Chapter

Chapter:10
What are Haloalkanes and Haloarenes ?
 In aliphatic or aromatic compounds, the replacement of hydrogen atom(s) by halogen

atoms(s) results in the formation of alkyl halide (haloalkane) and aryl halide
(haloarene), respectively.
 In case of haloalkanes, halogen atom is attached to the sp3 hybridised carbon atom of
an alkyl group whereas in haloarenes, halogen atom is attached to sp2 hybridised
carbon atom of an aryl group.
 Haloalkanes or haloarenes are classified as mono, di- tri-, tetra- haloalkanes or
haloarenes, etc., according to the one, two, three, four, etc., halogen atoms
respectively present in their molecule.
 On the basis of the halogen atom attached to primary, secondary and tertiary carbon
atoms alkyl halides are further classified as classified as 1°, 2°, 3°, allylic, benzylic,
vinylic and aryl derivatives.
Classification of Haloalkane s and Haloar enes

Compounds containing sp3 C–X Bond
 ➥ Alkyl halides or haloalkanes (R–X)
 ➥ Allylic halides This have X bonded to the carbon atom adjacent to C–C double bond.
 ➥ Benezylic halidesThis have X bonded to the carbon atom adjacent to a benzene ring.
Compounds containing sp2 C–X Bond

 ➥ Vinylic halides This have a halogen atom (X) bonded to a C–C double bond.
 ➥ Aryl halides This have a halogen atom bonded to a benzene ring.
Nature Of C-x Bond

Since halogen atoms are more electronegative than carbon, the carbon-halogen
bond of alkyl halide is polarised; the carbon atom bears a partial positive
charge whereas the halogen atom bears a partial negative charge.
Methods Of Preparation Of Haloalkanes

Haloalkanes can be prepared from displacement of alcoholic group in alkyl alcohol by
halogen acid, PCl5 and PCl3. Haloalkanes can also be prepared by addition of halogen
acids or halogens on alkene and alkyne. Alkyl halides can aslo be prepared by free
radical halogenation of alkene.
Finkelstein Reaction
𝑅−𝑋+𝑁𝑎𝐼→𝑋=𝐶𝑙,𝑟𝑎𝑐𝑒𝑡𝑜𝑛𝑒𝑅—𝐼+𝑁𝑎𝑋R−X+NaIacetoneX=Cl,BrR—I+NaX
Swarts Reaction
𝐻3𝐶−𝐵𝑟+𝐴𝑔𝐹⟶𝐻3𝐶−𝐹+𝐴𝑔𝐵𝑟H3C−Br+AgF⟶H3C−F+AgBr
𝐻𝑔2𝐹2, 𝐶𝑂𝐹2 𝑎𝑛𝑑 𝑆𝑏𝐹3 can also be used as a reagent for Swarts reacti
on.Hg2F2, COF2 and SbF3 can also be used as a reagent for Swarts react
ion.
Hunsdiecker Reaction
𝐶𝐻3𝐶𝑂𝑂𝐴𝑔+𝐵𝑟2→𝐶𝐶𝑙4𝐶𝐻3𝐵𝑟+𝐴𝑔𝐵𝑟+𝐶𝑂2CH3COOAg+Br2CCl4CH3
Br+AgBr+CO2
Free Radical halogenat ion of alkane
Physical Properties Of Haloalkanes
 Boiling point orders 1. R-I > R - Br > R-Cl > R -F
 CH3–(CH2)2–CH2Br > (CH3)2CHCH2Br > (CH3)3CBr
 CH3CH2CH2 > CH3CH2X > CH3X
 Bond strength of haloalkanes decreases as the size of the halogen atom increases.
Thus, the order of bond strength is CH3F > CH3Cl > CH3Br > CH3I.
 Dipole moment decreases as the electronegativity of the halogen decreases.
 Haloalkanes though polar but are insoluble in water as they do not form hydrogen
bonding with water.
 Density order is RI> RBr > RCl > RF (for the same alkyl group) CH3I > C2H5I > C3H7I
Chemical Properties Of Haloalkanes
Relative reactivity of alkyl halides for same alkyl group is RI > RBr > RCI> RF
(I) Nucleophilic Substitution R eactions (S N reactions)

