williamson’s Synthesis reaction) - with dry silver oxide

c. By cyano group (-CN)

with alc.KCN

d. By isocyanide group (-NC)

with silver cyanide

(-CN / -NC are ambident nucleophile)

e. By amino group (-NH2)

with all.Ammonia in sealed tube. If haloalkane is in excess the

reaction may proceed to form secondary or tertiary amines.
Formation of tetra alkyl ammonium halide is called Ho mann
Ammonolysis.

f. By Nitrite group (-O-N=O)

with Na/K nitrate.

g. By nitro group (-NO2)

with silver nitrate. (-NO2 / -ONO are both ambident

nucleophiles)

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h. By carboxyl group (R-COO-)

with silver salt of fatty acid in ethanol.

i. By hydrogen sulphide group (-SH)

with sodium hydrogen sulphide/ potassium hydrogen sulphide

in aq.ethanol solution.

j. By alkyl sulphide group (-SR)

with sodium alkyl sulphide or sodium sulphide in aq.ethanol.

k. By azide group (-N3)

with sodium azide in aq.ethanol.

l. By alkynyl group (-CCR)

with sodium alkynides.

2. Elimination reaction
it is beta-elimination reaction results in formation of alkene. It
is called as dehydrohalogenation.

#alc.KOH forms elimination product while aq.KOH forms

substitution product.

3. Reaction with metals

a. Formation of grignards reagent (in dry ether & Mg)

b. Wurtz reaction

c. Reaction with Li/Zn/Pb (formation of orgometallic

compounds)

4. Reduction
a. Ni/Pd at 525K

b. Zn/Cu couple with C2H5OH.

c. Red P

5. Rearrangement
with anhyd.AlCl3 at 573K.

Chemical Properties of Haloarenes

1. Nucleophilic substitution reaction
a. By -OH (formation of phenol)

with NaOH at 623K, 300atm, dil.HCl

b. By amino group (formation of aniline)

With NH3 , Cu2O at 473K, 60atm

c. By cyan group (formation of cyanobenzene)

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 with CuCN and pyridine at 475K.

2. Reaction with metals

a. Reaction with magnesium/ Lithium

b. Wurtz- ttig & Fitting reaction

c. Ulmann reaction

3. Reduction
with LiAlH4 or Ni-Al alloy with NaOH forms benzene.

4. Ring substitution
Haloarenes undergo electrophilic substitutiton reaction slower
than benzene. They are o,p- directing group.

a. Halogenation

b. Nitration

c. Sulphonation

d. F.C.Alkylation

e. F.C.Acylation

Commercially important compounds

1. Di chloromethane

2. Chloroform

3. Iodoform

4. Carbon tetra chloride

5. Freons

6. DDT

#Their uses are required for exams.

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