Nucleophilic Substitution R eactions
(II) Eliminat ion Reactions
Dehydrohalogenation is a -elimination reaction in which halogen is from α carbon
atom and the hydrogen from the β carbon according to Saytzeff rule, e.g.,
(III) Reduction
C2H5—Br+H2→Ni, 575 KC2H6+HBrC2H5I+HI→Red P, 420 KC2H6
+I2C2H5—Br+H2Ni, 575 KC2H6+HBrC2H5I+HIRed P, 420 KC2H6+I2
Chemical Properties Of Haloarenes

Aromatic nucleophilic s ubstitution reaction Haloarenes do not undergo
nucleophilic substitution reaction readily. This is due to C–X bond in aryl halide is
short and strong and also the aromatic ring is a centre of high electron density. The
halogen of haloarenes can be substituted by OH-, NH2 -, or CN- with appropriate
nucleophilic reagents at high temperature and pressure. For Example :
𝐶6𝐻5𝐶𝑙+𝑁𝑎𝑂𝐻Chlorobenzene→300𝑎𝑡𝑚350°𝐶𝐶6𝐻5𝑂𝐻+𝑁𝑎𝐶𝑙Chlorob
enzeneChlorobenzeneC6H5Cl+NaOH350°C300atmChlorobenzeneC6H5OH+NaCl
𝐶6𝐻5𝐶𝑙+2𝑁𝐻3Chlorobenzene→50𝑎𝑡𝑚250°𝐶𝐶6𝐻5𝑁𝐻2+𝑁𝐻4𝐶𝑙Anilin
eChlorobenzeneC6H5Cl+2NH3250°C50atmAnilineC6H5NH2+NH4Cl
𝐶6𝐻5𝐶𝑙+𝐶𝑢𝐶𝑁Chlorobenzene→𝑃𝑦𝑟𝑖𝑑𝑖𝑛𝑒250°𝐶𝐶6𝐻5𝐶𝑁+𝐶𝑢𝐶𝑙Phenyl
cyanideChlorobenzeneC6H5Cl+CuCN250°CPyridinePhenylcyanideC6H5CN+CuCl
Polyhalogen Compounds: Uses And Environmental

Effects
(i) Dichloromethane (Methylene chloride)
 It is used as solvent, paint remover, propellant in aerosols, process solvent in
the manufacture of drugs and in the metal cleaning and finishing solvent.
(ii) Triiodomethane (Iodoform)

 They are used as an antiseptic due to the liberation of free iodine. It is not because of
Iodoform itself.
(iii) Trichloromethane (Chloroform)

 It is used as anesthetic because when pure chloroform is inhaled it affects
the heart due to which after mixing with ether and other suitable anesthetics
chloroform can be used as anesthetic.
(iv) Tetra Chloromethane (Carbon Tetrachloride)

 They are used in manufacturing refrigerants, propellants for aerosol cans and for the
synthesis of chlorofluorocarbons, pharmaceutical etc.
(v) Freons
 The Chlorofluorocarbon compounds of methane and ethane are jointly called freons.
 They are very stable, non-corrosive, non-toxic, and unreactive liquefiable gases.
(vi) P,P'-Dichlorodiphenyltrichloroethane (DDT)

 DDT stands to be the first chlorinated organic insecticides. It is highly
poisonous to all living organisms as it does not get metabolized
rapidly by animals and gets deposited and stored in the fatty tissues.

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Chapter:10

What are Haloalkanes and Haloarenes ?

 In aliphatic or aromatic compounds, the replacement of hydrogen atom(s) by halogen

Classification of Haloalkane s and Haloar enes

Compounds containing sp2 C–X Bond

Nature Of C-x Bond

Methods Of Preparation Of Haloalkanes

(I) Nucleophilic Substitution R eactions (S N reactions)

Chemical Properties Of Haloarenes

Polyhalogen Compounds: Uses And Environmental

(ii) Triiodomethane (Iodoform)

(iii) Trichloromethane (Chloroform)

(iv) Tetra Chloromethane (Carbon Tetrachloride)

(vi) P,P'-Dichlorodiphenyltrichloroethane (DDT)

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